On the buffer capacity of CO2-charged seawater used for carbonation and subsequent mineral sequestration

Successful mineral trapping of carbon dioxide faces the challenge of effectively titrating a CO2-charged acidic injection solution to pH conditions favorable to carbonate precipitation -using the rock as primary alkalinity source. To illustrate the magnitude of this task, buffer capacities of seawater solutions equilibrated with different partial pressure of CO2 are presented, under open and closed conditions. A number of mechanisms can be evoked to overcome the large buffer intensity of the injection fluid, including dilution, dissolution kinetic catalysis and increasing reaction temperature. Buffer capacity – pH plots are presented to aid in understanding how buffer capacity changes as a function of the presence and concentration of key solutes, like fluoride

Geochemical modelling of petroleum well data from the Perth Basin. Implications for potential scaling during low enthalpy geothermal exploration from a hot sedimentary aquifer

Chemical analyses derived from petroleum exploration wells are notorious for their lack of key solute data and their potential to represent mixtures of reservoir and drilling fluids rather than pristine formation compositions. These drawbacks notwithstanding, they usually pose the only access to the reservoir geochemistry. Two literature protocols were applied to a dataset of incomplete major element analyses from 148 petroleum well samples from a database compilation of the Perth Basin whose deeper aquifers may serve as potential hot sedimentary aquifers for geothermal direct heat applications. The first protocol included a set of quality control criteria that reduced the number of relatively genuine formation well samples from the raw data pool by 71%. The remaining well analyses are invariably NaCl solutions of low to medium alkalinity and an ionic strength only occasionally reaching seawater salinity. The low amount of total dissolved solids indicates the absence of extended evaporites in the North Perth Basin and the prevalence of meteoric water infiltration and circulation at depths.The culled well samples underwent as a second protocol a forced equilibrium treatment to reconstruct in situ reservoir concentrations of missing elements (Si, Al, K), organic acid anions and non-carbonate alkalinity, and pH. The petroleum well samples were modelled to be in equilibrium with chalcedony (and kaolinite, albite, and paragonite) in the reservoir which yielded better convergence than using quartz instead. The derived formation temperatures correspond to geothermal gradients in the majority of cases between 25 and 35°C, in accord with literature findings. Those wells drilled to depth 90% of the wells from the calculated pH, either due to degassed CO2 or unaccounted acetate alkalinity. The wells were further modelled to be undersaturated with respect to amorphous silica and anhydrite and not likely to experience scaling of any of these two phases during geothermal production at depth <3800 m. For calcite, scaling predictions depend in how far bubbling and phase segregation can be suppressed. For the six different stratigraphies investigated here, calculated bubble points were low, indicating that pressurisation of the entire production and re-injection line seems viable.Based on a calcite growth model from the literature it is shown that, if bubble formation and concomitant carbonate flash scaling cannot be averted, the production well should be as shallow as the temperature requirements of the geothermal production allow for. This study promotes the application of readily accessible protocols and a scaling model to deep well samples that may otherwise appear to have little geochemical value because of the way the samples were collected and handled. After data culling and treatment, insights into the geochemistry and scaling potential of deep clastic formations of the North Perth Basin that may hold the potential for geothermal exploitation as hot sedimentary aquifers can be gained

The syringe sampler: An inexpensive alternative borehole sampling technique for CO2-rich fluids during mineral carbon storage

Mineral carbon storage involves the dissolution of injected gaseous or supercritical CO2 followed by interaction of the carbonated solution with the host rock at depth resulting in the precipitation of carbonate minerals. Monitoring of elemental chemistry and tracers is required to evaluate the evolution of the fluid geochemistry and the degree of CO2 mineralization during its injection into the subsurface. To avoid degassing during sampling, which is a common feature of commercial groundwater samplers, especially vacuum samplers, a syringe-like sampler was designed, constructed, and tested in the lab and field. This system was successfully deployed during the injection of 175 tons of pure gaseous CO2 at the CarbFix injection site in Hellisheidi, SW Iceland. This study presents in detail this sampling tool and its application to the monitoring of the CO2-rich fluid evolution during subsurface carbonation. The syringe sampler was developed as a flexible and mobile unit of low investment and operating costs making it an attractive option for deployment at small scale carbon storage demonstration sites that do not command the budgets to deploy commercial alternatives, e.g. from the oil and gas industry

