Spatiotemporal changes in CO<Subscript>2</Subscript> emissions during the second ZERT injection,August–September 2008

This study reports the first field test of a multi-channel, auto-dilution, steady-state, soil–CO₂ flux monitoring system being developed to help understand the pathways by which fugitive CO₂ from a geologic sequestration site migrates to the surface. The test was conducted from late August through mid-October 2008 at the Zero Emissions Research and Technology project site located in Bozeman, MT. Twenty steady-state and five non-steady-state flux chambers were installed in a 10 × 15 m area, one boundary of which was directly above a shallow (2-m depth) horizontal injection well located 0.5 m below the water table. A total flux of 52 kg CO₂ day⁻¹ was injected into the well for 13 days and the efflux from the soil was monitored by the chambers before, during, and for 33 days after the injection. The results showed a rapid increase in soil efflux once injection started, with maximal values reached within 3–7 days in most chambers. Efflux returned to background levels within a similar time period after injection ceased. A radial efflux pattern was observed to at least 2 m from the injection well, and evidence for movement of the CO₂ plume during the injection, presumably due to groundwater flow, was seen. The steady-state chambers yielded very stable data, but threefold to fivefold higher fluxes than the non-steady-state chambers. The higher fluxes were attributed to vacuum induced in the steady-state chambers by narrow vent tubes. High winds resulted in significant decreases in measured soil CO₂ efflux, presumably by enhancing efflux from soil outside the chambers.     

Assessment of soil carbon pool,carbon sequestration and soil CO<Subscript>2</Subscript> flux in unreclaimed and reclaimed coal mine spoils

Surface coal mining inevitably deforests the land, reduces carbon (C) pool and generates different land covers. To re-establish the ecosystem C pool, post-mining lands are often afforested with fast-growing trees. A field study was conducted in the 5-year-old unreclaimed dump and reclaimed coal mine dump to assess the changes in soil CO₂ flux and compared with the reference forest site. Changes in soil organic carbon (SOC) and total nitrogen stocks were estimated in post-mining land. Soil CO₂ flux was measured using close dynamic chamber method, and the influence of environmental variables on soil CO₂ flux was determined. Woody biomass C and SOC stocks of the reference forest site were threefold higher than that of 5-year-old reclaimed site. The mean soil CO₂ flux was highest in 5-year-old reclaimed dump (2.37 μmol CO₂ m^?2 s^?1) and lowest in unreclaimed dump (0.21 μmol CO₂ m^?2 s^?1). Soil CO₂ flux was highly influenced by environmental variables, where soil temperature positively influenced the soil CO₂ flux, while soil moisture, relative humidity and surface CO₂ concentration negatively influenced the soil CO₂ flux. Change in soil CO₂ flux under different land cover depends on plant and soil characteristics and environmental variables. The study concluded that assessment of soil CO₂ flux in post-mining land is important to estimate the potential of afforestation to combat increased emission of soil CO₂ at regional and global scale.     

Assessment of soil moisture influence on CO2 flux: a laboratory experiment

Accurate measurements to assess the influence of soil moisture on CO₂ flux requires the absolute estimates of soil CO₂ flux. Thus, it was constructed a calibration system where CO₂ with fixed concentration flowed through the different porous material. Previous to measurement, in order to verify the performance and reliability of a closed dynamic chamber, different discontinuous air-mixing rates and times were tested. The CO₂ flux was estimated through sequential lectures and the best fit for flux measurements was obtained taking short readings every 3 min, during a total time of 12 min (R ² = 0.99). The best mixing rate was attained for 250 mL min⁻¹, allowing 25 s of mixing previous to CO₂ extraction for an infrared gas analyzer. The deviation of the measured values for dry sand from the reference CO₂ flux (0.097 and 0.071 g m⁻² min⁻¹) was 5 and 7%. On dry sandy loam soil (SLS) the deviation was 2%. The measured fluxes decreased 73 and 22% with content moisture of 20 and 10% (sand), and 78% with content moisture of 31% (SLS). This work allowed to estimate how much the measured emission rates deviate from the true ones for the specified chamber and sampling conditions.     

