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David L. Parkhurst

Publications and source records attributed to David L. Parkhurst.

At least 19 recordsLinked to original sources

Assessing the lead solubility potential of untreated groundwater of the United States

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 x Pb 1– x CO 3 ) and apatite [Ca x Pb 5-x (PO 4 ) 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.

Environmental Science & Technology

VS2DRTI: Simulating heat and reactive solute transport in variably saturated porous media

Variably saturated groundwater flow, heat transport, and solute transport are important processes in environmental phenomena, such as the natural evolution of water chemistry of aquifers and streams, the storage of radioactive waste in a geologic repository, the contamination of water resources from acid-rock drainage, and the geologic sequestration of carbon dioxide. Up to now, our ability to simulate these processes simultaneously with fully coupled reactive transport models has been limited to complex and often difficult-to-use models. To address the need for a simple and easy-to-use model, the VS2DRTI software package has been developed for simulating water flow, heat transport, and reactive solute transport through variably saturated porous media. The underlying numerical model, VS2DRT, was created by coupling the flow and transport capabilities of the VS2DT and VS2DH models with the equilibrium and kinetic reaction capabilities of PhreeqcRM. Flow capabilities include two-dimensional, constant-density, variably saturated flow; transport capabilities include both heat and multicomponent solute transport; and the reaction capabilities are a complete implementation of geochemical reactions of PHREEQC. The graphical user interface includes a preprocessor for building simulations and a postprocessor for visual display of simulation results. To demonstrate the simulation of multiple processes, the model is applied to a hypothetical example of injection of heated waste water to an aquifer with temperature-dependent cation exchange. VS2DRTI is freely available public domain software.

Groundwater

Water, Energy, and Biogeochemical Model (WEBMOD), user’s manual, version 1

The Water, Energy, and Biogeochemical Model (WEBMOD) uses the framework of the U.S. Geological Survey (USGS) Modular Modeling System to simulate fluxes of water and solutes through watersheds. WEBMOD divides watersheds into model response units (MRU) where fluxes and reactions are simulated for the following eight hillslope reservoir types: canopy; snowpack; ponding on impervious surfaces; O-horizon; two reservoirs in the unsaturated zone, which represent preferential flow and matrix flow; and two reservoirs in the saturated zone, which also represent preferential flow and matrix flow. The reservoir representing ponding on impervious surfaces, currently not functional (2016), will be implemented once the model is applied to urban areas. MRUs discharge to one or more stream reservoirs that flow to the outlet of the watershed. Hydrologic fluxes in the watershed are simulated by modules derived from the USGS Precipitation Runoff Modeling System; the National Weather Service Hydro-17 snow model; and a topography-driven hydrologic model (TOPMODEL). Modifications to the standard TOPMODEL include the addition of heterogeneous vertical infiltration rates; irrigation; lateral and vertical preferential flows through the unsaturated zone; pipe flow draining the saturated zone; gains and losses to regional aquifer systems; and the option to simulate baseflow discharge by using an exponential, parabolic, or linear decrease in transmissivity. PHREEQC, an aqueous geochemical model, is incorporated to simulate chemical reactions as waters evaporate, mix, and react within the various reservoirs of the model. The reactions that can be specified for a reservoir include equilibrium reactions among water; minerals; surfaces; exchangers; and kinetic reactions such as kinetic mineral dissolution or precipitation, biologically mediated reactions, and radioactive decay. WEBMOD also simulates variations in the concentrations of the stable isotopes deuterium and oxygen-18 as a result of varying inputs, mixing, and evaporation. This manual describes the WEBMOD input and output files, along with the algorithms and procedures used to simulate the hydrology and water quality in a watershed. Examples are presented that demonstrate hydrologic processes, weathering reactions, and isotopic evolution in an alpine watershed and the effect of irrigation on water flows and salinity in an intensively farmed agricultural area.

Techniques and Methods

Chemical considerations for an updated National assessment of brackish groundwater resources

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&ndash;77% of samples were oversaturated with respect to barite, calcite, or chalcedony. In the study, 5&ndash;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.

Groundwater

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

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/.

