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, respectively. 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.
Celestite crystals grow epitaxially on anhydrite surfaces that interact with aqueous solutions bearing Sr. Progressive polygonization and splitting during celestite growth drives to the development of striking crystal morphologies and textures.
Abstract. Carbonate biological hard tissues are valuable archives of environmental information. However, this information can be blurred or even completely lost as hard tissues undergo diagenetic alteration. This is more likely to occur in aragonitic skeletons because bioaragonite often transforms into calcite during diagenesis. For reliably using aragonitic skeletons as geochemical proxies, it is necessary to understand in depth the diagenetic alteration processes that they undergo. Several works have recently investigated the hydrothermal alteration of aragonitic hard tissues during short-term experiments at high temperatures (T > 160 ∘C). In this study, we conduct long-term (4 and 6 months) hydrothermal alteration experiments at 80 ∘C using burial-like fluids. We document and evaluate the changes undergone by the outer and inner layers of the shell of the bivalve Arctica islandica, the prismatic and nacreous layers of the hard tissue of the gastropod Haliotis ovina, and the skeleton of the coral Porites sp. combining a variety of analytical tools (X-ray diffraction, thermogravimetry analysis, laser confocal microscopy, scanning electron microscopy, electron backscatter diffraction and atomic force microscopy). We demonstrate that this approach is the most adequate to trace subtle, diagenetic-alteration-related changes in aragonitic biocarbonate structural hard materials. Furthermore, we unveil that the diagenetic alteration of aragonitic biological hard tissues is a complex multi-step process where major changes occur even at the low temperature used in this study, well before any aragonite into calcite transformation takes place. Alteration starts with biopolymer decomposition and concomitant generation of secondary porosity. These processes are followed by abiogenic aragonite precipitation that partially or totally obliterates the secondary porosity. Only subsequently does the transformation of the aragonite into calcite occur. The kinetics of the alteration process is highly dependent on primary microstructural features of the aragonitic biomineral. While the skeleton of Porites sp. remains virtually unaltered for the entire duration of the conducted experiments, Haliotis ovina nacre undergoes extensive abiogenic aragonite precipitation. The outer and inner shell layers of Arctica islandica are significantly affected by aragonite transformation into calcite. This transformation is extensive for the prismatic shell layer of Haliotis ovina. Our results suggest that the majority of aragonitic fossil archives are overprinted, even those free of clear diagenetic alteration signs. This finding may have major implications for the use of these archives as geochemical proxies.
The formation of micrometric-thick mineral cohesive layers is a novel method to prevent the deterioration of historical buildings. Here, we study the formation of thin, cohesive, pseudomorphic shells of strontianite (SrCO3) and witherite (BaCO3) on the surface of calcite (CaCO3) single crystals reacted with aqueous solutions bearing Sr2+ and Ba2+, respectively. The reaction front moves inward from the calcite–solution interface through a dissolution–crystallization reaction, which stops before the strontianite and witherite shells are barely 40 thick. These shells consist of elongated crystallites that grow oriented on the calcite substrate, with which they share very small contact areas. The calcite–strontianite and −witherite epitaxies are mono-dimensional and involve a parallelism between (101̅4)Cal||(021)Str/Wth. Strontianite and witherite cohesive layers remain strongly attached to the calcite substrates, which appear crack-free even after 2 years of reaction time. The formation of thin, cohesive, and durable replacement layers of strontianite and witherite may provide a long-lasting protection for calcitic marbles and limestones used as building stones in cultural heritage.
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