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Separation of Aluminum Phosphate Minerals From Kaolinite by Selective Solution

Description: Abstract: Wavellite, crandallite, and millisite are completely dissolved by boiling samples for 20 minutes with 1+1 hydrochloric acid; only 1 percent of the aluminum present in kaolinite is dissolved. This method of decomposition can therefore be used for differentiating the aluminum present in wavellite, crandallite, and millisite form that in kaolinite in samples from the aluminum phosphate zone. This method should prove valuable in prospecting and benefication studies.
Date: September 1955
Creator: May, Irving & Smith, Roberta
Partner: UNT Libraries Government Documents Department

Molecular modeling in support of CO2 sequestration and enhanced oil recovery.

Description: Classical molecular dynamics simulations were used to investigate the formation of water droplets on two kaolinite surfaces: the gibbsite-like surface which is hydrophilic and the silica surface which is hydrophobic. Two methods for calculating contact angles were investigated in detail. The method of Giovambattista et al. was successful in calculating contact angles on both surfaces that compare well to the experimental data available. This is the first time that contact angles have been calculated for kaolinite surfaces from molecular simulations. This preliminary study provides the groundwork for investigating contact angles for more complex systems involving multiple fluids (water, CO{sub 2}, oil) in contact with different minerals in the subsurface environment.
Date: January 1, 2011
Creator: Criscenti, Louise Jacqueline & Bracco, Jacquelyn (Georgia Institute of Technology, Atlanta, GA)
Partner: UNT Libraries Government Documents Department

EXPERIMENTAL EVALUATION OF CHEMICAL SEQUESTRATION OF CARBON DIOXIDE IN DEEP AQUIFER MEDIA - PHASE II

Description: In 1998 Battelle was selected by the U.S. Department of Energy's (DOE) National Energy Technology Laboratory (NETL) under a Novel Concepts project grant to continue Phase II research on the feasibility of carbon dioxide (CO{sub 2}) sequestration in deep saline formations. The focus of this investigation is to conduct detailed laboratory experiments to examine factors that may affect chemical sequestration of CO{sub 2} in deep saline formations. Reactions between sandstone and other geologic media from potential host reservoirs, brine solutions, and CO{sub 2} are being investigated under high-pressure conditions. Some experiments also include sulfur dioxide (SO{sub 2}) gases to evaluate the potential for co-injection of CO{sub 2} and SO{sub 2} related gases in the deep formations. In addition, an assessment of engineering and economic aspects is being conducted. This current Technical Progress Report describes the status of the project as of September 2000. The major activities undertaken during the quarter included several experiments conducted to investigate the effects of pressure, temperature, time, and brine composition on rock samples from potential host reservoirs. Samples (both powder and slab) were taken from the Mt. Simon Sandstone, a potential CO{sub 2} host formation in the Ohio, the Eau Claire Shale, and Rome Dolomite samples that form the caprock for Mt. Simon Sandstone. Also, a sample with high calcium plagioclase content from Frio Formation in Texas was used. In addition, mineral samples for relatively pure Anorthite and glauconite were experimented on with and without the presence of additional clay minerals such as kaolinite and montmorillonite. The experiments were run for one to two months at pressures similar to deep reservoirs and temperatures set at 50 C or 150 C. Several enhancements were made to the experimental equipment to allow for mixing of reactants and to improve sample collection methods. The resulting fluids (gases and ...
Date: November 28, 2000
Creator: Gupta, Neeraj; Sass, Bruce & Ickes, Jennifer
Partner: UNT Libraries Government Documents Department

