New remote sensing techniques for the detection and quantification of earth surface CO2 degassing

Earth degassing specifically of carbon dioxide CO₂ is of increasing interest with respect to the global carbon budget, related climate effects, earthquake and volcano eruption mechanisms, as well as plant physiological reactions in gas-rich environments. Investigations in all of these disciplines require the detection of surface CO₂ degassing structures and quantification of their emissions. We introduce minimal thermal change detection based on infrared imaging as a new remote sensing tool for the detection of earth surface thermal anomalies suiting among others to discover earth degassing locations of any origin. The method allows for seamless areal search and monitoring of degassing structures in any terrain. As proof of concept infrared imaging measurements were performed at the Bossoleto vent on the eastern master fault of the Siena Graben (Tuscany, Italy). It is known for the migration of a large amount of CO₂-rich gas from deep geothermal reservoirs. Field data acquired confirmed the qualification of the method. Detection of CO₂ degassing locations from infrared image time series worked reliably and optimal detection conditions were identified (dry, calm, cloudless weather between dusk and dawn). A simple model of heat exchange processes involved and observed was developed. In a first attempt this model was applied to determine the gas exit temperature, the area of gas thermal reach and the gas flux from recorded image series. It is the first method that allows remote areal survey of mofette fields and the associated CO₂ flux quantification sole from infrared image time series.     

河流水-气界面CO2脱气时间尺度变化研究进展

河流作为连接陆地和海洋碳库之间的通道,是全球内陆水体碳排放最主要的载体,在全球碳循环中发挥着至关重要的作用。全球河流水-气界面二氧化碳（CO₂）脱气显著的时间异质性特征研究有助于深入理解其碳循环过程与机制,也为准确评估碳通量以及完善碳循环模型提供了科学支撑。本文系统梳理了国内外的相关研究成果,总结了目前河流CO₂脱气通量在昼夜、季节以及多年尺度上的动态变化及其影响因素,指出其昼夜变化与季节变化存在一定的周期性,并对不同空间尺度上CO₂脱气通量的时间差异进行讨论。同时分析当前研究中的不足,认为缺乏河流二氧化碳分压（pCO₂）与CO₂脱气系数（k）高分辨率且长期连续的直接测量,限制了河流CO₂脱气通量时间尺度变化的周期性及相互之间关系的厘定,使得气候变化与人类活动对河流CO₂脱气时间动态的影响仍然难以量化与预测。最后,根据目前存在的问题,展望了未来的研究重点,为全球河流水-气界面碳循环过程与机制、模型研究提供新的思路与方向,以及可以更准确地评估和预测未来河流碳排放的变化趋势。     

Environmental influences on soil CO2 degassing at Furnas and Fogo volcanoes (São Miguel Island,Azores archipelago)

Since October 2001, four soil CO₂ flux stations were installed in the island of São Miguel (Azores archipelago), at Fogo and Furnas quiescent central volcanoes. These stations perform measurements by the accumulation chamber method and, as the gas flux may be influenced by external variables, the stations are equipped with several meteorological sensors. Multivariate regression analysis applied to the large datasets obtained allowed observing that the meteorological variables may influence the soil CO₂ flux oscillations from 18% to 50.5% at the different monitoring sites. Additionally, it was observed that meteorological variables (mainly soil water content, barometric pressure, wind speed and rainfall) play a different role in the control of the gas flux, depending on the selected monitoring site and may cause significant short-term (spike-like) fluctuations. These divergences may be potentially explained by the porosity and hydraulic conductivity of the soils, topographic effects, drainage area and different exposure of the monitoring sites to the weather conditions. Seasonal effects are responsible for long-term oscillations on the gas flux.     

Geochemical features of the geothermal CO2-watercarbonate rock system and analysis on its CO2 sources

Taking Huanglong Ravine and Kangding, Sichuan, and Xiage, Zhongdian, Yunnan, as examples, the authors summarize the hydrogeochemical and carbon stable isotopic features of the geothermal CO₂-water-carbonate rock system and analyze the CO₂ sources of the system. It was found that the hydrogeochemical and carbon stable isotopic features of such a system are different from those of shallow CO₂-water-carbonate rock system, which is strongly influenced by biosphere. The former has higher CO₂ partial pressure, and is rich in heavy carbon stable isotope. In addition, such a geothermal system is also different from that developed in igneous rock. The water in the latter system lacks Ca²⁺, and thus, there are few tufa deposits on ground surface, but it is rich in light carbon stable isotope. Further analysis shows that CO₂ of the geothermal CO₂-water-carbonate rock system is a mixture of metamorphic CO₂ and magmatic CO₂.     

