CO2 geological storage: The environmental mineralogy perspective

Geological storage of carbon dioxide (CO₂) is one of the options envisaged for mitigating the environmental consequences of anthropogenic CO₂ increases in the atmosphere. The general principle is to capture carbon dioxide at the exhaust of power plants and then to inject the compressed fluid into deep geological formations. Before implementation over large scales, it is necessary to assess the efficiency of the process and its environmental consequences. The goal of this paper is to discuss some environmental mineralogy research perspectives raised by CO₂ geological storage.     

Simulation of post-impact rotational changes through multi-dimensional parametrization

In this paper we propose firstly a full parametrization of an impact on a target body considered as ellipsoidal, including several geometrical parameters which are generally not included. Then we construct a more detailed and complete theoretical model of the rotational changes of the target body arising from a single impact, by taking into account the various parameters above. Secondly from these theoretical studies we carry out simulations of impacts and then we evaluate the influences of the various parameters on the rotational evolution of a specific target, in particular the angular speed of rotation and the direction of the axis of rotation. For that we consider two cases: in the first one, which we call accretion, the projectile is simply stuck to the target without a significant amount of ejected mass. In the second case, which we call craterization, the target body is eroded with formation of ejecta and a crater. The physical properties of the target are close to those of the Asteroid 21 Lutetia which Rosetta mission would fly in July 2010. We obtain quite different results according to the considered mode of impact (accretion or craterization): in the case of an impact with accretion the results are intuitively foreseeable whereas those corresponding to an impact with craterization are more difficult to interpret. Our work can be applied to obtain information on the rotational effects of an impact on a given target body with well constrained physical characteristics, in particular within the framework of the Don Quijote mission project.     

KArMars: A Breadboard Model for In Situ Absolute Geochronology Based on the K–Ar Method Using UV‐Laser‐Induced Breakdown Spectroscopy and Quadrupole Mass Spectrometry

We present a breadboard prototype to perform in situ dating applicable to planetary exploration. Based on the K–Ar dating method and using instruments inspired by flight‐proven analytical components, ‘KArMars’ ablated a geological sample under high vacuum with a quadrupled ultraviolet (UV at 266 nm) Nd:YAG laser. During ablation, the K content of the target material was given by laser‐induced breakdown spectroscopy and the released ⁴⁰Ar was measured with a quadrupole mass spectrometer. Because K was measured as a concentration and ⁴⁰Ar as a count of atoms, these values were converted using the ablated mass given by the product of the density and the ablated volume. The uncertainties of the age measurement were < 15%. The quality of the K–Ar measurements was enhanced by the advantages of UV laser ablation such as the minimisation of thermal effects on argon diffusion. This work demonstrates that a specialised instrument inspired by this set‐up could provide in situ absolute geochronology with sufficient precision for scientific investigations, particularly where the crater density counting provides higher uncertainties on Mars.     

Groundwater,Acid and Carbon Dioxide Dynamics Along a Coastal Wetland,Lake and Estuary Continuum

Coastal wetlands are hotspots for biodiversity and biological productivity, yet the hydrology and carbon cycling within these systems remains poorly understood due to their complex nature. By using a novel spatiotemporal approach, this study quantified groundwater discharge and the related inputs of acidity and CO₂ along a continuum of a modified coastal acid sulphate soil (CASS) wetland, a coastal lake and an estuary under highly contrasting hydrological conditions. To increase the resolution of spatiotemporal data and advance upon previous methodologies, we relied on automated observations from four simultaneous time-series stations to develop multiple radon mass balance models to estimate groundwater discharge and related groundwater inputs of acidity and dissolved inorganic carbon (DIC), along with surface water to atmosphere CO₂ fluxes. Spatial surveys indicated distinct acid hotspots with minimum surface water pH of 2.91 (dry conditions) and 2.67 (flood conditions) near a non-remediated (drained) CASS area. Under flood conditions, groundwater discharge accounted for ～14.5 % of surface water entering the lake. During the same period, acid discharge from the acid sulphate soil section of the continuum produced ～4.8 kg H₂SO₄?ha^?1 day^?1, a rate much higher than previous studies in similar systems. During baseflow conditions, the low pH water was rapidly buffered within the estuarine lake, with the pH increasing from 4.22 to 6.07 over a distance of ～250 m. The CO₂ evasion rates within the CASS were extremely high, averaging 2163?±?125 mmol m^?2 day^?1 in the dry period and 4061?±?259 mmol m^?2 day^?1 under flood conditions. Groundwater input of DIC could only account for 0.4 % of this evasion in the dry conditions and ～5 % during the flood conditions. We demonstrated that by utilising a spatiotemporal (multiple time-series stations) approach, the study was able to isolate distinct zones of differing hydrology and biogeochemistry, whilst providing more reasonable groundwater acid input estimates and air–water CO₂ flux estimates than some traditional sampling designs. This study highlights the notion that modified CASS wetlands can release large amounts of CO₂ to the atmosphere because of high groundwater acid inputs and extremely low surface water pH.     

