PHREEQC version 2 is a computer program written in the C programming language that is designed to perform a wide variety of low-temperature aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations; (2) batch-reaction and onedimensional (1D) transport calculations involving reversible reactions, which include aqueous, mineral, gas, solidsolution, surface-complexation, and ion-exchange equilibria, and irreversible reactions, which include specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and temperature changes; and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for differences in composition between waters, within specified compositional uncertainty limits. New features in PHREEQC version 2 relative to version 1 include capabilities to simulate dispersion (or diffusion) and stagnant zones in 1D-transport calculations, to model kinetic reactions with user-defined rate expressions, to model the formation or dissolution of ideal, multicomponent or nonideal, binary solid solutions, to model fixed-volume gas phases in addition to fixed-pressure gas phases, to allow the number of surface or exchange sites to vary with the dissolution or precipitation of minerals or kinetic reactants, to include isotope mole balances in inverse modeling calculations, to automatically use multiple sets of convergence parameters, to print user-defined quantities to the primary output file and (or) to a file suitable for importation into a spreadsheet, and to define solution compositions in a format more compatible with spreadsheet programs. This report presents the equations that are the basis for chemical equilibrium, kinetic, transport, and inverse modeling calculations in PHREEQC; describes the input for the program; and presents examples that demonstrate most of the program's capabilities.

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User's guide to PHREEQC (Version 2)-a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

Verification and validation of numerical models of natural systems is impossible. This is because natural systems are never closed and because model results are always nonunique. Models can be confirmed by the demonstration of agreement between observation and prediction, but confirmation is inherently partial. Complete confirmation is logically precluded by the fallacy of affirming the consequent and by incomplete access to natural phenomena. Models can only be evaluated in relative terms, and their predictive value is always open to question. The primary value of models is heuristic.

https://science.sciencemag.org/content/sci/263/5147/641.full.pdf

Verification, Validation, and Confirmation of Numerical Models in the Earth Sciences

CHAPTER 1. INTRODUCTION TO KARST. 1.1 Definitions. 1.2 The Relationship Between Karst And General Geomorphology And Hydrogeology. 1.3 The Global Distribution Of Karst. 1.4 The Growth Of Ideas. 1.5 Aims Of The Book. 1.6 Karst Terminology. CHAPTER 2. THE KARST ROCKS. 2.1 Carbonate Rocks And Minerals. 2.2 Limestone Compositions And Depositional Facies. 2.3 Limestone Diagenesis And The Formation Of Dolomite. 2.4 The Evaporite Rocks. 2.5. Quartzites And Siliceous Sandstones. 2.6 Effects Of Lithologic Properties Upon Karst Development. 2.7 Interbedded Clastic Rocks. 2.8 Bedding Planes, Joints, Faults And Fracture Traces. 2.9 Fold Topography. 2.10 Paleokarst Unconformities. CHAPTER 3. DISSOLUTION: CHEMICAL AND KINETIC BEHAVIOUR OF THE KARST ROCKS. 3.1 Introduction. 3.2 Aqueous Solutions And Chemical Equilibria. 3.3 The Dissolution Of Anhydrite, Gypsum And Salt. 3.4 The Dissolution Of Silica. 3.5 Bicarbonate Equilibria And The Dissolution Of Carbonate Rocks In Normal Meteoric Waters. 3.6 The S-O-H System And The Dissolution Of Carbonate Rocks. 3.7 Chemical Complications In Carbonate Dissolution. 3.8 Biokarst Processes. 3.9 Measurements In The Field And Lab Computer Programs. 3.10 Dissolution And Precipitation Kinetics Of Karst Rocks. CHAPTER 4. DISTRIBUTION AND RATE OF KARST DENUDATION. 4.1 Global Variations In The Solutional Denudation Of Carbonate Terrains. 4.2 Measurement And Calculation Of Solutional Denudation Rates. 4.3 Solution Rates In Gypsum, Salt And Other Non-Carbonate Rocks. 4.4 Interpretation Of Measurements. CHAPTER 5. KARST HYDROLOGY. 5.1 Basic Hydrological Concepts, Terms And Definitions. 5.2 Controls On The Development Of Karst Hydrologic Systems. 5.3 Energy Supply And Flow Network Development. 5.4 Development Of The Water Table And Phreatic Zones. 5.5 Development Of The Vadose Zone. 5.6 Classification And Characteristics Of Karst Aquifers. 5.7 Applicability Of Darcy's Law To Karst. 5.8 The Fresh Water/Salt Water Interface. CHAPTER 6. ANALYSIS OF KARST DRAINAGE SYSTEMS. 6.1 The 'Grey Box' Nature Of Karst. 6.2 Surface Exploration And Survey Techniques. 6.3 Investigating Recharge And Percolation In The Vadose Zone. 6.4 Borehole Analysis. 6.5 Spring Hydrograph Analysis. 6.6 Polje Hydrograph Analysis. 6.7 Spring Chemograph Interpretation. 6.8 Storage Volumes And Flow Routing Under Different States Of The Hydrograph. 6.9 Interpreting The Organisation Of A Karst Aquifer. 6.10 Water Tracing Techniques. 6.11 Computer Modelling Of Karst Aquifers. CHAPTER 7. SPELEOGENESIS: THE DEVELOPMENT OF CAVE SYSTEMS. 7.1 Classifying Cave Systems. 7.2 Building The Plan Patterns Of Unconfined Caves. 7.3 Unconfined Cave Development In Length And Depth. 7.4 System Modifications Occurring Within A Single Phase. 7.5 Multi-Phase Cave Systems. 7.6 Meteoric Water Caves Developed Where There Is Confined Circulation Or Basal Injection Of Water. 7.7 Hypogene Caves: (A) Hydrothermal Caves Associated Chiefly With Co2. 7.8 Hypogene Caves: (B) Caves Formed By Waters Containing H2s. 7.9 Sea Coast Eogenetic Caves. 7.10 Passage Cross-Sections And Smaller Features Of Erosional Morphology. 7.11 Condensation, Condensation Corrosion, And Weathering In Caves. 7.12 Breakdown In Caves. CHAPTER 8. CAVE INTERIOR DEPOSITS. 8.1 Introduction. 8.2 Clastic Sediments. 8.3 Calcite, Aragonite And Other Carbonate Precipitates. 8.4 Other Cave Minerals. 8.5 Ice In Caves. 8.6 Dating Of Calcite Speleothems And Other Cave Deposits. 8.7 Paleo-Environmental Analysis Of Calcite Speleothems. 8.8 Mass Flux Through A Cave System: The Example Of Friar's Hole, W.Va. CHAPTER 9. KARST LANDFORM DEVELOPMENT IN HUMID REGIONS. 9.1 Coupled Hydrological And Geochemical Systems. 9.2 Small Scale Solution Sculpture - Microkarren And Karren. 9.3 Dolines - The 'Diagnostic' Karst Landform? 9.4 The Origin And Development Of Solution Dolines. 9.5 The Origin Of Collapse And Subsidence Depressions. 9.6 Polygonal Karst. 9.7 Morphometric Analysis Of Solution Dolines. 9.8 Landforms Associated With Allogenic Inputs. 9.9 Karst Poljes. 9.10 Corrosional Plains And Shifts In Baselevel. 9.11 Residual Hills On Karst Plains. 9.12 Depositional And Constructional Karst Features. 9.13 Special Features Of Evaporite Terrains. 9.14 Karstic Features Of Quartzose And Other Rocks. 9.15 Sequences Of Carbonate Karst Evolution In Humid Terrains. CHAPTER 10.THE INFLUENCE OF CLIMATE, CLIMATIC CHANGE AND OTHER ENVIRONMENTAL FACTORS ON KARST DEVELOPMENT. 10.1 The Precepts Of Climatic Geomorphology. 10.2 The Hot Arid Extreme. 10.3 The Cold Extreme: 1 Karst Development In Glaciated Terrains. 10.4 The Cold Extreme: 2 Karst Development In Permafrozen Terrains. 10.5 Sea Level Changes, Tectonic Movement And Implications For Coastal Karst Development. 10.6 Polycyclic, Polygenetic And Exhumed Karsts. CHAPTER 11. KARST WATER RESOURCES MANAGEMENT. 11.1 Water Resources And Sustainable Yields. 11.2 Determination Of Available Water Resources. 11.3 Karst Hydrogeological Mapping. 11.4 Human Impacts On Karst Water. 11.5 Groundwater Vulnerability, Protection, And Risk Mapping. 11.6 Dam Building, Leakages, Failures And Impacts. CHAPTER 12. HUMAN IMPACTS AND ENVIRONMENTAL REHABILITATION. 12.1 The Inherent Vulnerability Of Karst Systems. 12.2 Deforestation, Agricultural Impacts And Rocky Desertification. 12.3 Sinkholes Induced By De-Watering, Surcharging, Solution Mining And Other Practices On Karst. 12.4 Problems Of Construction On And In The Karst Rocks - Expect The Unexpected! 12.5 Industrial Exploitation Of Karst Rocks And Minerals. 12.6 Restoration Of Karstlands And Rehabilitation Of Limestone Quarries. 12.7 Sustainable Management Of Karst. 12.8 Scientific, Cultural And Recreational Values Of Karstlands.

