GROUNDWATER GEOCHEMISTRY
TABLE OF CONTENTS 1 THEORETICAL BACKGROUND 11 EQUILIBRIUM REACTIONS 111 INTRODUCTION 112 THERMODYNAMIC FUNDAMENTALS 1121 MASS ACTION LAW 1122 GIBBS FREE ENERGY 1123 GIBBS PHASE RULE 1124 ACTIVITY 1125 IONIC STRENGTH 1126 CALCULATION OF ACTIVITY COEFFICIENT 11261 THEORY OF ION DISSOCIATION 11262 THEORY OF ION INTERACTION 1127 THEORIES OF ION DISSOCIATION AND ION INTERACTION 113 INTERACTIONS AT THE LIQUID-GASEOUS PHASE BOUNDARY 1131 HENRY-LAW 114 INTERACTIONS AT THE LIQUID-SOLID PHASE BOUNDARY 1141 DISSOLUTION AND PRECIPITATION 11411 SOLUBILITY PRODUCT 11412 SATURATION INDEX 11413 LIMITING MINERAL PHASES 1142 SORPTION 11421 HYDROPHOBIC /HYDROPHILIC SUBSTANCES 11422 ION EXCHANGE 11423 MATHEMATICAL DESCRIPTION OF THE SORPTION 115 INTERACTIONS IN THE LIQUID PHASE 1151 COMPLEXATION 1152 REDOX PROCESSES 11521 MEASUREMENT OF THE REDOX POTENTIAL 11522 CALCULATION OF THE REDOX POTENTIAL 11523 PRESENTATION IN PREDOMINANCE DIAGRAMS 11524 REDOX BUFFER 11525 SIGNIFICANCE OF REDOX REACTIONS 12 KINETICS 121 KINETICS OF VARIOUS CHEMICAL PROCESSES 1211 HALF-LIFE 1212 KINETICS OF MINERAL DISSOLUTION 122 CALCULATION OF THE REACTION RATE 1221 SUBSEQUENT REACTIONS 1222 PARALLEL REACTIONS 123 CONTROLLING FACTORS ON THE REACTION RATE 124 EMPIRIC APPROACHES FOR KINETICALLY CONTROLLED REACTIONS 13 REACTIVE MASS TRANSPORT 131 INTRODUCTION 132 FLOW MODELS 133 TRANSPORT MODELS 1331 DEFINITION 1332 IDEALIZED TRANSPORT CONDITIONS 1333 REAL TRANSPORT CONDITIONS 13331 EXCHANGE WITHIN DOUBLE-POROSITY AQUIFERS 1334 NUMERICAL METHODS OF TRANSPORT MODELING 13341 FINITE-DIFFERENCE / FINITE-ELEMENT METHOD 13342 COUPLED METHODS 2 HYDROGEOCHEMICAL MODELING PROGRAMS 21 GENERAL 211 GEOCHEMICAL ALGORITHMS 212 PROGRAMS BASED ON MINIMIZING FREE ENERGY 213 PROGRAMS BASED ON EQUILIBRIUM CONSTANTS 2131 PHREEQC 2132 EQ 3/6 2133 COMPARISON PHREEQC – EQ 3/6 214 THERMODYNAMIC DATA SETS 2141 GENERAL 2142 STRUCTURE OF THERMODYNAMIC DATA SETS 215 PROBLEMS AND SOURCES OF ERROR IN GEOCHEMICAL MODELING 22 USE OF PHREEQC 221 STRUCTURE OF PHREEQC UNDER THE WINDOWS SURFACE 2211 INPUT 2212 THERMODYNAMIC DATA 2213 OUTPUT 2214 GRID 2215 CHART 222 INTRODUCTORY EXAMPLES FOR PHREEQC MODELING 2221 EQUILIBRIUM REACTIONS 22211 EXAMPLE 1: STANDARD OUTPUT – SEAWATER ANALYSIS 22212 EXAMPLE 2 EQUILIBRIUM – SOLUTION OF GYPSUM 2222 INTRODUCTORY EXAMPLES FOR KINETICS 22221 DEFINING REACTION RATES 22222 BASIC WITHIN PHREEQC 2223 INTRODUCTORY EXAMPLE FOR REACTIVE MASS TRANSPORT 3 EXERCISES 31 EQUILIBRIUM REACTIONS 311 GROUNDWATER - LITHOSPHERE 3111 STANDARD-OUTPUT WELL ANALYSIS 3112 EQUILIBRIUM REACTION - SOLUBILITY OF GYPSUM 3113 DISEQUILIBRIUM REACTION - SOLUBILITY OF GYPSUM 3114 TEMPERATURE DEPENDENCY OF GYPSUM SOLUBILITY IN WELL WATER 3115 TEMPERATURE DEPENDENCY OF GYPSUM SOLUBILITY IN DISTILLED WATER 3116 TEMPERATURE AND P(CO2) DEPENDENT CALCITE SOLUBILITY 3117 CALCITE PRECIPITATION AND DOLOMITE DISSOLUTION 3118 CALCITE SOLUBILITY IN AN OPEN AND A CLOSED SYSTEM 3119 PYRITE WEATHERING 312 ATMOSPHERE – GROUNDWATER – LITHOSPHERE 3121 PRECIPITATION UNDER THE INFLUENCE OF SOIL CO2 3122 BUFFERING