## 2 Samples and Methods
### Numerical Simulation  
The program TOUGHREACT was used in the numerical simulations. This program is a non-isothermal, multiphase reactive transport simulation code that was used here to simulate fluid-rock interactions [21]. The kinetic data used during the simulation are shown in Table 2.  
According to the columnar autoclaves employed by the physical simulation, three identical cubic grids with volumes of 77.7 cm\({}^{3}\) were used to construct the model (Figure 3). The upper and lower grids were used as boundary cells, while the middle grid was the objective model grid for simulating the processes of injection and sampling. The numerical model simulated six autoclave reactions, corresponding to the laboratory experiment, with the same mineralogical cores, temperature, pressure, and pore fluids. We used the simulation duration to mimic the six numbered autoclaves. The entire simulation ran for 16 days with intermittent sampling on day 0, 4, 7, 10, 13, and 16, corresponding  
\begin{table}
\begin{tabular}{c c c c c} \hline \hline \multirow{2}{*}{**Mineral**} & \multirow{2}{*}{**A/(cm\({}^{2}\)/g)**} & \multicolumn{3}{c}{**Geochemical Kinetic Rate Constants**} \\ \cline{3-5}  & & **K\({}_{25}\)/(mol/(m\({}^{2}\cdot\)s))** & **E\({}_{a}\)/(kJ/mol)** & **n\({}^{a}\) H\({}^{+}\)** \\ \hline Quartz & 9.8 & & & \\ Kaolinite & 151.6 & \(4.9\times 10^{-12}\) & 65.9 & 0.8 \\ Illite & 151.6 & \(1.0\times 10^{-11}\) & 23.6 & 0.3 \\ K-feldspar & 9.8 & \(8.7\times 10^{-11}\) & 51.7 & 0.5 \\ albite & 9.8 & \(6.9\times 10^{-11}\) & 65.0 & 0.5 \\ Chlorite & 9.8 & \(7.8\times 10^{-12}\) & 88.0 & 0.5 \\ Calcite & 9.8 & \(5.0\times 10^{-1}\) & 14.4 & 1.0 \\ Dolomite & 9.8 & \(6.5\times 10^{-4}\) & 36.1 & 0.5 \\ Siderite & 9.8 & \(6.5\times 10^{-4}\) & 36.1 & 0.5 \\ Ankerite & 9.8 & \(1.6\times 10^{-4}\) & 36.1 & 0.5 \\ Dawsonite & 9.8 & \(1.6\times 10^{-4}\) & 36.1 & 0.5 \\ Magnesite & 9.8 & \(4.2\times 10^{-7}\) & 14.4 & 1.0 \\ Pyrite & 12.9 & \(3.0\times 10^{-8}\) & 56.9 & \(-0.5\) \\ \hline \hline \end{tabular} Note that: (1) All rate constants are listed for dissolution; (2) A is specific surface area, k\({}_{25}\) is kinetic constant at 25 \({}^{\circ}\)C, E\({}_{a}\) is activation energy, and n is the power term (Equation (A1) in Appendix A); (3) The power terms n for acid mechanisms are with respect to H\({}^{+}\). Data from [PERSON] and [PERSON] (2004) [29].  
\end{table}
Table 2: List of minerals considered and parameters for calculating the kinetic rate constants.  
Figure 2: Synthetic core samples made by the physical experiment.  
to the physical simulation. At the start of simulation (Day zero), the numerical model had an initial mineralogical composition and visual porosity, which corresponded to Autoclave # 2. In the same way, Day 4 corresponded to Autoclave # 1, Day 7 corresponded to Autoclave # 3, Day 10 corresponded to Autoclave # 4, Day 13 corresponded to Autoclave # 5, and Day 16 corresponded to Autoclave # 6. Accordingly, these results of different simulation duration from the numerical models can be used for comparison with the results from the physical simulations. The boundary cell here is an \"inactive\" element, whose thermodynamic conditions do not change at all from fluid or heat exchange with finite-size blocks (numerical model cell) in the flow domain. The boundary cell can confine geochemical interactions that only occur in the numerical model, which makes the results more reasonable.