Soil CO2 flux baseline in an urban monogenetic volcanic field: the Auckland Volcanic Field, New Zealand

The Auckland Volcanic Field (AVF) is a dormant monogenetic basaltic field located in Auckland, New Zealand. Though soil gas CO₂ fluxes are routinely used to monitor volcanic regions, there have been no published studies of soil CO₂ flux or soil gas CO₂ concentrations in the AVF to date or many other monogenetic fields worldwide. We measured soil gas CO₂ fluxes and soil gas CO₂ concentrations in 2010 and 2012 in varying settings, seasons, and times of day to establish a baseline soil CO₂ flux and to determine the major sources of and controlling influences on Auckland's soil CO₂ flux. Soil CO₂ flux measurements varied from 0 to 203 g m^?2 day^?1, with an average of 27.1 g m^?2 day^?1. Higher fluxes were attributed to varying land use properties (e.g., landfill). Using a graphical statistical approach, two populations of CO₂ fluxes were identified. Isotope analyses of δ¹³CO₂ confirmed that the source of CO₂ in the AVF is biogenic with no volcanic component. These data may be used to assist with eruption forecasting in the event of precursory activity in the AVF, and highlight the importance of knowing land use history when assessing soil gas CO₂ fluxes in urban environments.     

The effect of CO2 on the measurement of 220Rn and 222Rn with instruments utilising electrostatic precipitation

In some volcanic systems, thoron and radon activity and CO₂ flux, in soil and fumaroles, show a relationship between (²²⁰Rn/²²²Rn) and CO₂ efflux. It is theorized that deep, magmatic sources of gas are characterized by high ²²²Rn activity and high CO₂ efflux, whereas shallow sources are indicated by high ²²⁰Rn activity and relatively low CO₂ efflux. In this paper we evaluate whether the observed inverse relationship is a true geochemical signal, or potentially an analytical artifact of high CO₂ concentrations. We report results from a laboratory experiment using the RAD7 radon detector, known ²²²Rn (radon) and ²²⁰Rn (thoron), and a controllable percentage of CO₂ in the carrier gas. Our results show that for every percentage of CO₂, the ²²⁰Rn reading should be multiplied by 1.019, the ²²²Rn radon should be multiplied by 1.003 and the ²²⁰Rn/²²²Rn ratio should be multiplied by 1.016 to correct for the presence of the CO₂.     

Natural 222Rn as a tracer of mixing and volatilization in a shallow aquifer during a CO2 injection experiment

This study aims to evaluate the application of ²²²Rn in groundwater as a tracer for monitoring CO₂ plume migration in a shallow groundwater system, which is important to detect potential CO₂ leakage in the carbon capture and storage (CCS) project. For this research, an artificial CO₂-infused water injection experiment was performed in a shallow aquifer by monitoring hydrogeochemical parameters, including ²²²Rn. Radon in groundwater can be a useful tracer because of its sensitivity to sudden changes in subsurface environment. To monitor the CO₂ plume migration, the data were analysed based on (a) the influence of mixing processes on the distribution of ²²²Rn induced by the artificial injection experiment and (b) the influence of a carrier gas role by CO₂ on the variation of ²²²Rn. The spatio-temporal distributions of radon concentrations were successfully explained in association with horizontal and vertical mixing processes by the CO₂-infused water injection. Additionally, the mixing ratios of each monitoring well were calculated, quantitatively confirming the influence of these mixing processes on the distribution of radon concentrations. Moreover, one monitoring well showed a high positive relationship between ²²²Rn and Total dissolved inorganic carbon (TIC) by the carrier gas effect of CO₂ through volatilization from the CO₂ plume. It indicated the applicability of ²²²Rn as a sensitive tracer to directly monitor CO₂ leakage. When with a little effect of carrier gas, natural ²²²Rn in groundwater can be used to compute mixing ratio of CO₂-infused water indicative of CO₂ migration pathways. CO₂ carrier gas effect can possibly increase ²²²Rn concentration in groundwater and, if fully verified with more field tests, will pose a great potential to be used as a natural tracer for CO₂.     