Diffuse CO2 emission rate from Pululahua and the lake-filled Cuicocha calderas,Ecuador

We report herein the first results of two soil CO₂ efflux surveys carried out at Cuicocha lake-filled and Pululahua caldera volcanic systems, Ecuador. A total of 172 and 217 soil CO₂ efflux measurements were taken at the surface environment of Pululahua and Cuicocha calderas respectively, by means of the “accumulation chamber” method during the summer of 2006 to constrain the total CO₂ output from the studied area. Soil CO₂ efflux values ranged from non-detectable up to 48.5 and 141.7 g m^{− 2} d^{− 1} for Cuicocha and Pululahua calderas respectively. In addition, probability graphs were used to distinguish the existence of different geochemical populations. Sequential Gaussian Simulation was used to construct an average map for 100 simulations and to compute the total CO₂ emission at each studied area: 106 and 270 t d^{− 1} (metric tons per day) for Cuicocha (13.3 km²) and Pululahua (27.6 km²) volcanoes respectively.     

Limestone assimilation and the origin of CO2 emissions at the Alban Hills (Central Italy): Constraints from experimental petrology

The Alban Hills volcanic region (20 km south of Rome, in the Roman Province) emitted a large volume of potassic magmas (> 280 km³) during the Quaternary. Chemical interactions between ascending magmas and the ∼ 7000–8000-m-thick sedimentary carbonate basement are documented by abundant high temperature skarn xenoliths in the eruptive products and have been frequently corroborated by geochemical surveys. In this paper we characterize the effect of carbonate assimilation on phase relationships at 200 MPa and 1150–1050 °C by experimental petrology. Calcite and dolomite addition promotes the crystallization of Ca-rich pyroxene and Mg-rich olivine respectively, and addition of both carbonates results in the desilication of the melt. Furthermore, carbonate assimilation liberates a large quantity of CO₂-rich fluid. A comparison of experimental versus natural mineral, glass and bulk rock compositions suggests large variations in the degree of carbonate assimilation for the different Alban Hills eruptions. A maximum of 15 wt.% assimilation is suggested by some melt inclusion and clinopyroxene compositions; however, most of the natural data indicate assimilation of between 3 and 12 wt.% carbonate. Current high CO₂ emissions in this area most likely indicate that such an assimilation process still occurs at depth. We calculate that a magma intruding into the carbonate basement with a rate of ∼ 1 – 2 · 10⁶ m³/year, estimated by geophysical studies, and assimilating 3–12 wt.% of host rocks would release an amount of CO₂ matching the current yearly emissions at the Alban Hills. Our results strongly suggest that current CO₂ emissions in this region are the shallow manifestation of hot mafic magma intrusion in the carbonate-hosted reservoir at 5–6 km depth, with important consequences for the present-day volcanic hazard evaluation in this densely populated and historical area.     

A stochastic model for daily subsurface CO2 concentration and related soil respiration

Near-surface soil CO₂ gas-phase concentration (C) and concomitant incident rainfall (P_i) and through-fall (P_t) depths were collected at different locations in a temperate pine forest every 30 min during the 2005 and 2006 growing seasons (and then averaged to the daily timescale). At the daily scale, C temporal variations were well described by a sequence of monotonically decreasing functions interrupted by large positive jumps induced by rainfall events. A stochastic model was developed to link rainfall statistics responsible for these jumps to near-surface C dynamics. The model accounted for the effect of daily rainfall variability, both in terms of timing and amount of water, and permitted an analytical derivation of the C probability density function (pdf) using the parameters of the rainfall pdf. Given the observed positive correlation between daily C and soil CO₂ fluxes to the atmosphere (F_s), the effects of various rainfall regimes on the statistics of F_s can be deduced from the behavior of C under different climatic conditions. The predictions from this analytical model are consistent with flux measurements reported in manipulative experiments that varied rainfall amount and frequency.     

Multi-scale modeling of CO2 dispersion leaked from seafloor off the Japanese coast

A numerical simulation was conducted to predict the change of pCO₂ in the ocean caused by CO₂ leaked from an underground aquifer, in which CO₂ is purposefully stored. The target space of the present model was the ocean above the seafloor. The behavior of CO₂ bubbles, their dissolution, and the advection-diffusion of dissolved CO₂ were numerically simulated. Here, two cases for the leakage rate were studied: an extreme case, 94,600 t/y, which assumed that a large fault accidentally connects the CO₂ reservoir and the seafloor; and a reasonable case, 3800 t/y, based on the seepage rate of an existing EOR site. In the extreme case, the calculated increase in ΔpCO₂ experienced by floating organisms was less than 300 ppm, while that for immobile organisms directly over the fault surface periodically exceeded 1000 ppm, if momentarily. In the reasonable case, the calculated ΔpCO₂ and pH were within the range of natural fluctuation.     