Mine Water and the Environment

Description of input and examples for PHREEQC version 3: A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

PHREEQC version 3 is a computer program written in the C and C++ programming languages that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC implements several types of aqueous models: two ion-association aqueous models (the Lawrence Livermore National Laboratory model and WATEQ4F), a Pitzer specific-ion-interaction aqueous model, and the SIT (Specific ion Interaction Theory) aqueous model. Using any of these aqueous models, PHREEQC has capabilities for (1) speciation and saturation-index calculations; (2) batch-reaction and one-dimensional (1D) transport calculations with reversible and irreversible reactions, which include aqueous, mineral, gas, solid-solution, surface-complexation, and ion-exchange equilibria, and specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and pressure 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. Many new modeling features were added to PHREEQC version 3 relative to version 2. The Pitzer aqueous model ( pitzer.dat database, with keyword PITZER ) can be used for high-salinity waters that are beyond the range of application for the Debye-Hückel theory. The Peng-Robinson equation of state has been implemented for calculating the solubility of gases at high pressure. Specific volumes of aqueous species are calculated as a function of the dielectric properties of water and the ionic strength of the solution, which allows calculation of pressure effects on chemical reactions and the density of a solution. The specific conductance and the density of a solution are calculated and printed in the output file. In addition to Runge-Kutta integration, a stiff ordinary differential equation solver (CVODE) has been included for kinetic calculations with multiple rates that occur at widely different time scales. Surface complexation can be calculated with the CD-MUSIC (Charge Distribution MUltiSIte Complexation) triple-layer model in addition to the diffuse-layer model. The composition of the electrical double layer of a surface can be estimated by using the Donnan approach, which is more robust and faster than the alternative Borkovec-Westall integration. Multicomponent diffusion, diffusion in the electrostatic double layer on a surface, and transport of colloids with simultaneous surface complexation have been added to the transport module. A series of keyword data blocks has been added for isotope calculations— ISOTOPES, CALCULATE_VALUES, ISOTOPE_ALPHAS, ISOTOPE_RATIOS, and NAMED_EXPRESSIONS . Solution isotopic data can be input in conventional units (for example, permil, percent modern carbon, or tritium units) and the numbers are converted to moles of isotope by PHREEQC. The isotopes are treated as individual components (they must be defined as individual master species) so that each isotope has its own set of aqueous species, gases, and solids. The isotope-related keywords allow calculating equilibrium fractionation of isotopes among the species and phases of a system. The calculated isotopic compositions are printed in easily readable conventional units. New keywords and options facilitate the setup of input files and the interpretation of the results. Keyword data blocks can be copied (keyword COPY ) and deleted (keyword DELETE ). Keyword data items can be altered by using the keyword data blocks with the _MODIFY extension and a simulation can be run with all reactants of a given index number (keyword RUN_CELLS ). The definition of the complete chemical state of all reactants of PHREEQC can be saved in a file in a raw data format ( DUMP and _RAW keywords). The file can be read as part of another input file with the INCLUDE$ keyword. These keywords facilitate the use of IPhreeqc, which is a module implementing all PHREEQC version 3 capabilities; the module is designed to be used in other programs that need to implement geochemical calculations; for example, transport codes. Charting capabilities have been added to some versions of PHREEQC. Charting capabilities have been added to Windows distributions of PHREEQC version 3. (Charting on Linux requires installation of Wine.) The keyword data block USER_GRAPH allows selection of data for plotting and manipulation of chart appearance. Almost any results from geochemical simulations (for example, concentrations, activities, or saturation indices) can be retrieved by using Basic language functions and specified as data for plotting in USER_GRAPH . Results of transport simulations can be plotted against distance or time. Data can be added to a chart from tab-separated-values files. All input for PHREEQC version 3 is defined in keyword data blocks, each of which may have a series of identifiers for specific types of data. This report provides a complete description of each keyword data block and its associated identifiers. Input files for 22 examples that demonstrate most of the capabilities of PHREEQC version 3 are described and the results of the example simulations are presented and discussed.

Techniques and Methods

Phast4Windows: A 3D graphical user interface for the reactive-transport simulator PHAST

Phast4Windows is a Windows® program for developing and running groundwater-flow and reactive-transport models with the PHAST simulator. This graphical user interface allows definition of grid-independent spatial distributions of model properties—the porous media properties, the initial head and chemistry conditions, boundary conditions, and locations of wells, rivers, drains, and accounting zones—and other parameters necessary for a simulation. Spatial data can be defined without reference to a grid by drawing, by point-by-point definitions, or by importing files, including ArcInfo® shape and raster files. All definitions can be inspected, edited, deleted, moved, copied, and switched from hidden to visible through the data tree of the interface. Model features are visualized in the main panel of the interface, so that it is possible to zoom, pan, and rotate features in three dimensions (3D). PHAST simulates single phase, constant density, saturated groundwater flow under confined or unconfined conditions. Reactions among multiple solutes include mineral equilibria, cation exchange, surface complexation, solid solutions, and general kinetic reactions. The interface can be used to develop and run simple or complex models, and is ideal for use in the classroom, for analysis of laboratory column experiments, and for development of field-scale simulations of geochemical processes and contaminant transport.

