Geochemistry of silicate-rich rocks can curtail spreading of carbon dioxide in subsurface aquifers.

Pools of carbon dioxide are found in natural geological accumulations and in engineered storage in saline aquifers. It has been thought that once this CO2 dissolves in the formation water, making it denser, convection streams will transport it efficiently to depth, but this may not be so. Here, we assess theoretically and experimentally the impact of natural chemical reactions between the dissolved CO2 and the rock formation on the convection streams in the subsurface. We show that, while in carbonate rocks the streaming of dissolved carbon dioxide persists, the chemical interactions in silicate-rich rocks may curb this transport drastically and even inhibit it altogether. These results challenge our view of carbon sequestration and dissolution rates in the subsurface, suggesting that pooled carbon dioxide may remain in the shallower regions of the formation for hundreds to thousands of years. The deeper regions of the reservoir can remain virtually carbon free.J. T. H. A. gratefully acknowledges the Schlumberger Foundation for financial support for her PhD study.This is the accepted manuscript. The final version is available from NPG at http://www.nature.com/ncomms/2014/141211/ncomms6743/full/ncomms6743.html

Mixing and reaction in turbulent plumes: The limits of slow and instantaneous chemical kinetics

We investigate the behaviour of a reactive plume in the two limiting cases of slow and instantaneous chemical reactions. New laboratory measurements show that, whereas the slow reaction between the source and entrained chemical species takes place within the whole volume of each eddy in the plume, the fast reaction develops preferentially at the periphery of the eddies. We develop a new model that quantifies the mixing of the reactive buoyant fluids at the Batchelor scale and thereby the progress of the fast reaction. We present a series of new experimental results that suggest that a critical distance from the source, $z_{crit}$, exists at which the volume of fluid that is entrained from the ambient is equal to that which is mixed within the plume at the Batchelor scale. For z>z_{crit}, only a fraction of the entrained fluid is rapidly mixed and reacts with the plume fluid. The results of the new experiments enable us to quantify the distance from the source at which an instantaneous reaction reaches completion, and show that it can be significantly larger than the distance $L_{s}$ at which the stoichiometric dilution of the plume fluid is achieved. In the limit of an instantaneous reaction, the longitudinal profiles of source chemical concentration in the plume depend on $(z_{crit}/L_{s})^{5/6}$. The predictions of the model are validated against the experimental results, and the profiles of source chemical concentration in the plume for slow and fast reactions are compared.</jats:p

Reactive-convective dissolution in a porous medium: the storage of carbon dioxide in saline aquifers

We quantify the destabilising effect of a first-order chemical reaction on the fingering instability of a diffusive boundary layer in a porous medium. Using scaling, we show that the dynamics of such a reactive boundary layer is fully determined by two dimensionless groups: Da/Ra$^{2}$, which measures the timescale for convection compared to those for reaction and diffusion; and βC/βA, which reflects the density change induced by the product relative to that of the diffusing solute. Linear stability and numerical results for βC/βA in the range 0–10 and Da/Ra$^{2}$ in the range 0–0.01 are presented. It is shown that the chemical reaction increases the growth rate of a transverse perturbation and favours large wavenumbers compared to the inert system. Higher βC/βA and Da/Ra$^{2}$ not only accelerate the onset of convection, but crucially also double the transport of the solute compared to the inert system. Application of our findings to the storage of carbon dioxide in carbonate saline aquifers reveals that chemical equilibrium curtails this increase of CO$_{2}$ flux to 50%.P. G. gratefully acknowledges the Dr Manmohan Singh Scholarship from St. John's College, Cambridge and the grant of study leave from Jadavpur University, Kolkata, India

Formation and Structures of Horizontal Submarine Fluid Conduit and Venting Systems Associated With Marine Seeps

Funder: Spanish Marine Science and Technology ProgramAbstract: Methane‐rich water moves through conduits beneath the seafloor whose surfaces are formed through precipitation reactions. To understand how such submarine fluid conduit and venting systems form and grow, we develop a detailed mathematical model for this reaction‐advection system and we quantify the evolution of an ensemble of similar filaments. We show that this growth can be described by a superposition of advection and dispersion. We analyze analog laboratory experiments of chemical‐garden type to study the growth of a single filament undergoing a precipitation reaction with the surrounding environment. We apply these findings to geological fluid conduit and venting systems, showing that their irregular trajectories can lead to very effective spreading within the surrounding seabed, thus enhancing contact and exchanges of chemicals between the conduit and external fluids. We discuss how this methane venting leads to the formation of marine authigenic carbonate rocks, and for confirmation, we analyze two field samples from the Gulf of Cadiz for composition and mineralogy of the precipitates. We note the implications of this work for hydrate melting and methane escape from the seabed

