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Measurement and control of pH in hydrothermal solutions

Description: Hydrogen-electrode concentration cells with liquid junction are routinely used to measure the pH of aqueous solutions from 0 to 300 C. Results include the dissociation constants of common acids and bases and the hydrolysis and complexation of metal ions in aqueous electrolytes over a wide range of salinities. Recently, we have utilized these cells to examine the sorption of H{sup +} on mineral surfaces, the solubility of minerals with continuous in situ pH measurement, and the thermal decompositon rates of organic acids.
Date: December 31, 1995
Creator: Wesolowski, D.J.; Palmer, D.A. & Mesmer, R.E.
Partner: UNT Libraries Government Documents Department

The aqueous chemistry of aluminum: A new approach to high temperature solubility measurements

Description: The solubility of boehmite, AlO(OH), has been measured as a function of pH (2-10, depending on ionic strength) temperature (100- 250{degrees}C) and ionic strength (0.03-1 molal, NaCl) in a hydrogen- electrode concentration cell, HECC, which provided in situ measurement of hydrogen ion molality. Samples of the solution were withdrawn after the pH reading stabilized for analysis of total aluminum content by ion chromatography. Acidic or basic titrant could then be metered into the cell to affect a change in the pH of the solution. The direction of approach to the equilibrium saturated state could be readily varied to ensure that the system was reversible thermodynamically. This represents our second application of direct pH measurement to high temperature solubility studies. The results as low ionic strength are compared with those from two recently-reported high-temperature studies of boehmite solubility, which relied on the conventional batch technique. Comparisons are also made with the low temperature (<90{degrees}C) hydrolysis constants for aluminum garnered from solubility measurements with gibbsite as the stable phase. Based on these preliminary results, it is possible to draw some general conclusions concerning the relative importance of the aluminum species in solution and to reduce significantly the number of experiments needed to define this complex system in a thermodynamic sense.
Date: January 1, 1996
Creator: Palmer, D.A.; Wesolowski, D.J. & Benezeth, P.
Partner: UNT Libraries Government Documents Department

LIFETIME PREDICTIONS OF TOXIC AND RADIOACTIVE WASTE DISPOSAL AND REMEDIATION SCHEMES

Description: Nuclear power production epitomizes the need for predictive geoscience (Ewing, 2004). Current global carbon emissions of {approx}7 Gt/y, largely from fossil fuel consumption, are expected to grow and result in a variety of adverse global effects, including acid rain, toxic smog, and hypothetically, sea level rise and increased frequency and severity of adverse weather conditions. One of the most reliable and sufficiently large alternative sources of energy is nuclear power, which currently provides about 17% of the world's electricity, equivalent to a reduction in carbon emissions of {approx}0.5 Gt/y. The U.S. currently consumes {approx}40% of the world's fossil fuel production, but generates only about 20% of it's electricity from nuclear plants. One major factor inhibiting increased power production form this source in the US. is the lack of a licensed repository for spent nuclear fuel, and Yucca Mountain is the only site being considered at this time. The licensing issue hinges on DOE's ability to present a credible case before the Nuclear Regulatory Commission that releases of radionuclides from the repository will not pose a threat to the accessible environment. This case is being built using a performance assessment model that incorporates a thermochemical database (EQ3/6) fed by experiments and theoretical developments in aqueous geochemistry and fluid rock interactions, coupled reaction/transport models which combine both the chemical and physical aspects of fluid and heat transport through porous and fractured media, geohazard and climate change models, and information gleaned from natural analogs. The assessment period is currently 10,000 years, but this has recently been challenged in a court of law, and may be extended to 300,000 years or more. Yucca Mountain has a design capacity that only marginally exceeds the current U.S. inventory of commercial spent fuel, currently stored on site at power plants through the country. Some analysts suggest that ...
Date: June 28, 2005
Creator: Wesolowski, D.J.; Ewing, R.C. & Bruno, J.
Partner: UNT Libraries Government Documents Department