Continuous monitoring of distal gas emanations at Vulcano,southern Italy

The increasing activity of Vulcano Island (Italy) since 1985 led to the initiation of continuous geochemical monitoring of the lateral soil gas emissions. On the basis both of their relative geochemical characteristics and of local considerations, three gaseous components were selected for monitoring, namely CO₂, He and ²²²Rn. Monitoring has been performed by means of specific analysers. Gases extracted from a water well located at the foot of the active cone were selected for monitoring, on the basis of their geochemical and isotopic characters that indicate their genetic link with central high temperature fumarolic gases emitted at the crater. Very strong variations of gas composition can be observed within one day (from 1 to about 94% for CO₂). Some variations display a daily character and can be correlated with that of atmospheric pressure. The three monitored gases are highly correlated, suggesting very high kinetics of gas transfer in the system. Because of these considerable variations of chemical composition, bulk concentrations obviously are not suitable for monitoring at Vulcano. However, the evolution with time of ratios such as ²²²Rn/CO₂ and He/CO₂ (the latter being corrected for atmospheric contamination) supplies numerical parameters that the expected to characterize the intensity of the degassing process. A new input of magmatic gases, that would lead to an increase in the ²²²Rn/CO₂ and He/CO₂ ratios, should therefore be detected by such a monitoring station.     

Continuous gas monitoring in the West Bohemian earthquake area,Czech Republic: First results

Two stations monitoring concentrations of carbon dioxide and radon in soil gas (Oldřišská and Novy Kostel) and one station monitoring flow of carbon dioxide at a mofette (Soos) have been operated in the area of the West Bohemian earthquake swarms. We present preliminary results obtained on the base of four-year observations. We found that data are not influenced considerably by barometric pressure. Although the CO₂ concentration varies greatly, the long-term trends at stations Oldřišská and Novy Kostel are similar, which indicates that the CO₂ flow is controlled by common geogenic processes. Also temporal trends of CO₂ and Rn concentrations in soil gas at individual stations are analogous. We found diurnal variations of both CO₂ concentration in soil gas and the CO₂ flow at mofettes due to the earth tides. A response to tides of semi-diurnal period is insignificant in CO₂ concentration and only weak in the CO₂ flow. We also examined possible pre-seismic, co-seismic and post-seismic effects of the intensive 2008 earthquake swarm on the CO₂ concentration at Oldřišská and Novy Kostel, and on the CO₂ flow at Soos. However, all potential indications were insignificant and there has not been proven any influence of the swarm on the CO₂ concentration as well as on the CO₂ flow. Nevertheless, a gradual decrease of amplitudes of diurnal variations before the swarm and the lowest amplitudes during the swarm is a noteworthy phenomenon, which might indicate the strain changes of the rock associated with earthquake swarm.     

辽宁金州断裂断层土壤气地球化学调查

对辽宁南部地区重点活动断裂的8条剖面进行跨断层土壤气Rn、CO₂和H₂浓度测量。测量结果表明,各测量剖面土壤气Rn、CO₂和H₂的浓度平均值变化范围分别为10.65~39.50kBq/m³、0.59%~3.37%和9.74~306.28ppm。研究区土壤气Rn、CO₂和H₂浓度异常主要集中在海城老震区和盖州震群地区,土壤气空间变化特征显示Rn、CO₂和H₂浓度从南至北有逐渐增高变化趋势,这与辽南地区地震活动分布、地下低速层分布、地质特征及地壳垂直变形速率等变化相对应,表明辽南地区金州断裂土壤气地球化学特征主要受控于辽南地区地震活动、地下介质结构和地壳垂直形变速率的影响,同时也受到测量场地地质特征的影响。     

Inter-annual and seasonal variations in the air–sea CO2 balance in the central Baltic Sea and the Kattegat

