Volcanic ash ice nucleation activity is variably reduced by aging in water and sulfuric acid: the effects of leaching, dissolution, and precipitation

Volcanic ash nucleates ice when immersed in supercooled water droplets, giving it the potential to influence weather and climate from local to global scales. This ice nucleation activity (INA) is...

Evaluating carbonate dissolution and precipitation in a short time-frame using SEM: techniques and preliminary results from Postojna Cave, Slovenia

Carbonate dissolution and precipitation are important geological processes whose rates often require quantification. In natural settings, these processes may be taking place at a slow rate, and thus, it may not be easily visible which of these processes is occurring. Alternatively, if the effects of precipitation/dissolution are visible, it may not be clear if they are still underway or an artefact of past conditions. Moreover, these two opposing processes may flip states depending on the environmental conditions, such as, on a seasonal basis. Here, we present the technical details and preliminary results of a method using carbonate tablets and Scanning Electron Microscopy (SEM) to evaluate which process (carbonate dissolution or precipitation) is occurring, using as an example, a cave environment. Our method involves making tablets by encasing blocks of carbonate rock into resin and polishing these to form a completely flat and smooth “zero surface”. These tablets are observed under SEM in exactly the same points both before and after exposure to the field environment, using a system of marking lines at specific locations on the resin. Our results show significant differences in the before and after images of the tablet surface after just six weeks in the cave. Furthermore, the use of the insoluble resin zero surface permits a comparison of the starting height with the new dissolved/precipitated surface that can be used to quantitatively estimate the rate of dissolution/precipitation happening at a field location in a relatively short time-frame (weeks/months). This method could be used in numerous natural and industrial settings to identify these processes that can be caused purely geochemically, but also through microbialmediation and physical weathering.

Combining innovative experimental approaches and cross-scale reactive transport modelling for assessing coupled hydrogeochemical processes at interfaces in deep geological repositories for radioactive waste

Deep geological repositories with a multi-barrier concept are foreseen by various countries for the disposal of high-level radioactive waste. A reliable and consistent assessment of the safety of these repositories over time scales of some hundred thousand years requires an advancement of process understanding. Simulation tools need to be developed for a close-to-reality description of repository evolution scenarios. This is especially required to resolve the challenging task of comparing and assessing the safety of different repository concepts in different host rocks within the German site-selection process. The construction of underground galleries and geotechnical barriers in the host rock formation and the emplacement of nuclear waste packages will create perturbations induced by chemical, thermal and pressure gradients at the interfaces of the different barriers, leading to mineral dissolution and precipitation to achieve re-equilibration. Such coupled hydrogeochemical processes generate non-linear responses in transport and mechanical properties of barrier materials and host rocks, which have to be taken into account for a more rigorous assessment of repository system evolution. Reactive transport modeling (RTM) can be applied to investigate these perturbations and processes across temporal and spatial scales, from the micro-scale at interfaces via the repository near field to the entire repository system – information not accessible through experiments alone. Although RTM is capable of addressing highly complex hydrogeochemical phenomena, the application of RTM codes to real systems is impeded by the often simplified description of coupled processes. To enhance the predictive capabilities of reactive transport models and to gain fundamental insights into the coupling between solute and radionuclide transport properties (e.g., permeability and diffusivity) of porous media and dissolution/precipitation processes, we conducted experiments on “simplified” chemical systems combined with pore-scale and continuum-scale reactive transport modelling to study processes in isolation, with the final aim of improving conceptual approaches for process couplings implemented in reactive transport codes. In this context, we investigated the effects of coupled mineral dissolution and precipitation in porous media on changes in permeability using flow-through experiments conducted in a magnetic resonance imaging scanner, which enabled the in situ investigation of porosity evolution in combination with monitoring changes in permeability and mineralogy. Our observations showed that classical implementations in reactive transport codes such as the Kozeny–Carman equation (Carman, 1937) failed to reproduce the changes in permeability and that more sophisticated approaches are required (Poonoosamy et al., 2020a, b). Moreover, we developed a novel “lab-on-a-chip” setup, i.e., micronized counter diffusion reactors with in operando 3D Raman tomography (Poonoosamy et al., 2019, 2020c), which enables evaluation of the alteration in pore architecture and study of the effect of coupled mineral dissolution and precipitation on the diffusive transport of solutes and radionuclides in porous media. Our approach enables the development of process-based theoretical models which allow for improvements in RTM codes and for predicting the evolution of perturbed interfaces in waste repositories, thus building confidence in the predictive capabilities of reactive transport models and reducing uncertainties with respect to future repository evolution.