Changes in the chemistry of shallow groundwater related to the 2008 injection of CO2 at the ZERT field site, Bozeman, Montana

Approximately 300 kg/day of food-grade CO₂ was injected through a perforated pipe placed horizontally 2–2.3 m deep during July 9–August 7, 2008 at the MSU-ZERT field test to evaluate atmospheric and near-surface monitoring and detection techniques applicable to the subsurface storage and potential leakage of CO₂. As part of this multidisciplinary research project, 80 samples of water were collected from 10 shallow monitoring wells (1.5 or 3.0 m deep) installed 1–6 m from the injection pipe, at the southwestern end of the slotted section (zone VI), and from two distant monitoring wells. The samples were collected before, during, and following CO₂ injection. The main objective of study was to investigate changes in the concentrations of major, minor, and trace inorganic and organic compounds during and following CO₂ injection. The ultimate goals were (1) to better understand the potential of groundwater quality impacts related to CO₂ leakage from deep storage operations, (2) to develop geochemical tools that could provide early detection of CO₂ intrusion into underground sources of drinking water (USDW), and (3) to test the predictive capabilities of geochemical codes against field data. Field determinations showed rapid and systematic changes in pH (7.0–5.6), alkalinity (400–1,330 mg/l as HCO₃), and electrical conductance (600–1,800 μS/cm) following CO₂ injection in samples collected from the 1.5 m-deep wells. Laboratory results show major increases in the concentrations of Ca (90–240 mg/l), Mg (25–70 mg/l), Fe (5–1,200 ppb), and Mn (5–1,400 ppb) following CO₂ injection. These chemical changes could provide early detection of CO₂ leakage into shallow groundwater from deep storage operations. Dissolution of observed carbonate minerals and desorption-ion exchange resulting from lowered pH values following CO₂ injection are the likely geochemical processes responsible for the observed increases in the concentrations of solutes; concentrations generally decreased temporarily following four significant precipitation events. The DOC values obtained are 5 ± 2 mg/l, and the variations do not correlate with CO₂ injection. CO₂ injection, however, is responsible for detection of BTEX (e.g. benzene, 0–0.8 ppb), mobilization of metals, the lowered pH values, and increases in the concentrations of other solutes in groundwater. The trace metal and BTEX concentrations are all significantly below the maximum contaminant levels (MCLs). Sequential leaching of core samples is being carried out to investigate the source of metals and other solutes.     

Measuring daytime CO2 fluxes from the inter-tidal mangrove soils of Indian Sundarbans

The aim of this research was to measure the rate of carbon dioxide (CO₂) exchange between the soil and atmosphere in the inter-tidal forest floor of the Indian Sundarbans mangrove ecosystem and to study its response with soil temperature and soil water content. Soil CO₂ effluxes were monitored every month at two stations (between April, 2011 and March, 2012); one situated at the land–ocean boundary of the Bay of Bengal (outer part of the mangrove forest) and the other lying 55 km inshore from the coast line (inner part of the mangrove forest). The static closed chamber technique was implemented at three inter-tidal positions (landward, seaward and bare mudflats) in each station. Fluxes were measured in the daytime every half an hour by circulating chamber headspace air through a sampling manifold assembly and a closed-path non-dispersive infrared gas analyser. The fluxes ranged between 0.15 and 2.34 μmol m^?2 s^?1 during the annual course of sampling. Effluxes of higher magnitude were measured during summer; however, it abruptly decreased during the monsoon. CO₂ flux from the forest floor was strongly related to soil temperature, with the highest correlation found with temperature at 2 cm depth. No such significant relationship between soil water content and CO₂ efflux could be properly ascertained; however, excessively high soil water content was found to be the only reason which hampered the rate of effluxes during the monsoon. On the whole, landward (LW) sites of the mangrove forest emitted more than the seaward (SW) sites. Q ₁₀ values (obtained from simple exponential model) which denote the multiplicative factor by which the efflux rate increases for a 10 °C rise in temperature ranged between 2.07 and 4.05.     

