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.     

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。     

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.     

Distribution of sea urchins living near shallow water CO2 vents is dependent upon species acid–base and ion-regulatory abilities

To reduce the negative effect of climate change on Biodiversity, the use of geological CO₂ sequestration has been proposed; however leakage from underwater storages may represent a risk to marine life. As extracellular homeostasis is important in determining species’ ability to cope with elevated CO₂, we investigated the acid–base and ion regulatory responses, as well as the density, of sea urchins living around CO₂ vents at Vulcano, Italy. We conducted in situ transplantation and field-based laboratory exposures to different pCO₂/pH regimes. Our results confirm that sea urchins have some ability to regulate their extracellular fluid under elevated pCO₂. Furthermore, we show that even in closely-related taxa divergent physiological capabilities underlie differences in taxa distribution around the CO₂ vent. It is concluded that species distribution under the sort of elevated CO₂ conditions occurring with leakages from geological storages and future ocean acidification scenarios, may partly be determined by quite subtle physiological differentiation.     

Carbon dioxide and radon gas hazard in the Alban Hills area (central Italy)

The sudden and catastrophic, or slow and continuous, release at surface of naturally occurring toxic gases like CO₂, H₂S and Rn poses a serious health risk to people living in geologically active regions. In general this problem receives little attention from local governments, although public concern is raised periodically when anomalous toxic-gas concentrations suddenly kill humans or livestock. For example, elevated CO₂ concentrations have been linked to the death of at least 10 people in the central Italian region of Lazio over the last 20 years, while it was the CO₂ asphyxiation of 30 cows in a heavily populated area near Rome in 1999 which prompted the present soil-gas study into the distribution of the local health risk. A detailed geochemical survey was carried out in an area of about 4 km² in the Ciampino and Marino districts, whereby a total of 274 soil-gas samples were collected and analysed for more than 10 major and trace gas species. Data were then processed using both statistical and geostatistical methods, and the resulting maps were examined in order to highlight areas of elevated risk. General trends of elevated CO₂ and Rn concentrations imply the presence of preferential pathways (i.e. faults and fractures) along which deep gases are able to migrate towards the surface. The CO₂ and Rn anomalous trends often correspond to and are usually elongated parallel to the Apennine mountain range, the controlling structural feature in central Italy. Because of this fundamental anisotropy in the factors controlling the soil-gas distribution, it was found that a geostatistical approach using variogram analysis allowed for a better interpretation of the data. With regard to the health risk to local inhabitants, it was found that although some high risk areas had been zoned as parkland, others had been heavily developed for residential purposes. For example, many new houses were found to have been built on ground which has soil-gas CO₂ concentrations of more than 70% and radon values of more than 250 kBq m⁻³. It is recommended that land-use planners incorporate soil-gas and/or gas flux measurements in environmental assessments in areas of possible risk (i.e. volcanic or structurally active areas).     

典型农业流域不同类型池塘水体CO2排放特征

内陆水体是大气CO₂收支估算的重要组成部分。农业流域分布着大量池塘景观水体,且具备蓄洪抗旱、消纳污染、水产养殖等多种功能。但是,农业流域不同功能的小型池塘CO₂排放特征尚不清楚。本研究以极具农业流域代表性的烔炀河流域为研究对象,选取流域中用于水产养殖(养殖塘)、生活污水承纳(村塘)、农业灌溉(农塘)、蓄水(水塘)的4个功能不同的景观池塘,基于为期1年的野外实地观测,以明确农业流域小型池塘CO₂排放特征。结果表明,不同功能池塘水体CO₂排放差异显著,受养殖活动、生活污水输入和农田灌溉等人类活动影响,养殖塘((80.37±100.39) mmol/(m²·d))、村塘((48.69±65.89) mmol/(m²·d))和农塘((13.50±15.81) mmol/(m²·d))是大气CO₂的热点排放源,其CO₂排放通量分别是自然蓄水塘((4.52±23.26) mmol/(m²·d))的18、11和3倍。统计分析也表明,该流域池塘CO₂排放变化总体上受溶解氧、营养盐等因素驱动。4个不同景观池塘CO₂排放通量全年均值为(37.31±67.47) mmol/(m²·d),是不容忽视的CO₂排放源,其中养殖塘和村塘具有较高的CO₂排放潜力,在未来研究中需要重点关注。     

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.     

Compliance of Royal Naval ships with nitrogen oxide emissions legislation

Nitrogen oxide (NO_x) emissions from marine diesel engines pose a hazard to human health and the environment. From 2021, demanding emissions limits are expected to be applied to sea areas that the Royal Navy (RN) accesses. We analyze how these future constraints affect the choice of NO_x abatement systems for RN ships, which are subject to more design constraints than civilian ships. A weighted matrix approach is used to facilitate a quantitative assessment.     