Wear-Resistant TiC Strengthening CoCrNi-Based High-Entropy Alloy Composite

In order to improve the wear resistance of CoCrNi alloy, TiC was introduced into the alloy and wear-resistant CoCrNi/(TiC)x composites were designed. The effects of TiC contents on the microstructure, mechanical properties, and wear resistance of CoCrNi matrix were investigated, respectively. It was found that the TiC produced dissolution and precipitation process in CoCrNi alloy, and a large number of needled and blocky TiC particles were precipitated in the composites. The compressive yield strength of CoCrNi/(TiC)x composites increased with the increasing TiC content. Compared with the CoCrNi alloy, the yield strength of CoCrNi/(TiC)x composites increased from 108 to 1371 MPa, and the corresponding strengthening mechanism contributed to the second phase strengthening. The wear resistance of CoCrNi/(TiC)x composites was also greatly improved due to the strengthening of TiC. Compared with the CoCrNi alloy, the specific wear rate of CoCrNi/(TiC)1.0 alloy was reduced by about 77%. The wear resistance of CoCrNi/(TiC)x composites was enhanced with the increasing content of TiC addition.

Mineralogical Analysis of Bentonite from the ABM5 Heater Experiment at Äspö Hard Rock Laboratory, Sweden

The present study reports on the analysis of all blocks of the ABM5 test, which is a medium scale bentonite buffer deposition test. In contrast to similar tests, the ABM5 was conducted at higher temperature (up to 250 °C). The aim of the study was to characterize the chemical and mineralogical reactions and to identify the effect of the extraordinarily high temperature. Reactions observed were similar to those observed in previous and/or similar tests covering cation exchange, anion inflow, dissolution and precipitation of C- and S-phases, Fe corrosion, and Mg increase at the heater. Neither the type nor the extent of the different reactions could be related to the significantly higher temperature. However, due to the absence of lubricant used between heater and bentonite, it could be proved that the calcite previously present was dissolved and precipitated as siderite at the contact, pointing towards the importance of the presence of carbonate when considering different Fe corrosion products. Moreover, for the first time, a decrease of the Mg content at the heater was observed, which was probably because a Mg-rich clay was used. The reasons for Mg increase or decrease are still not completely understood.

Microbially-mediated carbonate dissolution and precipitation; towards a protocol for ex-situ, cave-analogue cultivation experiments

Subterranean calcite dissolution and precipitation are often considered as strictly geochemical processes. The active involvement of microbes in these processes is commonly underestimated in the literature due to general oligotrophic conditions in caves, except in particular cave conditions, such as sulfidic caves and moonmilk deposits, where the presence of microbes likely plays a key role in mineral deposition. Here, we study the possible involvement of microbes from Postojna Cave, Slovenia, in carbonate dissolution (litholysis) and precipitation (lithogenesis). Microbes were sampled from small pools below hydrologically diverse drip sites and incubated on polished limestone tablets at 10 and 20°C for 2 and 14 weeks under cave-analogue conditions. The tablets were then observed under scanning electron microscope to investigate microbe–rock interactions. Our experiments showed the presence of various microbial morphotypes, often associated with extracellular polymeric substances, firmly attached on the surfaces. Unfortunately, our surface sterilization method using 96% and 70% ethanol could not establish the complete aseptic conditions in deep natural cracks in the experimental limestone tablets. Nonetheless, our results emulate the interaction of environmental microbes with limestone rock. Conspicuous calcite dissolution and precipitation were observed in association with these microbes. Furthermore, we show evidence of entombment of microbes in a Si-rich precipitate during nutrient-depleted growth conditions and we suggest that microbial involvement in silica mobilization under ambient conditions may be a widespread and often overlooked phenomenon. Our findings have important implications for microbial-mediation of cave carbonate dissolution and precipitation, including the preservation of past climate proxy signals in speleothems and prehistoric cave art. Improvements to the methodology and further work are suggested to enable more robust ex-situ cultivation experiments in the future, facilitating better and more detailed research into this topic.