Competitive sorption of cadmium and lead in acid soils of central Spain

Description: The bioavailability and ultimate fate of heavy metals in the environment are controlled by chemical sorption. To assess competitive sorption of Pb and Cd, batch equilibrium experiments (generating sorption isotherms) and kinetics sorption studies were performed using single and binary metal solutions in surface samples of four soils from central Spain. For comparisons between soils, as well as, single and binary metal solutions, soil chemical processes were characterized using the Langmuir equation, ionic strength, and an empirical power function for kinetic sorption. In addition, soil pH and clay mineralogy were used to explain observed sorption processes. Sorption isotherms were well described by the Langmuir equation and the sorption kinetics were well described by an empirical power function within the reaction times in this study. Soils with higher pH and clay content (characterized by having smectite) had the greatest sorption capacity as estimated by the maximum sorption parameter (Q) of the Langmuir equation. All soils exhibited greater sorption capacity for Pb than Cd and the presence of both metals reduced the tendency for either to be sorbed although Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (k) was always greater for Pb than for Cd. However, these k values tended to increase as a result of the simultaneous presence of both metals, that may indicate competition for sorption sites promoting the retention of both metals on more specific sorption sites. The kinetic experiments showed that Pb sorption is initially faster than Cd sorption from both single and binary solutions although the simultaneous presence of both metals affected the sorption of Cd at short times while only a minor effect was observed on Pb. The estimated exponents of the kinetic function were in all cases smaller for Pb than for Cd, likely due ...
Date: January 30, 2004
Creator: Serrano, S.; Garrido, F.; Campbell, C.G. & Garcia-Gonzolez, Maria Teresa
Partner: UNT Libraries Government Documents Department

IMPROVED MISCIBLE NITROGEN FLOOD PERFORMANCE UTILIZING ADVANCED RESERVOIR CHARACTERIZATION AND HORIZONTAL LATERALS IN A CLASS I RESERVOIR - EAST BINGER (MARCHAND) UNIT

Description: The first horizontal well ever in the Marchand sandstone has been drilled. Although major difficulties arose with certain aspects of the drilling operation, a horizontal section of approximately 1300 was drilled. The section was left open hole as planned. The shales just above and between the Marchand sands appear to be very water-sensitive, requiring careful drilling practices. These shales were encountered in the middle part of the curve (45{sup o}-60{sup o}), which can be the most difficult part of a directional well to clean. Difficulties with these shales and cleaning this section led to a parted drill string, requiring a sidetrack. There were no major geologic ''surprises'', such as formation tops coming in much shallower or deeper than expected, or unexpected faults. Thin kaolinite beds were encountered in the horizontal section of the well. Previous descriptions of the mineralogy of this formation did not mention any kaolinite. The lateral extent of these beds is unknown. Completion of the well is under way. One additional injection profile was gathered during the quarter. Results are consistent with other recently profiles that show gas within the C Sand is overriding the oil and failing to sweep the deeper parts of the reservoir. International Reservoir Technologies, Inc. has completed the construction of the pilot area reservoir simulation model and the updating of historical production and injection data. They have begun fine-tuning the history match to better match production data and recently acquired pressure and profile data.
Date: August 10, 2001
Creator: Sinner, Joe
Partner: UNT Libraries Government Documents Department

