Soil Gas CO2 Research Articles

Constraining the Geochemical Fingerprints of Gases from the UK Carboniferous Coal Measures at the Glasgow Geoenergy Observatories Field Site, Scotland

Usage of thermal energy contained in abandoned, flooded, coal mines has the potential to contribute to low carbon heating or cooling supply and assist in meeting net-zero carbon emission targets. However, hazardous ground gases, such as CH4 and CO2, can be found naturally in superficial deposits, coal bearing strata and abandoned mines. Determining the presence, magnitude, and origin of subsurface gases, and how their geochemical fingerprints evolve within the shallow subsurface is vital to developing an understanding of how to manage the risk posed by ground gases in geoenergy technology development. Here, we present the first CH4 and CO2 concentration-depth profiles and stable isotope (δ13CCH4, δ13CCO2, and δDCH4) profiles obtained from UK mine workings, through analysis of headspace gas samples degassed from cores and chippings collected during construction of the Glasgow Observatory. These are used to investigate the variability of gas fingerprints with depth within unmined Carboniferous coal measures and Glasgow coal mine workings. Stable isotope compositions of CH4 (δ13CCH4 = −73.4‰ to −14.3‰; δ13CCO2 = −29‰ to −6.1‰; δDCH4 = −277‰ to −88‰) provide evidence of a biogenic source, with carbonate reduction being the primary pathway of CH4 production. Gas samples collected at depths of 63–79 m exhibit enrichments in 13CCH4 and 2H, indicating the oxidative consumption of CH4. This correlates with their proximity to the Glasgow Ell mine workings, which will have increased exposure to O2 from the atmosphere as a result of mining activities. CO2 gas is more abundant than CH4 throughout the succession in all three boreholes, exhibiting high δ13CCO2 values relative to the CH4 present. Gases from unmined bedrock exhibit the highest δ13CCO2 values, with samples from near-surface superficial deposits having the lowest δ13CCO2 values. δ13CCO2 values become progressively lower at shallower depths (above 90 m), which can be explained by the increasing influence of shallow groundwaters containing a mixture of dissolved marine carbonate minerals (∼0‰) and soil gas CO2 (−26‰) as depth decreases. Our findings provide an insight into the variability of mine derived gases within 200 m of the surface, providing an important ‘time-zero’ record of the site, which is required in the design of monitoring approaches.

Geochemical precursory characteristics of soil gas Rn, Hg, H2, and CO2 related to the 2019 Xiahe Ms5.7 earthquake across the northern margin of West Qinling fault zone, Central China

The Xiahe Ms5.7 earthquake occurred in Xiahe county, Gannan prefecture, China (35.10°N, 102.69°E) on October 28, 2019, with a source depth of 10 km. This study investigates the spatial and temporal evolution characteristics of cross-fault soil gas concentrations prior to the Xiahe Ms5.7 earthquake by analyzing Rn, Hg, H2, and CO2 data collected from 11 profiles across the northern margin of the West Qinling fault zone from 2016 to 2019. The spatial distribution of these gases showed varying trends, with Rn concentration intensity decreasing from the Wushan segment to the east and west sections, while Hg, H2, and CO2 all broke the trend in the West Qinling fault zone's northern margin. The soil gas concentration intensity demonstrated a significant response to the Xiahe Ms5.7 earthquake, particularly in the west Ganjia sections. By integrating the seismogenic model and numerical simulation results, we explored the physical mechanism underlying these abnormal trends. Our findings suggest that the continuous decline characteristic of fault gas could be a valuable indicator of fracture tectonic activity, while an upward trend after continuous decline may signal a medium and short-term seismogenic event in the source area. These results provide a foundation for improved tracking of earthquake location and timing in a fault zone through cross-fault soil gas methods, highlighting the importance of enhancing deep fluid flow monitoring and seismogenic model research in fault zones.

