pychnosz 1.1.12__cp310-cp310-macosx_15_0_x86_64.whl

pychnosz/geochemistry/minerals.py

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+"""
+Mineral equilibria and phase diagram calculations for CHNOSZ.
+
+This module implements mineral stability calculations, phase diagrams,
+and solid-solution equilibria for geological applications.
+"""
+
+import numpy as np
+import pandas as pd
+from typing import Union, Dict, List, Optional, Tuple, Any
+import warnings
+
+from ..core.subcrt import subcrt
+from ..core.equilibrium import EquilibriumSolver
+from ..core.speciation import SpeciationEngine
+
+
+class MineralEquilibria:
+    """
+    Mineral equilibria calculator for geological systems.
+    
+    This class handles mineral stability calculations, including:
+    - Mineral solubility equilibria
+    - Phase stability diagrams
+    - Mineral-water reactions
+    - Solid solution equilibria
+    """
+    
+    def __init__(self):
+        """Initialize the mineral equilibria calculator."""
+        self.equilibrium_solver = EquilibriumSolver()
+        self.speciation_engine = SpeciationEngine()
+        
+        # Common mineral dissolution reactions (simplified)
+        self.dissolution_reactions = {
+            'quartz': {'SiO2': 1, 'H2O': 0, 'H4SiO4': -1},
+            'calcite': {'CaCO3': 1, 'H+': 2, 'Ca+2': -1, 'HCO3-': -1, 'H2O': -1},
+            'pyrite': {'FeS2': 1, 'H+': 8, 'SO4-2': -2, 'Fe+2': -1, 'H2O': -4},
+            'hematite': {'Fe2O3': 1, 'H+': 6, 'Fe+3': -2, 'H2O': -3},
+            'magnetite': {'Fe3O4': 1, 'H+': 8, 'Fe+2': -1, 'Fe+3': -2, 'H2O': -4},
+            'albite': {'NaAlSi3O8': 1, 'H+': 1, 'H2O': 4, 'Na+': -1, 'Al+3': -1, 'H4SiO4': -3},
+            'anorthite': {'CaAl2Si2O8': 1, 'H+': 8, 'H2O': 0, 'Ca+2': -1, 'Al+3': -2, 'H4SiO4': -2},
+            'kaolinite': {'Al2Si2O5(OH)4': 1, 'H+': 6, 'Al+3': -2, 'H4SiO4': -2, 'H2O': -1}
+        }
+    
+    def mineral_solubility(self, mineral: str, 
+                          T: float = 298.15, P: float = 1.0,
+                          pH_range: Optional[Tuple[float, float]] = None,
+                          ionic_strength: float = 0.0) -> Dict[str, Any]:
+        """
+        Calculate mineral solubility as a function of pH.
+        
+        Parameters
+        ----------
+        mineral : str
+            Mineral name
+        T : float, default 298.15
+            Temperature in Kelvin
+        P : float, default 1.0
+            Pressure in bar
+        pH_range : tuple, optional
+            pH range (min, max). Default: (0, 14)
+        ionic_strength : float, default 0.0
+            Solution ionic strength
+            
+        Returns
+        -------
+        dict
+            Solubility data vs pH
+        """
+        
+        if pH_range is None:
+            pH_range = (0, 14)
+        
+        pH_values = np.linspace(pH_range[0], pH_range[1], 100)
+        
+        if mineral.lower() not in self.dissolution_reactions:
+            warnings.warn(f"Dissolution reaction not defined for {mineral}")
+            return {'pH': pH_values, 'solubility': np.zeros_like(pH_values)}
+        
+        reaction = self.dissolution_reactions[mineral.lower()]
+        
+        try:
+            # Get equilibrium constant for dissolution
+            species_names = list(reaction.keys())
+            coefficients = list(reaction.values())
+            
+            # Calculate logK at T, P
+            result = subcrt(species_names, coefficients, T=T, P=P, show=False)
+            if result.out is not None and 'logK' in result.out.columns:
+                logK = result.out['logK'].iloc[0]
+            else:
+                logK = 0.0
+                warnings.warn(f"Could not calculate logK for {mineral} dissolution")
+            
+        except Exception as e:
+            warnings.warn(f"Error calculating equilibrium constant: {e}")
+            logK = 0.0
+        
+        # Calculate solubility at each pH
+        solubility = np.zeros_like(pH_values)
+        
+        for i, pH in enumerate(pH_values):
+            try:
+                # Simplified solubility calculation
+                # This would be more complex in a full implementation
+                
+                if 'H+' in reaction:
+                    h_coeff = reaction['H+']
+                    # Basic pH dependence
+                    log_solubility = logK - h_coeff * pH
+                else:
+                    log_solubility = logK
+                
+                # Convert to molality
+                solubility[i] = 10**log_solubility
+                
+                # Apply ionic strength corrections if needed
+                if ionic_strength > 0:
+                    # Simple activity coefficient correction
+                    gamma = self._estimate_activity_coefficient(ionic_strength)
+                    solubility[i] *= gamma
+                
+            except:
+                solubility[i] = 1e-20  # Very low solubility
+        
+        return {
+            'pH': pH_values,
+            'solubility': solubility,
+            'logK': logK,
+            'mineral': mineral,
+            'T': T,
+            'P': P
+        }
+    
+    def stability_diagram(self, minerals: List[str],
+                         x_axis: str, x_range: Tuple[float, float],
+                         y_axis: str, y_range: Tuple[float, float],
+                         T: float = 298.15, P: float = 1.0,
+                         resolution: int = 50) -> Dict[str, Any]:
+        """
+        Create mineral stability diagram.