Reactive barriers for {sup 137}Cs retention

Description: {sup 137}Cs was dispersed globally by cold war activities and, more recently, by the Chernobyl accident. Engineered extraction of {sup 137}Cs from soils and groundwaters is exceedingly difficult. Because the half life of {sup 137}Cs is only 30.2 years, remediation might be more effective (and less costly) if {sup 137}Cs bioavailability could be demonstrably limited for even a few decades by use of a reactive barrier. Essentially permanent isolation must be demonstrated in those few settings where high nuclear level wastes contaminated the environment with {sup 135}Cs (half life 2.3x10{sup 6} years) in addition to {sup 137}Cs. Clays are potentially a low-cost barrier to Cs movement, though their long-term effectiveness remains untested. To identify optimal clays for Cs retention Cs resorption was measured for five common clays: Wyoming Montmorillonite (SWy-1), Georgia Kaolinites (KGa-1 and KGa-2), Fithian Illite (F-Ill), and K-Metabentonite (K-Mbt). Exchange sites were pre-saturated with 0.16 M CsCl for 14 days and readily exchangeable Cs was removed by a series of LiNO{sub 3} and LiCl washes. Washed clay were then placed into dialysis bags and the Cs release to the deionized water outside the bags measured. Release rates from 75 to 139 days for SWy-1, K-Mbt and F- 111 were similar; 0.017 to 0.021% sorbed Cs released per day. Both kaolinites released Cs more rapidly (0.12 to 0.05% of the sorbed Cs per day). In a second set of experiments, clays were doped for 110 days and subjected to an extreme and prolonged rinsing process. All the clays exhibited some capacity for irreversible Cs uptake so most soils have some limited ability to act as a natural barrier to Cs migration. However, the residual loading was greatest on K-Mbt ({approximately} 0.33 wt% Cs). Thus, this clay would be the optimal material for constructing artificial reactive barriers.
Date: May 19, 2000
Creator: KRUMHANSL,JAMES L.; BRADY,PATRICK V. & ANDERSON,HOWARD L.
Partner: UNT Libraries Government Documents Department

Short-Term Environmental Impacts of Illite Clays When Used As An In SITU Method for Remediating 137Cs-Contaminated Wetland

Description: Over 1,200 hectares (3,000 acres) of wetlands such as L-Lake; Par Pond; Ponds A, 2, 4, 5, and B; canals; and several creeks (e.g. Steel Creek, Lower Three Runs, and Pen Branch) on the Savannah River Site (SRS) are contaminated with 560 Ci of 137Cs. These environmentally sensitive wetlands pose a significant remediation challenge to the Department of Energy (DOE). A new technology is needed to avoid environmentally destructive remediation. Current muck and truck technologies destroy the sensitive ecosystems, and may increase dose to workers. Because of relatively low amount of clay and weak 137Cs retention capabilities of kaolinite dominant sediments on the SRS, 137Cs has a greater bioavailability here than at any other DOE site. We have previously shown that naturally occurring illite minerals, with a high complexing capability for 137Cs, can sequester 137Cs and reduce its bioavailability when applied to 137Cs contaminated wetlands. Previous research showed that an in situ remediation method using illite minerals reduced 137Cs concentrations in the water 25- to 30-fold, in aquatic plants 3- to 5-fold, and in fish 2- to 3-fold. During this funding period (Fy03) we re-sampled study sites in Pond A and R-Canal that had been treated in 2001 with illite clays. The data revealed that 137Cs concentrations in water are still lower than untreated control sites, some 112 weeks later. This encouraging result indicates that the in situ remediation technique has a longer-term effectiveness than was previously reported. This positive finding occurred despite the study site experiencing a severe drought, as well as flooded conditions during the two-year period. Studies on the in situ application of illite minerals to 137Cs-contaminated wetlands continue to produce positive results. Additional measurements are needed, however, to determine the long-term effectiveness of the technique, and the environmental impacts on parameters not measured in this study. ...
Date: May 17, 2004
Creator: KAPLAN, D.I.
Partner: UNT Libraries Government Documents Department

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

Description: In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka marine terrace chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized (White et al., 2008, GCA) and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisser and [2006] or the aluminum inhibition model proposed by Oelkers et al. [1994], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO{sub 2}(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. ...
Date: February 25, 2009
Creator: Maher, K.; Steefel, C. I.; White, A.F. & Stonestrom, D.A.
Partner: UNT Libraries Government Documents Department

Experimental Determination of Contaminant Metal Mobility as a Function of Temperature, Time and Solution Chemistry