Groundwater

Simulated flow of groundwater and brine from a flooded salt mine in Livingston County, New York, and effects of remedial pumping on an overlying aquifer

Two ceiling collapses in the Retsof salt mine near Geneseo in upstate New York in spring 1994 resulted in the upward propagation of two columns of rubble through 600 feet of overlying shale and carbonate bedrock. This upward propagation formed a hydraulic connection between the lower confined aquifer (LCA) and the mine and allowed water from the aquifer and bedrock fracture zones that intersected the rubble columns to flow into the mine at a rate of 18,000 gallons per minute (gal/min) . All salt mining ceased in September 1995, and the mine was completely flooded by January 1996. The flow of water from the lower confined aquifer into the mine caused widespread drawdowns, and water levels in the aquifer declined by as much as 400 feet near the collapse area and by more than 50 feet at wells 7 miles to the north and south. Within 3 to 4 weeks of the collapses, water levels in about a dozen domestic and industrial wells had declined severely, and some wells went dry. Water levels in at least 58 wells in the lower and middle confined aquifers were affected by mine flooding. Groundwater in the upper unconfined aquifer and surface water in streams were unaffected by water-level drawdown, but channels of the Genesee River and Beards Creek were altered by land subsidence related to the mine collapse. Water levels recovered from 1996 through 2006, but the mine is now filled with about 15 billion gallons of saturated halite brine. The weight of the overlying rock and sediment is expected to cause the salt beds to deform and fill the mine cavity during the next several hundred years; this in turn could displace as much as 80 percent of the brine and cause it to move upward through the rubble chimneys, rendering the LCA unusable as a source of water supply. Saline water was detected in the LCA in 2002 but was found to be derived primarily from fractures in the limestone and shale units between the mine and the LCA, rather than from the mine. In September 2006, the mine company began a brine-mitigation project that entailed pumping five wells finished in limestone and shale units within the collapse areas to alter the flow gradient and thereby prevent further movement of brine and saline water into the LCA. The pumped brine was routed to an onsite desalination plant. At the same time, the U.S. Geological Survey (USGS) began a study in cooperation with the New York State Office of the Attorney General to construct numerical models to analyze the groundwater chemistry and delineate the directions of flow. Specific objectives of the study were to: * Assess the sources of salinity within the collapse area and identify the factors that control the movement and mixing of freshwater, saline waters from fracture zones, and brine; * Evaluate the likelihood that the pumping will induce anhydrite dissolution and lead to continued land subsidence; * Construct variable-density groundwater flow models to predict the effect of remedial pumping on salinity within the LCA; * Evaluate the effectiveness of remedial pumping in preventing the movement of saline water into the LCA; and * Predict the extent of brine migration 8 years after a hypothetical shutdown of all pumping in 2008. This report (1) summarizes the hydrogeologic setting and effects of mine flooding, (2) describes the geochemical and variable-density model simulations and their principal results, (3) discusses the implications of (a) continued pumping and desalination to protect the LCA and (b) a full shutdown of pumping after 2008, and (4) suggests further research that could lead to refinement of model predictions. Additional information may be found in Yager and others (2001 and 2009). These reports can be accessed at http://pubs.usgs.gov/pp/pp1611/ and http://pubs.usgs.gov/pp/pp1767/, respectively. A summary of simulation results can be accessed at http://ny.water.usgs.gov/projects/Coram/seawat/seawat.html.

New York

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&mdash;for example, Excel&reg;, Visual Basic&reg;, 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

Programming PHREEQC calculations with C++ and Python a comparative study

The new IPhreeqc module provides an application programming interface (API) to facilitate coupling of other codes with the U.S. Geological Survey geochemical model PHREEQC. Traditionally, loose coupling of PHREEQC with other applications required methods to create PHREEQC input files, start external PHREEQC processes, and process PHREEQC output files. IPhreeqc eliminates most of this effort by providing direct access to PHREEQC capabilities through a component object model (COM), a library, or a dynamically linked library (DLL). Input and calculations can be specified through internally programmed strings, and all data exchange between an application and the module can occur in computer memory. This study compares simulations programmed in C++ and Python that are tightly coupled with IPhreeqc modules to the traditional simulations that are loosely coupled to PHREEQC. The study compares performance, quantifies effort, and evaluates lines of code and the complexity of the design. The comparisons show that IPhreeqc offers a more powerful and simpler approach for incorporating PHREEQC calculations into transport models and other applications that need to perform PHREEQC calculations. The IPhreeqc module facilitates the design of coupled applications and significantly reduces run times. Even a moderate knowledge of one of the supported programming languages allows more efficient use of PHREEQC than the traditional loosely coupled approach.

