: Geochemical reaction path modeling is useful for rapidly assessing the extent of water-aqueous-gas interactions both in natural systems and in industrial processes. Modeling of some systems, such as those at low temperature with relatively high hydrologic flow rates, or those perturbed by the subsurface injection of industrial waste such as CO2 or H2S, must account for the relatively slow kinetics of mineral-gas-water interactions. We have therefore compiled parameters conforming to a general Arrhenius-type rate equation, for over 70 minerals, including phases from all the major classes of silicates, most carbonates, and many other non-silicates. These data have been added to a computer code that simulates an infinitely well-stirred batch reactor, allowing computation of mass transfer as a function of time. Actual equilibration rates are expected to be much slower than those predicted by the selected computer code, primarily because actual geochemical processes commonly involve flow through porous or fractured media, wherein the development of concentration gradients in the aqueous phase near mineral surfaces, which results in decreased absolute chemical affinity and slower reaction rates. Further differences between observed and computed reaction rates may occur because of variables beyond the scope of most geochemical simulators, such as variation in grain size, aquifer heterogeneity, preferred fluid flow paths, primary and secondary mineral coatings, and secondary minerals that may lead to decreased porosity and clogged pore throats.

/pdf/a-compilation-of-rate-parameters-of-water-mineral-1o9qltikkk.pdf

A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling

Hydration of the <1 μm size fraction of SWy-1 source clay (low-charge montmorillonite) was studied by modeling of X-ray diffraction (XRD) patterns recorded under controlled relative humidity (RH) conditions on Li-, Na-, K-, Mg-, Ca-, and Sr-saturated specimens. The quantitative description of smectite hydration, based on the relative proportions of different layer types derived from the fitting of experimental XRD patterns, was consistent with previous reports of smectite hydration. However, the coexistence of smectite layer types exhibiting contrasting hydration states was systematically observed, and heterogeneity rather than homogeneity seems to be the rule for smectite hydration. This heterogeneity can be characterized qualitatively using the standard deviation of the departure from rationality of the 00 l reflection series (ξ), which is systematically larger than 0.4 A when the prevailing layer type accounts for ~70% or less of the total layers (~25% of XRD patterns examined). In addition, hydration heterogeneities are not distributed randomly within smectite crystallites, and models describing these complex structures involve two distinct contributions, each containing different layer types that are interstratifed randomly. As a result, the different layer types are partially segregated in the sample. However, these two contributions do not imply the actual presence of two populations of particles in the sample.

XRD profile modeling also has allowed the refinement of structural parameters, such as the location of interlayer species and the layer thickness corresponding to the different layer types, for all interlayer cations and RH values. From the observed dependence of the latter parameter on the cation ionic potential ( v / r; v = cation valency and r = ionic radius) and on RH, the following equations were derived:

\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \[Layer\ thickness\ (1W)\ =\ 12.556\ +\ 0.3525\ {\times}\ ({\nu}/\mathit{r}\ {-}\ 0.241)\ {\times}\ ({\nu}\ {\times}\ RH\ {-}\ 0.979)\] \end{document} 

\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \[Layer\ thickness\ (2W)\ =\ 15.592\ +\ 0.6472\ {\times}\ ({\nu}/\mathit{r}\ {-}\ 0.839)\ {\times}\ ({\nu}\ {\times}\ RH\ {-}\ 1.412)\] \end{document} 

which allow the quantification of the increase of layer thickness with increasing RH for both 1W (one water) and 2W (two water) layers. In addition, for 2W layers, interlayer H2O molecules are probably distributed as a unique plane on each side of the central interlayer cation. This plane of H2O molecules is located at ~1.20 A from the central interlayer cation along the c* axis.

/pdf/investigation-of-smectite-hydration-properties-by-modeling-4d3mn4ajay.pdf

Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns: Part I. Montmorillonite hydration properties

Clay-rich sedimentary deposits are often sites of organic matter preservation and have therefore been sought in Mars exploration. However, regional deposits of hydrous minerals, including phyllosilicates and sulphates are not typically associated with valley networks and layered sediments that provide geomorphic evidence of surface water transport on early Mars. The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) has recently identified phyllosilicates within three lake basins with fans or deltas that indicate sustained sediment deposition: Eberswalde crater Holden crater and Jezero crater. Here we use high-resolution data from the Mars Reconnaissance Orbiter (MRO) to identify clay-rich fluvial–lacustrine sediments within Jezero crater, which has a diameter of 45 km. The crater is an open lake basin on Mars with sedimentary deposits of hydrous minerals sourced from a smectite-rich catchment in the Nili Fossae region. We find that the two deltas and the lowest observed stratigraphic layer within the crater host iron–magnesium smectite clay. Jezero crater holds sediments that record multiple episodes of aqueous activity on early Mars. We suggest that this depositional setting and the smectite mineralogy make these deltaic deposits well suited for the sequestration and preservation of organic material.

http://www.planetary.brown.edu/pdfs/3580.pdf

Clay minerals in delta deposits and organic preservation potential on Mars

Geological disposal is the preferred option for the final storage of high-level nuclear waste and spent nuclear fuel in most countries. The selected host rock may be different in individual national programs for radioactive-waste management and the engineered barrier systems that protect and isolate the waste may also differ, but almost all programs are considering an engineered barrier. Clay is used as a buffer that surrounds and protects the individual waste packages and/or as tunnel seal that seals off the disposal galleries from the shafts leading to the surface.