Description: During the FY96-FY99 funding cycle we examined the uptake of aqueous strontium onto goethite, kaolinite, and amorphous silica surfaces as a function of pH, total strontium, and temperature. Our overall goal was to produce a mechanistic sorption model that can be used in reaction-transport calculations to predict the mobility and attenuation of radioactive strontium ({sup 90}Sr)in the environment. Our approach was to combine structural information derived from EXAFS analysis together with macroscopic uptake data and surface complexation models to clarify the physical and chemical structure of sorbed complexes. We chose to study these solids because of the prevalence of clays and iron hydroxides in natural systems, and because silica colloids probably form beneath leaking tanks at Hanford as caustic waste is neutralized. We have published the spectroscopic work in two papers in the Journal of Colloid and Interface Science [1, 2], and will soon submit at third manuscript to Geochemical Transactions [3] combining the sorption and spectroscopic data with a mechanistic complexation model. Early in the study we learned that strontium sorption was independent of temperature (25 to 80 C). All subsequent work was conducted at room temperature.
Date: March 1, 2000
Creator: Carroll, S A & O'Day, P A
Partner: UNT Libraries Government Documents Department

A study of competitive adsorption of organic molecules onto mineral oxides using DRIFTS

Description: Analysis of DRIFTS spectra was used for a quantitative study of competitive adsorption of myristic and salicylic acids onto kaolinite or {gamma}-alumina. Peaks unique to the ring or the chain were selected and single molecule studies used as calibration. Samples were exposed to hexane solution containing equal molecular quantities of each acid. The surface loading of salicylic acid was not influenced by the presence of myristic acid on either mineral but the maximum loading of myristic acid was decreased (46-50%) by salicylic acid. Displacement of myristic acid from {gamma}-alumina, but not kaolinite, was observed when excess salicylic acid remained in solution. A 25% increase in the maximum loading was observed for kaolinite, but not for{gamma}-alumina. On {gamma}-alumina, after a loading of 1 molecule per nm{sup 2}, increased exposure resulted in salicylic acid adsorption only, this value is approximately the same for salicylic acid adsorption from aqueous solution or for water washed hexane treated samples. Thus a set of sites for adsorption of either acid is indicated together with other energetically less favorable sites, which can be occupied by salicylic, but not by myristic, acid.
Date: February 1, 2010
Creator: Joan E. Thomas, Michael J. Kelley
Partner: UNT Libraries Government Documents Department

Kaolinite dissolution and precipitation kinetics at 22oC and pH4

Description: Dissolution and precipitation rates of low defect Georgia kaolinite (KGa-1b) as a function of Gibbs free energy of reaction (or reaction affinity) were measured at 22 C and pH 4 in continuously stirred flow through reactors. Steady state dissolution experiments showed slightly incongruent dissolution, with a Si/Al ratio of about 1.12 that is attributed to the re-adsorption of Al on to the kaolinite surface. No inhibition of the kaolinite dissolution rate was apparent when dissolved aluminum was varied from 0 and 60 {micro}M. The relationship between dissolution rates and the reaction affinity can be described well by a Transition State Theory (TST) rate formulation with a Temkin coefficient of 2 R{sub diss} (mol/m{sup 2}s) = 1.15 x 10{sup -13} [1-exp(-{Delta}G/2RT)]. Stopping of flow in a close to equilibrium dissolution experiment yielded at solubility constant for kaolinite at 22 C of 10{sup 7.57}. Experiments on the precipitation kinetics of kaolinite showed a more complex behavior. One conducted using kaolinite seed that had previously undergone extensive dissolution under far from equilibrium conditions for 5 months showed a quasi-steady state precipitation rate for 105 hours that was compatible with the TST expression above. After this initial period, however, precipitation rates decreased by an order of magnitude, and like other precipitation experiments conducted at higher supersaturation and without kaolinite seed subjected to extensive prior dissolution, could not be described with the TST law. The initial quasi-steady state rate is interpreted as growth on activated sites created by the dissolution process, but this reversible growth mechanism could not be maintained once these sites were filled. Long-term precipitation rates showed a linear dependence on solution saturation state that is generally consistent with a two dimensional nucleation growth mechanism following the equation R{sub ppt}(mol/m{sup 2}s) = 3.38 x 10{sup -14} exp[181776/T{sup 2}1n{Omega}]. Further analysis using Synchrotron Scanning ...
Date: July 16, 2007
Creator: Yang, Li & Steefel, Carl I.
Partner: UNT Libraries Government Documents Department

Abiotic degradation rates for carbon tetrachloride and chloroform: Final report.