微囊藻CO2-浓缩机制基因型的动态变化及其对CO2的竞争效应

由于具有高效的CO₂-浓缩机制,蓝藻在低CO₂浓度条件下具有竞争优势。然而,随着大气中CO₂浓度急剧增加,蓝藻CO₂-浓缩机制如何响应的研究较少。因此,本文以常见水华蓝藻——微囊藻为研究对象,通过对滇池微囊藻水华动态及不同CO₂-浓缩机制基因型进行监测,探讨蓝藻CO₂-浓缩机制基因的微进化特征及其动态变化。同时,设置高(0.08%)、中(0.04%)、低(0.02%)CO₂浓度(V/V)进一步揭示微囊藻不同CO₂-浓缩机制基因微进化对CO₂的竞争效应。结果表明:滇池无机碳浓度在4个采样点存在空间差异性,均呈现先降低后升高的趋势,并以HCO₃^-为主要无机碳存在形式。调查期间,东大河、观音山、洛龙河和生态所4个采样点的微囊藻均以sbtA基因型占绝对优势,相对丰度远高于bicA基因型。在不同水华时期,bicA基因型和sbtA基因型呈现相反的变化趋势,即从...     

CO2/CaCl2 solution interfacial tensions under CO2 geological storage conditions: Influence of cation valence on interfacial tension

The effectiveness of CO₂ storage in deep saline aquifers and hydrocarbon reservoirs is governed, among other factors, by the interfacial tension between the injected CO₂ and formation water (brine). Experimental data on CO₂/water and CO₂/NaCl solution have revealed that the interfacial tension depends on the pressure, temperature and water salinity. However, there is still a lack of data for other salts (such as MgCl₂ and CaCl₂) which are also present in aquifers and carbonate reservoirs.     

Time-lapse processing of 2D seismic profiles with testing of static correction methods at the CO2 injection site Ketzin (Germany)

The Ketzin project provides an experimental pilot test site for the geological storage of CO₂. Seismic monitoring of the Ketzin site comprises 2D and 3D time-lapse experiments with baseline experiments in 2005. The first repeat 2D survey was acquired in 2009 after 22 kt of CO₂ had been injected into the Stuttgart Formation at approximately 630 m depth. Main objectives of the 2D seismic surveys were the imaging of geological structures, detection of injected CO₂, and comparison with the 3D surveys. Time-lapse processing highlighted the importance of detailed static corrections to account for travel time delays, which are attributed to different near-surface velocities during the survey periods. Compensation for these delays has been performed using both pre-stack static corrections and post-stack static corrections. The pre-stack method decomposes the travel time delays of baseline and repeat datasets in a surface consistent manner, while the latter cross-aligns baseline and repeat stacked sections along a reference horizon.Application of the static corrections improves the S/N ratio of the time-lapse sections significantly. Based on our results, it is recommended to apply a combination of both corrections when time-lapse processing faces considerable near-surface velocity changes. Processing of the datasets demonstrates that the decomposed solution of the pre-stack static corrections can be used for interpretation of changes in near-surface velocities. In particular, the long-wavelength part of the solution indicates an increase in soil moisture or a shallower groundwater table in the repeat survey.Comparison with the processing results of 2D and 3D surveys shows that both image the subsurface, but with local variations which are mainly associated to differences in the acquisition geometry and source types used. Interpretation of baseline and repeat stacks shows that no CO₂ related time-lapse signature is observable where the 2D lines allow monitoring of the reservoir. This finding is consistent with the time-lapse results of the 3D surveys, which show an increase in reflection amplitude centered around the injection well. To further investigate any potential CO₂ signature, an amplitude versus offset (AVO) analysis was performed. The time-lapse analysis of the AVO does not indicate the presence of CO₂, as expected, but shows signs of a pressure response in the repeat data.     

