The formation of barite and celestite through the replacement of gypsum

Barite (BaSO4) and celestite (SrSO4) are the end-members of a nearly ideal solid solution. Most of the exploitable deposits of celestite occur associated with evaporitic sediments which consist of gypsum (CaSO4·2H2O) or anhydrite (CaSO4). Barite, despite having a broader geological distribution is rarely present in these deposits. In this work, we present an experimental study of the interaction between gypsum crystals and aqueous solutions that bear Sr or Ba. This interaction leads to the development of dissolution-crystallization reactions that result in the pseudomorphic replacement of the gypsum crystals by aggregates of celestite or barite, espectively. The monitoring of both replacement reactions shows that they take place at very different rates. Millimeter-sized gypsum crystals in contact with a 0.5 M SrCl2 solution are completely replaced by celestite aggregates in less than 1 day. In contrast, only a thin barite rim replaces gypsum after seven days of interaction of the latter with a 0.5 M BaCl2 solution. We interpret that this marked difference in the kinetics of the two replacement reactions relates the different orientational relationship that exists between the crystals of the two replacing phases and the gypsum substrate. This influence is further modulated by the specific crystal habit of each secondary phase. Thus, the formation of a thin oriented layer of platy barite crystals effectively armors the gypsum surface and prevents its interaction with the Ba-bearing solution, thereby strongly hindering the progress of the replacement reaction. In contrast, the random orientation of celestite crystals with respect to gypsum guarantees that a significant volume of porosity contained in the celestite layer is interconnected, facilitating the continuous communication between the gypsum surface and the fluid phase and guaranteeing the progress of the gypsum-by-celestite replacement

Metastable phenomena on calcite {1014} surfaces growing from Sr2+–Ca2+–CO3 2- aqueous solutions

In situ atomic force microscopy (AFM) experiments, scanning electron microscopy (SEM) imaging and composition analysis, and X-ray diffraction have provided information about the growth, dissolution and transformation processes promoted by Sr2 + –Ca2 + –CO3 2 aqueous solutions in contact with calcite {101¯4} surfaces. Experiments have shown a wide variety of surface phenomena, such as the influence of the Sr-bearing newly-formed surface on the subsequent growth (template effect), the growth and subsequent dissolution of surfaces and the nucleation of secondary three-dimensional nuclei on calcite surfaces. These phenomena reveal the metastability of the crystallisation system and are a consequence of the interplay between thermodynamics (the relative stability of the two calcite and aragonite structure solid solutions that can be formed), supersaturation of the aqueous solution with respect to the two possible solid solutions, and the crystallographic control of the surfaces on cation incorporation

Estudio de AFM del crecimiento epitaxial de rodocrosita sobre la superficie {1014} de calcita

Depto. de Mineralogía y PetrologíaFac. de Ciencias GeológicasTRUEEspaña. Ministerio de Educación y CienciaUniversidad Complutense de MadridMadrid (Comunidad Autónoma)pu

The effect of CO2-3 on the growth of barite {001} and {210} surfaces: An AFM study

The growth of barite {001} and {210} faces from aqueous solutions moderately supersaturated with respect to barite (βbarite ≈ 12 for experiments on {001} surfaces and βbarite ≈ 7 for experiments on {210} surfaces) and bearing different concentrations of carbonate has been studied in situ using an atomic force microscope (AFM). Nanoscopic observations show that, above a certain carbonate concentration threshold in the aqueous solution, the advancement of monolayers (~3.5Å in height) on barite {001} and {210} surfaces is strongly inhibited. However, inhibition never affects the growth of the first monolayer, whose growth rate increases in the presence of carbonate. In contrast, the second monolayer growth rate decreases as the concentration of carbonate in the solution increases. For high carbonate concentrations in the solution, growth stops after the formation of the first monolayer. While on barite {001} faces, the formation of a second monolayer does not occur for carbonate concentrations higher than 0.2 mM, on barite {210} faces the complete inhibition of the second monolayer is observed for carbonate concentrations higher than 0.05 mM. Once growth on {001} or {210} faces is completely inhibited, i.e. such surfaces are in the ‘‘dead zone’’, growth can be recovered by increasing supersaturation. In order to study the recovery behaviour of barite {001} and {210} faces from the ‘‘dead zone’’, an additional series of AFM experiments have been conducted. In these experiments, carbonate-free aqueous solutions with increasing supersaturations with respect to barite were passed over {001} and {210} surfaces previously ‘‘poisoned’’ with carbonate. Our experimental results show that the recovery of growth on barite {001} faces requires an important increase of the solution supersaturation. In contrast, the recovery of barite {210} surface growth does not require any supersaturation increase, but spontaneously occurs in a few minutes. Our observations of inhibition and growth recovery on barite surfaces at a nano-scale are discussed and compared with the descriptions given by the classical crystal growth inhibition models