Settling-driven gravitational instabilities associated with volcanic clouds: new insights from experimental investigations

Downward propagating instabilities are often observed at the bottom of volcanic plumes and clouds. These instabilities generate fingers that enhance the sedimentation of fine ash. Despite their potential influence on tephra dispersal and deposition, their dynamics is not entirely understood, undermining the accuracy of volcanic ash transport and dispersal models. Here, we present new laboratory experiments that investigate the effects of particle size, composition and concentration on finger generation and dynamics. The experimental set-up consists of a Plexiglas tank equipped with a removable plastic sheet that separates two different layers. The lower layer is a solution of water and sugar, initially denser than the upper layer, which consists of water and particles. Particles in the experiments include glass beads as well as andesitic, rhyolitic and basaltic volcanic ash. During the experiments, we removed the horizontal plastic sheet separating the two fluids. Particles were illuminated with a laser and filmed with a HD camera; particle image velocimetry (PIV) is used to analyse finger dynamics. Results show that both the number and the downward advance speed of fingers increase with particle concentration in the upper layer, while finger speed increases with particle size but is independent of particle composition. An increase in particle concentration and turbulence is estimated to take place inside the fingers, which could promote aggregation in subaerial fallout events. Finally, finger number, finger speed and particle concentration were observed to decrease with time after the formation of fingers. A similar pattern could occur in volcanic clouds when the mass supply from the eruptive vent is reduced. Observed evolution of the experiments through time also indicates that there must be a threshold of fine ash concentration and mass eruption rate below which fingers do not form; this is also confirmed by field observations.Published395V. Dinamica dei processi eruttivi e post-eruttiviJCR Journa

Turbulent plumes with internal generation of buoyancy by chemical reaction

Turbulent plumes, which are seen in a wide number of industrial and natural flows, have been extensively studied; however, very little attention has been paid to plumes which have an internal mechanism for changing buoyancy. Such plumes arise in e.g. industrial chimneys, where species can react and change the density of the plume material. These plumes with chemical reaction are the focus of this study. An integral model describing the behaviour of a plume undergoing a second-order chemical reaction between a component in the plume (A) and a component in the surrounding fluid (B), which alters the buoyancy flux, is considered. The behaviour of a reactive plume is shown to depend on four dimensionless groups: the volume and momentum fluxes at the source, the parameter ϵ which indicates the additional buoyancy flux generated by the reaction and γ which is a dimensionless rate of depletion of species B. Additionally, approximate analytical solutions are sought for a reactive plume rising from a point source of buoyancy when species B is in great excess. These analytical results show excellent agreement with numerical simulations. It is also shown that the behaviour of a reactive plume in the far field is equivalent to an inert plume issuing from a virtual source downstream of the real source, and the dependence of the location of the virtual source on ϵ and γ is discussed. The effects of varying the volume flux at the source and the Morton source parameter Γ0 are further investigated by solving the full governing equations numerically. These solutions indicate that ϵ is important in determining the buoyancy generated by the reaction, and the length scale over which this reaction occurs depends on γ when γ > 1. It is also shown that when the dimensionless buoyancy ϵ < − 1, the reaction can cause the plume to collapse

Turbulent plumes with internal generation of buoyancy by chemical reaction

Turbulent plumes, which are seen in a wide number of industrial and natural flows, have been extensively studied; however, very little attention has been paid to plumes which have an internal mechanism for changing buoyancy. Such plumes arise in e.g. industrial chimneys, where species can react and change the density of the plume material. These plumes with chemical reaction are the focus of this study. An integral model describing the behaviour of a plume undergoing a second-order chemical reaction between a component in the plume (A) and a component in the surrounding fluid (B), which alters the buoyancy flux, is considered. The behaviour of a reactive plume is shown to depend on four dimensionless groups: the volume and momentum fluxes at the source, the parameter ϵ which indicates the additional buoyancy flux generated by the reaction and γ which is a dimensionless rate of depletion of species B. Additionally, approximate analytical solutions are sought for a reactive plume rising from a point source of buoyancy when species B is in great excess. These analytical results show excellent agreement with numerical simulations. It is also shown that the behaviour of a reactive plume in the far field is equivalent to an inert plume issuing from a virtual source downstream of the real source, and the dependence of the location of the virtual source on ϵ and γ is discussed. The effects of varying the volume flux at the source and the Morton source parameter Γ0 are further investigated by solving the full governing equations numerically. These solutions indicate that ϵ is important in determining the buoyancy generated by the reaction, and the length scale over which this reaction occurs depends on γ when γ > 1. It is also shown that when the dimensionless buoyancy ϵ < − 1, the reaction can cause the plume to collapse