+        
+        Parameters
+        ----------
+        minerals : list of str
+            Mineral names to consider
+        x_axis : str
+            X-axis variable ('pH', 'log_activity_SiO2', etc.)
+        x_range : tuple
+            X-axis range (min, max)
+        y_axis : str
+            Y-axis variable
+        y_range : tuple
+            Y-axis range (min, max)
+        T : float, default 298.15
+            Temperature in Kelvin
+        P : float, default 1.0
+            Pressure in bar
+        resolution : int, default 50
+            Grid resolution
+            
+        Returns
+        -------
+        dict
+            Stability diagram data
+        """
+        
+        x_values = np.linspace(x_range[0], x_range[1], resolution)
+        y_values = np.linspace(y_range[0], y_range[1], resolution)
+        X, Y = np.meshgrid(x_values, y_values)
+        
+        # Initialize stability field array
+        stable_mineral = np.zeros_like(X, dtype=int)
+        
+        # Calculate stability at each grid point
+        for i in range(len(y_values)):
+            for j in range(len(x_values)):
+                x_val, y_val = X[i, j], Y[i, j]
+                
+                # Find most stable mineral at this point
+                min_energy = np.inf
+                stable_idx = 0
+                
+                for k, mineral in enumerate(minerals):
+                    try:
+                        # Calculate relative stability
+                        # This would involve full equilibrium calculations
+                        # For now, use simplified energy estimates
+                        
+                        energy = self._calculate_stability_energy(
+                            mineral, x_axis, x_val, y_axis, y_val, T, P)
+                        
+                        if energy < min_energy:
+                            min_energy = energy
+                            stable_idx = k
+                        
+                    except Exception as e:
+                        warnings.warn(f"Error calculating stability for {mineral}: {e}")
+                        continue
+                
+                stable_mineral[i, j] = stable_idx
+        
+        return {
+            x_axis: x_values,
+            y_axis: y_values,
+            'stable_mineral': stable_mineral,
+            'mineral_names': minerals,
+            'T': T,
+            'P': P
+        }
+    
+    def phase_equilibrium(self, reaction: Dict[str, float],
+                         T_range: Optional[Tuple[float, float]] = None,
+                         P_range: Optional[Tuple[float, float]] = None) -> Dict[str, Any]:
+        """
+        Calculate phase equilibrium curve.
+        
+        Parameters
+        ----------
+        reaction : dict
+            Reaction stoichiometry {species: coefficient}
+        T_range : tuple, optional
+            Temperature range (min, max) in K
+        P_range : tuple, optional
+            Pressure range (min, max) in bar
+            
+        Returns
+        -------
+        dict
+            Equilibrium curve data
+        """
+        
+        if T_range is None and P_range is None:
+            T_range = (273.15, 673.15)  # 0-400°C
+        
+        if T_range is not None:
+            # T-P curve at equilibrium
+            T_values = np.linspace(T_range[0], T_range[1], 50)
+            P_equilibrium = np.zeros_like(T_values)
+            
+            for i, T in enumerate(T_values):
+                try:
+                    # Calculate equilibrium pressure
+                    # This would involve iterative solution
+                    # For now, use simplified correlation
+                    P_equilibrium[i] = self._calculate_equilibrium_pressure(reaction, T)
+                    
+                except:
+                    P_equilibrium[i] = 1.0  # Default
+            
+            return {
+                'T': T_values,
+                'P': P_equilibrium,
+                'reaction': reaction
+            }
+        
+        else:
+            # P-T curve - similar logic
+            P_values = np.linspace(P_range[0], P_range[1], 50)
+            T_equilibrium = np.zeros_like(P_values)
+            
+            for i, P in enumerate(P_values):
+                try:
+                    T_equilibrium[i] = self._calculate_equilibrium_temperature(reaction, P)
+                except:
+                    T_equilibrium[i] = 298.15
+            
+            return {
+                'P': P_values,
+                'T': T_equilibrium,
+                'reaction': reaction
+            }
+    
+    def solid_solution(self, end_members: List[str], compositions: List[float],
+                      T: float = 298.15, P: float = 1.0,
+                      model: str = 'ideal') -> Dict[str, Any]:
+        """
+        Calculate solid solution thermodynamics.