Soil gas CO2 emissions from active faults: a case study from the Anninghe—Zemuhe fault, Southeastern Tibetan Plateau, China

Introduction: Carbon dioxide emissions from non-volcanic areas are undervalued in the carbon cycle.Methods: First estimates of diffuse CO2 flux from the Anninghe—Zemuhe fault (AZF), Southeastern Tibetan Plateau, China, which suggests this could equal 15% emissions from all volcanoes in China. Following the accumulation chamber method, CO2 flux was investigated at 1,483 points, and along 67 profiles crossing the AZF. Results and discussion: Total CO2 emissions from the AZF were estimated 1.2 Mt yr-1. The relationship between soil gas CO2 fluxes, earthquakes, and fault activity was discussed. The intense fault activity in the southern part of the Zemuhe fault (ZMHF) and the northern part of the Anninghe fault (ANH) was inferred, which could have enhanced the porosity of the soil, and accelerated the water-rock interactions and soil gas emission within the fault zone. The chemical and isotopic data indicated that biogenic CO2 was the primary source of CO2 from the AZF. Produced by interactions between groundwaters and carbonates, soil gas CO2 could migrate to the near surface through cracks. Spatial variations of CO2 flux in soil gas indicate that seismic activity could be responsible for the jumpy variations of CO2 flux. The diffuse CO2 from deep faults may contribute considerably to the greenhouse gas cycles.

Gas Emissions and Subsurface Architecture of Fault‐Controlled Geothermal Systems: A Case Study of the North Abaya Geothermal Area

AbstractEast Africa hosts significant reserves of untapped geothermal energy. Exploration has focused on geologically young (<1 Ma) silicic calderas, yet there are many sites of geothermal potential where there is no clear link to an active volcano. The origin and architecture of these systems are poorly understood. Here, we combine remote sensing and field observations to investigate a fault‐controlled geothermal play located north of Lake Abaya in the Main Ethiopian Rift. Soil gas CO2 and temperature surveys were used to examine permeable pathways and showed elevated values along a ∼110 m high fault, which marks the western edge of the Abaya graben. Ground temperatures are particularly elevated where multiple intersecting faults form a wedged horst structure. This illustrates that both deep penetrating graben bounding faults and near‐surface fault intersections control the ascent of hydrothermal fluids and gases. Total CO2 emissions along the graben fault are ∼300 t d−1; a value comparable to the total CO2 emission from silicic caldera volcanoes. Fumarole gases show δ13C of −6.4‰ to −3.8‰ and air‐corrected 3He/4He values of 3.84–4.11 RA, indicating a magmatic source originating from an admixture of upper mantle and crustal helium. Although our model of the North Abaya geothermal system requires a deep intrusive heat source, we find no ground deformation evidence for volcanic unrest or recent volcanism along the graben fault. This represents a key advantage over the active silicic calderas that typically host these resources and suggests that fault‐controlled geothermal systems offer viable prospects for geothermal exploration.

Spatial variations of Rn and CO2 emissions in the Wuzhong–Lingwu region, northwest China

Soil gas Rn and CO2 in surface rupture and deep-seated fault zones are important indicators for tectonic and seismic activities. The spatial distributions of Rn and CO2 concentrations and their relationships with earthquakes and stress state in the Wuzhong–Lingwu area of Ningxia, Northwest China, were investigated through field observations based on 76 measurement points, spatial interpolation and six crossing-fault profiles along Yellow River Fault zone (YRF). Observed results of the soil gas Rn and CO2 in different segments of Yellow River Fault zone illustrated that YRF has features of both strike-slip and certain normal fault characteristics. Moreover, the difference in seismic activity could also account for the differences in gas concentration and relative activity intensity (RAI) in the Yellow River Fault zone. Significant differences in the spatial distributions of Rn and CO2 were identified in gridded observation mode. By comparing these spatial distributions with the surface latent heat flux (SLHF), volumetric soil water layer (SWVL), and lithology, an anomalous high-Rn area was identified in the east and south Qingtongxia, and associated with Permian sandstone and mudstone in a piedmont setting. Away from a strong impact of irrigation in the Yinchuan Basin, CO2 anomalies were identified in the transition area between the Yinchuan Basin and the mountains and coincided with a dramatic negative variation of surface latent heat flux, which was considered to reflect humus accumulation, rich organic matter, and strong soil microorganism activity in loosely accumulated mountain alluvial deposits. After excluding gas anomalies related to shallow soils and surface geology, anomalies of Rn and CO2 in the west of Lingwu were consistent with the distribution of low seismic b-values and frequent seismic activity in plane and profile. According to similar studies in the north-south seismic belts, it is believed that high stress and strong seismic activity increased the permeability of rocks and boosted the gas emission in the west of Lingwu. Base on a crustal thickness variation belt, high-velocity bodies, and in this region, an higher seismic hazard was illustrated. This study offers new insight into combining geochemical characteristics of soil gas and seismological methods to estimate regional seismic hazards.

