Impact of Solution {Ba2+}:{SO42–} on Charge Evolution of Forming and Growing Barite (BaSO4) Crystals:: A ζ─Potential Measurement Investigation

The impact of solution stoichiometry on formation of BaSO4 (barite) crystals and the development of surface charge was investigated at various predefined stoichiometries (raq = 0.01, 0.1, 1, 10, and 100, where raq = {Ba2+}:{SO42-}). Synthesis experiments and zeta potential (ζ-potential) measurements were conducted at a fixed initial degree of supersaturation (Ωbarite = 1000, where Ωbarite = {Ba2+}{SO42-}/Ksp), at circumneutral pH of ∼6, 0.02 M NaCl, and ambient temperature and pressure. Mixed-mode measurement-phase analysis light scattering (M3-PALS) showed that the particles stayed negative for raq 1. At raq = 1, two populations with a positive or negative ζ-potential prevailed for ∼2.5 h before a population with a circumneutral ζ-potential (−10 to +10 mV) remained. We relate the observations of particle charge evolution to particle size and morphology evolution under the experimental conditions. Furthermore, we showed that the ζ-potential became more negative when the pH was increased for every raq. In addition, our results demonstrated that the type of monovalent background electrolyte did not influence the ζ-potential of barite crystals significantly, although NaCl showed slightly different behavior compared to KCl and NaNO3. Our results show the important role of surface charge (evolution) during ionic crystal formation under nonstoichiometric conditions. Moreover, our combined scanning electron microscopy and ζ-potential results imply that the surface charge during particle formation can be influenced by solution stoichiometry, besides the pH and ionic strength, and may aid in predicting the fate of barite in environmental settings and in understanding and improving industrial barite (surface chemistry) processes

The impact of pore-throat shape evolution during dissolution on carbonate rock permeability: pore network modelling and experiments

Pore network model simulation (PNM) is an important method to simulate reactive transport processes in porous media and to investigate constitutive relationships between permeability and porosity that can be implemented in continuum-scale reactive-transport modeling. The existing reactive transport pore network models (rtPNMs) assume that the initially cylindrical pore throats maintain their shape and pore throat conductance is updated using a form of Hagen-Poiseuille relation. However, in the context of calcite dissolution, earlier studies have shown that during dissolution, pore throats can attain a spectrum of shapes, depending upon the imposed reactive-flow conditions (Agrawal et al., 2020). In the current study, we derived new constitutive relations for the calculation of conductance as a function of pore throat volume and shape evolution for a range of imposed flow and reaction conditions. These relations were used to build animproved new reactive pore network model (nrtPNM). Using the new model, the porosity-permeability changes were simulated and compared against the existing pore network models. In order to validate the reactive transport pore network model, we conducted two sets of flow-through experiments on two Ketton limestone samples. Acidic solutions (pH 3.0) were injected at two Darcy velocities i.e., 7.3 x 10(-4) and 1.5 x 10(-4) m.s(-1) while performing X-ray micro-CT scanning. Experimental values of the changes in sample permeability were estimated in two independent ways: through PNM flow simulation and through Direct Numerical Simulation. Both approaches used images of the samples from the beginning and the end of experiments. Extracted pore networks, obtained from the micro-CT images of the sample from the beginning of the experiment, were used for reactive transport PNMs (rtPNM and nrtPNM). We observed that for the experimental conditions, most of the pore throats maintained the initially prescribed cylindrical shape such that both rtPNM and nrtPNM showed a similar evolution of porosity and permeability. This was found to be in reasonable agreement with the porosity and permeability changes observed in the experiment. Next, we have applied a range of flow and reaction regimes to compare permeability evolutions between rtPNM and nrtPNM. We found that for certain dissolution regimes, neglecting the evolution of the pore throat shape in the pore network can lead to an overestimation of up to 27% in the predicted permeability values and an overestimation of over 50% in the fitted exponent for the porosity-permeability relations. In summary, this study showed that while under high flow rate conditions the rtPNM model is accurate enough, it overestimates permeability under lower flow rates

Control of brine composition over reactive transport processes in calcium carbonate rock dissolution:: Time-lapse imaging of evolving dissolution patterns

This study investigates the impact of brine composition—specifically calcium ions and NaCl-based salinity—on the development of dissolution features in Ketton, a porous calcium carbonate rock. Utilizing a laboratory XMT (X-ray microtomography) scanner, we captured time-lapse in situ images of Ketton samples throughout various dissolution experiments, conducting four distinct flow-through experiments with differing brine solutions at a flow rate of 0.26 ml min⁻1. The scans yielded a voxel size of 6 μm, enabling the assessment of the temporal evolution of porosity and pore structure through image analysis and permeability evaluations via single-phase fluid flow simulations employing direct numerical solutions and network modeling, as opposed to direct measurement. Time-lapse imaging technique has delineated the extent to which the concentrations of CaCl₂ and NaCl in the injecting solution control the structural evolution of dissolution patterns, subsequently triggering the development of characteristic dissolution pattern. The inflow solution with no Ca2+ ions and with the minimal salt content manifested maximum dissolution near the sample inlet, coupled with the formation of numerous dissolution channels, i.e., wormholes. Conversely, solutions with a trace amount of Ca2⁺ ions induced focused dissolution, resulting in the formation of sparsely located channels. Inflow solutions with high concentrations of both Ca2⁺ ions and salt facilitated uniformly dispersed dissolution, primarily within microporous domains, initiating particle detachment and displacement and leading to localized pore-clogging. The relative increase in permeability, in each experiment, was correlated with the developed dissolution pattern. It was discerned that varying ratios of salt and calcium concentrations in the injected solution systematically influenced image-based permeability simulations and porosity, allowing for the depiction of an empirical porosity-permeability relationship