Conference Paper

A geochemical module for "AMDTreat" to compute caustic quantity, effluent quantity, and sludge volume

Treatment with caustic chemicals typically is used to increase pH and decrease concentrations of dissolved aluminum, iron, and/or manganese in largevolume, metal-laden discharges from active coal mines. Generally, aluminum and iron can be removed effectively at near-neutral pH (6 to 8), whereas active manganese removal requires treatment to alkaline pH (~10). The treatment cost depends on the specific chemical used (NaOH, CaO, Ca(OH) 2 , Na 2 CO 3 , or NH 3 ) and increases with the quantities of chemical added and sludge produced. The pH and metals concentrations do not change linearly with the amount of chemical added. Consequently, the amount of caustic chemical needed to achieve a target pH and the corresponding effluent composition and sludge volume can not be accurately determined without empirical titration data or the application of geochemical models to simulate the titration of the discharge water with caustic chemical(s). The AMDTreat computer program (http://amd.osmre.gov/ ) is widely used to compute costs for treatment of coal-mine drainage. Although AMDTreat can use results of empirical titration with industrial grade caustic chemicals to compute chemical costs for treatment of net-acidic or net-alkaline mine drainage, such data are rarely available. To improve the capability of AMDTreat to estimate (1) the quantity and cost of caustic chemicals to attain a target pH, (2) the concentrations of dissolved metals in treated effluent, and (3) the volume of sludge produced by the treatment, a titration simulation is being developed using the geochemical program PHREEQC (wwwbrr.cr.usgs.gov/projects/GWC_coupled/phreeqc/) that will be coupled as a module to AMDTreat. The simulated titration results can be compared with or used in place of empirical titration data to estimate chemical quantities and costs. This paper describes the development, evaluation, and potential utilization of the PHREEQC titration module for AMDTreat.

Pennsylvania

PHAST version 2-A program for simulating groundwater flow, solute transport, and multicomponent geochemical reactions

The computer program PHAST (PHREEQC And HST3D) simulates multicomponent, reactive solute transport in three-dimensional saturated groundwater flow systems. PHAST is a versatile groundwater flow and solute-transport simulator with capabilities to model a wide range of equilibrium and kinetic geochemical reactions. The flow and transport calculations are based on a modified version of HST3D that is restricted to constant fluid density and constant temperature. The geochemical reactions are simulated with the geochemical model PHREEQC, which is embedded in PHAST. Major enhancements in PHAST Version 2 allow spatial data to be defined in a combination of map and grid coordinate systems, independent of a specific model grid (without node-by-node input). At run time, aquifer properties are interpolated from the spatial data to the model grid; regridding requires only redefinition of the grid without modification of the spatial data. PHAST is applicable to the study of natural and contaminated groundwater systems at a variety of scales ranging from laboratory experiments to local and regional field scales. PHAST can be used in studies of migration of nutrients, inorganic and organic contaminants, and radionuclides; in projects such as aquifer storage and recovery or engineered remediation; and in investigations of the natural rock/water interactions in aquifers. PHAST is not appropriate for unsaturated-zone flow, multiphase flow, or density-dependent flow. A variety of boundary conditions are available in PHAST to simulate flow and transport, including specified-head, flux (specified-flux), and leaky (head-dependent) conditions, as well as the special cases of rivers, drains, and wells. Chemical reactions in PHAST include (1) homogeneous equilibria using an ion-association or Pitzer specific interaction thermodynamic model; (2) heterogeneous equilibria between the aqueous solution and minerals, ion exchange sites, surface complexation sites, solid solutions, and gases; and (3) kinetic reactions with rates that are a function of solution composition. The aqueous model (elements, chemical reactions, and equilibrium constants), minerals, exchangers, surfaces, gases, kinetic reactants, and rate expressions may be defined or modified by the user. A number of options are available to save results of simulations to output files. The data may be saved in three formats: a format suitable for viewing with a text editor; a format suitable for exporting to spreadsheets and postprocessing programs; and in Hierarchical Data Format (HDF), which is a compressed binary format. Data in the HDF file can be visualized on Windows computers with the program Model Viewer and extracted with the utility program PHASTHDF; both programs are distributed with PHAST.

Techniques and Methods

Geochemistry of the Arbuckle-Simpson Aquifer

The Arbuckle-Simpson aquifer in south-central Oklahoma provides water for public supply, farms, mining, wildlife conservation, recreation, and the scenic beauty of springs, streams, and waterfalls. A new understanding of the aquifer flow system was developed as part of the Arbuckle-Simpson Hydrology Study, done in 2003 through 2008 as a collaborative research project between the State of Oklahoma and the Federal government. The U.S. Geological Survey collected 36 water samples from 32 wells and springs in the Arbuckle-Simpson aquifer in 2004 through 2006 for geochemical analyses of major ions, trace elements, isotopes of oxygen and hydrogen, dissolved gases, and dating tracers. The geochemical analyses were used to characterize the water quality in the aquifer, to describe the origin and movement of ground water from recharge areas to discharge at wells and springs, and to determine the age of water in the aquifer.

