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D.L. Parkhurst

Publications and source records attributed to D.L. Parkhurst.

10 recordsLinked to original sources
USGS2011

Modules based on the geochemical model PHREEQC for use in scripting and programming languages

The geochemical model PHREEQC is capable of simulating a wide range of equilibrium reactions between water and minerals, ion exchangers, surface complexes, solid solutions, and gases. It also has a general kinetic formulation that allows modeling of nonequilibrium mineral dissolution and precipitation, microbial reactions, decomposition of organic compounds, and other kinetic reactions. To facilitate use of these reaction capabilities in scripting languages and other models, PHREEQC has been implemented in modules that easily interface with other software. A Microsoft COM (component object model) has been implemented, which allows PHREEQC to be used by any software that can interface with a COM server—for example, Excel®, Visual Basic®, Python, or MATLAB". PHREEQC has been converted to a C++ class, which can be included in programs written in C++. The class also has been compiled in libraries for Linux and Windows that allow PHREEQC to be called from C++, C, and Fortran. A limited set of methods implements the full reaction capabilities of PHREEQC for each module. Input methods use strings or files to define reaction calculations in exactly the same formats used by PHREEQC. Output methods provide a table of user-selected model results, such as concentrations, activities, saturation indices, and densities. The PHREEQC module can add geochemical reaction capabilities to surface-water, groundwater, and watershed transport models. It is possible to store and manipulate solution compositions and reaction information for many cells within the module. In addition, the object-oriented nature of the PHREEQC modules simplifies implementation of parallel processing for reactive-transport models. The PHREEQC COM module may be used in scripting languages to fit parameters; to plot PHREEQC results for field, laboratory, or theoretical investigations; or to develop new models that include simple or complex geochemical calculations.

Computers & Geosciences↗
USGS2004

Calculation of individual isotope equilibrium constants for geochemical reactions

Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc . 562–581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by α = (K ex ) 1/n , where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13 C 16 O 18 O and 1 H 2 H 18 O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO 2g = CO 2aq for all species that can be formed from 12 C, 13 C, 16 O, and 18 O; for the reaction between 12 C 18 O 2aq and 1 H 2 18 O l ; and among the various 1 H, 2 H, 16 O, and 18 O species of H 2 O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H 2 O in the solvent 1 H 2 16 O l , and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO 2 in an acidic aqueous solution.

Geochimica et Cosmochimica Acta↗
USGS1995

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

PHREEQC is a computer program written in the C programming language that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations, (2) reaction-path and advective-transport calculations involving specified irreversible reactions, mixing of solutions, mineral and gas equilibria surface-complex-ation reactions, and ion-exchange reactions, and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for composition differences between waters, within specified compositional uncertainties. PHREEQC is derived from the Fortran program PHREEQE, but it has been completely rewritten in C with the addition many new capabilities. New features include the capabilities to use redox couples to distribute redox elements among their valence states in speciation calculations; to model ion-exchange and surface-complex-ation reactions; to model reactions with a fixed-pressure, multicomponent gas phase (that is, a gas bubble); to calculate the mass of water in the aqueous phase during reaction and transport calculations; to keep track of the moles of minerals present in the solid phases and determine automatically the thermodynamically stable phase assemblage; to simulate advective transport in combination with PHREEQC's reaction-modeling capability; and to make inverse modeling calculations that allow for uncertainties in the analytical data. The user interface is improved through the use of a simplified approach to redox reactions, which includes explicit mole-balance equations for hydrogen and oxygen; the use of a revised input that is modular and completely free format; and the use of mineral names and standard chemical symbolism rather than index numbers. The use of (2) eliminates nearly all limitations on army sizes, including numbers of elements, aqueous species, solutions, phases, and lengths of character strings. A new equation solver that optimizes a set of equalities subject to both equality and inequality constraints is used to determine the thermodynamically stable set of phases in equilibrium with a solution. A more complete Newton-Raphson formulation, master-species switching, and scaling of the algebraic equations reduce the number of failures of the numerical method in PHREEQC relative to PHREEQE. This report presents the equations that are the basis for chemical equilibrium and inverse-modeling calculations in PHREEQC, describes the input for the program, and presents twelve examples that demonstrate most of the program's capabilities.

Water-Resources Investigations Report↗
USGS1988

A computer program incorporating Pitzer's equations for calculation of geochemical reactions in brines

The program named PHRQPITZ is a computer code capable of making geochemical calculations in brines and other electrolyte solutions to high concentrations using the Pitzer virial-coefficient approach for activity-coefficient corrections. Reaction-modeling capabilities include calculation of (1) aqueous speciation and mineral-saturation index, (2) mineral solubility, (3) mixing and titration of aqueous solutions, (4) irreversible reactions and mineral water mass transfer, and (5) reaction path. The computed results for each aqueous solution include the osmotic coefficient, water activity , mineral saturation indices, mean activity coefficients, total activity coefficients, and scale-dependent values of pH, individual-ion activities and individual-ion activity coeffients , and scale-dependent values of pH, individual-ion activities and individual-ion activity coefficients. A data base of Pitzer interaction parameters is provided at 25 C for the system: Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O, and extended to include largely untested literature data for Fe(II), Mn(II), Sr, Ba, Li, and Br with provision for calculations at temperatures other than 25C. An extensive literature review of published Pitzer interaction parameters for many inorganic salts is given. Also described is an interactive input code for PHRQPITZ called PITZINPT. (USGS)

Water-Resources Investigations Report↗
USGS1987

Ground-water quality assessment of the central Oklahoma Aquifer, Oklahoma; project description