The impact of stoichiometry on the initial steps of crystal formation: Stability and lifetime of charged triple-ion complexes

Minerals form in natural systems from solutions with varying ratios of their lattice ions, yet non-stoichiometric conditions have generally been overlooked in investigations of new formation (nucleation) of ionic crystals. Here, we investigated the influence of cation:anion ratio in the solution on the initial steps of nucleation by studying positively and negatively charged triple ion complexes and subsequent particle size evolution. Our model systems are carbonates and sulfates of calcium and barium, as it was recently shown that solution stoichiometry affects the timing and rate of their nucleation. Molecular dynamics (MD) simulations and dynamic light scattering (DLS) flow experiments show that nucleation correlates with the stability and lifetime of the initial complexes, which were significantly impacted by the cation:anion stoichiometry and ion type. Specifically, (Formula presented.) was found to have higher association constants and its lifetime was twofold longer than (Formula presented.). Similar trends were observed for (Formula presented.) and (Formula presented.). Contrastingly, for (Formula presented.), (Formula presented.) was found to have lower association constants and its lifetime was shorter than (Formula presented.). These trends in stability and lifetime follow the same asymmetrical behaviour as observed experimentally for particle formation using techniques like DLS. This suggests a causal relationship between the stability and lifetime of the initial charged complexes and the nucleation under non-stoichiometric conditions

Evolution of pore-shape and its impact on pore conductivity during CO2 injection in calcite : Single pore simulations and microfluidic experiments

Injection of CO2 into carbonate rocks causes dissolution and alters rock transport properties. The extent of the permeability increases, due to the increased pore volume and connectivity, strongly depends on the regimes of transport and dissolution reactions. Identification of these regimes and their parametrization at the microscopic scale is required for an understanding of the injection processes, and, afterward, for calculating the effective macroscopic parameters for field-scale simulations. Currently, a commonly used approach for calculating the rock effective parameters is the Pore Network Method, PNM, but a better understanding of the validity of its basic assumptions and their areas of applicability is essential. Here, we performed a combined microscopic experimental and numerical study to explore pore-shape evolution over a wide range of transport and dissolution reaction regimes. Experiments were conducted by flowing an acidic solution through a microscopic capillary channel in a calcite crystal at two different flow rates. The experimental results were used to validate our pore-scale reactive transport model that could reproduce the measured effluent composition as well as pore shape changes. Two key stages in pore shape evolution were observed, a transient phase and a quasi-steady-state phase. During the first stage, the shape of the single pore evolved very fast, depending on the flow regime. Under advective-dominant flow, the pore shape remained nearly cylindrical, while under diffusive-dominant transport, the pore shape developed into a half-hyperboloid shape. During the quasi-steady-state stage, the pore volume continued to increase, however, without or with diminutive change of the pore shape. In this stage, only a long period of injection may result in a significant deviation of the pore shape from its original cylinder shape, which is a common assumption in PNMs. Furthermore, we quantitatively evaluated the impact of evolved pore shape spectrum on the conductance calculations and compared it to the formulations currently used for pore network modeling of reactive transport. Under low flow rates, neglecting the developed non-uniform pore shape during the non-steady stage may lead to an overestimation of pore conductance up to 80%

Towards a stable astronomical time scale for the Paleocene : Aligning Shatsky Rise with the Zumaia – Walvis Ridge ODP Site 1262 composite

The construction of a permanent astronomical time scale for the Paleocene tuned to stable 405-kyr eccentricity is hampered by uncertainties in the number of eccentricity-related cycles between the Cretaceous-Paleogene (K/Pg) boundary and the Early Late Paleocene Event (ELPE) situated just below the Selandian-Thanetian boundary. Here we re-examine available stratigraphic information to align the Zumaia section (Spain), and Shatsky Rise (northern Pacific) and Walvis Ridge (southern Atlantic) ODP Leg 198 and 208 sites. Our review indicates that the composite of the Zumaia section and ODP Leg 208 Site 1262 is most suitable for establishing an integrated (cyclo-)stratigraphic framework and astronomical tuning for the entire Paleocene. This composite contains 25 405-kyr eccentricity-related cycles and is identical to the composite used to construct the early Paleogene time scale in GTS2012. ODP Leg 198 sites are incorporated in this framework by using the carbon isotope excursion (CIE) associated with the Latest Danian Event (LDE) at the top of C27n as tie-point. Eccentricity-related variations in Fecounts and associated reddish and dark color bands visible on core photographs of ODP Site 1209 and 1210 are correlated to the Zumaia-ODP Site 1262 composite down to the K/Pg boundary. This procedure constrains the duration of an aberrant interval above the K/Pg boundary at Site 1209, previously labeled “Strange Interval”, to approximately two 405-kyr cycles. This duration for the Strange Interval is in line with sedimentation rates calculated on the basis of the observed precession-related cyclicity. The correlations to Zumaia indicate that the interval above the K/Pg boundary is continuous at all Shatsky Rise sites, including DSDP Site 577, and, hence, that Site 1209 does not contain a hiatus as inferred from Os-isotope data. The correlations further substantiate the presence of 25 405-kyr cycles in the Paleocene and an age of ∼ 66.0 Ma for the K/Pg boundary