Short-term greenhouse emission lowering effect of biochars from solid organic municipal wastes

Qatar economy has been growing rapidly during the last two decades during which waste generation and greenhouse gas emissions increased exponentially making them among the main environmental challenges facing the country. Production of biochar from municipal solid organic wastes (SOWs) for soil application may offer a sustainable waste management strategy while improving crop productivity and sequestering carbon. This study was conducted to (1) investigate the physicochemical parameters of biochars for SOW, (2) select the best-performing biochars for soil fertility, and (3) evaluate the potential benefits of these biochars in lowering greenhouse gases (GHGs) during soil incubation. Biochars were produced from SOW at pyrolysis temperatures of 300–750 °C and residence times of 2–6 h. Biochars were characterized before use in soil incubation to select the best-performing treatment and evaluation of potential GHG-lowering effect using CO₂ emission as proxy. Here, soil–biochar mixtures (0–2%w/w) were incubated in greenhouse settings for 120 days at 10% soil moisture. Soil properties, such as pH, EC, TC, and WHC, were significantly improved after soil amendment with biochar. Two biochars produced from mixed materials at 300–500 °C for 2 h and used at 0.5–1% application rate performed the best in enhancing soil fertility parameters. A significant decrease in CO₂ emission was observed in vials with soil–biochar mixtures, especially for biochars produced at 500 °C compared the corresponding raw materials which exhibited an exponential increase in the CO₂ emission. Hence, application of biochar to agricultural soils could be beneficial for simultaneously improving soil fertility/crop productivity while sequestering carbon, thereby reducing anthropogenic emissions of GHGs.     

Soil CO2 concentration in biological soil crusts and its driving factors in a revegetated area of the Tengger Desert,Northern China

Biological soil crusts (BSCs) are an important cover in arid desert landscapes, and have a profound effect on the CO₂ exchange in the desert system. Although a large number of studies have focused on the CO₂ flux at the soil–air interface, relatively few studies have examined the soil CO₂ concentration in individual layers of the soil profile. In this study, the spatiotemporal dynamics of CO₂ concentration throughout the soil profile under two typical BSCs (algae crusts and moss crusts) and its driving factors were examined in a revegetated sandy area of the Tengger Desert from Mar 2010 to Oct 2012. Our results showed that the mean values of the vertical soil CO₂ concentrations under algal crusts and moss crusts were 600–1,200 μmol/mol at the 0–40 cm soil profiles and increased linearly with soil depth. Daily CO₂ concentrations showed a single-peak curve and often had a 1–2 h time delay after the maximum soil temperature. During the rainy season, the mean soil CO₂ concentration profile was 1,200–2,000 μmol/mol, which was 2–5 times higher as compared to the dry season (400–800 μmol/mol). Annually, soil moisture content was the key limiting factor of the soil CO₂ concentration, but at the daily time scale, soil temperature was the main limiting factor. Combined with infiltration depth of crusted soils, we predicted that precipitation of 10–15 mm was the most effective driving factor in arid desert regions.     

Exploring the effects of data quality,data worth,and redundancy of CO2 gas pressure and saturation data on reservoir characterization through PEST inversion