In April 1986, the U.S. Geological Survey began a pilot program to assess the quality of the Nation's surface-water and ground-water resources. The program, known as the National Water-Quality Assessment (NAWQA) program, is designed to acquire and interpret information about a variety of water-quality issues. The Central Oklahoma aquifer project is one of three ground-water pilot projects that have been started. The NAWQA program also incudes four surface-water pilot projects. The Central Oklahoma aquifer project, as part of the pilot NAWQA program, will develop and test methods for performing assessments of ground-water quality. The objectives of the Central Oklahoma aquifer assessment are: (1) To investigate regional ground-water quality throughout the aquifer in the manner consistent with the other pilot ground-water projects, emphasizing the occurrence and distribution of potentially toxic substances in ground water, including trace elements, organic compounds, and radioactive constituents; (2) to describe relations between ground-water quality, land use, hydrogeology, and other pertinent factors; and (3) to provide a general description of the location, nature, and possible causes of selected prevalent water-quality problems within the study unit; and (4) to describe the potential for water-quality degradation of ground-water zones within the study unit. The Central Oklahoma aquifer, which includes in descending order the Garber Sandstone and Wellington Formation, the Chase Group, the Council Grove Group, the Admire Group, and overlying alluvium and terrace deposits, underlies about 3,000 square miles of central Oklahoma and is used extensively for municipal, industrial, commercial, and domestic water supplies. The aquifer was selected for study by the NAWQA program because it is a major source for water supplies in central Oklahoma and because it has several known or suspected water-quality problems. Known problems include concentrations of arsenic, chromium, selenium, and gross-alpha activity that exceed drinking-water standards. Suspected problems include possible contamination of the aquifer by oil-field brines and drilling fluids, pesticides, industrial chemicals, septic-tank effluent, fertilizers, and leakage from sewage systems and underground tanks used for storage of hydrocarbons. There are four major components of the Central Oklahoma aquifer project. The first component is the collection and analysis of existing information, including chemical, hydrologic, and land-use data. The second component is the geohydrologic and geochemical investigations of the aquifer flow system. The third component is the sampling for a wide variety of inorganic, organic, and radioactive constituents as part a regional survey that will produce a consistent set of data among all ground-water pilot projects. These data can be used to: (1) Define regional ground-water quality within the Central Oklahoma aquifer, and (2) compare water quality in the Central Oklahoma aquifer to the water quality in the other ground-water study units of the NAWQA program. The fourth component is topical studies that will address, in more detail, some of the major water-quality issues pertaining to the aquifer.

Open-File Report↗
USGS1984

Methods for the collection of geochemical data from the sediments of the tidal Potomac River and estuary and data for 1978-1980

The chemical composition of bottom sediments and their associated pore waters from the tidal Potomac River and Estuary was studied from May 1978 through June 1980. Pore waters were routinely analyzed for pH, Eh, alkalinity, and concentrations of sulfide, sulfate, phosphate, carbon, ammonium, silica, iron, manganese, chloride, sodium, potassium, calcium, and magnesium. Porosity, weight loss on ignition, and carbon, nitrogen, and phosphorus contents were determined for the solid sediments. The range of salinity and chemical composition encountered in the estuary frequently necessitated modifications of standard methods of analysis. Therefore, the methods used, their modifications, and their limitations are presented in some detail. The appendix lists the data obtained from six sampling periods. (USGS)

Open-File Report↗
USGS1983

Development of reaction models for ground-water systems

Methods are described for developing geochemical reaction models from the observed chemical compositions of ground water along a hydrologic flow path. The roles of thermodynamic speciation programs, mass balance calculations, and reaction-path simulations in developing and testing reaction models are contrasted. Electron transfer is included in the mass balance equations to properly account for redox reactions in ground water. The mass balance calculations determine net mass transfer models which must be checked against the thermodynamic calculations of speciation and reaction-path programs. Although reaction-path simulations of ground-water chemistry are thermodynamically valid, they must be checked against the net mass transfer defined by the mass balance calculations. An example is given testing multiple reaction hypotheses along a flow path in the Floridan aquifer where several reaction models are eliminated. Use of carbon and sulfur isotopic data with mass balance calculations indicates a net reaction of incongruent dissolution of dolomite (dolomite dissolution with calcite precipitation) driven irreversibly by gypsum dissolution, accompanied by minor sulfate reduction, ferric hydroxide dissolution, and pyrite precipitation in central Florida. Along the flow path, the aquifer appears to be open to CO 2 initially, and open to organic carbon at more distant points down gradient.

Geochimica et Cosmochimica Acta↗
USGS1983

Authigenic vivianite in Potomac River sediments: control by ferric oxy-hydroxides

Sand-size particles of vivianite (Fe 3 (PO 4 ) 2 .8H 2 O) have been identified in surficial sediments of the tidal Potomac River near a major sewage treatment plant. Vivianite is concentrated in a surface layer of coarse-sand dredge spoil, which overlies much finer sediment. Although saturation indices indicate that the pore waters of virtually all the sediments in the study area are supersaturated with respect to vivianite, it is found only in association with dredge spoil. Pore-water profiles of Fe, P, and Eh, and the size and morphology of individual grains, indicate that the vivianite is authigenic. The major control on the occurrence of the mineral is the presence or absence of amorphous ferric oxy-hydroxides, which react with pore-water phosphorus to form stable ferric hydroxy-phosphates preferentially to the formation of vivianite.--Modified journal abstract.

Journal of Sedimentary Petrology↗