SYSTEMS IN THE SOIL 3123 MINERAL PRECIPITATES AT HOT SULFUR SPRINGS 3124 FORMATION OF STALACTITES IN KARST CAVES 3125 EVAPORATION 313 GROUNDWATER 3131 THE PE-PH DIAGRAM FOR THE SYSTEM IRON 3132 THE FE PE-PH DIAGRAM CONSIDERING CARBON AND SULFUR 3133 THE PH DEPENDENCY OF URANIUM SPECIES 314 ORIGIN OF GROUNDWATER 3141 ORIGIN OF SPRING WATER 3142 PUMPING OF FOSSIL GROUNDWATER IN ARID REGIONS 3143 SALT WATER / FRESH WATER INTERFACE 315 ANTHROPOGENIC USE OF GROUNDWATER 3151 SAMPLING: CA TITRATION WITH EDTA 3152 CARBONIC ACID AGGRESSIVENESS 3153 WATER TREATMENT BY AERATION - WELL WATER 3154 WATER TREATMENT BY AERATION - SULFUR SPRING 3155 MIXING OF WATERS 316 REHABILITATION OF GROUNDWATER 3161 REDUCTION OF NITRATE WITH METHANOL 3162 FE(0) BARRIERS 3163 INCREASE IN PH THROUGH A CALCITE BARRIER 32 REACTION KINETICS 321 PYRITE WEATHERING 322 QUARTZ-FELDSPAR-DISSOLUTION 323 DEGRADATION OF ORGANIC MATTER WITHIN THE AQUIFER ON REDUCTION OF REDOX SENSITIVE ELEMENTS (FE, AS, U, CU, MN, S) 324 DEGRADATION OF TRITIUM IN THE UNSATURATED ZONE 33 REACTIVE TRANSPORT 331 LYSIMETER 332 KARST SPRING DISCHARGE 333 KARSTIFICATION (CORROSION ALONG A KARST FRACTURE) 334 THE PH INCREASE OF AN ACID MINE WATER 335 IN-SITU LEACHING 4 SOLUTIONS 41 EQUILIBRIUM REACTIONS 411 GROUNDWATER- LITHOSPHERE 4111 STANDARD-OUTPUT WELL ANALYSIS 4112 EQUILIBRIUM REACTION- SOLUBILITY OF GYPSUM 4113 DISEQUILIBRIUM REACTION – SOLUBILITY OF GYPSUM 4114 TEMPERATURE DEPENDENCY OF GYPSUMSOLUBILITY IN WELL WATER 4115 TEMPERATURE DEPENDENCY OF GYPSUM SOLUBILITY IN DISTILLED WATER 4116 TEMPERATURE AND P(CO2) DEPENDENT CALCITE SOLUBILITY 4117 CALCITE PRECIPITATION AND DOLOMITE DISSOLUTION 4118 COMPARISON OF THE CALCITE SOLUBILITY IN AN OPEN AND A CLOSED SYSTEM 4119 PYRITE WEATHERING 412 ATMOSPHERE – GROUNDWATER – LITHOSPHERE 4121 PRECIPITATION UNDER THE INFLUENCE OF SOIL CO2 4122 BUFFERING SYSTEMS IN THE SOIL 4123 MINERAL PRECIPITATIONS AT HOT SULFUR SPRINGS 4124 FORMATION OF STALACTITES IN KARST CAVES 4125 EVAPORATION 413 GROUNDWATER 4131 THE PE-PH DIAGRAM FOR THE SYSTEM IRON 4132 THE FE PE-PH DIAGRAM CONSIDERING CARBON AND SULFUR 4133 THE PH DEPENDENCY OF URANIUM SPECIES 414 ORIGIN OF GROUNDWATER 4141 ORIGIN OF SPRING WATER 4142 PUMPING OF FOSSIL GROUNDWATER IN ARID REGIONS 4143 SALT WATER / FRESH WATER INTERFACE 415 ANTHROPOGENIC USE OF GROUNDWATER 4151 SAMPLING: CA TITRATION WITH EDTA 4152 CARBONIC ACID AGGRESSIVENESS 4153 WATER TREATMENT BY AERATION - WELL WATER 4154 WATER TREATMENT BY AERATION - SULFUR SPRING 4155 MIXING OF WATERS 416 REHABILITATION OF GROUNDWATER 4161 REDUCTION OF NITRATE WITH METHANOL 4162 FE(0) BARRIERS 4163 INCREASE IN PH THROUGH A CALCITE BARRIER 42 REACTION KINETICS 421 PYRITE WEATHERING 422 QUARTZ-FELDSPAR-DISSOLUTION 423 DEGRADATION OF ORGANIC MATTER WITHIN THE AQUIFER ON REDUCTION OF REDOX SENSITIVE ELEMENTS (FE, AS, U, CU, MN, S) 424 DEGRADATION OF TRITIUM IN THE UNSATURATED ZONE 43 REACTIVE TRANSPORT 431 LYSIMETER 432 KARST SPRING DISCHARGE 433 KARSTIFICATION (CORROSION ALONG A KARST FRACTURE) 434 THE PH INCREASE OF AN ACID MINE WATER 435 IN-SITU LEACHING REFERENCES