We estimated the net annual air–sea exchange of carbon dioxide (CO₂) using monitoring data from the East Gotland Sea, Bornholm Sea, and Kattegat for the 1993–2009 period. Wind speed and the sea surface partial pressure of CO₂ (pCO₂^w), calculated from pH, total alkalinity, temperature, and salinity, were used for the flux calculations. We demonstrate that regions in the central Baltic Sea and the Kattegat alternate between being sinks (−) and sources (+) of CO₂ within the −4.2 to +5.2 mol m⁻² yr⁻¹ range. On average, for the 1994–2008 period, the East Gotland Sea was a source of CO₂ (1.64 mol m⁻² yr⁻¹), the Bornholm Sea was a source (2.34 mol m⁻² yr⁻¹), and the Kattegat was a sink (−1.16 mol m⁻² yr⁻¹). Large inter-annual and regional variations in the air–sea balance were observed. We used two parameterizations for the gas transfer velocity (k) and the choice varied the air–sea exchange by a factor of two. Inter-annual variations in pCO₂^w between summers were controlled by the maximum concentration of phosphate in winter. Inter-annual variations in the CO₂ flux and gas transfer velocity were larger between winters than between summers. This indicates that the inter-annual variability in the total flux was controlled by winter conditions. The large differences between the central Baltic Sea and Kattegat were considered to depend partly on the differences in the mixed layer depth.     

Riverine export of water,sediment and carbon during flood events in the arid to semi-arid Wuding River on the Chinese Loess Plateau

Floods have become increasingly important in fluvial export of water, sediment and carbon (C). Using high-frequency sampling, the export of water, sediment and C was examined in the Wuding River catchment on the Chinese Loess Plateau. With groundwater as an important contributor to runoff all year round, floods were relatively less important in the export of water. However, large floods were disproportionately important in exporting sediment and inorganic C (DIC) and organic C (DOC and POC). The three largest floods in each year transported 53.6–97.3 and 41.4–77% of the annual sediment and C fluxes, respectively. An extreme flood in 2017 alone contributed 94.6 and 73.1% of the annual sediment and C fluxes, respectively, in just 7 days, which included 20.3, 92.1 and 35.7% of the annual DOC, POC and DIC fluxes, respectively. A stable carbon isotope (δ¹³C) analysis of POC indicated that modern soils and C3 plants were its primary source. Furthermore, floods greatly accelerated CO₂ degassing due to elevated gas transfer velocity, although stream water CO₂ partial pressure (pCO₂) exhibited a decreasing trend with flow discharge. Although these results illustrated that increasing runoff diluted pCO₂, the timing and magnitude of floods were found to be critical in determining the response of pCO₂ to flow dynamics. Low-magnitude floods in the early wet season increased pCO₂ because of enhanced organic matter input, while subsequent large floods caused a lower pCO₂ due to greatly reduced organic matter supply. Finally, continuous monitoring of a complete flood event showed that the CO₂ efflux during the flood (2348 ± 664 mg C m^–2 day^–1) was three times that under low-flow conditions (808 ± 98 mg C m^–2 day^–1). Our study suggests that infrequent, heavy storm events, which are predicted to increase under climate change, will greatly alter the transport regimes of sediment and C. © 2020 John Wiley & Sons, Ltd.     

Quantifying the flow dynamics of supercritical CO2–water displacement in a 2D porous micromodel using fluorescent microscopy and microscopic PIV