The 222Rn and CO2 soil gas distribution at Lembang Fault Zone, West Java - Indonesia

Series of 222 Rn measurements had been employed around the Lembang Fault Zone, West Java – Indonesia to investigate its relationship with the fault zone. Furthermore, the mechanism of 222Rn transport is also investigated by performing soil gas CO2 and its δ13C measurements. The evaluation of 222Rn concentration shows that 34% data are within threshold values with an average of 14,117 Bq/m3, with anomalous concentration greater than 20,000 Bq/m3. The concentration of CO2 in soil gas is varied from 72 ppm to 13,241 ppm and consisted of three populations, with 40% of the data above 655 ppm. The spatial distribution pattern shows that most of Lembang Fault Zone segment coincides with high 222Rn concentration indicating high permeability zone. Furthermore, the average 222Rn concentration in western part of the fault is higher than the eastern part and this may be correlated with higher seismic activities. In contrast to 222Rn, CO2 concentration shows less correlation to the fault structure. Based on δ13C values, the source of soil CO2 is dominated by atmospheric CO2, with minor mixing of biogenic origin. Although Lembang Fault Zone is located in the south of an active volcano, there is no indication of magmatic CO2 origin. The lack of correlation between 222Rn and CO2 suggests that there is no indication of 222Rn transport by CO2 as carrier gas.

Geochemical features of fluid in Xiaojiang fault zone, Southeastern Tibetan plateau: Implications for fault activity

It is well established that fluid geochemistry in fault zones could provide reliable indicators for fault activity. Along these lines, in this work, Rn and CO2 fluxes were measured for soil gases along the Xiaojiang Fault Zone (XFZ), SW China. The relationship among the soil gas Rn and CO2 fluxes, hydrochemistry of hot springs, and fault activity were thoroughly examined based on the analytical results and regional geology. The water samples from the hot springs in the study area were the primary types of Ca·Mg-HCO3, Ca·Mg-HCO3·SO4, and Ca-SO4. It was believed that these types were probably affected by the interactions between the groundwater and carbonate rocks. Based on the weak correlation between the soil gas Rn and the CO2 fluxes, the existence of distinct sources was suggested. The manifestation of a relatively high temperature and ion concentration of the hot spring water samples, as well as the relatively high soil gas Rn and CO2 fluxes, led to a concentrated distribution in the northern and southern segments of the XFZ, which was consistent with the spatial distribution of the seismic activities and fault slip rate. The intense fault activity in the southern and northern segments could also enhance the permeability and accelerate both the water-rock interactions and soil gas emission within the fault zone. An assessment of the earthquake potential and radioactivity protection is considered of outmost significance for the southern and northern segments of the XFZ.

Present‐Day Activity of the Anninghe Fault and Zemuhe Fault, Southeastern Tibetan Plateau, Derived From Soil Gas CO2Emissions and Locking Degree

AbstractThe Anninghe fault (ANHF) and the Zemuhe fault (ZMHF), located in the southeast of the Tibetan Plateau, have a high level of seismic hazard and are among the most active faults in China. This study performed the first measurements of soil gas CO2at three sites across the ANHF and the ZMHF. The fault locking (FL) depth and extent of different segments of the ANHF and the ZMHF were inverted using the negative dislocation model based on global positioning system velocity data acquired during 2009–2015. Results showed that the degassing intensity of CO2in the ZMHF is substantially higher than in the ANHF, which is spatially consistent with the degree of inverted FL. The inversion results revealed that the level of coupling, including the locking depth and extent, along the southern segment of the ANHF is markedly greater than in the northern segment of the ZMHF. Soil gas CO2geochemistry yielded different spatially anomalous features, indicating that the faults have different properties and permeability. The intensive locking of the ANHF and ZMHF segments has reduced permeability through self‐sealing processes, which has restricted the escape of gas from the deep crust. Correspondingly, a creeping fault with a low level of coupling could maintain high permeability, which would be favorable for CO2migration.

