Geology topics

J.B. Fein

Publications and source records attributed to J.B. Fein.

3 recordsLinked to original sources

USGS2005

A universal surface complexation framework for modeling proton binding onto bacterial surfaces in geologic settings

Adsorption onto bacterial cell walls can significantly affect the speciation and mobility of aqueous metal cations in many geologic settings. However, a unified thermodynamic framework for describing bacterial adsorption reactions does not exist. This problem originates from the numerous approaches that have been chosen for modeling bacterial surface protonation reactions. In this study, we compile all currently available potentiometric titration datasets for individual bacterial species, bacterial consortia, and bacterial cell wall components. Using a consistent, four discrete site, non-electrostatic surface complexation model, we determine total functional group site densities for all suitable datasets, and present an averaged set of 'universal' thermodynamic proton binding and site density parameters for modeling bacterial adsorption reactions in geologic systems. Modeling results demonstrate that the total concentrations of proton-active functional group sites for the 36 bacterial species and consortia tested are remarkably similar, averaging 3.2 ?? 1.0 (1??) ?? 10-4 moles/wet gram. Examination of the uncertainties involved in the development of proton-binding modeling parameters suggests that ignoring factors such as bacterial species, ionic strength, temperature, and growth conditions introduces relatively small error compared to the unavoidable uncertainty associated with the determination of cell abundances in realistic geologic systems. Hence, we propose that reasonable estimates of the extent of bacterial cell wall deprotonation can be made using averaged thermodynamic modeling parameters from all of the experiments that are considered in this study, regardless of bacterial species used, ionic strength, temperature, or growth condition of the experiment. The average site densities for the four discrete sites are 1.1 ?? 0.7 ?? 10-4, 9.1 ?? 3.8 ?? 10-5, 5.3 ?? 2.1 ?? 10-5, and 6.6 ?? 3.0 ?? 10-5 moles/wet gram bacteria for the sites with pKa values of 3.1, 4.7, 6.6, and 9.0, respectively. It is our hope that this thermodynamic framework for modeling bacteria-proton binding reactions will also provide the basis for the development of an internally consistent set of bacteria-metal binding constants. 'Universal' constants for bacteria-metal binding reactions can then be used in conjunction with equilibrium constants for other important metal adsorption and complexation reactions to calculate the overall distribution of metals in realistic geologic systems.

American Journal of Science↗

USGS1992

Hydrothermal ore-forming processes in the light of studies in rock- buffered systems: I. Iron-copper-zinc-lead sulfide solubility relations

Experimental studies, using cold-seal and extraction vessel techniques, were conducted on Fe, Pb, Zn, and Cu sulfide solubilities in chloride solutions at temperatures from 300 degrees to 700 degrees C and pressures from 0.5 to 2 kbars. The solutions were buffered in pH by a quartz monzonite and the pure potassium feldspar-muscovite-quartz assemblage and in f (sub S 2 ) - f (sub O 2 ) largely by the assemblage pyrite-pyrrhotite-magnetite. Solubilities increase with increasing temperature and total chloride, and decrease with increasing pressure. The rise in solubility is particularly steep between 300 degrees and 500 degrees C and between 1,000 and 500 bars. With increasing temperature at any given pressure, or with decreasing pressure at any given temperature, metal solubility eventually passes through a maximum due to increasing competition for chloride by the alkali, hydrogen, and base metal ions and because intersection with a two-fluid region eventually occurs. In that portion of the two-fluid region encountered in the study, metal solubilities in the brine were very high, but solubilities in the gas phase also were significant. In a system controlled by the potassium feldspar-muscovite-quartz buffer, 1-m total Cl (super -) , and the assemblage pyrite-pyrrhotite-magnetite-sphalerite-galena-chalcopyrite, solubilities in ppm at 1 kbar and 300 degrees , 400 degrees , and 500 degrees C were 237, 1,216, and 5,636, for Fe; 51, 613, and 3,105 for Pb; 36, 423, and 2,649 for Zn; and 11, 40, and 113 for Cu, respectively. At 400 degrees C, 0.5 and 2 kbars, the values were 2,627 and 500 for Fe; 1,262 and 194 for Pb; 983 and 120 for Zn; and 60 and 29 for Cu, respectively. All of the above were in the single-fluid region. Single-metal solubilities also were investigated to assess the influence of iron on the solubility of the other metals and to corroborate preliminary dissociation constants for the metal chloride complexes involved. The effect of increasing chloride concentration on solubility reflects primarily a shift to lower pH via the silicate buffer reactions. The effect of decreasing pressure reflects primarily the relative change in the dissociation constants of the chloride complexes involved. Increasing sulfur fugacity lowers solubility, but in systems controlled at relatively low values by an f (sub S 2 ) buffer or wall-rock sulfidation reactions, solutions of high metal content relative to reduced sulfur will tend to develop at high chloride concentrations. Similarity in behavior with respect to the temperature and pressure of Fe, Zn, and Pb sulfide solubilities points to similarity in chloride speciation, and the neutral species appear to be dominant in the high-temperature region. At 500 degrees C and 1 kbar, the log K D values for FeCl degrees 2 , PbCl degrees 2 , ZnCl degrees 2 , and CuCl degrees are, respectively, -8.76, -9.14, -10.86, and -6.22.

