SOLUTION 0 #inject acidic solution of ph=2 temp 25 pH 2 units mmol/kgw Cl 10 charge C(4) 1e-9ENDSOLUTION 1 #initial solution around calcite grain, similar to influx solution temp 25 pH 2 units mmol/kgw Cl 10 charge C(4) 1e-9ENDSOLUTION 2 #within the grain having porosity 0.001 temp 25 pH 10 charge units mmol/kgw EQUILIBRIUM_PHASES Calcite 0.END

Calcite -start1 REM PARM(1) = specific surface area of Calcite (large grains), [m^2/m^3]10 si_cc = SR("Calcite")20 rate = 8.9125e-4*PARM(1)*MOL("H+")30 mole = rate*time #mol/m335 mole = mole #mol/l40 save mole -end

WARNING: Negative moles in solution 922 for C, -1.425926e-02. Recovering...WARNING: Negative moles in solution 922 for C, -9.981482e-04. Recovering...WARNING: Negative moles in solution 922 for C, -6.987039e-05. Recovering...WARNING: Negative moles in solution 922 for C, -3.171901e-05. Recovering...WARNING: Maximum iterations exceeded, 100WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying smaller step size, pe step size 10, 5 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying reduced tolerance 1e-16 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying increased tolerance 1e-14 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying diagonal scaling ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying diagonal scaling and reduced tolerance 1e-16 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying scaling pure_phase columns 1e-10 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying scaling pure_phase columns and diagonal scale 1e-10 ...WARNING: Negative moles in solution 669 for C, -1.425926e-02. Recovering...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Negative moles in solution 669 for C, -9.981482e-04. Recovering...WARNING: Trying delay removal of equilibrium phases 1 ...WARNING: Negative moles in solution 669 for C, -6.987039e-05. Recovering...WARNING: Maximum iterations exceeded, 100WARNING: Numerical method failed with this set of convergence parameters.WARNING: Negative moles in solution 669 for C, -3.175318e-05. Recovering...WARNING: Trying increased scaling 1e-09 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Skipping optimize equations for first 5 iterations ...WARNING: Maximum iterations exceeded, 100WARNING: Numerical method failed with this set of convergence parameters.WARNING: Adding inequality to make concentrations greater than zero.WARNING: Maximum iterations exceeded, 100WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying reduced tolerance 1e-17 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying reduced tolerance 1e-18 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: The program has failed to converge to a numerical solution.The following equations were not satisfied:ERROR: A(H2O) Activity of water has not converged. Residual: 3.140644e-06ERROR: Numerical method failed on all combinations of convergence parameters, cell/soln/mix 922Stopping.ERROR: ERROR: A(H2O) Activity of water has not converged. Residual: 3.140644e-06ERROR: Numerical method failed on all combinations of convergence parameters, cell/soln/mix 922WARNING: Maximum iterations exceeded, 100WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying smaller step size, pe step size 10, 5 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying reduced tolerance 1e-16 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying increased tolerance 1e-14 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying diagonal scaling ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying diagonal scaling and reduced tolerance 1e-16 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying scaling pure_phase columns 1e-10 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying scaling pure_phase columns and diagonal scale 1e-10 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying delay removal of equilibrium phases 1 ...WARNING: Maximum iterations exceeded, 100WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying increased scaling 1e-09 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Skipping optimize equations for first 5 iterations ...WARNING: Maximum iterations exceeded, 100WARNING: Numerical method failed with this set of convergence parameters.WARNING: Adding inequality to make concentrations greater than zero.WARNING: Maximum iterations exceeded, 100WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying reduced tolerance 1e-17 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: Trying reduced tolerance 1e-18 ...WARNING: Maximum iterations exceeded, 200WARNING: Numerical method failed with this set of convergence parameters.WARNING: The program has failed to converge to a numerical solution.The following equations were not satisfied:ERROR: A(H2O) Activity of water has not converged. Residual: 3.144049e-06ERROR: Numerical method failed on all combinations of convergence parameters, cell/soln/mix 669Stopping.ERROR: ERROR: A(H2O) Activity of water has not converged. Residual: 3.144049e-06ERROR: Numerical method failed on all combinations of convergence parameters, cell/soln/mix 669ERROR: A(H2O) Activity of water has not converged. Residual: 3.144049e-06ERROR: Numerical method failed on all combinations of convergence parameters, cell/soln/mix 669ERROR: A(H2O) Activity of water has not converged. Residual: 3.140644e-06ERROR: Numerical method failed on all combinations of convergence parameters, cell/soln/mix 922ERROR: PhreeqcRM failed.ERROR: PhreeqcRM::RunCellsterminate called after throwing an instance of 'PhreeqcRMStop' what(): Failure in PhreeqcRMAborted (core dumped)

RATESCalcite -start1 REM PARM(1) = specific surface area of Calcite (large grains), [m^2/m^3]10 si_cc = SR("Calcite")20 rate = 8.9125e-4*PARM(1)*MOL("H+")30 mole = rate*time #mol/m335 mole = mole #mol/l40 save mole -endENDSOLUTIONpH 2Cl 1 chargeENDUSE solution 1KINETICS 1Calcite-parm 20000-time 3600 in 10 stepsUSER_GRAPH 1 -headings Time TOT(Ca) SI(Calcite) -axis_titles "Time, seconds" "Molality" "Saturation index" -initial_solutions false -connect_simulations true -plot_concentration_vs x -start10 GRAPH_X TOTAL_TIME20 GRAPH_Y TOT("Ca")30 GRAPH_SY SI("Calcite") -end -active trueEND