Helium-carbon systematics of groundwaters in the Lassen Peak Region

Carbon dioxide emissions from active subaerial volcanoes represent 20–50% of the annual global volcanic CO2 flux (Barry et al., 2014). Passive degassing of carbon from the flanks of volcanoes, and the associated accumulation of dissolved inorganic carbon (DIC) within nearby groundwater, also represents a potentially important, yet poorly constrained flux of carbon to the surface (Werner et al., 2019). Here we investigate sources and sinks of DIC in groundwaters in the Lassen Peak region of California. Specifically, we report and interpret the relative abundance and isotopic composition of helium (3He, 4He) and carbon (12C, 13C, 14C) in 37 groundwater samples, from 24 distinct wells, collected between 20 and 60 km from Lassen Peak. Measured groundwater samples have air-corrected 3He/4He values between 0.19 and 7.44 RA (where RA = air 3He/4He = 1.39 × 10−6), all in excess of the radiogenic production value (~0.05 RA), indicating pervasive mantle-derived helium additions to the groundwater system in the Lassen Peak region. Stable carbon isotope ratios of DIC (δ13C) vary between −12.6 and − 27.7‰ (vs. VPDB). Measured groundwater DIC/3He values fall in the range of 2.2 × 1010 to 1.1 × 1012. Using helium and carbon isotope data, we explore several conceptual models to estimate surface carbon contributions and to differentiate between DIC derived from soil CO2 versus DIC derived from external (slab and mantle) carbon sources. Specifically, if we use 14C to identify soil-derived DIC (assuming decadal-to-centennial groundwater ages and a soil CO214C activity equal to that of the atmosphere), we calculate that a hypothetical external carbon source would have an apparent δ13C signature between −10.3 and − 59.3‰ (vs. Vienna Pee Dee Belemnite (VPDB)) and an apparent C/3He between 7.0 × 109 and 1.0 × 1012. These apparent δ13C and C/3He values are substantially isotopically lighter than and greater than canonical MORB values, respectively. We suggest that >95% of any external (non-soil-derived) DIC in groundwater must thus be non-mantle in origin (i.e., slab derived or assimilated organic carbon). We further investigate possible sources of external DIC to groundwater using two idealized conceptual approaches: a pure (unfractionated) source mixing model (after Sano and Marty, 1995) and a scenario that invokes fractionation due to calcite precipitation. Because the former model requires carbon contributions from an organic source component with unrealistically low δ13C (~ − 60‰), we suggest that the second scenario is more plausible. Importantly, however, we caution that all conceptual models are dependent on assumptions about initial 14C activity. Thus, we cannot rule out the possibility that the true fraction of non-surface-derived DIC in these samples is lower or negligible, despite the pervasive mantle-derived He isotope signatures throughout the region. Following the 14C approach to deconvolving sources of DIC, we determine that the maximum passive carbon flux could be up to ~2.2 × 106 kg/yr, which is lower than previous magmatic carbon flux estimates from the Lassen region (Rose and Davisson, 1996). We find that the passive dissolved carbon flux could represent a maximum of ~4–18% of the total Lassen geothermal CO2 degassing flux (estimated to be ~3.5 × 107 kg/yr Rose and Davisson, 1996; Gerlach et al., 2008), which is still more than an order of magnitude smaller than soil gas CO2 flux estimates (7.3–11 × 107 kg/yr) for nearby volcanoes (Sorey et al., 1998; Gerlach et al., 1999; Evans et al., 2002; Werner et al., 2014). We conclude that passive dissolved carbon fluxes should be combined with geothermal fluxes and soil gas fluxes to obtain a complete picture of volcanic carbon emissions globally. Our approach highlights the utility of measuring helium isotopes in concert with the full suite of noble gas abundances, tritium, δ13C and 14C, which when interpreted together can be used to better elucidate the various sources of DIC in groundwater.

Total diffuse CO2 flux from Yellowstone caldera incorporating high CO2 emissions from cold degassing sites