Oklahoma

Brine migration from a flooded salt mine in the Genesee Valley, Livingston County, New York: Geochemical modeling and simulation of variable-density flow

The Retsof salt mine in upstate New York was flooded from 1994 to 1996 after two roof collapses created rubble chimneys in overlying bedrock that intersected a confined aquifer in glacial sediments. The mine now contains about 60 billion liters of saturated halite brine that is slowly being displaced as the weight of overlying sediments causes the mine cavity to close, a process that could last several hundred years. Saline water was detected in the confined aquifer in 2002, and a brine-mitigation project that includes pumping followed by onsite desalination was implemented in 2006 to prevent further migration of saline water from the collapse area. A study was conducted by the U.S. Geological Survey using geochemical and variable-density flow modeling to determine sources of salinity in the confined aquifer and to assess (1) processes that control movement and mixing of waters in the collapse area, (2) the effect of pumping on salinity, and (3) the potential for anhydrite dissolution and subsequent land subsidence resulting from mixing of waters induced by pumping. The primary source of salinity in the collapse area is halite brine that was displaced from the flooded mine and transported upward by advection and dispersion through the rubble chimneys and surrounding deformation zone. Geochemical and variable-density modeling indicate that salinity in the upper part of the collapse area is partly derived from inflow of saline water from bedrock fracture zones during water-level recovery (January 1996 through August 2006). The lateral diversion of brine into bedrock fracture zones promoted the upward migration of mine water through mixing with lower density waters. The relative contributions of mine water, bedrock water, and aquifer water to the observed salinity profile within the collapse area are controlled by the rates of flow to and from bedrock fracture zones. Variable-density simulations of water-level recovery indicate that saline water has probably not migrated beyond the collapse area, while simulations of pumping indicate that further upward migration of brine and saline water is now prevented by groundwater withdrawals under the brine-mitigation project. Geochemical modeling indicates that additional land subsidence as a result of anhydrite dissolution in the collapse area is not a concern, as long as the rate of brine pumping is less than the rate of upward flow of brine from the flooded mine. The collapse area above the flooded salt mine is within a glacially scoured bedrock valley that is filled with more than 150 meters of glacial drift. A confined aquifer at the bottom of the glacial sediments (referred to as the lower confined aquifer, or LCA) was the source of most of the water that flooded the mine. Two rubble chimneys that formed above the roof collapses in 1994 hydraulically connect the flooded mine to the LCA through 180 meters of sedimentary rock. From 1996 through 2006, water levels in the aquifer system recovered and the brine-displacement rate ranged from 4.4 to 1.6 liters per second, as estimated from land-surface subsidence above the mine. A zone of fracturing within the bedrock (the deformation zone) formed around the rubble chimneys as rock layers sagged toward the mine cavity after the roof collapses. Borehole geophysical surveys have identified three saline-water-bearing fracture zones in the bedrock: at stratigraphic contacts between the Onondaga and Bertie Limestones (O/B-FZ) and the Bertie Limestone and the Camillus Shale (B/C-FZ), and in the Syracuse Formation (Syr-FZ). The only outlets for brine displaced from the mine are through the rubble chimneys, but some of the brine could be diverted laterally into fracture zones in the rocks that lie between the mine and the LCA. Inverse geochemical models developed using PHREEQC indicate that halite brine in the flooded mine is derived from a mixture of freshwater from the LCA (81 percent), saline water from bedrock fracture zones (16 percent), and an hypothesized bromide-rich brine (3 percent) assumed to originate from salt-bearing rocks above the flooded mine. Geochemical modeling results also indicate that halite brine entering the rubble chimneys is diluted by both bedrock water and aquifer water, and that water from the mine has not reached the bedrock surface. Forward geochemical models indicate that additional land subsidence could occur if pumping from the brine-mitigation project were to introduce either freshwater or bedrock water that is undersaturated with respect to anhydrite into the lower part of the rubble chimneys. In this unlikely scenario, the maximum subsidence rates are predicted to range from 0.6 to 1.1 centimeters per year—subsidence rates would be lower (0.1 to 0.6 centimeters per year) if ion-exchange reactions affect the water chemistry. Variable-density, transient groundwater-flow models were constructed using SEAWAT to simulate the movement of saline water, aquifer water, bedrock water, and brine within the rubble chimneys and surrounding deformation zone during the 10.7-year period following flooding of the salt mine. Two three-dimensional models reproduced the profile of halite saturation with depth measured in September 2006 reasonably well, and neither model indicated that saline water had migrated beyond the collapse area. The models differed in the number of fracture zones represented: one zone in model A (O/B-FZ) and three zones in model B (O/B-FZ, B/C-FZ, and Syr-FZ). It is unknown whether model A or model B better represents current conditions because the lateral extents of the B/C-FZ and Syr-FZ have not been delineated beyond the collapse area. In model A, the salinity of water in the upper part of the rubble chimneys is derived mainly from the inflow of bedrock water from the O/B-FZ, as indicated by geochemical models. Bedrock water that was pushed upward by brine during the 10.7-year simulation period formed a diffuse front above a nearly horizontal brine level in both chimneys. In model B, some of the salinity in the upper part of the rubble chimneys is derived from mine water. The rate of bedrock-water inflow from the O/B-FZ was lower in model B than in model A, and mixing with waters from the Syr-FZ and B/C-FZ transported mine water higher in the water column than in model A. Simulated brine levels in both chimneys sloped northward, reflecting lateral diversion of brine into the B/C-FZ, and less aquifer water was displaced from the collapse area than in model A. Models A and B were used to simulate changes in water levels and salinity produced by pumping for the brine-mitigation project from September 2006 through February 2008. Both simulations indicated that current pumping rates are sufficient to offset upward migration of brine and saline water through the collapse area and, therefore, to further prevent contamination of the LCA. A greater decrease in salinity was simulated in model B, however, because the porosity of the rubble chimneys was lower (6 percent compared to 10 percent in model A), and some brine and saline waters were diverted through the B/C-FZ. Model B better simulates the influent saturation to the desalination plant, the amount of halite produced, and the observed declines in saturations than model A, which is more consistent with results of geochemical modeling. Sensitivity analyses indicate that the actual brine-displacement rate could be lower than estimated because simulated declines in saturations underpredict the observed decline from September 2006 through February 2008. Although halite saturations within the upper part of the collapse area are predicted to decrease with continued pumping, brine displacement from the flooded mine is expected to continue for hundreds of years. Simulations of a shutdown of the brine-mitigation project indicate southward migration of saline water through the LCA, extending 700 meters to the model boundary within 10 years. Continued migration of saline water would eventually form a pool in the LCA in a bedrock depression 8 kilometers south of the collapse area near Sonyea, but the large relative density of the saline water would likely prevent it from reaching overlying aquifers. Simulations also indicate that brine will migrate through bedrock fracture zones—some brine could possibly emerge updip to the north where the subcrop area of the Bertie Limestone intersects the bedrock surface near Avon, but the projected time of travel is unknown.