Variations of near-surface atmospheric CO2 and H2O concentrations during summer on Muztagata

Expeditions during the summers of 2002 and 2003 implemented continuous monitoring of near-surface (2 m height) atmospheric CO₂ and H₂O concentrations at the 4500 m elevation on Muztagata. The resultant data sets reveal a slight decrease of CO₂ concentrations (of about 5 μmol·mol^-1) and changes in the diurnal variations from the end of June to the middle August. The daily maximum CO₂ concentrations occur between 02:30-05:30 AM (local time) and the minimum levels occur between 12:00-15:30 PM. The atmospheric CO₂ concentrations in the summer of 2002 were around 5 μmol·mol^-1 lower than those during the same period of 2003, whereas the diurnal amplitude was higher. In contrast, we found that the daily mean atmospheric H₂O content in 2003 was much lower than that in 2002 and there exists a striking negative correlation between CO₂ and H₂O concentrations. We therefore suggest that the near-surface atmospheric CO₂ concentration is affected not only by photosynthesis and respiration, but also by the air H₂O content in the glaciated region around Muztagata.     

Capillary pressure for the sand–CO2–water system under various pressure conditions. Application to CO2 sequestration

Accurate modeling of storage of carbon dioxide (CO₂) in heterogeneous aquifers requires experiments of the capillary pressure as function of temperature and pressure. We present a method with which static drainage and imbibition capillary pressures can be measured continuously as a function of saturation at various temperature (T) and pressure (P) conditions. The measurements are carried out at (T, P) conditions of practical interest. Static conditions can be assumed as small injection rates are applied. The capillary pressure curves are obtained for the unconsolidated sand–distilled water–CO₂ system. The experimental results show a decrease of drainage and imbibition capillary pressure for increasing CO₂ pressures and pronounced dissolution rate effects for gaseous CO₂. Significant capillary pressure fluctuations and negative values during imbibition are observed at near critical conditions. The measurement procedure is validated by a numerical model that simulates the experiments.     

三峡水库澎溪河消落区土-气界面CO2和CH4通量初探

水库近岸湿地(消落区)温室气体(CO₂、CH₄)产汇是水库温室气体效应问题的重要组成部分.本文以三峡水库支流澎溪河的白家溪、养鹿两处大面积消落区为研究对象,于2010年6 9月水库低水位运行期间,对近岸消落区土-气界面CO₂、CH₄通量进行监测.白家溪消落区土-气界面CO₂通量均值为12.38±2.42 mmol/(m²·h);CH₄通量均值为0.0112±0.0064 mmol/(m²·h).养鹿消落区CO₂、CH₄通量均值分别为10.54±5.17、0.14±0.16 mmol/(m²·h).总体上,6 9月土-气界面CO₂通量呈增加趋势,而CH₄通量水平呈现显著的递减趋势.消落区土地出露后植被恢复,在一定程度上促进了土壤有机质含量的增加,使得6 9月CO₂释放通量的总体趋势有所增加.消落区退耕后,其甲烷氧化菌的活性得到恢复,加之在土地出露曝晒过程中土壤透气性增强,使得消落区土壤对大气中CH₄吸收氧化潜势增强.尽管如此,仍需进一步的研究以明晰消落区土-气界面CO₂、CH₄产汇的主要影响因素.     

Interfacial tension measurements and wettability evaluation for geological CO2 storage

Interfacial interactions, namely interfacial tension, wettability, capillarity and interfacial mass transfer are known to govern fluid distribution and behavior in porous media. Therefore the interfacial interactions between CO₂, brine and oil and/or gas reservoirs have a significant influence on the effectiveness of any CO₂ storage operations. However, data and knowledge of interfacial properties in storage conditions are scarce. This issue becomes particularly true in the case of deep saline aquifers where limited, economically driven, data collection and archiving are available. In this paper, we present a complete set of brine–CO₂ interfacial tension data at pressure, temperature and salinity conditions, representative of a CO₂ storage operation. A semi-empirical correlation is proposed to calculate the interfacial tension from the experimental data. Wettability is studied at pore scale, using glass micromodels in order to track fluids distribution as a function of the thermodynamic properties and wettability conditions for water–CO₂ systems. With this approach, we show that, in strongly hydrophilic porous media, the CO₂ does not wet the solid surface whereas; if the porous media has less hydrophilic properties the CO₂ significantly wets the surface.     

Effects of CO2 on benthic biota: An in situ benthic chamber experiment in Storfjorden (Norway)

Carbon capture and storage (CCS) methods, either sub-seabed or in ocean depths, introduces risk of CO₂ leakage and subsequent interaction with the ecosystem. It is therefore important to obtain information on possible effects of CO₂. In situ CO₂ exposure experiments were carried out twice for 10 days during 2005 using a Benthic Chamber system at 400 m depth in Storfjorden, Norway. pCO₂ in the water above the sediment in the chambers was controlled at approximately 500, 5000 and 20,000 μatm, respectively. This article describes the experiment and the results from measured the biological responses within the chamber sediments. The results show effects of elevated CO₂ concentrations on biological processes such as increased nanobenthos density. Methane production and sulphate reduction was enhanced in the approximately 5000 μatm chamber.     