D/H and {sup 18}O/{sup 16}O partitioning between water liquid and vapor in the system H{sub 2}O-Na-K-Mg-Ca-Cl-SO{sub 4} from 0 to 350{degrees}C

Description: Oxygen and hydrogen isotope partitioning between liquid water and water vapor has been precisely determined by means of direct mass-spectrometric measurements of isotopic abundances of the two phases from room temperature to 350{degrees}C. Measurable changes in the liquid-vapor partitioning were observed upon the addition of salts (NaCl, KCl, MgCl{sub 2}, CaCl{sub 2}, Na{sub 2}SO{sub 4}, and MgSO{sub 4}) to the system. The results of isotope partitioning for the isotopic mixtures and the literature data of vapor pressure measurements of separate isotopic waters agree well for pure water, but show notable discrepancy for salt solutions.
Date: February 1, 1995
Creator: Horita, J.; Wesolowski, D. J. & Cole, D. R.
Partner: UNT Libraries Government Documents Department

Potentiometric studies at ORNL with hydrogen electrode concentration cells

Description: The absence of suitably stable reference electrodes for and to 300 C led ORNL to develop hydrogen electrode concentration cells for studies of equilibria of interest in reactor and steam generator systems to about 300 C during the late 1960`s and seventies. During the intervening two dozen years over twenty scientists have participated in potentiometric studies at Oak Ridge and much of that work will be summarized in this paper. A description of hydrogen electrode concentration cells developed in the late sixties and currently in use at Oak Ridge is given. The method of measurement, data interpretation, and published results are reviewed for studies of acid-base ionization, metal ion hydrolysis, and metal complexation reactions using principally such cells in titration or flow modes. 41 refs.
Date: December 31, 1994
Creator: Mesmer, R. E.; Palmer, D. A. & Wesolowski, D. J.
Partner: UNT Libraries Government Documents Department

Salt effects on stable isotope partitioning and their geochemical implications for geothermal brines

Description: It has long been recognized that dissolved salts in water can change oxygen and hydrogen isotope partitioning between water and other phases (i.e., vapor, minerals) due to the hydration of ions upon the dissolution of salts in water. However, their effects have not been well determined at elevated temperatures. We are currently conducting a series of hydrothermal experiments of the system brine-vapor or minerals to 350{degrees}C, in order to determine precisely the effects of dissolved salts abundant in brines on isotope partitioning at temperatures encountered in geothermal systems. The so-called ``isotope salt effect`` has important implications for the interpretation and modeling of isotopic data of brines and rocks obtained from geothermal fields. We will show how to use our new results of isotopic partitioning to help better evaluate energy resources of many geothermal fields.
Date: June 1, 1994
Creator: Horita, J.; Cole, D. R. & Wesolowski, D. J.
Partner: UNT Libraries Government Documents Department

New Measurements of the Solubility of Metal Oxides at High Temperature

Description: The results of high temperature solubility studies at ORNL are presented in which mainly direct pH measurements were made of aqueous solutions in contact with the crystalline solid phases: Al(OH){sub 3}, AlOOH, Fe{sub 3}O{sub 4}, Mg(OH){sub 2}, Nd(OH){sub 3}, and ZnO. Examples are highlighted of specific phenomena such as: the kinetics of gibbsite and boehmite dissolution and precipitation; the appearance of metastable equilibria in the dissolution of Fe{sub 3}O{sub 4}; the extremely rapid precipitation of crystalline brucite, Mg(OH){sub 2}; and anomalies in the apparent solubility profiles of AlO(OH) and ZnO. General trends associated with the effects of temperature and ionic strength are mentioned. Some of the potentiometric investigations were augmented by conventional batch [AlO(OH) and ZnO], and flow-through column (ZnO) experiments. In the additional case of ZnCr{sub 2}O{sub 4}, the extremely low solubility of this spinel permitted application of only the latter technique and these results are discussed in terms of the measured chromium levels that resulted from incongruent dissolution.
Date: June 30, 2000
Creator: Palmer, G.A.; Benezeth, P.; Wesolowski, D.J.; Wood, S.A. & Xiao, C.
Partner: UNT Libraries Government Documents Department