Description: This report documents the objectives, technical approach, and progress made through FY 2012 on a project initiated in FY 2006 to help address uncertainties related to the rates of hydrolysis in groundwater for carbon tetrachloride (CT) and chloroform (CF). The project also sought to explore the possible effects of contact with minerals and sediment (i.e., heterogeneous hydrolysis) on these rates. We conducted 114 hydrolysis rate experiments in sealed vessels across a temperature range of 20-93 °C for periods as long as 6 years, and used the Arrhenius equation to estimate activation energies and calculate half-lives for typical Hanford groundwater conditions (temperature of 16 °C and pH of 7.75). We calculated a half-life of 630 years for hydrolysis for CT under these conditions and found that CT hydrolysis was unaffected by contact with sterilized, oxidized minerals or Hanford sediment within the sensitivity of our experiments. In contrast to CT, hydrolysis of CF was generally slower and very sensitive to pH due to the presence of both neutral and base-catalyzed hydrolysis pathways. We calculated a half-life of 3400 years for hydrolysis of CF in homogeneous solution at 16 °C and pH 7.75. Experiments in suspensions of Hanford sediment or smectite, the dominant clay mineral in Hanford sediment, equilibrated to an initial pH of 7.2, yielded calculated half-lives of 1700 years and 190 years, respectively, at 16 °C. Experiments with three other mineral phases at the same pH (muscovite mica, albite feldspar, and kaolinite) showed no change from the homogeneous solution results (i.e., a half-life of 3400 years). The strong influence of Hanford sediment on CF hydrolysis was attributed to the presence of smectite and its ability to adsorb protons, thereby buffering the solution pH at a higher level than would otherwise occur. The project also determined liquid-vapor partition coefficients for CT under ...
Date: December 1, 2012
Creator: Amonette, James E.; Jeffers, Peter M.; Qafoku, Odeta; Russell, Colleen K.; Humphrys, Daniel R.; Wietsma, Thomas W. et al.
Partner: UNT Libraries Government Documents Department

Isolation of Metals from Liquid Wastes: Reactive Scavenging in Turbulent Thermal Reactors

Description: Sorption of cesium and strontium on kaolinite powders was investigated as a means to minimize the emissions of these metals during certain high temperature processes currently being developed to isolate and dispose of radiological and mixed wastes. In this work, non-radioactive aqueous cesium acetate or strontium acetate was atomized down the center of a natural gas flame supported on a variable-swirl burner in a refractory-lined laboratory-scale combustion facility. Kaolinite powder was injected at a post-flame location in the combustor. Cesium readily vaporizes in the high temperature regions of the combustor, but was reactively scavenged onto dispersed kaolinite. Global sorption mechanisms of cesium vapor on kaolinite were quantified, and are related to those available in the literature for sodium and lead. Both metal adsorption and substrate deactivation steps are important, and so there is an optimum temperature, between 1400 and 1500 K, at which maximum sorption occurs. The presence of chlorine inhibits cesium sorption. In contrast to cesium, and in the absence of chlorine, strontium was only partially vaporized and was, therefore, only partially scavengeable. The strontium data did not allow quantification of global kinetic mechanisms of interaction, although equilibrium arguments provided insight into the effects of chlorine on strontium sorption. These results have implications for the use of sorbents to control cesium and strontium emissions during high temperature waste processing including incineration and vitrification.
Date: December 16, 2004
Creator: Linak, William
Partner: UNT Libraries Government Documents Department