Previous calculations of total diffuse carbon dioxide (CO2) emissions from Yellowstone National Park have been based on flux measurements from thermally active, altered basins. However, our recent measurements show that thermally inactive, cold degassing sites can emit more diffuse CO2 per km2 than thermally active basins. The contribution of these cold degassing sites must be included in calculations of total diffuse CO2 flux for adequate quantification of Yellowstone's role as a major contributor within the global CO2 budget.We acquired 1342 diffuse CO2 flux point measurements across 19 different sites in Yellowstone National Park during summer 2018 and 2019. Eleven of the measured sites are thermally active with heat flux elevated above background, four sites are vegetation sites, and four sites are thermally inactive, cold degassing sites outside the caldera. Our measurements of diffuse CO2 flux agree with previous findings that the highest average flux occurs in acid sulfate soils (706 ± 79 gm−2 day−1, average for both thermally active and cold degassing sites) with lower diffuse CO2 flux in travertine (189 ± 98 gm−2 day−1) and neutral-chloride (19 ± 8 gm−2 day−1) soils. All cold degassing sites measured were in acid sulfate dominated soil chemistries. The average diffuse CO2 flux for these cold degassing sites was higher (840 ± 163 gm−2 day−1) than the average flux through acid sulfate soils in thermally active basins (625 ± 79 gm−2 day−1). We also measured the carbon isotope composition of diffuse CO2 soil gas samples from most sites to characterize the potential source(s) of these emissions. The majority of carbon isotope values from cold degassing sites are within the typical range of values for Yellowstone fumaroles. This suggests that cold degassing sites have a similar magmatic source for diffuse CO2.Previous calculations of the total daily diffuse CO2 emitted through Yellowstone National Park use the arithmetic average flux per soil chemistry and extrapolate that value across the entire park using only thermally active altered soils. Instead, we calculate the total CO2 flux per site in tons CO2 per km2 per day using Gaussian Geostatistical Simulations through the Geostatistical Analyst toolbox in ArcGIS. To account for the large component of cold degassing CO2, we extrapolate the average emission rate per soil chemistry to all hydrothermally altered soils rather than only thermally active soils across the entire area of Yellowstone National Park. We calculate a total deeply sourced (biogenic flux removed) CO2 flux of 24 ± 12 kt CO2 per day, with nearly two-thirds of that flux estimated to be from cold degassing acid sulfate soils. Cold diffuse degassing sites can be significant sources of magmatic carbon emissions and this has implications for the relationship between the flux of CO2 and heat as well as for global contributions from mantle CO2 emissions.

Soil carbon dioxide fluxes to atmosphere: The role of rainfall to control CO2 transport

In order to observe the relationships between the temporal variations of CO2 surface fluxes and the CO2 soil gas transport in soil profile before and during rainfall events, two experiments were conducted in a controlled natural environment at different time periods. These experiments consisted in injecting pure CO2 in a lysimeter at 160 cm depth and simulating heavy rainfall event at its surface for 2 weeks. During the whole experiments, CO2 soil gas concentrations and surface fluxes were continuously monitored. These measurements showed that the flux measured through the flux chamber were consistent with the concentration profiles. During simulated rainfall events, the concentrations and fluxes showed a clear change linked to the presence of water on the top of the water profile. The results clearly show a significant decrease of CO2 flux to atmosphere induced by rainfall infiltration and consequential wash-out of the CO2 present in the soil.

Geochemical Characteristics of Soil Gas and Strong Seismic Hazard Potential in the Liupanshan Fault Zone (LPSFZ)

Eight soil gas measurements were performed in the Liupanshan fault zone (LPSFZ) to observe the concentration and flux of soil gas radon (Rn) and CO2 in October 2017 and October 2018. By combining the historical strong earthquake background and modern seismic activity of the fault zone, the relation between the geochemical distribution characteristics of soil gas and the seismicity of the fault zone was studied herein. Furthermore, the strong seismic hazard potential of the fault zone was discussed. Results show that the concentration of soil gas Rn and CO2 considerably varies in the northern segment of the LPSFZ and is relatively stable in the southern segment. The spatial distribution of the concentration intensity and flux is strong in the north and weak in the south. However, the southern segment of the LPSFZ has a seismic gap that has not been ruptured by strong earthquakes with Ms ≥ 6.5 for the last 1400 years, whereas the seismic activity in the northern segment is relatively frequent, indicating that the fault zone locking degree of the southern segment is higher than that of the northern segment. This observation is completely consistent with the geochemical characteristic distribution of soil gas. Therefore, the southern segment of the LPSFZ should be considered a hazardous segment, where major or strong earthquakes can occur in the future.