Solubility and Reaction Rates of Aluminum Solid Phases Under Geothermal Conditions

Description: Experimental studies involving equilibrium solubility and dissolution/precipitation rates were initiated on aluminum hydroxide phases prevalent under geothermal reservoir conditions. A large capacity, hydrogen-electrode concentration cell (HECC) was constructed specifically for this purpose.
Date: May 28, 2000
Creator: Benezeth, P.; Palmer, D.A.; Wesolowski, D.J. & Anovitz, L.M.
Partner: UNT Libraries Government Documents Department

Experimental studies in high temperature aqueous chemistry at Oak Ridge National Laboratory

Description: Experimental research is conducted and models developed in a long- standing program at Oak Ridge on aqueous chemistry at high temperatures of broad classes of electrolytes emphasizing thermodynamics of reaction equilibria and excess thermodynamic properties of electrolytes. Experimental methods, their capabilities, data analysis, and results are summarized. Relevance of the work to problems in power plants, natural and industrial processes as well as basic solution chemistry and geochemistry are given. Progress in potentiometry, electrical conductivity, flow calorimetry, and isopiestic research is described. Future in this field demands greater precision in measurements and significant gains in our understanding of the solvation phenomena especially in the vicinity and beyond the critical point for water. The communities who do research on scattering, spectroscopy, and computer simulations can help guide these efforts through studies at extreme conditions.
Date: January 1, 1996
Creator: Mesmer, R.E.; Palmer, D.A.; Simonson, J.M.; Holmes, H.F.; Ho, P.C.; Wesolowski, D.J. et al.
Partner: UNT Libraries Government Documents Department

Solubility of, and hydrogen ion adsorption on, some metal oxides in aqueous solutions to high temperatures

Description: Solubility of boehmite (AlOOH), ferrous hydroxide (Fe(OH)2)/magnetite (Fe3O4), zincite (ZnO), and brucite (Mg(OH)2) were measured over a range of temperatures (AlOOH, 100-290 C; Fe(OH)2/Fe3O4, 100-250 C; ZnO, 50-290 C; Mg(OH)2, 60-200 C) using in situ pH measurements. A hydrogen-electrode concentration cell was used; the pH range depended on the oxide. The solubility results for boehmite mainly demonstrate the method viability, while those for zincite are mainly restricted to mildly acidic to neutral pH where Zn{sup 2+} predominates in solution. The magnetite (presumably coated with Fe(OH)2) solubilities extend from pHs > 5 and, because of relevance to water/steam cycles of power plants, are compared in detail with previous studies. The same cell was used to investigate the surface adsorption-desorption thermodynamics of H ions on rutile (TiO2) and zincite to 290 C. Behavior of pH at zero-point-of-charge as function of temperature and application of the Stern-3-layer model were determined for this solid. The zincite study is still incomplete; preliminary results show trends that can be rationalized only qualitatively now with the zero- point-of-charge being apparently affected by hydration of the surface in basic solutions and specific adsorption of Na ions under the same conditions.
Date: August 1, 1997
Creator: Palmer, D.A.; Benezeth, P.; Wesolowski, D.J.; Anovitz, L.M.; Machesky, M.L.; Hayashi, Ken-ichiro et al.
Partner: UNT Libraries Government Documents Department