New York

Geochemical investigation of the Arbuckle-Simpson Aquifer, South-Central Oklahoma, 2004-06

A geochemical reconnaissance investigation of the Arbuckle-Simpson aquifer in south-central Oklahoma was initiated in 2004 to characterize the ground-water quality at an aquifer scale, to describe the chemical evolution of ground water as it flows from recharge areas to discharge in wells and springs, and to determine the residence time of ground water in the aquifer. Thirty-six water samples were collected from 32 wells and springs distributed across the aquifer for chemical analysis of major ions, trace elements, isotopes of oxygen and hydrogen, dissolved gases, and age-dating tracers. In general, the waters from wells and springs in the Arbuckle-Simpson aquifer are chemically suitable for all regulated uses, such as public supplies. Dissolved solids concentrations are low, with a median of 347 milligrams per liter (mg/L). Two domestic wells produced water with nitrate concentrations that exceeded the U.S. Environmental Protection Agency's nitrate maximum contaminant level (MCL) of 10 mg/L. Samples from two wells in the confined part of the aquifer exceeded the secondary maximum contaminant level (SMCL) for chloride of 250 mg/L and the SMCL of 500 mg/L for dissolved solids. Water samples from these two wells are not representative of water samples from the other wells and springs completed in the unconfined part of the aquifer. No other water samples from the Arbuckle-Simpson geochemical reconnaissance exceeded MCLs or SMCLs, although not every chemical constituent for which the U.S. Environmental Protection Agency has established a MCL or SMCL was analyzed as part of the Arbuckle-Simpson geochemical investigation. The major ion chemistry of 34 of the 36 samples indicates the water is a calcium bicarbonate or calcium magnesium bicarbonate water type. Calcium bicarbonate water type is found in the western part of the aquifer, which is predominantly limestone. Calcium magnesium bicarbonate water is found in the eastern part of the aquifer, which is predominantly a dolomite. The major ion chemistry for these 34 samples is consistent with a set of water-rock interactions. Rainfall infiltrates the soil zone, where the host rock, limestone or dolomite, dissolves as a result of uptake of carbon dioxide gas. Some continued dissolution of dolomite and precipitation of calcite occur as the water flows through the saturated zone. The major ion chemistry of the two samples from wells completed in the confined part of the aquifer indicates the water is a sodium chloride type. Geochemical inverse modeling determined that mixing of calcite-saturated recharge water with brine and dissolving calcite, dolomite, and gypsum accounts for the water composition of these two samples. One of the two samples, collected at Vendome Well in Chickasaw National Recreation Area, had a mixing fraction of brine of about 1 percent. The brine component of the sample at Vendome Well is likely to account for the relatively large concentrations of many of the trace elements (potassium, fluoride, bromide, iodide, ammonia, arsenic, boron, lithium, selenium, and strontium) measured in the water sample. Carbon-14, helium-3/tritium, and chlorofluorocarbons were used to calculate ground-water ages, recharge temperatures, and mixtures of ground water in the Arbuckle-Simpson aquifer. Thirty four of 36 water samples recharged the aquifer after 1950, indicating that water is moving quickly from recharge areas to discharge at streams and springs. Two exceptions to this classification were noted in samples 6 and 15 (Vendome Well). Ground-water ages determined for these two samples by using carbon-14 are 34,000 years (site 6) and 10,500 years (site 15). Concentrations of dissolved argon, neon, and xenon in water samples were used to determine the temperature of the water when it recharged the aquifer. The mean annual air temperature at Ada, Oklahoma, is 16 degrees Celsius (C) and the median temperature of the 30 reconnaissance water samples was 18.1 C. The av