Spatial Distribution of Rn, CO2, Hg, and H2 Concentrations in Soil Gas Across a Thrust Fault in Xinjiang, China

Spatial distribution characteristics and origin of soil gases were discussed in this study. We also examine the correlation between the spatial variation of soil gases and fault activity, based on the measurements of Rn, Hg, H2, and CO2 concentrations in the eastern segment of the BLT fault zone in the southern Tianshan Mountains, Xinjiang, China. The results show that the Rn and CO2 concentrations on the hanging wall were higher than those near the fault zone and on the footwall of the fault. Moreover, the Hg and H2 concentrations on the footwall were also higher than those near the fault and on the hanging wall of the fault. The main factors affecting the variations in soil gas spatial distribution were gaseous origin structure of the crust, fault activity, fault fracture degree, stratigraphic lithology, and the cover layer. The results of active structural fault mapping show that the BLT fault has been active since the Late Quaternary and the thrust has broken the fault surface. Under the influence of tectonic compressive stress, the tension zone was formed on the hanging wall of the fault and fractures were developed. This result is consistent with the characteristics of soil gas concentrations measured in this study, indicating that the concentrations of Rn, Hg, H2, and CO2 are closely related to the fault activity. These findings can be applied to identify seismic precursors from gas monitoring data of the studied area.

Shear-wave splitting properties of the upper crust, during the 2013–2014 seismic crisis, in the CO2-rich field of Florina Basin, Greece

The Florina basin (NW Greece) embodies sources of natural CO2 emissions, which are aligned parallel to the NE-SW striking regional major normal faults. The study area is characterized by low to moderate seismicity, as historical information and instrumental data reveal. During February 2013 to January 2014 an outburst of seismic activity emerged, consisting of more than 2000 located earthquakes, with a mainshock of Mw = 4.1 on 17 February 2013 (16:48 UTC). A local temporary network was installed in July 2013, whose recordings provided the necessary data for performing a Shear-wave Splitting (SwS) study of the upper crust. After the application of strict selection criteria, 532 SwS measurements were obtained for two stations, using a mixture of manual and fully automatic methods. Two polarization directions of the fast shear-wave were identified at one of the stations, with the main one striking NE-SW and the secondary in a NW-SE direction. The first direction is in agreement with the local stress field, as it is identified by focal mechanisms, and with the strike of faults along which soil gas CO2 concentrations are distributed and can be explained by the Anisotropic Poro-Elasticity (APE) model. The second direction is consistent with the strike of mapped local faults, inherited since the Late Miocene extension, which are responsible for the formation of the Florina basin. The SwS results at the second station revealed an almost N-S dominant polarization direction, which is not consistent with the local stress field. This direction, obtained from events belonging to the southern group of the sequence, that was probably triggered by fluid intrusion, might be interpreted by spatiotemporal patterns of seismicity and CO2 upwelling.

Distribution of methane and carbon dioxide concentrations in the near-surface zone over regional fault zones and their genetic characterization in the Pszczyna-Oświęcim area (SE part of the Upper Silesian Coal Basin, Poland)

The objective of this paper was to characterize the variability of methane (CH4) and carbon dioxide (CO2) concentrations in the near-surface zone, measured along 4 selected sampling lines positioned perpendicularly to regional fault zones, in the SE part of the Upper Silesian Coal Basin (USCB), Poland. This way it was possible to check the migration activity of these gases to the surface through low-permeable Miocene strata. It was also possible to evaluate the applicability of surface geochemical survey methodology to the identification of potential accumulations of free natural gas in the topmost parts of the Carboniferous formations in the USCB. The results of 319 soil-gas samples were supported by stable isotope analyses and related to the geological setting and the distribution of methane potential at various depths. Moreover, the sampling included the area of the closed and remediated Andrzej VII mining shaft, where 5 soil-gas samples were taken. Additionally, gas flux was evaluated at 3 measurement points at which increased gas concentrations were detected. The maximum concentrations of CH4 and CO2 in soil gases were 15.4 and 9.39 vol%, respectively. Soil gases contain both thermogenic and microbial CH4 and CO2 that migrated from secondary and primary gas zones within the Pennsylvanian coal-bearing strata. In some sites, CO2 was also generated by the oxidation of soil organic matter and/or CH4 in a near-surface zone. Anomalous CH4 concentrations were generally found over elevated fragments of erosional structures of Carboniferous coal-bearing formations. This indicates the presence of free CH4 accumulations beneath the Miocene overburden. However, the surface anomalies did not always correlate with the zones of CH4 secondary accumulations. Anomalous concentrations of CH4 and CO2 correlated with the regional fault zones that cut through the Carboniferous formations. This indicates the potential presence of fault traps saturated with free CH4 in the upper parts of Carboniferous formations. Relatively low values were observed for both CH4 and CO2 emissions (maximum: 25 and 4320 mg m−2 d−1, respectively). This suggests relatively low dynamics of gas migration from the depth to the soil zone.