Impacts of Methane on Carbon Dioxide Storage in Brine Formations

In the context of geological carbon sequestration (GCS), carbon dioxide (CO₂) is often injected into deep formations saturated with a brine that may contain dissolved light hydrocarbons, such as methane (CH₄). In this multicomponent multiphase displacement process, CO₂ competes with CH₄ in terms of dissolution, and CH₄ tends to exsolve from the aqueous into a gaseous phase. Because CH₄ has a lower viscosity than injected CO₂, CH₄ is swept up into a ‘bank’ of CH₄‐rich gas ahead of the CO₂ displacement front. On the one hand, this may provide a useful tracer signal of an approaching CO₂ front. On the other hand, the emergence of gaseous CH₄ is undesirable because it poses a leakage risk of a far more potent greenhouse gas than CO₂ if the cap rock is compromised. Open fractures or faults and wells could result in CH₄ contamination of overlying groundwater aquifers as well as surface emissions. We investigate this process through detailed numerical simulations for a large‐scale GCS pilot project (near Cranfield, Mississippi) for which a rich set of field data is available. An accurate cubic‐plus‐association equation‐of‐state is used to describe the non‐linear phase behavior of multiphase brine‐CH₄‐CO₂ mixtures, and breakthrough curves in two observation wells are used to constrain transport processes. Both field data and simulations indeed show the development of an extensive plume of CH₄‐rich (up to 90 mol%) gas as a consequence of CO₂ injection, with important implications for the risk assessment of future GCS projects.     

Modelling biofilm growth in the presence of carbon dioxide and water flow in the subsurface

The concentration of greenhouse gases – particularly carbon dioxide (CO₂) – in the atmosphere has been on the rise in the past decades. One of the methods which have been proposed to help reduce anthropogenic CO₂ emissions is the capture of CO₂from large, stationary point sources and storage in deep geological formations. The caprock is an impermeable geological layer which prevents the leakage of stored CO₂, and its integrity is of utmost importance for storage security. Due to the high pressure build-up during injection, the caprock in the vicinity of the well is particularly at risk of fracturing. Biofilms could be used as biobarriers which help prevent the leakage of CO₂ through the caprock in injection well vicinity by blocking leakage pathways. The biofilm could also protect well cement from corrosion by CO₂-rich brine.     

Monitoring CO2 saturation using time‐lapse amplitude versus offset analysis of 3D seismic data from the Ketzin CO2 storage pilot site,Germany

The injection of CO₂ at the Ketzin pilot site commenced in June 2008 and was terminated in August 2013 after 67 kT had been injected into a saline formation at a depth of 630–650 m. As part of the site monitoring program, four 3D surface seismic surveys have been acquired to date, one baseline and three repeats, of which two were conducted during the injection period, and one during the post‐injection phase. The surveys have provided the most comprehensive images of the spreading CO₂ plume within the reservoir layer. Both petrophysical experiments on core samples from the Ketzin reservoir and spectral decomposition of the 3D time‐lapse seismic data show that the reservoir pore pressure change due to CO₂ injection has a rather minor impact on the seismic amplitudes. Therefore, the observed amplitude anomaly is interpreted to be mainly due to CO₂ saturation. In this study, amplitude versus offset analysis has been applied to investigate the amplitude versus offset response from the top of the sandstone reservoir during the injection and post‐injection phases, and utilize it to obtain a more quantitative assessment of the CO₂ gaseous saturation changes. Based on the amplitude versus offset modelling, a prominent decrease in the intercept values imaged at the top of the reservoir around the injection well is indeed associated solely with the CO₂ saturation increase. Any change in the gradient values, which would, in case it was positive, be the only signature induced by the reservoir pressure variations, has not been observed. The amplitude versus offset intercept change is, therefore, entirely ascribed to CO₂ saturation and used for its quantitative assessment. The estimated CO₂ saturation values around the injection area in the range of 40%–60% are similar to those obtained earlier from pulsed neutron‐gamma logging. The highest values of 80% are found in the second seismic repeat in close vicinity to the injection and observation wells.     

The oxygen minimum zone (OMZ) off Chile as intense source of CO2 and N2O

The oxygen minimum zones (OMZs) are recognized as intense sources of N₂O greenhouse gas (GHG) and could also be potential sources of CO₂, the most important GHG for the present climate change. This study evaluates, for one of the most intense and shallow OMZ, the Chilean East South Pacific OMZ, the simultaneous N₂O and CO₂ fluxes at the air–sea interface. Four cruises (2000–2002) and 1 year of monitoring (21°–30°–36°S) off Chile allowed the determination of the CO₂ and N₂O concentrations at the sea surface and the analysis of fluxes variations associated with different OMZ configurations. The Chilean OMZ area can be an intense GHG oceanic local source of both N₂O and CO₂. The mean N₂O fluxes are 5–10 times higher than the maximal previous historical source in an OMZ open area as in the Pacific and Indian Oceans. For CO₂, the mean fluxes are also positive and correspond to very high oceanic sources. Even if different coupling and decoupling between N₂O and CO₂ are observed along the Chilean OMZ, 65% of the situations represent high CO₂ and/or N₂O sources. The high GHG sources are associated with coastal upwelling transport of OMZ waters rich in N₂O and probably also in CO₂, located at a shallow depth. The integrated OMZ role on GHG should be better considered to improve our understanding of the past and future atmospheric CO₂ and N₂O evolutions.     