Oklahoma

NetpathXL - An excel interface to the program NETPATH

NetpathXL is a revised version of NETPATH that runs under Windows? operating systems. NETPATH is a computer program that uses inverse geochemical modeling techniques to calculate net geochemical reactions that can account for changes in water composition between initial and final evolutionary waters in hydrologic systems. The inverse models also can account for the isotopic composition of waters and can be used to estimate radiocarbon ages of dissolved carbon in ground water. NETPATH relies on an auxiliary, database program, DB, to enter the chemical analyses and to perform speciation calculations that define total concentrations of elements, charge balance, and redox state of aqueous solutions that are then used in inverse modeling. Instead of DB, NetpathXL relies on Microsoft Excel? to enter the chemical analyses. The speciation calculation formerly included in DB is implemented within the program NetpathXL. A program DBXL can be used to translate files from the old DB format (.lon files) to NetpathXL spreadsheets, or to create new NetpathXL spreadsheets. Once users have a NetpathXL spreadsheet with the proper format, new spreadsheets can be generated by copying or saving NetpathXL spreadsheets. In addition, DBXL can convert NetpathXL spreadsheets to PHREEQC input files. New capabilities in PHREEQC (version 2.15) allow solution compositions to be written to a .lon file, and inverse models developed in PHREEQC to be written as NetpathXL .pat and model files. NetpathXL can open NetpathXL spreadsheets, NETPATH-format path files (.pat files), and NetpathXL-format path files (.pat files). Once the speciation calculations have been performed on a spreadsheet file or a .pat file has been opened, the NetpathXL calculation engine is identical to the original NETPATH. Development of models and viewing results in NetpathXL rely on keyboard entry as in NETPATH.

Techniques and Methods

Geochemical effects of induced stream-water and artificial recharge on the Equus Beds Aquifer, South-Central Kansas, 1995-2004

Artificial recharge of the Equus Beds aquifer is part of a strategy implemented by the city of Wichita, Kansas, to preserve future water supply and address declining water levels in the aquifer of as much as 30 feet caused by withdrawals for water supply and irrigation since the 1940s. Water-level declines represent a diminished water supply and also may accelerate migration of saltwater from the Burrton oil field to the northwest and the Arkansas River to the southwest into the freshwater of the Equus Beds aquifer. Artificial recharge, as a part of the Equus Beds Ground-Water Recharge Project, involves capturing flows larger than base flow from the Little Arkansas River and recharging the water to the Equus Beds aquifer by means of infiltration or injection. The geochemical effects on the Equus Beds aquifer of induced stream-water and artificial recharge at the Halstead and Sedgwick sites were determined through collection and analysis of hydrologic and water-quality data and the application of statistical, mixing, flow and solute-transport, and geochemical model simulations. Chloride and atrazine concentrations in the Little Arkansas River and arsenic concentrations in ground water at the Halstead recharge site frequently exceeded regulatory criteria. During 30 percent of the time from 1999 through 2004, continuous estimated chloride concentrations in the Little Arkansas River at Highway 50 near Halstead exceeded the Secondary Drinking-Water Regulation of 250 milligrams per liter established by the U.S. Environmental Protection Agency. Chloride concentrations in shallow monitoring wells located adjacent to the stream exceeded the drinking-water criterion five times from 1995 through 2004. Atrazine concentrations in water sampled from the Little Arkansas River had large variability and were at or near the drinking-water Maximum Contaminant Level of 3.0 micrograms per liter as an annual average established by the U.S. Environmental Protection Agency. Atrazine concentrations were much smaller than the drinking-water criterion and were detected at much smaller concentrations in shallow monitoring wells and diversion well water located adjacent to the stream probably because of sorption on aquifer sediment. Before and after artificial recharge, large, naturally occurring arsenic concentrations in the recharge water for the Halstead diversion well and recharge site exceeded the Maximum Contaminant Level of 10 micrograms per liter established by the U.S. Environmental Protection Agency for drinking water. Arsenic and iron concentrations decreased when water was recharged through recharge basins or a trench; however, chemical precipitation and potential biofouling eventually may decrease the artificial recharge efficiency through basins and trenches. At the Sedgwick site, chloride concentrations infrequently exceeded regulatory criteria. Large concentrations of atrazine were treated to decrease concentrations to less than regulatory criteria. Recharge of treated stream water through recharge basins avoids potentially large concentrations of arsenic and iron that exist at the Halstead diversion site. Results from a simple mixing model using chloride as a tracer indicated that the water chemistry in shallow monitoring well located adjacent to the Little Arkansas River was 80 percent of stream water, demonstrating effective recharge of the alluvial aquifer by the stream. Results also indicated that about 25 percent of the water chemistry of the diversion well water was from the shallow part of the aquifer. Additionally, diverting water through a diversion well located adjacent to the stream removed about 75 percent of the atrazine, probably through sorption to aquifer sediment, and decreased the need for additional water treatment to remove atrazine.