Spatial and temporal variations of CO2 emissions from the active fault zones in the capital area of China

The chemical and isotopic composition of 26 soil gas wells and 11 springs along the active fault zones in the capital area of China was determined to investigate the origin of CO2, the spatial and temporal variations of CO2 emission, and their mechanisms. The chemical and isotopic data indicated that biogenic CO2 was the primary source for CO2 from the soil gas wells in both the basin and orogen regions, the crust-derived and mantle-derived CO2 could have ascended through the deep-cut faults and got into the springs, with a few diffusing into the soil gas wells. Minor air could have intruded into the soil gas wells in the orogen region through the faults cutting the surface, owing to the barometric pressure fluctuation. Relatively high He concentration, CO2 concentration, and flux of soil gas from wells were observed in the basin region than those in the orogen region. A significant amount of CO2 is produced during the process of oxidation of organic matter in the basin, where the organic matter accumulates in thick clayey strata. Further amounts of CO2 are produced by interactions between groundwaters and carbonates, which are widely represented in the basin region and by intruded air into the soil gas wells in the orogen region due to barometric pressure fluctuations. Temporal variations of CO2 concentration and CO2 flux were observed in soil gas wells in the basin region, where seismic activity is more frequent compared to those in the orogen, indicating that seismic activity could be responsible for the jumpily temporal variations of CO2 concentration and flux in wells. Monitoring activities of soil gas CO2 concentrations and CO2 fluxes in active fault zones should be carried out.

Soil gas monitoring at the Illinois Basin – Decatur Project carbon sequestration site

An extensive monitoring, verification, and accounting (MVA) program was carried out from 2011 to 2016 as part of the Illinois Basin – Decatur Project (IBDP), a large-scale carbon capture and storage (CCS) demonstration project in Decatur, Illinois, USA. As part of the monitoring program, a near-surface monitoring network for soil gas was used to characterize the natural variability of CO2 and identify anomalies that could be associated with CO2 leakage in the vadose zone. In the fall of 2011, 21 permanent soil gas sampling nests were installed on-site and three nests were installed off-site as reference locations. Soil gas was collected from three depth intervals (15–30, 47–61, 107–122 cm) at each nest. Fixed gas (CO2, N2, O2, and light hydrocarbon) concentrations, stable carbon isotopic composition (δ13C), and radiocarbon (14C) content of CO2 in soil gas were monitored during the pre-injection, injection, and post-injection phases from 2011 to 2016. Both CO2 concentrations and carbon isotopic compositions showed large spatial and temporal variations; however, the relationships among CO2, N2, and O2 concentrations in soil gas indicated that these variations should be attributed to natural processes and not CO2 leakage. Soil CO2 concentrations responded to temperature and precipitation variations and increased with increasing soil depth. While 14C cannot be used to determine the occurrence of CO2 leakage at IBDP site due to the indistinctive signature between injected CO2 and soil gas CO2, experiences at IBDP validated that δ13C can serve as an effective natural tracer at this site. Results from this project have value for future industrial CCS projects that plan to use soil gas monitoring techniques for site characterization and leakage detection.

Soil-Gas Concentrations and Flux Monitoring at the Lacq-Rousse CO2-Geological Storage Pilot Site (French Pyrenean Foreland): From Pre-Injection to Post-Injection

Soil-gas concentrations and flux were measured during 20 separate measurement campaigns at the TOTAL Lacq-Rousse carbon capture and storage (CCS) pilot site, southern France, where 51,000 tons of CO2 were injected in a depleted natural gas field. Baseline data (September 2008 to December 2009) are compared to monitoring data from the injection (March 2010 to March 2013) and post-injection (February 2014 to December 2015) periods. CO2 soil-gas concentrations varied from atmospheric concentrations to more than 16% vol. with 1.4% as median value. Summer data showed high CO2 concentrations in the soil that remained quite high during winter. Median CO2 flux at the soil/atmosphere interface was close to 4.4 cm3·min−1·m−2. Carbon-isotope ratios measured on CO2 in soil gas had a mean value of −23.5 ± 3.1‰, some deviation being due to atmospheric CO2. Comparison between different gas species and the influence of temperature, pressure and soil-water content suggest that gases in near-surface environments are produced locally and naturally, and are unrelated to CO2 ascending from the storage reservoir. Monitoring of CO2 injection and the use of threshold levels is discussed as part of a practical approach considering specific regulations for the Lacq-Rousse CCS pilot experiment and constraints for the site operator.