Nanoscale phenomena during the growth of solid solutions on calcite {101¯4} surfaces

This work deals with the growth behaviour of calcite {101¯4} surfaces in contact with multicomponent aqueous solutions containing divalent cations (Ba2+, Sr2+, Mn2+, Cd2+, or Mg2+). The result is the formation of solid solutions, with calcite or aragonite as one of the end-members. In situ atomic force microscopy has revealed a wide variety of surface phenomena occurring during the formation of these solid solutions. Among them are: (1) the thickening of growth steps and the subsequent dissolution of surfaces followed by the nucleation of secondary three-dimensional nuclei on calcite surfaces, (2) the transition between growth mechanisms, (3) the formation of an epitaxial layer that armours the substrate from further dissolution and (4) the inhibitory effect of the newly formed surface on the subsequent growth (template effect). The two last phenomena can considerably limit coprecipitation as an effective mechanism for divalent metal uptake. All the phenomena described are a consequence of the interplay between thermodynamics, supersaturation of the aqueous solution with respect to the possible solid solutions and the crystallographic control of the surfaces on the cation incorporation, and indicates that there are many differences between the crystal growth of solid solutions and phases with fixed composition

Microscopic and spectroscopic investigation of the calcite surface interacted with Hg(II) in aqueous solutions

The interaction of the {101¯4} cleavage surface of calcite with Hg(CH3COO)2 aqueous solutions with concentration of 5 mM Hg(II) (pH ≈3.5), was investigated using microscopic and spectroscopic techniques. In situ atomic force microscopy experiments showed that surface microtopography changes significantly as a result of the interaction, and that the initial rhombic etch pits induced by H2O dissolution are rapidly transformed to deeper etch pits exhibiting an unusual triangular shape. The growth of these etch pits is strongly anisotropic, moving faster along the [22¯1] direction than along the [010] direction (with step-retreat velocities of ~12 nm s –1 and ~4 nm s–1, respectively). The modified etch pits are due to Hg(II) sorption in the surface, rather than due to the effect of the acetate anion. The sorption (adsorption and probably absorption also) of Hg(II), in the first minutes of the interaction, is shown by X-ray photoelectron spectroscopy. After ~2 h, the triangular etch pits are interconnected to form larger hexagonal etch pits, while Hg(II)-bearing phases (confirmed later by SEM-EDS) grow onto the surface through a heterogeneous nucleation process. The crystal growth of orthorhombic (montroydite-type) hydrated Hg(II) oxide (HgO·nH2O) on the surface of calcite was confirmed by XRD patterns and FT-IR spectra from samples exposed for longer times to Hg(CH3COO)2 solution

Cristalización de malaquita en medios porosos: características de la nucleación y evolución morfológica

Depto. de Mineralogía y PetrologíaFac. de Ciencias GeológicasTRUEpu

Aproximación experimental a la formación de yacimientos de celestina: El efecto del bario

Depto. de Mineralogía y PetrologíaFac. de Ciencias GeológicasTRUEMinisterio de EconomíaMinisterio de Universidadespu

Nanoscopic Characteristics of Anhydrite (100) Growth

The growth of anhydrite (100) surface in contact with supersaturated aqueous solutions (βanh = 1 -3.6) under low hydrothermal conditions (T = 60 -120 ºC) has been studied by use of a hydrothermal atomic force microscope (HAFM). Our observations show that growth on this surface occurs by lateral spreading ofmonomolecular layers (3.5 Å in height) and is highly anisotropic, with [001] and [001] alternating as fast and slow directions in successive monolayers. This anisotropic growth is evidence of strong structural control, which becomes less intense as temperature and/or supersaturation increases. The growth anisotropy affects the development of spirals, determining the combination of fast-moving and slow-moving steps to form bilayer steps around the emergence point of screw dislocations and leading to nonconstant spread rates. As a result, the overall efficiency of spiral growth mechanism is highly dependent on the interaction between slow-moving bilayers and fast-moving monolayers originating from different dislocations. Formation of two-dimensional nuclei occurs only at Tg>º80 ºCand βanhg>2, two-dimensional nucleation density always being very low (< 1nucleus/μm2) under the conditions explored. These facts, together with the slow kinetics of anhydrite growth in comparison to the much faster kinetics of gypsum growth, might explain the frequentmetastable formation of gypsum crystals under temperatures corresponding to the stability field of anhydrite