Interfacial tension between CO2 and brine (NaCl + CaCl2) at elevated pressures and temperatures: The additive effect of different salts

An extensive laboratory study was conducted to measure the interfacial tension (IFT) between CO₂ and brine consisting in equal molal concentrations of NaCl and CaCl₂. The experiments were repeated at various pressures, temperatures and salinities that are representative of conditions prevailing during CO₂ storage in deep saline aquifers. The dependence of CO₂/brine IFT on pressure and temperature is similar to that previously reported for the systems: CO₂/NaCl solution and CO₂/CaCl₂ solution. CO₂/brine IFT increases linearly with water salinity and the magnitude of this increase was found equal to the sum of the individual CO₂/NaCl solution and CO₂/CaCl₂ solution IFT increments, indicating a strong additive effect on IFT when the brine is composed of various salts.     

夏季金沙江下游水-气界面CO2、CH4通量特征初探

河流是连接大陆和海洋两大碳库的桥梁,在全球碳循环中的作用举足轻重.金沙江作为长江的上游段,对区域碳循环及区域化学风化的影响非常重要.于2015年8月8-18日对金沙江下游水-气界面CO_2与CH_4通量特征进行监测与分析.采用顶空平衡法结合薄边界层模型估算法计算表层水体CO_2与CH_4的分压以及水-气界面的交换通量,并分析环境变量与其之间的相关性.研究发现,金沙江下游表层水体p(CO_2)平均值为2724.84±477.18μatm,表层水体p(CH_4)平均值为59.96±6.74μatm;水-气界面CO_2通量平均值为2.24±0.50 mmol/(m2·h),CH_4通量平均值为0.000163±0.00009 mmol/(m2·h),通量与分压趋势基本保持一致.表层水体p(CO_2)与溶解性无机碳浓度、碱度均呈显著正相关,而p(CH_4)与水温、叶绿素a浓度均呈显著正相关,CO_2通量与p(CO_2)、溶解性无机碳浓度、碱度均呈正相关,CH_4通量与p(CH_4)、风速均呈正相关,其他环境因素对通量的影响不明显,仍需进一步研究.金沙江下游水-气界面CH_4扩散通量较低,而CO_2扩散通量在世界主要河流中属于中等水平.     

A contribution to risk analysis for leakage through abandoned wells in geological CO2 storage

The selection and the subsequent design of a subsurface CO₂ storage system are subject to considerable uncertainty. It is therefore important to assess the potential risks for health, safety and environment. This study contributes to the development of methods for quantitative risk assessment of CO₂ leakage from subsurface reservoirs. The amounts of leaking CO₂ are estimated by evaluating the extent of CO₂ plumes after numerically simulating a large number of reservoir realizations with a radially symmetric, homogeneous model. To conduct the computationally very expensive simulations, the ‘CO₂ Community Grid’ was used, which allows the execution of many parallel simulations simultaneously. The individual realizations are set up by randomly choosing reservoir properties from statistical distributions. The statistical characteristics of these distributions have been calculated from a large reservoir database, holding data from over 1200 reservoirs. An analytical risk equation is given, allowing the calculation of average risk due to multiple leaky wells with varying distance in the surrounding of the injection well. The reservoir parameters most affecting risk are identified. Using these results, the placement of an injection well can be optimized with respect to risk and uncertainty of leakage. The risk and uncertainty assessment can be used to determine whether a site, compared to others, should be considered for further investigations or rejected for CO₂ storage.     

CO2气体在地震孕育与发生过程中的作用及其机理研究

通过甘东南地震危险区地震宏观异常观测实例分析,系统研究CO_2气体在地震构造活动过程中的地球化学演化过程,以及发生的一系列酸碱平衡和氧化还原化学反应。结果表明地下深部CO_2气体不仅是其他微量气体Rn等向地表方向运移的载体,而且参与酸碱平衡和氧化还原反应,是地下深部生物化学反应的重要影响条件,地震前兆及宏观异常现象的发生常伴随着CO_2的异常变化。因此CO_2气体可以作为良好的示踪气体,在地震前兆观测及重大异常落实中尤其要重视对其进行监测。