This study examined the impacts of reservoir properties on carbon dioxide (CO₂) migration after subsurface injection and evaluated the possibility of characterizing reservoir properties using CO₂ monitoring data such as spatial–temporal distributions of gas pressure, which can be reasonably monitored in practice. The injection reservoir was assumed to be located 1,400–1,500 m below the ground surface such that CO₂ remained in the supercritical state. The reservoir was assumed to contain layers with alternating conductive and resistive properties, which is analogous to actual geological formations such as the Mount Simon Sandstone unit. The CO₂ injection simulation used a cylindrical grid setting in which the injection well was situated at the center of the domain, which extended out 8,000 m from the injection well. The CO₂ migration was simulated using the latest version of the simulator, subsurface transport over multiple phases (the water–salt–CO₂–energy module), developed by Pacific Northwest National Laboratory. A nonlinear parameter estimation and optimization modeling software package, Parameter ESTimation (PEST), is adopted for automated reservoir parameter estimation. The effects of data quality, data worth, and data redundancy were explored regarding the detectability of reservoir parameters using gas pressure monitoring data, by comparing PEST inversion results using data with different levels of noises, various numbers of monitoring wells and locations, and different data collection spacing and temporal sampling intervals. This study yielded insight into the use of CO₂ monitoring data for reservoir characterization and how to design the monitoring system to optimize data worth and reduce data redundancy. The feasibility of using CO₂ saturation data for improving reservoir characterization was also discussed.     

腾冲新生代火山区温泉CO2气体排放通量研究

近期研究表明,不仅火山喷发期会向当时的大气圈输送大量的温室气体,火山间歇期同样会释放大量的温室气体。在火山活动间歇期,火山区主要以喷气孔、温(热)泉以及土壤微渗漏等形式向大气圈释放温室气体。腾冲是我国重要的新生代火山区,同时也是重要的水热活动区,那里出露大量的温泉,然而目前未见腾冲火山区温泉气体排放通量的研究报道。本文利用数字皂膜通量仪测量了腾冲新生代火山区温泉中CO₂的排放通量。研究结果表明,腾冲新生代火山区温泉向当今大气圈输送的CO₂通量达3.58×10³ t·a^-1,相当于意大利锡耶纳Bassoleto地热区温泉中CO₂的排放规模。腾冲火山区温泉的CO₂释放通量主要受深部岩浆囊、断裂分布、地下水循环、围岩成分等多方面因素的影响。本文根据温泉中CO₂的排放特征,将腾冲温泉分为南北两区,南区温泉CO₂通量远高于北区的温泉,热海地热区的通量为腾冲CO₂通量的最大值。在北温泉区,CO₂通量主要受控于断裂的分布;而在南温泉区,除受到断裂控制外,热海地热区底部的岩浆囊及其与围岩的相互作用成为CO₂气体的重要物质来源,同时高温的岩浆囊为温泉及CO₂的形成提供了重要热源。     

CO<Subscript>2</Subscript> flux variation and its contribution area in the debris-covered area of Koxkar Glacier,Mt. Tianshan in China

During the formation and development of glacial meltwater runoff, hydrochemical erosion is abundant, especially the hydrolysis of K/Na feldspar and carbonates, which can consume H⁺ in the water, promote the formation of bicarbonate by dissolving atmospheric CO₂, and affect the regional carbon cycle. From July 21, 2015, to July 18, 2017, the CO₂ concentration and flux were observed by the eddy covariance (EC) method in the relatively flat and open moraine cover area of Koxkar Glacier in western Mt. Tianshan, China. We found that: (1) atmospheric CO₂ fluxes ranged from ??408.95 to 81.58 mmol m^?2 day^?1 (average ? 58.68 mmol m^?2 day^?1), suggesting that the study area is a significant carbon sink, (2) the CO₂ flux footprint contribution areas were primarily within 150 m of the EC station, averaging total contribution rates of 93.30%, 91.39%, and 90.17% of the CO₂ flux in the snow accumulation, snow melting, and glacial melting periods, respectively. Therefore, the contribution areas with significant influences on CO₂ flux observed at EC stations were concentrated, demonstrating that grassland CO₂ flux around the glaciers had little effect at the EC stations, (3) in the predominant wind direction, under stable daytime atmospheric stratification, the measurement of CO₂ flux, as interpreted by the Agroscope Reckenholz Tanikon footprint tool, was 79.09% ± 1.84% in the contribution area. This was slightly more than seen at night, but significantly lower than the average under unstable atmospheric stratification across the three periods of interest (89%). The average distance of the farthest point of the flux footprint under steady state atmospheric conditions was 202.61?±?69.33 m, markedly greater than that under non-steady state conditions (68.55?±?10.34 m). This also indicates that the CO₂ flux observed using EC was affected primarily by hydrochemical erosion reactions in the glacier area, (4) a good negative correlation was found between net glacier exchange (NGE) of CO₂ and air temperature on precipitation-free days. Strong ice and snow ablation could promote hydrochemical reactions of soluble substances in the debris area and accelerated sinking of atmospheric CO₂. Precipitation events might reduce snow and ice melting, driven by reduced regional temperatures. However, a connection between NGE and precipitation, when less than 8.8 mm per day, was not obvious. When precipitation was greater than 8.8 mm per day, NGE decreased with increasing precipitation, (5) graphically, the slope of NGE, related to daily runoff, followed a trend: snow melting period?>?snow accumulation period?>?early glacial ablation period?>?late glacier ablation period?>?dramatic glacier ablation period. The slope was relatively large during snow melting, likely because of CO₂ sinking caused by water–rock interactions. The chemical reaction during elution in the snow layer might also promote atmospheric CO₂ drawdown. At the same time, the damping effect of snow cover and the almost-closed glacier hydrographic channel inhibited the formation of regional runoff, possibly providing sufficient time for the chemical reaction, thus promoting further CO₂ drawdown.     