Bentonite and bentonite/sand mixtures are selected primarily because of their low hydraulic permeability in a saturated state. This ensures that diffusion will be the dominant transport mechanism in the barrier. Another key advantage is the swelling pressure, which ensures a self-sealing ability and closes gaps in the installed barrier and the excavation-damaged zone around the emplacement tunnels. Bentonite is a natural geological material that has been stable over timescales of millions of years and this is important as the barriers need to retain their properties for up to 106 y.

In order to be able to license a final repository for high-level radioactive waste, a solid understanding of how the barriers evolve with time is needed. This understanding is based on scientific knowledge about the processes and boundary conditions acting on the barriers in the repository. These are often divided into thermal, hydraulic, mechanical, and (bio)chemical processes. Examples of areas that need to be evaluated are the evolution of temperature in the repository during the early stage due to the decay heat in the waste, re-saturation of the bentonite blocks installed, build-up of swelling pressure on the containers and the surrounding rock, and degradation of the montmorillonite component in the bentonite. Another important area of development is the engineering aspects: how can the barriers be manufactured, subjected to quality control, and installed?

Geological disposal programs for radioactive waste have generated a large body of information on the safety-relevant properties of clays used as engineered barriers. The major relevant findings of the past 35 y are reviewed here.

The Use of Clay as an Engineered Barrier in Radioactive-Waste Management a Review

Colloid analysis by single particle inductively coupled plasma-mass spectroscopy: a feasibility study

Kinetics of montmorillonite dissolution in granitic solutions

The Neogene volcanic region of Cabo de Gata, Almeria, SE Spain, is dotted with many outcrops of bentonite, some of them of significant economic interest. The bentonites have their origin in the hydrothermal alteration of pyroclastic rocks (15-7 Ma). The deposits are usually associated with fractures. The major mineral is a dioctahedral Fe- and Mg-smectite (89-75%) and this is accompanied by minor amounts of feldspars, quartz, amphiboles, pyroxenes, biotite, zeolites, disordered tridymite, calcite, etc. This paper describes the geological background, the general characteristics of the bentonites and major aspects of their formation, e.g. type of low-temperature hydrothermal solutions, mass balance, chemical evolutions of the smectites and geochemistry of trace elements. Finally, the characteristics of three of the most important deposits are described.

Bentonites from Cabo de Gata, Almería, Spain : a mineralogical and geochemical overview

Hydrothermal synthesis of kaolinite: method and characterization of synthetic materials

Na/K, Na/Mg, and Na/Ca exchange isotherms have been experimentally determined for the FEBEX bentonite. Na-homoionized FEBEXbentonite was reacted at room temperature with mixedsalt dissolution of NaCl/KCl, NaCl/MgCl2, or NaCl/CaCl2, while keeping a total cation normality of 0.5 eq L-1. Isotherm exchange experiments were performed using ten (duplicated)experimental points, which cover the complete range of the corresponding binary equivalent fractions. Results indicate that for the Na/K exchange reaction, Vanselow coefficients are larger than one, what is in agreement with the tendency of the smectite of having greater affinity for K than for Na. The exchange constant decreases as K progressively replaces Na in the smectite. This tendency ends when the equivalent fraction of potassium, E
K, reaches a value of around 0.250.3. From this point to higher K contents, it remains nearly constant irrespective of E
K but slightly decreasing again at values near one. The Vanselow selectivity coefficient for the Na/Mg isotherm indicates a preference for the divalent cation. It is nearly constant (Kv ≍ 5.6) for E
Mg < 0.6, but increases up to 10.2 for a nearly Mg-saturated smectite. The Na/Ca exchange resembles that of Na/Mg, although the selectivity coefficients are larger (Kv ≍ 7.0 for E
Ca < 0.6). The comparison of the selectivity coefficients for the Na/Mg and Na/Ca exchange reactions indicates that the smectite has a slightly higher affinity for Ca than for Mg. This result is consistent with those observed for the Wyoming bentonite.

Ion Exchange Behavior of the Febex Bentonite. 1. Na/K, Na/Mg and Na/Ca Experimental Exchange Isotherms

Ion exchange experiments have been performed with the FEBEX bentonite. Five grams of dry powder of this clay were put inside dialysis bags, which were located inside PFA reactors filled with 125 ml of water of a given chemical composition (Moody, Grimsel, and bentonitic-granitic type waters). The reactors containing the clay powder/water mixture were heated to different temperatures (from room temperature up to 80°C) along a time span ranging from 1 day to 1 year. Water was renewed according to a prescribed schedule but not the clay, which remained in place for the whole extent of each test. After each water renewal, major cations, silica, total inorganic carbon, and pH were analyzed. At the end of each test, the exchange complex and CEC of the bentonite were measured. These experiments have been modeled with a conveniently modified version of the EQ3/6 software package where ion exchange reactions were formulated as half reactions and added to its database. In general, model results are in fairly good agreement with experimental data, especially in the case of dissolved cations. Computed values of exchanged concentrations also match the measurements, although in some cases they deviate from them. The fact that the numerical results reproduce the observed patterns of exchange tests indicates that the adopted geochemical conceptual model is appropriate. Some features of the geochemical evolution of these tests also take place at the “mock-up” and “in situ” FEBEX tests.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S1946427400646808

F. Huertas

Papers

Kinetics of montmorillonite dissolution in granitic solutions

Bentonites from Cabo de Gata, Almería, Spain : a mineralogical and geochemical overview

Hydrothermal synthesis of kaolinite: method and characterization of synthetic materials

Ion Exchange Behavior of the Febex Bentonite. 1. Na/K, Na/Mg and Na/Ca Experimental Exchange Isotherms

Ion Exchange Behavior of the Febex Bentonite: 2. Batch Experiments and Geochemical Modeling