Kansas

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

The hydrologic and geochemical effects of aquifer storage recovery were evaluated to determine the potential for supplying the city of Charleston, South Carolina, with large quantities of potable water during emergencies, such as earthquakes, hurricanes, or hard freezes. An aquifer storage recovery system, including a production well and three observation wells, was installed at a site located on the Charleston peninsula. The focus of this study was the 23.2-meter thick Tertiary-age carbonate and sand aquifer of the Santee Limestone and the Black Mingo Group, the northernmost equivalent of the Floridan aquifer system. Four cycles of injection, storage, and recovery were conducted between October 1999 and February 2002. Each cycle consisted of injecting between 6.90 and 7.19 million liters of water for storage periods of 1, 3, or 6 months. The volume of recovered water that did not exceed the U.S. Environmental Protection Agency secondary standard for chloride (250 milligrams per liter) varied from 1.48 to 2.46 million liters, which is equivalent to 21 and 34 percent of the total volume injected for the individual tests. Aquifer storage recovery testing occurred within two productive zones of the brackish Santee Limestone/Black Mingo aquifer. The individual productive zones were determined to be approximately 2 to 4 meters thick, based on borehole geophysical logs, electromagnetic flow-meter testing, and specific-conductance profiles collected within the observation wells. A transmissivity and storage coefficient of 37 meters squared per day and 3 x 10-5, respectively, were determined for the Santee Limestone/Black Mingo aquifer. Water-quality and sediment samples collected during this investigation documented baseline aquifer and injected water quality, aquifer matrix composition, and changes in injected/aquifer water quality during injection, storage, and recovery. A total of 193 water-quality samples were collected and analyzed for physical properties, major and minor ions, and nutrients. The aquifer and treated surface water were sodiumchloride and calcium/sodium-bicarbonate water types, respectively. Forty-five samples were collected and analyzed for total trihalomethane. Total trihalomethane data collected during aquifer storage recovery cycle 4 indicated that this constituent would not restrict the use of recovered water for drinking-water purposes. Analysis of six sediment samples collected from a cored well located near the aquifer storage recovery site showed that quartz and calcite were the dominant minerals in the Santee Limestone/Black Mingo aquifer. Estimated cation exchange capacity ranged from 12 to 36 milliequivalents per 100 grams in the lower section of the aquifer. A reactive transport model was developed that included two 2-meter thick layers to describe each of the production zones. The four layers composing the production zones were assigned porosities ranging from 0.1 to 0.3 and hydraulic conductivities ranging from 1 to 8.4 meters per day. Specific storage of the aquifer and confining units was estimated to be 1.5 x 10-5 meter-1. Longitudinal dispersivity of all layers was specified to be 0.5 meter. Leakage through the confining unit was estimated to be minimal and, therefore, not used in the reactive transport modeling. Inverse geochemical modeling indicates that mixing, cation exchange, and calcite dissolution are the dominant reactions that occur during aquifer storage recovery testing in the Santee Limestone/Black Mingo aquifer. Potable water injected into the Santee Limestone/Black Mingo aquifer evolved chemically by mixing with brackish background water and reaction with calcite and cation exchangers in the sediment. Reactive-transport model simulations indicated that the calcite and exchange reactions could be treated as equilibrium processes.

South Carolina