Economic Geology↗

USGS1992

Experimental study of iron-chloride complexing in hydrothermal fluids

Mineral assemblage solubilities were measured in cold-seal pressure vessels as a function of pressure, temperature, and potassium chloride concentration in order to determine the nature and thermodynamic properties of iron-chloride complexes under hydrothermal conditions. The assemblage pyritepyrrhotite-magnetite was used to buffer ƒS 2 "> ƒS 2 and ƒO 2 "> ƒO 2 , and K + H + "> K + H + ratios were buffered at reasonable geologic values using the assemblage potassium feldspar-muscovite (or andalusite)-quartz. The pressure-temperature ranges were 0.5-2.0 kbar and 300–600°C, and initial fluid compositions ranged from 0.01–2.0 molal KCl. With all other factors constant, the concentration of iron in solution increases with increasing temperature, with decreasing pressure, and with increasing total potassium chloride concentration. Changes in iron concentrations as a function of KCl concentration, in conjunction with charge balance, mass action, and mass balance constraints on the system, place constraints on the stoichiometry of the important iron-chloride complexes under each of the experimental conditions. Using least-squared linear regression fits to determine these slopes, the calculations yield values for the average ligand numbers that are in the range 1.2-1.9, with uncertainties ranging from ±0.1-0.6 at the several PT conditions considered. The slopes of the regressed fits to the data suggest that both FeCl + and FeCl 2 0 are important in the experimental fluids, with FeCl 2 0 becoming dominant at the higher temperatures. Theoretical calculations, however, indicate that FeCl + does not contribute significantly to the solubility. Because of the large uncertainties associated with some of the calculated average ligand numbers, we base our data analysis on the theoretical calculations. A statistical analysis is applied to the solubility data in order to determine the values and uncertainties of the dissociation constant for FeCl 2 0 that best fit the data at each of the experimental pressures and temperatures. The calculated stability of FeCl 2 0 increases with increasing temperature and total chloride concentration, and with decreasing pressure. The values of the dissociation constant of FeCl 2 0 that are calculated in this study are in moderately good agreement with FeCl 2 0 dissociation constants from other studies of iron-chloride complexing in supercritical fluids. Differences are likely due to different assumptions made concerning activity coefficients of aqueous species. Log k d values for full dissociation of FeCl 2 0 at 0.5 kbar—300°C—and at 1 kbar—400, 500, and 600°C, respectively—are −3.75 ± 0.40, −6.25 ± 0.10, −9.19 ± 0.44, and −13.29 ± 0.09.

Geochimica et Cosmochimica Acta↗