Sustainable groundwater resources exploration and management in a complex geological setting as part of a humanitarian project (Mahafaly Plateau,Madagascar)

Southwestern Madagascar is a semi-arid region and a hot-spot of global change. On the Mahafaly plateau, people live with quasi-permanent water stress and groundwater, the only available resource, is difficult to exploit due to a complex hydrogeological environment. A methodology (suitable for humanitarian projects; <?40 k€) was developed in four phases to assess the sustainable exploitation of the water resource: (A) regional scale exploration, (B) village scale exploration, (C) drilling campaign, and (D) hydro-climatic monitoring. This integrated hydrogeophysical approach involves geophysical measurements (262 TEM-fast soundings, 2588 Slingram measurements, 35 electrical soundings), hydrochemical analyses (112 samples), and a piezometric survey (127 measurements). Two groundwater resources were identified, one deep (below 150 m) and one shallow (<?20 m). Hydrochemical results highlighted the vulnerability of both resources: anthropic contamination for the shallower and seawater intrusion for the deeper. Therefore, subsequent geophysical surveys supported the siting of six boreholes and three wells in the shallow aquifer. This methodological approach was successful in this complex geological setting and requires testing at other sites in and outside Madagascar. The study demonstrates that geophysical results should be used in addition to drilling campaigns and to help monitor the water resource. In fact, to prevent over-exploitation, piezometric and meteorological sensors were installed to monitor the water resource. This unique hydro-climatic observatory may help (1) non-governmental organization and local institutions prevent future water shortages and (2) scientists to understand better how global change will affect this region of the world.     

Dissolution kinetics of diopside as a function of solution saturation state: Macroscopic measurements and implications for modeling of geological storage of CO2

Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔG_r) in a continuously stirred flow-through reactor at 90 °C and pH_90 °C = 5.05. The overall relation between r and ΔG_r was determined over a free energy range of −130.9 < ΔG_r < −47.0 kJ mo1⁻¹. The data define a highly non-linear, sigmoidal relation between r and ΔG_r. At far-from-equilibrium conditions (ΔG_r ? −76.2 kJ mo1⁻¹), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔG_r. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔG_r region defined by −76.2 < ΔG_r ? −61.5 kJ mo1⁻¹. Dissolution closer to equilibrium (ΔG_r > −61.5 kJ mo1⁻¹) is characterised by a much weaker inverse dependence of the rates on ΔG_r. Modeling the experimental r-ΔG_r data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔG_r relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO₂ over long time spans. In order to take into account the actual experimental r-ΔG_r relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO₂ interactions performed with classical geochemical codes should be evaluated with great caution.     

Peak Minerals: Theoretical Foundations and Practical Application

This article reviews the theoretical foundations for the concept of peak minerals; drawing on similarities and differences with peak oil as modelled using Hubbert style curves. Whilst several studies have applied peak modelling to selected minerals, discussion of the appropriateness of using Hubbert style curves in the minerals context remains largely unexplored. Our discussion focuses on a comparison between oil and minerals, on the key variables: rates of discovery, estimates of ultimately recoverable resources and demand and production trends. With respect to minerals, there are several obstacles which complicate the application of Hubbert style curves to the prediction of future mineral production, including the lack of accurate discovery data, the effect of uncertain reserve estimates, and varying ore quality and quantity. Another notable difference is that while oil is often combusted during use, minerals are used to make metals which are inherently recyclable. Notwithstanding, by using a range of estimates of resources and/or reserves, a period of time can be identified which indicates when a peak in minerals production may occur. This information may then be used to plan for a transition from using a potentially constrained resource, to using substitutes if available, or to reducing demand for that mineral in society.     

