Acid Erosion of Carbonate Fractures and Accessibility of Arsenic-Bearing Minerals: In Operando Synchrotron-Based Microfluidic Experiment.

ABSTRACT

Underground flows of acidic fluids through fractured rock can create new porosity and increase accessibility to hazardous trace elements such as arsenic. In this study, we developed a custom microfluidic cell for an in operando synchrotron experiment using X-ray attenuation. The experiment mimics reactive fracture flow by passing an acidic fluid over a surface of mineralogically heterogeneous rock from the Eagle Ford shale. Over 48 h, calcite was preferentially dissolved, forming an altered layer 200-500 µm thick with a porosity of 63-68% and surface area >10× higher than that in the unreacted shale as shown by xCT analyses. Calcite dissolution rate quantified from the attenuation data was 3 × 10-4 mol/m2s and decreased to 3 × 10-5 mol/m2s after 24 h because of increasing diffusion limitations. Erosion of the fracture surface increased access to iron-rich minerals, thereby increasing access to toxic metals such as arsenic. Quantification using XRF and XANES microspectroscopy indicated up to 0.5 wt % of As(-I) in arsenopyrite and 1.2 wt % of As(V) associated with ferrihydrite. This study provides valuable contributions for understanding and predicting fracture alteration and changes to the mobilization potential of hazardous metals and metalloids.