Interdiffusion of H2O and CO2 in metamorphic fluids at ∼490 to 690°C and 1 GPa

Interdiffusion coefficients have been determined for H₂O-CO₂ mixtures by quantifying the flux of CO₂ between two fluid-filled chambers in a specially designed piston-cylinder cell. The two chambers, which are maintained at 1.0 GPa and at temperatures differing by ∼100°C, each contain the X_CO2-buffering assemblage calcite + quartz + wollastonite, in H₂O. The positive dependence of X_CO2 on temperature results in a down-temperature, steady-state flux of CO₂ through a capillary tube that connects the two chambers. This flux drives the wollastonite = calcite + quartz equilibrium to the right in the cooler chamber, producing a measurable amount of calcite that is directly related to CO₂-H₂O interdiffusion rates. Diffusivities calculated from seven experiments range from 1.0 × 10⁻⁸ to 6.1 × 10⁻⁸ m²/s for mean capillary temperatures between ∼490 and 690°C. The data set can be approximated by an Arrhenius-type relation:

     

Environmental Controls on Net Ecosystem CO2 Exchange Over a Reed (Phragmites australis) Wetland in the Yellow River Delta, China

Using the Eddy Covariance (EC) technique, we analyzed temporal variation in net ecosystem CO₂ exchange (NEE) and determined the effects of environmental factors on the balance between ecosystem photosynthesis and respiration in a reed (Phragmites australis) wetland in the Yellow River Delta, China. Our results indicated that diurnal and seasonal patterns of NEE and its components (ecosystem respiration (R _eco), gross primary production (GPP)) varied markedly among months for the growing season (May to October). The cumulative CO₂ emission was 1,657 g CO₂ m^?2, while 2,612 g CO₂ m^?2 was approximately accumulated as GPP, which resulted in the reed wetland being a net sink of 956 g CO₂ m^?2. The ratio of R _eco to GPP in reed wetland was 0.68, which was close to other temperate wetlands. Soil temperature and soil moisture exerted the primary controls on R _eco during the growing season. Daytime NEE values during the growing season were strongly correlated with photosynthetically active radiation. Aboveground biomass showed significant linear relationships with 24-h average NEE, daytime GPP, and R _eco, respectively. Thus, we conclude that the coastal wetland acted as a carbon sink during the growing season despite the variations in environmental conditions, and long-term flux measurements over these ecosystems are undoubtedly necessary.     