Carbon cycling in the mantled karst of the Ozark Plateaus, central United States

The nature of carbon (C) cycling in the unsaturated zone where groundwater is in contact with abundant gas-filled voids is poorly understood. The objective of this study was to trace inorganic-C cycling in a karst landscape using stable-C isotopes, with emphasis on a shallow groundwater flow path through the soil, to an underlying cave, and to the spring outlet of a cave stream in the Ozark Plateaus of northwestern Arkansas. Carbon dioxide (CO2) concentration and isotopic composition (δ13C-CO2) in gas and dissolved inorganic carbon (DIC) concentration and isotopic composition (δ13C-DIC) in water were measured in samples collected from two suction-cup soil samplers above the cave, three sites in the cave, and at the spring outlet of the cave stream. Soil-gas CO2 concentration (median 2,578ppm) and δ13C-CO2 (median −21.5‰) were seasonally variable, reflecting the effects of surface temperature changes on soil-CO2 production via respiration and organic-matter decomposition. Cave-air CO2 (median 1,026ppm) was sourced from the soil zone and the surface atmosphere, with seasonally changing proportions of each source controlled by surface temperature-driven air density gradients. Soil-DIC concentration (median 1.7mgL−1) was lower and soil-δ13C-DIC (median −19.5‰) was lighter compared to the cave (median 23.3mgL−1 and −14.3‰, respectively) because carbonate-bedrock dissolution provided an inorganic source of C to the cave. Carbon species in the soil had a unique, light stable-C isotopic signature compared to the cave. Discrimination of soil-C sources to karst groundwater was achieved, which is critical for developing hydrologic budgets using environmental tracers such as C.

Gas source attribution techniques for assessing leakage at geologic CO2 storage sites: Evaluating a CO2 and CH4 soil gas anomaly at the Cranfield CO2-EOR site

At the Cranfield CO2 enhanced oil recovery (CO2-EOR) site, a localized area of high concentrations of CO2 (up to 44%) and CH4 (up to 47%) in soil gas was detected near a plugged and abandoned well. The complexity of attributing this anomaly, especially in a CO2-EOR setting, underscores the need for careful attribution techniques and provides rare and valuable experiential knowledge on attributing blind anomalies. An extensive geochemical monitoring program utilizing process-based soil gas ratios, stable and radioactive isotopes of CO2 and CH4, light hydrocarbon concentrations, noble gases, and perfluorocarbon and sulfur hexafluoride tracers was undertaken from 2009 through 2014. The goals were to attribute source, assess the usefulness of various attribution techniques, and begin to develop a framework for attribution in complex CO2-EOR settings. Initial process-based assessment indicated an “exogenous” source meaning that it was not the result of natural in-situ processes (Romanak et al., 2012). We report on the additional analyses used to determine the degree to which the anomaly was related to CO2 injection. This work included characterization of potential non-reservoir gas sources within the overburden using mud-gas samples collected during a new drill and downhole fluids collected from wells within the field. Two hydrocarbon gas sources, one within the reservoir (Tuscaloosa) and one in the above-zone (Wilcox) were geochemically distinct. Stable carbon isotopes (δ13C) of CH4 in the anomaly were similar to those of the reservoir, but stable hydrogen isotopes (δD) indicated that anomalous gases originate from an undetermined microbial source rather than either of the subsurface gas reservoirs. Hydrocarbon geochemical parameters were therefore not only useful for attribution, but were also found to have a high potential for leading to inaccurate conclusions because of alteration via CH4 oxidation. Noble gases and introduced tracers proved least effective for attribution in this case. The most useful indicator was radioactive isotopes of CO2 and CH4, which contained >100% modern carbon indicating a negligible input, if any, from the reservoir.