Karst Hydrogeology and Geomorphology

The attention of environmental decision makers is increasingly being focused on the movement of pollutants into ground water. Of particular importance is the transport and speciation of metals. The MINTEQA2 model is a versatile, quantitative tool for predicting the equilibrium behavior of metals in a variety of chemical environments. MINTEQA2 is a geochemical speciation model capable of computing equilibria among the dissolved, adsorbed, solid, and gas phases in an environmental setting. MINTEQA2 includes an extensive database of reliable thermodynamic data that is also accessible to PRODEFA2, an interactive program designed to be executed prior to MINTEQA2 for the purpose of creating the required MINTEQA2 input file. The report describes how to use the MINTEQA2 model. The chemical and mathematical structure of MINTEQA2 and the structure of the database files also are described. The use of both PRODEFA2 and MINTEQA2 are illustrated through the presentation of an example PRODEFA2 dialogue reproduced from interactive sessions and the presentation of MINTEQA2 output files and error diagnostics. The content and format of database files also are explained.

MINTEQA2/PRODEFA2, a geochemical assessment model for environmental systems: Version 3. 0 user's manual

The solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O

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Description of Input and Examples for PHREEQC Version 3?A Computer Program for Speciation, Batch-Reaction, One-Dimensional Transport, and Inverse Geochemical Calculations

The kinetics of calcite dissolution in CO 2 -water systems at 5 degrees to 60 degrees C and 0.0 to 1.0 atm CO 2

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User's guide to phreeqc a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations

From abstract: This report "presents PHREEQE, a Fortran IV computer program designed to mode1 geochemical reactions and calculate pH, redox potential, and mass transfer as a function of reaction progress "It contains tables and other figures

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David L. Parkhurst

Papers

User's guide to PHREEQC (Version 2)-a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

Description of Input and Examples for PHREEQC Version 3?A Computer Program for Speciation, Batch-Reaction, One-Dimensional Transport, and Inverse Geochemical Calculations

The kinetics of calcite dissolution in CO 2 -water systems at 5 degrees to 60 degrees C and 0.0 to 1.0 atm CO 2

User's guide to phreeqc a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations

Phreeqe--A Computer Program for Geochemical Calculations