Balancing the Oceanic Calcium Carbonate Cycle: Consequences of Variable Water Column ��

The paired chemical reactions, Ca²⁺ + 2HCO₃ ^? ? CaCO₃ + CO₂ + H₂O, overestimate the ratio of CO₂ flux to CaCO₃ flux during the precipitation or dissolution of CaCO₃ in seawater. This ratio, which has been termed ??, is about 0.6 in surface seawater at 25°C and at equilibrium with contemporary atmospheric CO₂ and increases towards 1.0 as seawater cools and pCO₂ increases. These conclusions are based on field observations, laboratory experiments, and equilibrium calculations for the seawater carbonate system. Yet global geochemical modeling indicates that small departures of ?? from 1.0 would cause dramatic, rapid, and unrealistic change in atmospheric CO₂. ?? can be meaningfully calculated for a water sample whether or not it is in equilibrium with the atmosphere. The analysis presented here demonstrates that the atmospheric CO₂ balance can be maintained constant with respect to seawater CaCO₃ reactions if one considers the difference between CaCO₃ precipitation and burial and differing values for ?? (both <1.0) in regions of precipitation and dissolution within the ocean.     

Annual soil CO2 efflux in a wet meadow during active layer freeze–thaw changes on the Qinghai-Tibet Plateau

Soil CO₂ efflux from an ecosystem responds to the active layer thawing depth (H) significantly. A Li-8100 system was used to monitor the CO₂ exchange from a wet meadow ecosystem during a freeze–thaw cycle of the active layer in a permafrost region on the Qinghai-Tibet Plateau. An exponential regression equation ( $ F_{\text{soil\, flux}} = 1.84e^{0.023H} + 5.06\,R^{2} = 0.96 $ ) has been established on the basis of observed soil CO₂ efflux versus the thawed soil thickness. Using this equation, the total soil CO₂ efflux during an annual freeze–thaw cycle has been calculated to be approximately 8.18 × 10¹⁰ mg C. The results suggest that freeze–thaw cycles in the active layer play an important role in soil CO₂ emissions and that thawed soil thickness is the major factor controlling CO₂ fluxes from the wet meadow ecosystem in permafrost regions on the Qinghai-Tibet Plateau. It can be concluded that with active layer thickening due to permafrost degradation, massive amounts of soil carbon would be emitted as greenhouse gases, and the permafrost region would become a carbon source with a positive feedback effect on climate warming. Hence, more attention should be paid to the influences of the active layer changes on soil carbon emission from these permafrost regions.     

Experimental and numerical studies of the O exchange between CO2 and water in the atmosphere-soil invasion flux

The ¹⁸O/¹⁶O ratio of CO₂ is a potentially powerful tracer of carbon dioxide fluxes from the soil to the atmosphere, which is influenced by complex interactions involving both biotic and abiotic soil processes. We use a simplified experimental approach and numerical simulations to examine in isolation the ¹⁸O exchange between CO₂ and soil water associated with the abiotic invasion of atmospheric CO₂ into soil. This allowed us to verify, in particular, whether the ¹⁸O of the retro-diffusion flux of CO₂ from the soil reflects ¹⁸O equilibration with water at the soil surface, or at some depth. Sterile soil samples with known water isotopic composition were placed in a closed box attached to a specially designed flow chamber and the changes in δ¹⁸O of CO₂ between the chamber inlet and outlet, due only to invasion effects, were determined. Numerical simulations constrained by the laboratory gas exchange measurements indicated that between the two commonly used diffusion models [Penman, H.L. (1940). Gas and vapor movements in soil, 1: the diffusion of vapors through porous solids. Int. J. Agric. Sci.30, 437-462; Moldrup, P., Olesen, T., Yamaguchi, T., Schjonning, P., Rolston, D.E. (1999). Modeling diffusion and reaction in soils, IX, the Backingham-Burdine-Campbell equation for gas diffusivity in undisturbed soil. Soil Sci.164, 542-551], only the former provided good agreement with the measurements over a wide range of soil water contents. Based on the model calculations constrained by experimental data, and on comparison of characteristic diffusion/reaction times, we conclude that the depth required for full CO₂-water ¹⁸O equilibration ranges between 2 and 8.5 cm. The depth depends, in order of importance, on (1) soil moisture content; (2) temperature, which dominates the rate of hydration isotopic exchange; (3) CO₂ residence time, which is determined by the time of replacement of the column air above the soil; and (4) soil structure, including porosity, tortuosity and grain size, with the later probably influencing the water surface area exposed to CO₂ exchange. Using field data from a semi-arid forest site in Israel, numerical simulations indicated that the ¹⁸O full equilibrium depth varied at this site between 4 cm (January) and 8 cm (November), being sensitive mostly to temperature and soil water content. Deepening of the equilibration depth as the soil dries should limit the effects of ¹⁸O evaporative enrichment at the surface on the isotopic composition of the soil-atmosphere CO₂ flux.     

