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

The thermodynamic properties of 154 mineral end-members, 13 silicate liquid end-members and 22 aqueous fluid species are presented in a revised and updated data set. The use of a temperature-dependent thermal expansion and bulk modulus, and the use of high-pressure equations of state for solids and fluids, allows calculation of mineral–fluid equilibria to 100 kbar pressure or higher. A pressure-dependent Landau model for order–disorder permits extension of disordering transitions to high pressures, and, in particular, allows the alpha–beta quartz transition to be handled more satisfactorily. Several melt end-members have been included to enable calculation of simple phase equilibria and as a first stage in developing melt mixing models in NCKFMASH. The simple aqueous species density model has been extended to enable speciation calculations and mineral solubility determination involving minerals and aqueous species at high temperatures and pressures. The data set has also been improved by incorporation of many new phase equilibrium constraints, calorimetric studies and new measurements of molar volume, thermal expansion and compressibility. This has led to a significant improvement in the level of agreement with the available experimental phase equilibria, and to greater flexibility in calculation of complex mineral equilibria. It is also shown that there is very good agreement between the data set and the most recent available calorimetric data.

An internally consistent thermodynamic data set for phases of petrological interest

DOI 10.1007/s10040-0010176-2 Abstract Various techniques are available to quantify recharge; however, choosing appropriate techniques is often difficult. Important considerations in choosing a technique include space/time scales, range, and reliabili- ty of recharge estimates based on different techniques; other factors may limit the application of particular tech- niques. The goal of the recharge study is important be- cause it may dictate the required space/time scales of the recharge estimates. Typical study goals include water-re- source evaluation, which requires information on re- charge over large spatial scales and on decadal time scales; and evaluation of aquifer vulnerability to contam- ination, which requires detailed information on spatial variability and preferential flow. The range of recharge rates that can be estimated using different approaches should be matched to expected recharge rates at a site. The reliability of recharge estimates using different tech- niques is variable. Techniques based on surface-water and unsaturated-zone data provide estimates of potential recharge, whereas those based on groundwater data gen- erally provide estimates of actual recharge. Uncertainties in each approach to estimating recharge underscore the need for application of multiple techniques to increase

http://images.water.nv.gov/images/Misc/spring%20valley%20hearings/SNWA/568.pdf

Choosing appropriate techniques for quantifying groundwater recharge

Denitrification is a critical process regulating the removal of bioavailable nitrogen (N) from natural and human-altered systems. While it has been extensively studied in terrestrial, freshwater, and marine systems, there has been limited communication among denitrification scientists working in these individual systems. Here, we compare rates of denitrification and controlling factors across a range of ecosystem types. We suggest that terrestrial, freshwater, and marine systems in which denitrification occurs can be organized along a continuum ranging from (1) those in which nitrification and denitrification are tightly coupled in space and time to (2) those in which nitrate production and denitrification are relatively decoupled. In aquatic ecosystems, N inputs influence denitrification rates whereas hydrology and geomorphology influence the proportion of N inputs that are denitrified. Relationships between denitrification and water residence time and N load are remarkably similar across lakes, river reaches, estuaries, and continental shelves. Spatially distributed global models of denitrification suggest that continental shelf sediments account for the largest portion (44%) of total global denitrification, followed by terrestrial soils (22%) and oceanic oxygen minimum zones (OMZs; 14%). Freshwater systems (groundwater, lakes, rivers) account for about 20% and estuaries 1% of total global denitrification. Denitrification of land-based N sources is distributed somewhat differently. Within watersheds, the amount of land-based N denitrified is generally highest in terrestrial soils, with progressively smaller amounts denitrified in groundwater, rivers, lakes and reservoirs, and estuaries. A number of regional exceptions to this general trend of decreasing denitrification in a downstream direction exist, including significant denitrification in continental shelves of N from terrestrial sources. Though terrestrial soils and groundwater are responsible for much denitrification at the watershed scale, per-area denitrification rates in soils and groundwater (kg Nkm � 2 � yr � 1 ) are, on average, approximately one-tenth the per-area rates of denitrification in lakes, rivers, estuaries, continental shelves, or OMZs. A number of potential approaches to increase denitrification on the landscape, and thus decrease N export to sensitive coastal systems exist. However, these have not generally been widely tested for their effectiveness at scales required to significantly reduce N export at the whole watershed scale.