The multi-phase flow of liquid/supercritical CO₂ and water (non-wetting and wetting phases, respectively) in a two-dimensional silicon micromodel was investigated at reservoir conditions (80 bar, 24 °C and 40 °C). The fluorescent microscopy and microscopic particle image velocimetry (micro-PIV) techniques were combined to quantify the flow dynamics associated with displacement of water by CO₂ (drainage) in the porous matrix. To this end, water was seeded with fluorescent tracer particles, CO₂ was tagged with a fluorescent dye and each phase was imaged independently using spectral separation in conjunction with microscopic imaging. This approach allowed simultaneous measurement of the spatially-resolved instantaneous velocity field in the water and quantification of the spatial configuration of the two fluid phases. The results, acquired with sufficient time resolution to follow the dynamic progression of both phases, provide a comprehensive picture of the flow physics during the migration of the CO₂ front, the temporal evolution of individual menisci, and the growth of fingers within the porous microstructure. During that growth process, velocity jumps 20–25 times larger in magnitude than the bulk velocity were measured in the water phase and these bursts of water flow occurred both in-line with and against the bulk flow direction. These unsteady velocity events support the notion of pressure bursts and Haines jumps during pore drainage events as previously reported in the literature [1–3]. After passage of the CO₂ front, shear-induced flow was detected in the trapped water ganglia in the form of circulation zones near the CO₂–water interfaces as well as in the thin water films wetting the surfaces of the silicon micromodel. To our knowledge, the results presented herein represent the first quantitative spatially and temporally resolved velocity-field measurements at high pressure for water displacement by liquid/supercritical CO₂ injection in a porous micromodel.     

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.     

Diffuse CO<Subscript>2</Subscript> degassing at Vesuvio,Italy

At Vesuvio, a significant fraction of the rising hydrothermal–volcanic fluids is subjected to a condensation and separation process producing a CO₂–rich gas phase, mainly expulsed through soil diffuse degassing from well defined areas called diffuse degassing structures (DDS), and a liquid phase that flows towards the outer part of the volcanic cone. A large amount of thermal energy is associated with the steam condensation process and subsequent cooling of the liquid phase. The total amount of volcanic–hydrothermal CO₂ discharged through diffuse degassing has been computed through a sequential Gaussian simulation (sGs) approach based on several hundred accumulation chamber measurements and, at the time of the survey, amounted to 151 t d^–1. The steam associated with the CO₂ output, computed assuming that the original H₂O/CO₂ ratio of hydrothermal fluids is preserved in fumarolic effluents, is 553 t d^–1, and the energy produced by the steam condensation and cooling of the liquid phase is 1.47×10¹² J d^–1 (17 MW). The location of the CO₂ and temperature anomalies show that most of the gas is discharged from the inner part of the crater and suggests that crater morphology and local stratigraphy exert strong control on CO₂ degassing and subsurface steam condensation. The amounts of gas and energy released by Vesuvio are comparable to those released by other volcanic degassing areas of the world and their estimates, through periodic surveys of soil CO₂ flux, can constitute a useful tool to monitor volcanic activity.Editorial responsibility: H. Shinohara     

Geochemistry of Quaternary travertines in the region north of Rome (Italy): structural, hydrologic and paleoclimatic implications

In the Tyrrhenian region of central Italy, late Quaternary fossil travertines are widespread along two major regional structures: the Tiber Valley and the Ancona-Anzio line. The origin and transport of spring waters from which travertines precipitate are elucidated by chemical and isotopic studies of the travertines and associated thermal springs and gas vents. There are consistent differences in the geochemical and isotopic signatures of thermal spring waters, gas vents and present and fossil travertines between east and west of the Tiber Valley. West of the Tiber Valley, δ¹³C of CO₂ discharged from gas vents and δ¹³C of fossil travertines are higher than those to the east. To the west the travertines have higher strontium contents, and gases emitted from vents have higher ³He/⁴He ratios and lower N₂ contents, than to the east. Fossil travertines to the west have characteristics typical of thermogene (thermal spring) origin, whereas those to the east have meteogene (low-temperature) characteristics (including abundant plant casts and organic impurities). The regional geochemical differences in travertines and fluid compositions across the Tiber Valley are interpreted with a model of regional fluid flow. The regional Mesozoic limestone aquifer is recharged in the main axis of the Apennine chain, and the groundwater flows westward and is discharged at springs. The travertine-precipitating waters east of the Tiber Valley have shallower flow paths than those to the west. Because of the comparatively short fluid flow paths and low (normal) heat flow, the groundwaters to the east of the Tiber Valley are cold and have CO₂ isotopic signatures, indicating a significant biogenic contribution acquired from soils in the recharge area and limited deeply derived CO₂. In contrast, spring waters west of the Tiber Valley have been conductively heated during transit in these high heat-flow areas and have incorporated a comparatively large quantity of CO₂ derived from decarbonation of limestone. The elevated strontium content of the thermal spring water west of the Tiber Valley is attributed to deep circulation and dissolution of a Triassic evaporite unit that is stratigraphically beneath the Mesozoic limestone. U-series age dates of fossil travertines indicate three main periods of travertine formation (ka): 220-240, 120-140 and 60-70. Based on the regional flow model correlating travertine deposition at thermal springs and precipitation in the recharge area, we suggest that pluvial activity was enhanced during these periods. Our study suggests that travertines preserve a valuable record of paleofluid composition and paleoprecipitation and are thus useful for reconstructing paleohydrology and paleoclimate.     