Numerical simulation of carbon dioxide injection for enhanced gas recovery (CO2-EGR) in Altmark natural gas field

This paper studied the CO₂-EGR in Altmark natural gas field with numerical simulations. The hydro-mechanical coupled simulations were run using a linked simulator TOUGH2MP-FLAC3D. In order to consider the gas mixing process, EOS7C was implemented in TOUGH2MP. A multi-layered 3D model (4.4 km × 2 km × 1 km) which consists of the whole reservoir, caprock and base rock was generated based on a history-matched PETREL model, originally built by GDF SUEZ E&P Deutschland GmbH for Altmark natural gas field. The model is heterogeneous and discretized into 26,015 grid blocks. In the simulation, 100,000 t CO₂ was injected in the reservoir through well S13 within 2 years, while gas was produced from the well S14. Some sensitivity analyses were also carried out. Simulation results show that CO₂ tends to migrate toward the production well S14 along a NW–SE fault. It reached the observation wells S1 and S16 after 2 years, but no breakthrough occurred in the production well. After 2 years of CO₂ injection, the reservoir pressure increased by 2.5 bar, which is beneficial for gas recovery. The largest uplift (1 mm) occurred at the bottom of the caprock. The deformation was small (elastic) and caprock integrity was not affected. With the injection rate doubled the average pressure increased by 5.3 bar. Even then the CO₂ did not reach the production well S14 after 2 years of injection. It could be concluded that the previous flow field was established during the primary gas production history. This former flow field, including CO₂ injection/CH₄ production rate during CO₂-EGR and fault directions and intensity are the most important factors affecting the CO₂ transport.     

Continuous in situ measurements of volcanic gases with a diode-laser-based spectrometer: CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>O concentration and soil degassing at Vulcano (Aeolian islands: Italy)

We report on a continuous-measurement campaign carried out in Vulcano (Aeolian islands, Sicily), devoted to the simultaneous monitoring of CO₂ and H₂O concentrations. The measurements were performed with an absorption spectrometer based on a semiconductor laser source emitting around a 2-μm wavelength. The emitted radiation was selectively absorbed by two molecular ro-vibrational transitions specific of the investigated species. Data for CO₂ and H₂O concentrations, and CO₂ soil diffusive flux using an accumulation chamber configuration, were collected at several interesting sampling points on the island (Porto Levante beach- PLB, Fossa Grande Crater – FOG- and Valley of Palizzi, PAL). CO₂/H₂O values, measured on the ground, are very similar (around 0.019 (± 0.006)) and comparable to the previous discrete detected values of 0.213 (Fumarole F5-La Fossa crater rim) and 0.012 (Fumarole VFS – Baia Levante beach) obtaid during the 1977–1993 heating phase of the crater fumaroles.     