/pdf/denitrification-across-landscapes-and-waterscapes-a-ei9e1947rb.pdf

Denitrification across landscapes and waterscapes: a synthesis.

Emerging organic contaminants in groundwater: A review of sources, fate and occurrence

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

The use of Chlorofluorocarbons (CFCs) as an age-dating tool and tracer in shallow groundwaters has been investigated. New methodology for field sampling and preserving groundwaters containing parts per trillion concentrations of the CFCs, F-1l and F-12, is presented. Samples are analyzed by purge-and-trap gas chromatography with an electron capture detector. Physical and chemical processes that can alter natural concentrations (air-water equilibrium) of CFCs were investigated to assess dating uncertainties. CFC model recharge ages appear to be defined within 2 years under optimum conditions. The method was applied to central Oklahoma to demonstrate the usefulness of CFCs as (1) an age-dating tool of shallow groundwaters, (2) a tracer of sewage effluent in surface and shallow groundwaters, and (3) a tracer of shallow groundwater. Results of dating indicate two primary recharge periods in central Oklahoma over the past 45 years that correspond to the wet periods 1945–1960 and 1967–1975.

Use of chlorofluorocarbons (CCl3F and CCl2F2) as hydrologic tracers and age-dating tools: The alluvium and terrace system of central Oklahoma

Sulfur hexafluoride (SF6) is primarily of anthropogenic origin but also occurs naturally The troposphere concentration of SF6 has increased from a steady state value of 0054±0009 to more than 4 parts per trillion volume during the past 40 years An analytical procedure was developed for measuring concentrations of SF6 to less than 001 fmol/L in water Groundwater can be dated with SF6 if it is in equilibrium with atmospheric SF6 at the time of recharge and does not contain significant SF6 from other sources The dating range of SF6 is currently 0 to 30 years The tracer was successfully used to date shallow groundwater of the Atlantic Coastal Plain sand aquifers of the United States and springs issuing near the top of the Blue Ridge Mountains of Virginia Significant concentrations of naturally occurring SF6 were found in some igneous, volcanic, and sedimentary rocks and in some hydrothermal fluids

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2000WR900151

Dating young groundwater with sulfur hexafluoride: Natural and anthropogenic sources of sulfur hexafluoride

Kinetic and thermodynamic factors controlling the distribution of SO32− and Na+ in calcites and selected aragonites

This paper describes a direct comparison of apparent ages derived from 3H/3He, chlorofluorocarbons (CCl3F and CCl2F2), and 85Kr measurements in shallow groundwater. Wells chosen for this study are completed in the unconfined surficial aquifers in late Cenozoic Atlantic Coastal Plain sediments of the Delmarva Peninsula, on the east coast of the United States. Most of the apparent tracer ages agree within 2 years of each other for recharge dates between 1965 and 1990. Discrepancies in apparent tracer ages usually can be explained by hydrological processes such as mixing in a discharge area. Recharge rate calculations based on apparent tracer age gradients at multilevel well locations agree with previous recharge estimates. High recharge rates on the Delmarva Peninsula result in nearly complete dissolved-gas confinement in the groundwater. The remarkable agreement between the different tracer ages indicates negligible mixing of waters of different ages, insignificant dispersion, minimal gas loss to the atmosphere, and insignificant sorption-desorption processes at this location.

Eurybiades Busenberg

Papers

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

Use of chlorofluorocarbons (CCl3F and CCl2F2) as hydrologic tracers and age-dating tools: The alluvium and terrace system of central Oklahoma

Dating young groundwater with sulfur hexafluoride: Natural and anthropogenic sources of sulfur hexafluoride

Kinetic and thermodynamic factors controlling the distribution of SO32− and Na+ in calcites and selected aragonites

Dating of shallow groundwater: Comparison of the transient tracers 3H/3He, chlorofluorocarbons, and 85Kr