1. Wochenbericht ANT-XXVI/1

ANT-XXVI/1, Wochenbericht Nr. 1 16. Oktober 2009 - 25. Oktober 2009 [POLARSTERN

Basalt-CO2-brine wettability at storage conditions in basaltic formations

© 2020 Elsevier Ltd CO2 geo-storage in basaltic formations has recently been demonstrated as a viable solution to rapidly sequester and mineralize CO2. In case CO2 is injected into such basalt reservoirs in supercritical form, a two-phase system (reservoir brine and supercritical CO2) is created, and it is of key importance to specify the associated CO2-basalt wettability so that fluid distributions and CO2 flow through the reservoir can be predicted. However, there is a serious lack of data for basalt CO2-wettability. We therefore measured water contact angles on basalt substrates in CO2 atmosphere. The results indicate that at shallow depth (below 500 m) basalt is strongly water-wet. With increasing depth the basalt becomes less hydrophilic, and turns intermediate-wet at a depth of 900 m. We conclude that basalt is more CO2-wet than chemically clean minerals (quartz, calcite), especially at depths below 900 m. However, the basalt had a CO2-wettability similar to some caprock samples and a gas-reservoir sandstone. The data presented in this paper will thus aid in the prediction and optimization of CO2 geo-storage in basalt formations

The effect of pH, grain size, and organic ligands on biotite weathering rates

Biotite dissolution rates were determined at 25 °C, at pH 2–6, and as a function of mineral composition, grain size, and aqueous organic ligand concentration. Rates were measured using both open- and closed-system reactors in fluids of constant ionic strength. Element release was non-stoichiometric and followed the general trend of Fe, Mg > Al > Si. Biotite surface area normalised dissolution rates (ri) in the acidic range, generated from Si release, are consistent with the empirical rate law: ri=kH,iaxiH+ where kH,i refers to an apparent rate constant, aH+ designates the activity of protons, and xi stands for a reaction order with respect to protons. Rate constants range from 2.15 × 10−10 to 30.6 × 10−10 (molesbiotite m−2 s−1) with reaction orders ranging from 0.31 to 0.58. At near-neutral pH in the closed-system experiments, the release of Al was stoichiometric compared to Si, but Fe was preferentially retained in the solid phase, possibly as a secondary phase. Biotite dissolution was highly spatially anisotropic with its edges being ∼120 times more reactive than its basal planes. Low organic ligand concentrations slightly enhanced biotite dissolution rates. These measured rates illuminate mineral–fluid–organism chemical interactions, which occur in the natural environment, and how organic exudates enhance nutrient mobilisation for microorganism acquisition

CO2 sequestration in basaltic rocks in Iceland: Development of a piston-type downhole sampler for CO2 rich fluids and tracers

The reduction of atmospheric CO2 is one of the challenges that scientists face today. University of Iceland, Reykjavik Energy, CNRS in Toulouse and Columbia University have started a cooperative project called CarbFix (www.carbfix.com) aiming at CO2 mineral sequestration into basalts at Hellisheidi, SW Iceland. Gaseous CO2 will be injected into a borehole where it will be carbonated with Icelandic groundwater. The CO2 charged injection fluid will be released into the target aquifer at ca. 500 m depth at about 35°C and 40 bar. The aim is to permanently bind CO2 into carbonates upon water-rock interaction. In order to evaluate the hydro-geochemical patterns and proportions of CO2 mineralization in the aquifer, full scale monitoring is needed. This will involve monitoring of conservative and gas tracers injected with the carbonated fluid, isotope ratios and major and trace elemental chemistry. A crucial issue of the monitoring is the quality of the sampling at depth and under pressure. Commonly, gas bubbles are observed when using commercial downhole samplers (bailers) and in order to avoid this problem, a piston-type downhole bailer was designed, constructed and tested as part of the project

Experimental observations of CO2-water-basaltic glass interaction in a large column reactor experiment at 50 °C

