Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
To test the impact of fluid flow on the reactivity of porous (ultra-)mafic rocks, reactive percolation experiments were realized during which CO2-enriched water was injected at two different injection rates (Q = 0.1 and 1 mL h−1) through sintered analogues of olivine-accumulation zones in basaltic flows at temperature and fluid composition conditions (T = 180 °C; NaHCO3 buffered solution) favorable for CO2-mineralization (carbonation).All experiments resulted in silicate dissolution, carbonate precipitation upstream and (proto-)serpentine formation downstream indicating a decrease in the fluid reactivity along flow paths. The measured bulk carbonation rates ranged from 4 to 7 × 10−8 s−1; these values were significantly lower than previously published values of olivine carbonation rate obtained on powders in closed batch and flow-through reactors. Our study show complex couplings, at pore scale, between fluid flow, localization of reaction zones, and chemical reaction kinetics which in turn control hydrodynamic properties, carbonation rate and efficiency and fluid reactivity. This results in carbonation rates being higher when injection rates are high and permeability ultimately controlling carbonation reactions by limiting fluid input. During experiments, notable changes in permeability occurred for only minor changes in porosity indicating a control by the geometry of the porous network: heterogeneities in the distribution of flow paths favored the localization of precipitated minerals which in turn resulted in the closure of flow paths. This mechanism was particularly efficient at low injection rates. These results imply that controlling the injection rate could allow enhancing/limiting the efficiency of in situ carbonation.
ISSN: 0883-2927

hal-01115284
https://hal.archives-ouvertes.fr/hal-01115284
DOI : 10.1016/j.apgeochem.2014.11.024

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
This paper presents a multicontinuum approach to model fractal temporal scaling of catchment response in hydrological systems. The temporal scaling of discharge is quantified in frequency domain by the transfer function HðxÞ, which is defined as the ratio between the spectra of catchment response and recharge time series. The transfer function may scale with frequency x as HðxÞ x2b. While the classical linear and Dupuit models predict exponents of b52 and b51, observations indicate scalings with noninteger exponents b. Such behaviors have been described by multifractal models, which, however, often lack a relation to the medium characteristics. We revisit and extend the classical linear Dupuit aquifer models and discuss their physical meanings in the light of the resulting aquifer dynamics. On the basis of these classical models, we derive a multicontinuum approach that provides physical recharge models which are able to explain fractal behaviors with exponents 1=2 < b < 2. Furthermore, this approach allows to link the fractal dynamics of the discharge process to the physical aquifer characteristics as reflected in the distribution of storage time scales. We systematically analyze the catchment responses in the proposed multicontinuum models, and identify and quantify the time scales which characterize the dynamics of the catchment response to recharge.
ISSN: 0043-1397

insu-00952537
https://hal-insu.archives-ouvertes.fr/insu-00952537
https://hal-insu.archives-ouvertes.fr/insu-00952537/document
https://hal-insu.archives-ouvertes.fr/insu-00952537/file/russian.pdf
DOI : 10.1002/2013WR014255

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Heletz sandstone (Israel) reactivity is studied by means of CO2-rich brine percolation experiments and modeling. Experiments are performed at in situ temperature and pressure conditions with two distinctly different injection flow rates and for two different brine compositions: the genuine Heletz brine and a similar brine but in equilibrium with gypsum. The Heletz sandstone is composed of quartz, dolomite, ankerite, K-feldspar, clay minerals and minor amounts of gypsum and pyrite. The main reaction is the dissolution of the carbonates which is fastest for the highest flow rate injection and for the genuine Heletz brine. Permeability increases during the five percolation experiments, regardless of flow rate and brine type. This increase in permeability is associated to a decrease in porosity during the gypsum-equilibrated brine experiments due to gypsum precipitation. The precipitation of secondary minerals (kaolinite, muscovite and smectite) is mainly controlled by the dissolution of K-feldspar and largest at low flow rate injection, indicating that these precipitation processes are diffusion-controlled and localized in immobile zones where favorable chemical micro-environments exist. These processes are quantified by means of a reactive transport model. These results indicated that the CO2 injection at the Heletz site should trigger both permeability increase in interface between brine and CO2, which may extend over a large extension and where mixing processes are very active, especially near the well under intermittent injection conditions.
ISSN: 1750-5836

hal-01356329
https://hal.archives-ouvertes.fr/hal-01356329
DOI : 10.1016/j.ijggc.2015.10.023

Éditeur(s) : HAL CCSD Elsevier
Résumé : The correct characterization of the effective reactive transport dynamics is an important issue for modeling reactive transport on the Darcy scale, specifically in situations in which reactions are localized, that is when different reactions occur in different portions of the porous medium. Under such conditions the conventional approach of homogenizing only the porous medium chemistry is not appropriate. We consider here reactive transport in a porous medium that is characterized by mass transfer between a mobile and a distribution of immobile regions. Chemical and physical heterogeneities are reflected by distributions of kinetic reaction rate constants and residence times in the immobile zones. We derive an effective reactive transport equation for the mobile solute that is characterized by non-local physical mass transfer and reaction terms. Specifically, chemical heterogeneity is upscaled in terms of a reactive memory function that integrates both chemical and physical heterogeneity. Mass transfer limitations due to physical heterogeneity yield effective kinetic rate coefficients that can be much smaller than the volumetric average of the local scale coefficients. These results help to explain and quantify the often reported discrepancy between observed field reaction rate constants and the ones obtained under well mixed laboratory conditions. Furthermore, these results indicate that transport under physical and chemical heterogeneity cannot be upscaled separately.
ISSN: 0169-7722

hal-00617674
https://hal.archives-ouvertes.fr/hal-00617674
DOI : 10.1016/j.jconhyd.2010.06.002

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
We derive a general formulation of the time domain random walk (TDRW) approach to model the hydrodynamic transport of inert solutes in complex geometries and heterogeneous media. We demonstrate its formal equivalence with the discretized advection-dispersion equation and show that the TDRW is equivalent to a continuous time random walk (CTRW) characterized by space-dependent transition times and transition probabilities. The transition times are exponentially distributed. We discuss the implementation of different concentration boundary conditions and initial conditions as well as the occurrence of numerical dispersion. Furthermore, we propose an extension of the TDRW scheme to account for mobile-immobile multirate mass transfer. Finally, the proposed TDRW scheme is validated by comparison to analytical solutions for spatially homogeneous and heterogeneous transport scenarios.
ISSN: 0043-1397

hal-01356319
https://hal.archives-ouvertes.fr/hal-01356319
DOI : 10.1002/2015WR018511