High CO2 Levels in Boreholes at El Teide Volcano Complex (Tenerife, Canary Islands): Implications for Volcanic Activity Monitoring

Emissions of CO₂ have been known for more than a hundred years as fumarolic activity at the terminal crater of El Teide volcano and as diffuse emissions at numerous water prospection drillings in the volcanic island of Tenerife. Large concentrations of CO₂ (>10% in volume) have been found inside galleries, long horizontal tunnels excavated for water mining. However, CO₂ concentrations of only 2900 ppm have been observed at the surface of the central region of the island (Las Cañadas del Teide caldera). In this work we analysed CO₂ concentrations in the subsurface of Las Cañadas caldera, in an attempt to study the vertical distribution of carbon dioxide and, in particular, the low emissions at the surface. This has been done through a series of 17 vertical profiles in two deep boreholes excavated in the Caldera. We found high levels of CO₂, varying in time from 13 vol% up to 40 vol% in different profiles directly above the water table, while no significant concentrations were detected above the thermal inversion that takes places in both boreholes at approximately 100 m from the water table. Water analyses also showed high dissolved CO₂ levels in equilibrium with the air, and an average 13C value in DIC of +4.7 (PDB), apparently induced by fast CO₂ degassing in the bicarbonated water.     

Effects of elevated pCO2 on reproductive properties of the benthic copepod Tigriopus japonicus and gastropod Babylonia japonica

We investigated the effects of elevated pCO₂ in seawater both on the acute mortality and the reproductive properties of the benthic copepod Tigriopus japonicus and gastropod Babylonia japonica with the purpose of accumulating basic data for assessing potential environmental impacts of sub-sea geological storage of anthropogenic CO₂ in Japan. Acute tests showed that nauplii of T. japonicus have a high tolerance to elevated pCO₂ environments. Full life cycle tests on T. japonicus indicated NOEC = 5800 μatm and LOEC = 37,000 μatm. Adult B. japonica showed remarkable resistance to elevated pCO₂ in the acute tests. Embryonic development of B. japonica showed a NOEC = 1500 μatm and LOEC = 5400 μatm. T. japonicus showed high resistance to elevated pCO₂ throughout the life cycle and B. japonica are rather sensitive during the veliger stage when they started to form their shells.     

Carbon and water cycling in a Bornean tropical rainforest under current and future climate scenarios

We examined how the projected increase in atmospheric CO₂ and concomitant shifts in air temperature and precipitation affect water and carbon fluxes in an Asian tropical rainforest, using a combination of field measurements, simplified hydrological and carbon models, and Global Climate Model (GCM) projections. The model links the canopy photosynthetic flux with transpiration via a bulk canopy conductance and semi-empirical models of intercellular CO₂ concentration, with the transpiration rate determined from a hydrologic balance model. The primary forcing to the hydrologic model are current and projected rainfall statistics. A main novelty in this analysis is that the effect of increased air temperature on vapor pressure deficit (D) and the effects of shifts in precipitation statistics on net radiation are explicitly considered. The model is validated against field measurements conducted in a tropical rainforest in Sarawak, Malaysia under current climate conditions. On the basis of this model and projected shifts in climatic statistics by GCM, we compute the probability distribution of soil moisture and other hydrologic fluxes. Regardless of projected and computed shifts in soil moisture, radiation and mean air temperature, transpiration was not appreciably altered. Despite increases in atmospheric CO₂ concentration (C_a) and unchanged transpiration, canopy photosynthesis does not significantly increase if C_i/C_a is assumed constant independent of D (where C_i is the bulk canopy intercellular CO₂ concentration). However, photosynthesis increased by a factor of 1.5 if C_i/C_a decreased linearly with D as derived from Leuning stomatal conductance formulation [R. Leuning. Plant Cell Environ 1995;18:339–55]. How elevated atmospheric CO₂ alters the relationship between C_i/C_a and D needs to be further investigated under elevated atmospheric CO₂ given its consequence on photosynthesis (and concomitant carbon sink) projections.     

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.     

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.     

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。     

Effects of elevated CO2 on the reproduction of two calanoid copepods

Some planktonic groups suffer negative effects from ocean acidification (OA), although copepods might be less sensitive. We investigated the effect of predicted CO₂ levels (range 480–750 ppm), on egg production and hatching success of two copepod species, Centropages typicus and Temora longicornis. In these short-term incubations there was no significant effect of high CO₂ on these parameters. Additionally a very high CO₂ treatment, (CO₂ = 9830 ppm), representative of carbon capture and storage scenarios, resulted in a reduction of egg production rate and hatching success of C. typicus, but not T. longicornis. In conclusion, reproduction of C. typicus was more sensitive to acute elevated seawater CO₂ than that of T. longicornis, but neither species was affected by exposure to CO₂ levels predicted for the year 2100. The duration and seasonal timing of exposures to high pCO₂, however, might have a significant effect on the reproduction success of calanoid copepods.     

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.