+        
+        Parameters
+        ----------
+        end_members : list of str
+            End-member mineral names
+        compositions : list of float
+            Mole fractions of end-members (must sum to 1)
+        T : float, default 298.15
+            Temperature in Kelvin
+        P : float, default 1.0
+            Pressure in bar
+        model : str, default 'ideal'
+            Mixing model ('ideal', 'regular', 'margules')
+            
+        Returns
+        -------
+        dict
+            Solid solution properties
+        """
+        
+        if len(end_members) != len(compositions):
+            raise ValueError("Number of end-members must match number of compositions")
+        
+        if abs(sum(compositions) - 1.0) > 1e-6:
+            raise ValueError("Compositions must sum to 1.0")
+        
+        # Calculate end-member properties
+        end_member_props = []
+        for mineral in end_members:
+            try:
+                # This would get mineral properties from database
+                props = self._get_mineral_properties(mineral, T, P)
+                end_member_props.append(props)
+            except:
+                # Default properties
+                props = {'G': -1000000, 'H': -1200000, 'S': 100, 'V': 50, 'Cp': 100}
+                end_member_props.append(props)
+        
+        # Calculate mixing properties
+        if model == 'ideal':
+            # Ideal mixing
+            G_mix = 8.314 * T * sum(x * np.log(x) for x in compositions if x > 0)
+            H_mix = 0.0
+            S_mix = -8.314 * sum(x * np.log(x) for x in compositions if x > 0)
+            
+        elif model == 'regular':
+            # Regular solution (symmetric)
+            W = 10000  # Interaction parameter (J/mol) - would be mineral-specific
+            G_mix = W * compositions[0] * compositions[1]  # Binary case
+            H_mix = G_mix
+            S_mix = 0.0
+            
+        else:
+            # Default to ideal
+            G_mix = 8.314 * T * sum(x * np.log(x) for x in compositions if x > 0)
+            H_mix = 0.0
+            S_mix = -8.314 * sum(x * np.log(x) for x in compositions if x > 0)
+        
+        # Total properties
+        total_props = {}
+        for prop in ['G', 'H', 'S', 'V', 'Cp']:
+            total_props[prop] = sum(compositions[i] * end_member_props[i][prop] 
+                                  for i in range(len(end_members)))
+        
+        # Add mixing contributions
+        total_props['G'] += G_mix
+        total_props['H'] += H_mix
+        total_props['S'] += S_mix
+        
+        return {
+            'properties': total_props,
+            'mixing': {'G': G_mix, 'H': H_mix, 'S': S_mix},
+            'end_members': end_members,
+            'compositions': compositions,
+            'model': model
+        }
+    
+    def _estimate_activity_coefficient(self, ionic_strength: float) -> float:
+        """Estimate activity coefficient from ionic strength."""
+        if ionic_strength <= 0:
+            return 1.0
+        else:
+            # Simple Debye-Hückel approximation
+            A = 0.509
+            return 10**(-A * np.sqrt(ionic_strength))
+    
+    def _calculate_stability_energy(self, mineral: str, x_axis: str, x_val: float,
+                                  y_axis: str, y_val: float, T: float, P: float) -> float:
+        """Calculate relative stability energy for mineral."""
+        
+        # Simplified stability calculation
+        # Would involve full thermodynamic analysis
+        
+        base_energy = np.random.random() * 1000  # Placeholder
+        
+        # Add dependencies on axes
+        if 'pH' in x_axis:
+            base_energy += abs(x_val - 7) * 100  # pH dependence
+        
+        if 'log' in y_axis:
+            base_energy += abs(y_val + 3) * 50  # Activity dependence
+        
+        return base_energy
+    
+    def _calculate_equilibrium_pressure(self, reaction: Dict[str, float], T: float) -> float:
+        """Calculate equilibrium pressure for reaction at given T."""