Geochemistry of Aluminum in High Temperature Brines

Description: The objective ofthis research is to provide quantitative data on the equilibrium and thermodynamic properties of aluminum minerals required to model changes in permeability and brine chemistry associated with fluid/rock interactions in the recharge, reservoir, and discharge zones of active geothermal systems. This requires a precise knowledge of the thermodynamics and speciation of aluminum in aqueous brines, spanning the temperature and fluid composition rangesencountered in active systems. The empirical and semi-empirical treatments of the solubility/hydrolysis experimental results on single aluminum mineral phases form the basis for the ultimate investigation of the behavior of complex aluminosilicate minerals. The principal objective in FY 1998 was to complete the solubility measurements on boehmite (AIOOH) inNaC1 media( 1 .O and 5.0 molal ionic strength, IOO-250°C). However, additional measurements were also made on boehmite solubility in pure NaOH solutions in order to bolster the database for fitting in-house isopiestic data on this system. Preliminary kinetic Measurements of the dissolution/precipitation of boehmite was also carried out, although these were also not planned in the earlier objective. The 1999 objectives are to incorporate these treatments into existing codes used by the geothermal industry to predict the chemistry ofthe reservoirs; these calculations will be tested for reliability against our laboratory results and field observations. Moreover, based on the success of the experimental methods developed in this program, we intend to use our unique high temperature pH easurement capabilities to make kinetic and equilibrium studies of pH-dependent aluminosilicate transformation reactions and other pH-dependent heterogeneous reactions.
Date: May 18, 1999
Creator: Benezeth, P.; Palmer, D. A. & Wesolowski, D. J.
Partner: UNT Libraries Government Documents Department

Solubility and Surface Adsorption Characteristics of Metal Oxides to High Temperature

Description: The interaction of high temperature aqueous solutions with mineral surfaces plays a key role in many aspects of fossil, geothermal and nuclear energy production. This is an area of study in which the subsurface geochemical processes that determine brine composition, porosity and permeability changes, reservoir integrity, and fluid flow rates overlap with the industrial processes associated with corrosion of metal parts and deposition of solids in pipes and on heat exchanger surfaces. The sorption of ions on mineral surfaces is also of great interest in both the subsurface and ''above ground'' regimes of power production, playing a key role in subsurface migration of contaminants (nuclear waste disposal, geothermal brine re-injection, etc.) and in plant operations (corrosion mitigation, migration of radioactive metals from reactor core to heat exchanger, etc.). In this paper, results of the solubility and surface chemistry of metal oxides relevant to both regimes are summarized.
Date: May 4, 2001
Creator: Wesolowski, D.J.; Machesky, M.L.; Ziemniak, S.E.; Xiao, C.; Palmer, D.A.; Anovitz, L.M. et al.
Partner: UNT Libraries Government Documents Department

Microstructural Characterization of Water-Rich Boehmite (AlO(OH)): TEM Correlation of Apparently Divergent XRD and TGA Results

Description: An understanding of the solid-phase thermodynamics and aqueous speciation of aluminum is critical to our ability to understand and predict processes in a wide variety of geologic and industrial settings. Boehmite (AIO(OH)) is an important phase in the system Al<sub>2</sub>O<sub>3</sub>-H<sub>2</sub>O that has been the subject of a number of structural and thermodynamic studies since its initial synthesis [l] and discovery in nature [2]. Unfortunately, it has long been recognized that thermogravimetric analysis (TGA) of both synthetic and natural boehmite samples (that appear well crystallized by powder XRD methods) yields significant excess water - typically losing 16-16.5 wt. % on heating as compared with a nominal expected weight loss of 15.0 wt. % [3,4]. The boehmite used in our experiments was synthesized hydrothermally from acid-washed gibbsite (Al(OH)<suv>3</sub>) at 200°C. Powder XRD and SEM examination showed no evidence of the presence a contaminant phase. The TGA patterns do not suggest that this is due to adsorbed water, so a structural source is likely. We therefore undertook to examine this material by TEM to clarify this phenomenon.
Date: August 1999
Creator: Allard, L. F.; Anovitz, L. M.; Benezeth, P.; Coffey, D. W.; Palmer, D. A.; Porter, W. D. et al.
Partner: UNT Libraries Government Documents Department