Gas exchange between Baikal and the atmosphere during under-ice period

In the under-ice period, gas exchange between Baikal and the atmosphere is taking place through a system of coastal and perennial fractures and airholes in the ice, as well as through the surface of the ice-free part of the lake at the Angara source [24]. The total area of the open water never exceeds 0.03% of lake water area. The emission of CO₂ in the course of ice sublimation over the entire period is ≤0.02 g CO₂ from 1 m². The transport of dissolved gases from under-ice water into the atmosphere is limited by molecular diffusion in microfractions of ice cover. The narrow daily variations of CO₂ in the air in lake coastal zone is due to the effect of populated localities on its coast and large coniferous forests, which serve as diffuse sources of CO₂, as well as diurnal variations of the direction and velocity of air mass transport by local winds.     

Diffuse volcanic degassing and thermal energy release from Hengill volcanic system, Iceland

We report the first detailed study of spatial variations on the diffuse emission of carbon dioxide (CO₂) and hydrogen sulfide (H₂S) from Hengill volcanic system, Iceland. Soil CO₂ and H₂S efflux measurements were performed at 752 sampling sites and ranged from nondetectable to 17,666 and 722?g?m^?2?day^?1, respectively. The soil temperature was measured at each sampling site and used to evaluate the heat flow. The chemical composition of soil gases sampled at selected sampling sites during this study shows they result from a mixing process between deep volcanic/hydrothermal component and air. Most of the diffuse CO₂ degassing is observed close to areas where active thermal manifestations occur, northeast flank of the Hengill central volcano close to the Nesjavellir power plant, suggesting a diffuse degassing structure with a SSW?CNNE trend, overlapping main fissure zone and indicating a structural control of the degassing process. On the other hand, H₂S efflux values are in general very low or negligible along the study area, except those observed at the northeast flank of the Hengill central volcano, where anomalously high CO₂ efflux and soil temperatures were also measured. The total diffuse CO₂ emission estimated for this volcanic system was about 1,526?±?160?t?day^?1 of which 453?t?day^?1 (29.7?%) are of volcanic/hydrothermal origin. To calculate the steam discharge associated with the volcanic/hydrothermal CO₂ output, we used the average H₂O/CO₂ mass ratio from 12 fumarole samples equal to 88.6 (range, 9.4?C240.2) as a representative value of the H₂O/CO₂ mass ratios for Hengill fumarole steam. The resulting estimate of the steam flow associated with the gas flux is equal to 40,154?t?day^?1. The condensation of this steam results in thermal energy release for Helgill volcanic system of 1.07?×?10¹⁴?J?day^?1 or to a total heat flow of 1,237?MW_t.     

