L. Niel Plummer

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

Calculations based on approximately 350 new measurements (CaT-PCO2) of the solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants KC, KA, and KV respectively, for the reaction CaCO3(s) = Ca2+ + CO2−3: Log KC = −171.9065 − 0.077993T + 2839.319T + 71.595 log TLog KA = −171.9773 − 0.077993T + 2903.293T +71.595 log TLog KV = −172.1295 − 0.077993T + 3074.688T + 71.595 log T where T is in oK. At 25°C the logarithms of the equilibrium constants are −8.480 ± 0.020, −8.336 ± 0.020 and −7.913 ± 0.020 for calcite, aragonite and vaterite, respectively. The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO+3 and CaCO03 ion pairs, revised analytical expressions for CO2-H2O equilibria, and extended Debye-Huckel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO2-dependence if the CaHCO+3 association constant is Log KCahco+3 = 1209.120 + 0.31294T — 34765.05T − 478.782 log T between 0 and 90°C, corresponding to the value logKCahco+3 = 1.11 ± 0.07 at 25°C. The CaCO03 association constant was measured potentiometrically to be log KCaCO03 = −1228.732 − 0.299444T + 35512.75T + 485.818 log T between 5 and 80°C, yielding logKCaCO03 = 3.22 ± 0.14 at 25°C. The CO2-H2O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of KH, K1 and K2 are log KH = 108.3865 + 0.01985076T − 6919.53T − 40.45154 log T + 669365.T2, log K1 = −356.3094 − 0.06091964T + 21834.37T + 126.8339 log T — 1684915.T2 and logK2 = −107.8871 − 0.03252849T + 5151.79/T + 38.92561 logT − 563713.9/T2 which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures. Extensive measurements of the pH of Ca-HCO3 solutions at 25°C and 0.956 atm PCO2 using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH. Earlier arguments suggesting that the CaHCO+3 ion pair should not be included in the CaCO3-CO2-H2O aqueous model were based on less accurate calcite solubility data. The CaHCO+3 ion pair must be included in the aqueous model to account for the observed PCO2-dependence of aragonite solubility between 317 ppm CO2 and 100% CO2. Previous literature on the solubility of CaCO3 polymorphs have been critically evaluated using the aqueous model and the results are compared.

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

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.

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

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 0.054±0.009 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 0.01 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.

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

Abstract Significant amounts of SO42−, Na+, and OH− are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO42−. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na+, but very low concentrations of SO42−. The SO42− content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na+ and SO42− increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO42− beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO42− is the same as that of aragonite. Na+ appears to have very little effect on the solubility product of calcites. The amounts of Na+ and SO42− incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient ( D ) of SO42− in calcite at 25.0°C and 0.50 molal NaCl is described by the equation D = k 0 + k 1 R where k 0 and k 1 are constants equal to 6.16 × 10 −6 and 3.941 × 10 −6 , respectively, and R is the rate of crystal growth of calcite in mg·min−1·g−1 of seed. The data on Na+ are consistent with the hypothesis that a significant amount of Na+ occupies interstitial positions in the calcite structure. The distribution of Na+ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na+ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na+ contents of calcites are not very accurate indicators of environmental salinities.

Development of reaction models for ground-water systems

Abstract 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.

The dissolution of calcite in CO2-saturated solutions at 25°C and 1 atmosphere total pressure

The dissolution of Iceland spar in CO2-saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.

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

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.

The use of simulation and multiple environmental tracers to quantify groundwater flow in a shallow aquifer

Measurements of the concentrations of chlorofluorocarbons (CFCs), tritium, and other environmental tracers can be used to calculate recharge ages of shallow groundwater and estimate rates of groundwater movement. Numerical simulation also provides quantitative estimates of flow rates, flow paths, and mixing properties of the groundwater system. The environmental tracer techniques and the hydraulic analyses each contribute to the understanding and quantification of the flow of shallow groundwater. However, when combined, the two methods provide feedback that improves the quantification of the flow system and provides insight into the processes that are the most uncertain. A case study near Locust Grove, Maryland, is used to investigate the utility of combining groundwater age dating, based on CFCs and tritium, and hydraulic analyses using numerical simulation techniques. The results of the feedback between an advective transport model and the estimates of groundwater ages determined by the CFCs improve a quantitative description of the system by refining the system conceptualization and estimating system parameters. The plausible system developed with this feedback between the advective flow model and the CFC ages is further tested using a solute transport simulation to reproduce the observed tritium distribution in the groundwater. The solute transport simulation corroborates the plausible system developed and also indicates that, for the system under investigation with the data obtained from 0.9-m-long (3-foot-long) well screens, the hydrodynamic dispersion is negligible. Together the two methods enable a coherent explanation of the flow paths and rates of movement while indicating weaknesses in the understanding of the system that will require future data collection and conceptual refinement of the groundwater system.

Process and rate of dedolomitization: Mass transfer and 14C dating in a regional carbonate aquifer

Regional dedolomitization is the major process that controls the chemical character of water in the Mississippian Pahasapa Limestone (Madison equivalent) surrounding the Black Hills, South Dakota and Wyoming. The process of dedolomitization consists of dolomite dissolution and concurrent precipitation of calcite; it is driven by dissolution of gypsum. Deuterium and oxygen isotopic data from the ground water, coupled with regional potentiometric maps, show that recharge occurs on the western slope of the Black Hills and that the water flows northward and westward toward the Powder River Basin. A significant part flows around the southern end of the Black Hills to replenish the aquifer to the east of the Hills. Depth of flow was inferred from interpretation of the silica geothermometer based on the temperature-dependent solubilities of quartz and chalcedony in water. Chemical effects of warm water in the Pahasapa Limestone include changes in the solubility products of minerals, conversion of gypsum to anhydrite, solution and precipitation of minerals, and increases in the tendency for outgassing of carbon dioxide. Where sulfate reduction is not important, sulfur isotope data show that (1) in the Mississippian aquifer, most of the sulfate is from dissolution of gypsum and (2) some wells and springs have a hydrologic connection with overlying Permian and Pennsylvanian evaporites. Sulfate ion concentration, a progress variable, shows a strong correlation with pH as a result of the combined effects of the dedolomitization reactions. Mass-balance and mass-transfer calculations were used to adjust 14C values to determine a range of ground-water flow velocities between 2 and 20 m/yr. These velocities are characteristic of carbonate aquifers. The average rates of dolomite and gypsum dissolution are 1.7 × 10−4 and 3.4 × 10−4 mmol/kg of H2O/yr, respectively. The precipitation of calcite is occurring at the rate of 3.4 × 10−4 mmol/kg of H2O/yr. The close agreement among the model results demonstrates that dedolomitization is controlling water-rock interactions in this regional carbonate aquifer system.

Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations (Ωcalcite ≤ 1.5) from artificial sea water or NaClMgCl2CaCl2 solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations (Ωcalcite≥ 3) from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model ge = X(1− x)[A0 + A1(2x − 1)] , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0 and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln Kx = x(1−x)RT[A0 + A1(2x− 1)]+ (1 − x) ln [KC(1− x)]+ x ln (KDx) , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.