+        
+        # Simplified using Clapeyron equation approximation
+        # dP/dT = ΔS/ΔV
+        
+        # Estimate volume and entropy changes
+        delta_V = 5.0e-6  # m³/mol (typical for mineral reactions)
+        delta_S = 20.0    # J/(mol·K) (typical)
+        
+        # Integrate from reference conditions
+        T0, P0 = 298.15, 1.0
+        dP_dT = delta_S / delta_V * 1e-5  # Convert to bar/K
+        
+        P_eq = P0 + dP_dT * (T - T0)
+        
+        return max(P_eq, 0.1)  # Minimum 0.1 bar
+    
+    def _calculate_equilibrium_temperature(self, reaction: Dict[str, float], P: float) -> float:
+        """Calculate equilibrium temperature for reaction at given P."""
+        
+        # Inverse of pressure calculation
+        delta_V = 5.0e-6
+        delta_S = 20.0
+        
+        T0, P0 = 298.15, 1.0
+        dT_dP = delta_V / delta_S * 1e5  # K/bar
+        
+        T_eq = T0 + dT_dP * (P - P0)
+        
+        return max(T_eq, 273.15)  # Minimum 0°C
+    
+    def _get_mineral_properties(self, mineral: str, T: float, P: float) -> Dict[str, float]:
+        """Get thermodynamic properties of a mineral."""
+        
+        # This would look up mineral in database
+        # For now, return typical values
+        
+        typical_props = {
+            'quartz': {'G': -856300, 'H': -910700, 'S': 41.5, 'V': 22.7, 'Cp': 44.6},
+            'calcite': {'G': -1128800, 'H': -1207400, 'S': 91.7, 'V': 36.9, 'Cp': 83.5},
+            'pyrite': {'G': -160200, 'H': -171500, 'S': 52.9, 'V': 23.9, 'Cp': 62.2},
+            'hematite': {'G': -744400, 'H': -824200, 'S': 87.4, 'V': 30.3, 'Cp': 103.9}
+        }
+        
+        return typical_props.get(mineral.lower(), {
+            'G': -500000, 'H': -600000, 'S': 50, 'V': 30, 'Cp': 80
+        })
+
+
+# Global mineral equilibria calculator
+_mineral_calculator = MineralEquilibria()
+
+
+def mineral_solubility(mineral: str, pH_range: Tuple[float, float] = (0, 14),
+                      T: float = 298.15, P: float = 1.0) -> Dict[str, Any]:
+    """
+    Calculate mineral solubility vs pH.
+    
+    Parameters
+    ----------
+    mineral : str
+        Mineral name
+    pH_range : tuple, default (0, 14)
+        pH range for calculation
+    T : float, default 298.15
+        Temperature in Kelvin
+    P : float, default 1.0
+        Pressure in bar
+        
+    Returns
+    -------
+    dict
+        Solubility data
+    """
+    
+    return _mineral_calculator.mineral_solubility(mineral, T, P, pH_range)
+
+
+def stability_field(minerals: List[str], 
+                   variables: Tuple[str, str],
+                   ranges: Tuple[Tuple[float, float], Tuple[float, float]],
+                   T: float = 298.15, P: float = 1.0) -> Dict[str, Any]:
+    """
+    Calculate mineral stability fields.
+    
+    Parameters
+    ----------
+    minerals : list of str
+        Minerals to consider
+    variables : tuple of str
+        (x_variable, y_variable) for diagram
+    ranges : tuple of tuples
+        ((x_min, x_max), (y_min, y_max))
+    T : float, default 298.15
+        Temperature in Kelvin
+    P : float, default 1.0
+        Pressure in bar
+        
+    Returns
+    -------
+    dict
+        Stability diagram data
+    """
+    
+    x_var, y_var = variables
+    x_range, y_range = ranges
+    
+    return _mineral_calculator.stability_diagram(
+        minerals, x_var, x_range, y_var, y_range, T, P)
+
+
+def phase_boundary(reaction: Dict[str, float],
+                  T_range: Tuple[float, float] = (273.15, 673.15)) -> Dict[str, Any]:
+    """
+    Calculate phase boundary for a reaction.
+    
+    Parameters
+    ----------
+    reaction : dict
+        Reaction stoichiometry {species: coefficient}
+    T_range : tuple, default (273.15, 673.15)
+        Temperature range in Kelvin
+        
+    Returns
+    -------
+    dict
+        Phase boundary data
+    """
+    
+    return _mineral_calculator.phase_equilibrium(reaction, T_range=T_range)