Lower Groundwater 14C Age by Atmospheric CO2 Uptake During Sampling and Analysis

Uptake of atmospheric CO₂ during sample collection and analysis, and consequent lowering of estimated ages, has rarely been considered in radiocarbon dating of groundwater. Using field and laboratory experiments, we show that atmospheric CO₂ can be easily and rapidly absorbed in hyperalkaline solutions used for the extraction of dissolved inorganic carbon, resulting in elevated ¹⁴C measurements. Kinetic isotope fractionation during atmospheric CO₂ uptake may also result in decrease of δ¹³C, leading to insufficient corrections for addition of dead carbon by geochemical processes. Consequently, measured ¹⁴C values of groundwater should not be used for age estimation without corresponding δ¹³C values, and historical ¹⁴C data in the range of 1 to 10% modern Carbon should be re‐evaluated to ensure that samples with atmospheric contamination are recognized appropriately. We recommend that samples for ¹⁴C analysis should be collected and processed in the field and the laboratory without exposure to the atmosphere. These precautions are considered necessary even if ¹⁴C measurements are made with an accelerator mass spectrometer.     

Gas hazard assessment in a densely inhabited area of Colli Albani Volcano (Cava dei Selci, Roma)

The northwestern flank of the Colli Albani, a Quaternary volcanic complex near Rome, is characterised by high pCO₂ values and Rn activities in the groundwater and by the presence of zones with strong emission of gas from the soil. The most significant of these zones is Cava dei Selci where many houses are located very near to the gas emission site. The emitted gas consists mainly of CO₂ (up to 98 vol%) with an appreciable content of H₂S (0.8–2%). The He and C isotopic composition indicates, as for all fluids associated with the Quaternary Roman and Tuscany volcanic provinces, the presence of an upper mantle component contaminated by crustal fluids associated with subducted sediments and carbonates. An advective CO₂ flux of 37 tons/day has been estimated from the gas bubbles rising to the surface in a small drainage ditch and through a stagnant water pool, present in the rainy season in a topographically low central part of the area. A CO₂ soil flux survey with an accumulation chamber, carried out in February–March 2000 over a 12 000 m² surface with 242 measurement points, gave a total (mostly conductive) flux of 61 tons/day. CO₂ soil flux values vary by four orders of magnitude over a 160-m distance and by one order of magnitude over several metres. A fixed network of 114 points over 6350 m² has been installed in order to investigate temporal flux variations. Six surveys carried out from May 2000 to June 2001 have shown large variations of the total CO₂ soil flux (8–25 tons/day). The strong emission of CO₂ and H₂S, which are gases denser than air, produces dangerous accumulations in low areas which have caused a series of lethal accidents to animals and one to a man. The gas hazard near the houses has been assessed by continuously monitoring the CO₂ and H₂S concentration in the air at 75 cm from the ground by means of two automatic stations. Certain environmental parameters (wind direction and speed; atm P, T, humidity and rainfall) were also continuously recorded. At both stations, H₂S and CO₂ exceeded by several times the recommended concentration thresholds. The highest CO₂ and H₂S values were recorded always with wind speeds less than 1.5 m/s, mostly in the night hours. Our results indicate that there is a severe gas hazard for people living near the gas emission site of Cava dei Selci, and appropriate precautionary and prevention measures have been recommended both to residents and local authorities.     

Post‐stack stratigraphic inversion workflow applied to carbon dioxide storage: application to the saline aquifer of Sleipner field‡

In the Norwegian North Sea, the Sleipner field produces gas with a high CO₂ content. For environmental reasons, since 1996, more than 11 Mt of this carbon dioxide (CO₂) have been injected in the Utsira Sand saline aquifer located above the hydrocarbon reservoir. A series of seven 3D seismic surveys were recorded to monitor the CO₂ plume evolution. With this case study, time‐lapse seismics have been shown to be successful in mapping the spread of CO₂ over the past decade and to ensure the integrity of the overburden. Stratigraphic inversion of seismic data is currently used in the petroleum industry for quantitative reservoir characterization and enhanced oil recovery. Now it may also be used to evaluate the expansion of a CO₂ plume in an underground reservoir. The aim of this study is to estimate the P‐wave impedances via a Bayesian model‐based stratigraphic inversion. We have focused our study on the 1994 vintage before CO₂ injection and the 2006 vintage carried out after a CO₂ injection of 8.4 Mt. In spite of some difficulties due to the lack of time‐lapse well log data on the interest area, the full application of our inversion workflow allowed us to obtain, for the first time to our knowledge, 3D impedance cubes including the Utsira Sand. These results can be used to better characterize the spreading of CO₂ in a reservoir. With the post‐stack inversion workflow applied to CO₂ storage, we point out the importance of the a priori model and the issue to obtain coherent results between sequential inversions of different seismic vintages. The stacking velocity workflow that yields the migration model and the a priori model, specific to each vintage, can induce a slight inconsistency in the results.     