Publisher's version (útgefin grein).Mineralization of water dissolved carbon dioxide injected into basaltic rocks occurs within two years in field-scale settings. Here we present the results from a CO2-water-basaltic glass laboratory experiment conducted at 50 °C and 80 bar pressure in a Ti high-pressure column flow reactor. We explore the possible sequence of saturation with Fe-Mg-Ca-carbonate minerals versus Fe-Mg-clay and Ca-zeolite saturation states, which all compete for divalent cations and pore space during injection of CO2 into basaltic rocks. Pure water (initially with atmospheric CO2) – basaltic glass reactions resulted in high pH (9–10) water saturated with respect to Mg-Fe-clays (saponites), Ca-zeolites, and Ca-carbonate. As CO2-charged water (˜20 mM) entered the column and mixed with the high pH water, all the Fe-Mg-Ca-carbonates became temporarily supersaturated along with clays and zeolites. Injected waters with dissolved CO2 reached carbonate mineral saturation within 12 h of fluid-rock interaction. Once the pH of the outflow water stabilized below 6, siderite was the only thermodynamically stable carbonate throughout the injection period, although no physical evidence of its precipitation was found. When CO2 injection stopped while continuing to inject pure water, pH rose rapidly in the outflow and all carbonates became undersaturated, whereas zeolites became more saturated and Mg-Fe-saponites supersaturated. Resuming CO2 injection lowered the pH from >8 to about 6, resulting in an undersaturation of the clays and Na-zeolites. These results along with geochemical modelling underscore the importance of initial pCO2 and pH values to obtain a balance between the formation of carbonates versus clays and zeolites. Moreover, modelling indicates that pauses in CO2 injection while still injecting water can result in enhanced large molar volume Ca-Na-zeolite and Mg-Fe-clay formation that consumes pore space within the rocks.This publication has been produced with support from the European Commission through the projects CarbFix (EC Project 283148), CO2-React (EC Project 317235), and S4CE (EC Project 764810). The authors would like to thank editor Charles Jenkins for handling the manuscript and to the anonymous reviewers for their constructive comments that helped improve the manuscript. Special thanks to Giulia Alessandrini for her indispensable assistance in running the experiment, Sydney Gunnarson for material preparation, and Þorsteinn Jónsson for preparing, setting up, and taking apart the column. We would also like to acknowledge Rebecca Neely and Tobias Linke for their help in the laboratory in addition to Eric Oelkers, Peter Rendel, and the CarbFix group for their support.Peer Reviewe

Effect of desferrioxamine B and Suwannee River fulvic acid on Fe(III) release and Cr(III) desorption from goethite

Siderophores are biogenic chelating ligands that facilitate the solubilization of Fe(III) and form stable complexes with a range of contaminant metals and therefore may significantly affect their biogeochemical cycling. Desferrioxamine B (DFOB) is a trihydroxamate siderophore that acts synergistically with fulvic acid and low molecular weight organic ligands to release Fe from Fe(III) oxides. We report the results of batch dissolution experiments in which we determine the rates of Cr(III) desorption and Fe(III) release from Cr(III)-treated synthetic goethite as influenced by DFOB, by fulvic acid, and by the two compounds in combination. We observed that adsorbed Cr(III) at 3% surface coverage significantly reduced Fe(III) release from goethite for all combinations of DFOB and fulvic acid. When DFOB (270 µM) was the only ligand present, dissolved Fe(III) and Cr(III) increased approximately 1000-fold and 16-fold, respectively, as compared to the ligand-free system, a difference we attribute to the slow rate of water exchange of Cr(III). Suwannee River fuvic acid (SRFA) acts synergistically with DFOB by (i) reducing the goethite surface charge leading to increased HDFOB+ surface excess and by (ii) forming aqueous Fe(III)-SRFA species whose Fe(III) is subsequently removed by DFOB to yield aqueous Fe(III)-DFOB complexes. These observations shed new light on the synergistic relationship between DFOB and fulvic acid and reveal the mechanisms of Fe(III) acquisition available to plants and micro-organisms in Cr(III) contaminated environments