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

In the U.S., about 44 million people rely on self-supplied groundwater for drinking water. Because most self-supplied homeowners do not treat their water to control corrosion, drinking water can be susceptible to lead (Pb) contamination from metal plumbing. To assess the types and locations of susceptible groundwater, a geochemical reaction model that included pure Pb minerals and solid solutions of calcite (Ca xPb1- xCO3) and apatite [Ca xPb5-x(PO4)3(OH; Cl; F)] was developed to estimate the lead solubility potential (LSP) for over 8300 untreated groundwater samples collected from domestic and public-supply sites between 2000 and 2016 in the U.S. The LSP is the calculated amount of Pb metal that could dissolve at 25 °C before a Pb-bearing mineral precipitates. About 33% of untreated groundwater samples had LSP greater than 15 μg/L-the USEPA action level for dissolved plus particulate forms of Pb. Five percent of samples had high LSP (above 300 μg/L) and tended to occur in the eastern and southeastern U.S. Measured Pb concentrations above 15 μg/L were rarely detected (<1%) but always coincided with high LSP values. Future work will provide a better understanding of the relation between water chemistry, Pb-mineral formation, and dissolved Pb concentrations in tap water.

Assessing the Lead Solubility Potential of Untreated Groundwater of the United States.

Hydrologic and geochemical evaluation of aquifer storage recovery in the Santee Limestone/Black Mingo Aquifer, Charleston, South Carolina, 1998-2002

Brackish groundwater (BGW) is increasingly used for water supplies where fresh water is scarce, but the distribution and availability of such resources have not been characterized at the national scale in the United States since the 1960s. Apart from its distribution and accessibility, BGW usability is a function of the chemical requirements of the intended use, chemical characteristics of the resource, and treatment options to make the resource compatible with the use. Here, we discuss relations between these three chemical factors using national-scale examples and local case studies. In a preliminary compilation of BGW data in the United States, five water types accounted for the major-ion composition of 70% of samples. PHREEQC calculations indicate that 57-77% of samples were oversaturated with respect to barite, calcite, or chalcedony. In the study, 5-14% of samples had concentrations of arsenic, fluoride, nitrate, or uranium that exceeded drinking-water standards. In case studies of the potential use of BGW for drinking water, irrigation, and hydraulic fracturing, PHREEQC simulations of a hypothetical treatment process resembling reverse osmosis (RO) showed that BGW had the potential to form various assemblages of mineral deposits (scale) during treatment that could adversely affect RO membranes. Speciation calculations showed that most boron in the irrigation example occurred as boric acid, which has relatively low removal efficiency by RO. Results of this preliminary study indicate that effective national or regional assessments of BGW resources should include geochemical characterizations that are guided in part by specific use and treatment requirements.

Chemical Considerations for an Updated National Assessment of Brackish Groundwater Resources.

Gross-beta activity in ground water: natural sources and artifacts of sampling and laboratory analysis

Alkaline chemicals are commonly added to discharges from coal mines to increase pH and decrease concentrations of acidity and dissolved aluminum, iron, manganese, and associated metals. The annual cost of chemical treatment depends on the type and quantities of chemicals added and sludge produced. The AMDTreat computer program, initially developed in 2003, is widely used to compute such costs on the basis of the user-specified flow rate and water quality data for the untreated AMD. Although AMDTreat can use results of empirical titration of net-acidic or net-alkaline effluent with caustic chemicals to accurately estimate costs for treatment, such empirical data are rarely available. A titration simulation module using the geochemical program PHREEQC has been incorporated with AMDTreat 5.0+ to improve the capability of AMDTreat to estimate: (1) the quantity and cost of caustic chemicals to attain a target pH, (2) the chemical composition of the treated effluent, and (3) the volume of sludge produced by the treatment. The simulated titration results for selected caustic chemicals (NaOH, CaO, Ca(OH)2, Na2CO3, or NH3) without aeration or with pre-aeration can be compared with or used in place of empirical titration data to estimate chemical quantities, treated effluent composition, sludge volume (precipitated metals plus unreacted chemical), and associated treatment costs. This paper describes the development, evaluation, and potential utilization of the PHREEQC titration module with the new AMDTreat 5.0+ computer program available at http://www.amd.osmre.gov/
 .

David L. Parkhurst

Papers

Assessing the Lead Solubility Potential of Untreated Groundwater of the United States.

Hydrologic and geochemical evaluation of aquifer storage recovery in the Santee Limestone/Black Mingo Aquifer, Charleston, South Carolina, 1998-2002

Chemical Considerations for an Updated National Assessment of Brackish Groundwater Resources.

Gross-beta activity in ground water: natural sources and artifacts of sampling and laboratory analysis

AMDTreat 5.0+ with PHREEQC titration module to compute caustic chemical quantity, effluent quality, and sludge volume