Elucidating geochemical response of shallow heterogeneous aquifers to CO2 leakage using high-performance computing: Implications for monitoring of CO2 sequestration

Predicting and quantifying impacts of potential carbon dioxide (CO₂) leakage into shallow aquifers that overlie geologic CO₂ storage formations is an important part of developing reliable carbon storage techniques. Leakage of CO₂ through fractures, faults or faulty wellbores can reduce groundwater pH, inducing geochemical reactions that release solutes into the groundwater and pose a risk of degrading groundwater quality. In order to help quantify this risk, predictions of metal concentrations are needed during geologic storage of CO₂. Here, we present regional-scale reactive transport simulations, at relatively fine-scale, of CO₂ leakage into shallow aquifers run on the PFLOTRAN platform using high-performance computing. Multiple realizations of heterogeneous permeability distributions were generated using standard geostatistical methods. Increased statistical anisotropy of the permeability field resulted in more lateral and vertical spreading of the plume of impacted water, leading to increased Pb²⁺ (lead) concentrations and lower pH at a well down gradient of the CO₂ leak. Pb²⁺ concentrations were higher in simulations where calcite was the source of Pb²⁺ compared to galena. The low solubility of galena effectively buffered the Pb²⁺ concentrations as galena reached saturation under reducing conditions along the flow path. In all cases, Pb²⁺ concentrations remained below the maximum contaminant level set by the EPA. Results from this study, compared to natural variability observed in aquifers, suggest that bicarbonate (HCO₃⁻) concentrations may be a better geochemical indicator of a CO₂ leak under the conditions simulated here.     

A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage

CO₂ injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO₂ into the brine. The resulting neutralization will drive further dissolution of both CO₂ and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO₂), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H₂O–CO₂–Na–Cl–CaCO₃ system, so as to model CO₂ injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO₂ plume because the brine below the plume tends to reach high CO₂ concentrations quite rapidly. We conclude that carbonate dissolution needs not to be feared.     

Diffuse CO2 efflux from Iwojima volcano,Izu-Ogasawara arc,Japan

Iwojima volcano, located on the southernmost part of the Izu-Ogasawara arc, is characterized by the extrusion of trachyte or trachy andesite lavas and pyroclastic rocks of Holocene and surface thermal manifestations. Small phreatic explosions have been recorded frequently during the last 100 years with the most recent in 1999 and 2001. In order to elucidate the behavior of volcanic volatiles and to assess the potential activity of this volcano, diffuse CO₂ efflux, CO₂ content and δ¹³C–CO₂ in soil gas, and soil temperature at 30 cm depth were measured at 272 sites in March 2000, 112 sites in December 2000 and 40 sites in December 2001. We found that high CO₂ efflux values, of more than 100 g m⁻² day⁻¹, occurred at several locations on Motoyama volcano corresponding with high soil temperatures (more than 60 °C at 30 cm depth) region and with areas where CO₂ with magmatic δ¹³C was observed. Here, the magmatic δ¹³C determined for fumarolic CO₂ data ranged from −2‰ to +3‰, which is clearly higher than magmatic gas values (−8‰ to −2‰) typically found in island arc settings around the world. However, this can be explained in terms of carbon-isotope fractionation between calcite and CO₂ under subsurface temperature and pressure conditions at Iwojima. A total efflux of CO₂ for Iwojima volcano is estimated to be 760 t day⁻¹, with a magmatic contribution of about 450 t day⁻¹. This value is rather high compared with other volcanoes in island arc settings. Since Iwojima has no visible plume, almost all volcanic CO₂ is released as diffuse efflux through the volcanic edifice.