Textural and fluid inclusion constraints on the origin of the banded-iron-formation-hosted gold deposits at Maevatanana,central Madagascar

The Maevatanana deposits consist of gold-bearing quartz–sulphide veins crosscutting banded iron formation (BIF) within a metamorphosed 2.5 Ga greenstone belt. The host rocks are dominated by a sequence of migmatites, gneisses, amphibolites, magnetite-rich quartzites and soapstones, intruded by large granitoid batholiths (e.g. the 0.8 Ga Beanana granodiorite). In the mineralised rocks, pyrite is the dominant sulphide, in addition to accessory chalcopyrite and galena. Outside the immediate ore zone, the BIF is dominated by quartz + magnetite ± hematite, accompanied by cummingtonite, albite and biotite. Gold occurs as globular grains (usually <500 μm) within quartz crystals close to the sulphides and as invisible inclusions within pyrite and chalcopyrite (up to 2,500 ppm Au content). Fluid inclusion textural and microthermometric studies indicate heterogeneous trapping of a low-salinity (∼3.6 wt.% eq. NaCl) aqueous fluid coexisting with a carbonic fluid. Evidence for fluid-phase immiscibility during ore formation includes variable L/V ratios in the inclusions and the fact that inclusions containing different phase proportions occur in the same area, growth zone, or plane. Laser Raman spectroscopy confirms that the vapour phase in these inclusions is dominated by CO₂ but shows that it may contain small amounts of CH₄ (<1 mol%), H₂S (<0.05 mol%) and traces of N₂. Fluid inclusion trapping conditions ranged from 220 to 380°C and averaged 250°C. Pressure was on the order of 1–2 kbar. The abundant CO₂ and low salinity of the inclusions suggest a metamorphic origin for the fluid. Likewise, the presence of H₂S in the fluid and pyritisation of the wall-rock indicate that gold was likely transported by sulphide complexing. Fluid immiscibility was probably triggered by the pressure released by fracturing of the quartzites during fault movements due to competence differences with the softer greenstones. Fracturing greatly enhanced fluid circulation through the BIF, allowing reaction of the sulphide-bearing fluids with the iron oxides. This caused pyrite deposition and concomitant Au precipitation, enhanced by fluid phase separation as H₂S partitioned preferentially into the carbonic phase.     

Mineralogical and isotopic properties of inorganic nanocrystalline magnetites

Inorganic magnetite nanocrystals were synthesized in an aqueous medium at 25°C, atmospheric pressure, ionic strength of 0.1 M, oxygen fugacity close to 0, and under controlled chemical affinity, which was maintained constant during an experiment and varied between different experiments. The total concentration of iron in the initial solutions, with Fe(III)/Fe(II) ratios of 2, was varied in order to measure the role of this parameter on the reaction rate, particle morphology, and oxygen isotopic composition. The reaction rates were followed by a pHstat apparatus. The nature and morphology of particles were studied by transmission electron microscopy and electron energy loss spectroscopy. Fractionation factors of oxygen isotopes were determined by mass spectrometry after oxygen extraction from the solid on BrF₅ lines. At low total iron concentrations, goethite and poorly crystalline iron oxides were observed coexisting with magnetite. At higher concentrations, euhedral single crystals of pure magnetite with an average characteristic size of 10 nm were formed, based on a first-order rate law with respect to total iron concentration. These results confirm that, under high supersaturation conditions, low-temperature inorganic processes can lead to the formation of well-crystallized nanometric magnetite crystals with narrow size distribution. The observed oxygen isotope fractionation factor between magnetite crystals and water was of 0-1‰, similar to the fractionation factor associated with bacterially produced magnetite. We suggest that the solution chemistry used in this study for inorganic precipitation is relevant to better understanding of magnetite precipitation in bacterial magnetosomes, which might thus be characterized by high saturation states and pH.