Carbon dioxide in Postojna Cave (Slovenia): spatial distribution,seasonal dynamics and evaluation of plausible sources and sinks

The CO₂ concentration of the air in Postojna Cave (400–7900 ppm) is found to be induced by CO₂ sources (human respiration contributing?~?20,000–58,000 ppm per breath, outgassing of dripwater and water seeping from the vadose zone/epikarst with a pCO₂ values of 5000–29,000 ppm, and underground Pivka River having pCO₂ at 2344–4266 ppm) and CO₂ dilution (inflow of outside air with a CO₂ concentration of?~?400 ppm). Measurements show that sinking Pivka River has the lowest CO₂ concentration among plausible CO₂ sources but still continuously exceeds the surrounding cave air CO₂ concentration. During the winter months, intensive ventilation reduces the cave air CO₂ concentration to outside levels (~?400 ppm), even in the centre of the cave system. CO₂ dilution is less pronounced in summer (CO_2(min)?≈?800 ppm), since the ventilation rate is not as strong as in winter and the outside air that enters the cave through breathing holes and fractures is enriched with soil CO₂. During spring and autumn, the daily alternation of the ventilation regime with a smaller rate of air exchange results in yearly cave air CO₂ peaks of up to?~?2400 ppm. Some dead-end passages can be much less affected by ventilation, resulting in a cave air CO₂ concentration of up to 7900 ppm. The strongest diurnal CO₂ peaks due to human respiration were recorded during the spring holidays (increase of up to 1300 ppm day^?1), compared to considerably smaller summer peaks despite peak visits (increase of?~?600 ppm day^?1).     

Increased hydrocarbon recovery and CO2 management, a Croatian example

Enhanced oil recovery based on CO₂ injection is expected to increase recovery from Croatian oil fields. Large quantities of CO₂ are generated during hydrocarbon processing produced from gas and gas condensate fields situated in the north-western part of Croatia. First CO₂ injection project will be implemented on the Ivani? Oil Field. Numerical modelling based on Upper Miocene sandstone core samples testing results have shown the decrease of oil viscosity during CO₂ injection. Some of the characteristics of the testing samples are porosity 21.5–23.6 %, permeability 14–80 × 10^?15 m² and initial water saturation 28–38.5 %. Water alternating foam (WAF) and water alternating gas (WAG) simulations have provided satisfactory results. The WAF injection process has provided better results, but due to the process sensitivity and costs WAG is recommended for future application. During the pilot project 16 × 10⁶ m³ CO₂ and 5 × 10⁴ m³ of water were injected. Additional amounts of hydrocarbons (4,440 m³ of oil and 2.26 × 10⁶ m³ of gas) were produced which confirmed injection of CO₂ as a successful tertiary oil recovery mechanism in Upper Miocene sandstone reservoirs in the Croatian part of the Pannonian Basin System.     

Carbon dioxide emissions from the Three Gorges Reservoir,China

Carbon dioxide (CO₂) emission from the river-type reservoir is an hotspot of carbon cycle within inland waters. However, related studies on the different types of reservoirs are still inadequate. Therefore, we sampled the Three Gorges Reservoir (TGR), a typical river-type reservoir having both river and lake characteristics, using an online system (HydroCTM/CO₂) and YSI-6600v2 meter to determine the partial pressure of carbon dioxide (pCO₂) and physical chemical parameters in 2013. The results showed that the CO₂ flux from the mainstream ranged from 26.1 to 92.2 mg CO₂/m² h with average CO₂ fluxes of 50.0 mg/m² h. The CO₂ fluxes from the tributary ranged from ?10.91 to 53.95 mg CO₂/m² h with area-weighted average CO₂ fluxes of 11.4 mg/m² h. The main stream emits CO₂ to the atmosphere the whole year; however, the surface water of the tributary can sometimes act as a sink of CO₂ for the atmosphere. As the operation of the TGR, the tributary became more favorable to photosynthetic uptake of CO₂ especially in summer. The total CO₂ flux was estimated to be 0.34 and 0.03 Tg CO₂/year from the mainstream and the tributaries, respectively. Our emission rates are lower than previous estimates, but they are in agreement with the average CO₂ flux from temperate reservoirs estimated by Barros et al. (Nat Geosci 4(9):593–596, 2011).