Metal sorption on kaolinite

Description: A key issue in performance assessment of low-level radioactive waste sites is predicting the transport and retardation of radionuclides through local soils under a variety of hydrologic and geochemical conditions. Improved transport codes should include a mechanistic model of radionuclide retardation. The authors have been investigating metal sorption (Cs{sup +}, Sr{sup 2+}, and Ba{sup 2+}) on a simple clay mineral (kaolinite) to better understand the geochemical interactions of common soil minerals with contaminated groundwaters. These studies include detailed characterizations of kaolinite surfaces, experimental adsorption measurements, surface complexation modeling, and theoretical simulations of cation sorption. The aluminol edge (010) site has been identified as the most likely site for metal sorption on kaolinite in natural solutions. Relative metal binding strengths decrease from Ba{sup 2+} to Sr{sup 2+} to Cs{sup +}, with some portion sorbed on both kaolinite edges and basal surfaces. Some Cs{sup +} also appears to be irreversibly sorbed on both sites. Molecular dynamics simulations suggest that Cs{sup +} is sorbed at aluminol (010) edge sites as an inner-sphere complex and weakly sorbed as an outer-sphere complex on (001) basal surfaces. These results provide the basis to understand and predict metal sorption onto kaolinite, and a framework to characterize sorption processes on more complex clay minerals.
Date: March 1, 1997
Creator: Westrich, H.R.; Brady, P.V.; Cygan, R.T.; Nagy, K.L. & Anderson, H.L.
Partner: UNT Libraries Government Documents Department

Interactions between trace metals, sodium and sorbents in combustion. Quarterly report No. 5, October 1, 1995--December 30, 1995

Description: The proposed research is directed at an understanding of how to exploit interactions between sodium, toxic metals and sorbents, in order to optimize sorbents injection procedures,which can be used to capture and transform these metals into environmentally benign forms. The research will use a 17kW downflow, laboratory combustor, to yield data that can be interpreted in terms of fundamental kinetic mechanisms. Metals to be considered are lead, cadmium, and arsenic. Sorbents will be kaolinite, bauxite, and limestone. The role of sulfur will also be determined. The research is divided into the following five tasks: (1) combustor modifications; (2) screening experiments; (3) mechanisms; (4) applications and (5) mathematical modelling. Accomplishments for this past quarter are briefly described for tasks 1 and 2.
Date: June 1, 1996
Creator: Wendt, J.O.L. & Davis, S.
Partner: UNT Libraries Government Documents Department

The sorption behavior of Cs and Cd onto oxide and clay surfaces

Description: The sorption of Cs and Cd on model soil minerals was examined by complementary analytical and experimental procedures. X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR) spectroscopy were used to characterize the chemical and physical nature of Cs-reacted soil minerals. Cd and Cs adsorption isotherms for kaolinite were also measured at variable pH and temperature to establish likely reaction stoichiometries, while atomic force microscopy (AFM) was used to characterize the microtopography of the clay surface. XPS analyses of Cs-exchanged samples show that Cs is sorbed at mineral surfaces and at the interlayer site of smectite clays, although the spectral resolution of XPS analyses is insufficient to differentiate between basal, edge or interlayer sites. {sup 133}Cs MAS-NMR results also show that Cs is adsorbed primarily in an interlayer site of montmorillonite and on edge and basal sites for kaolinite. Cd adsorption isotherms on kaolinite were found to be additive using Al{sub 2}0{sub 3} + Si0{sub 2} Cd binding constants. AFM quantification of kaolinite crystallites suggest that edges comprise up to 50% of the BET surface area, and are consistent with NMR and surface charge results that Cs an Cd adsorption occur primarily at edge sites.
Date: March 1, 1995
Creator: Westrich, H.R.; Cygan, R.T.; Brady, P.V.; Nagy, K.L.; Anderson, H.L. & Kirkpatrick, R.J.
Partner: UNT Libraries Government Documents Department

Measurement of Optical Properties of Small Particles

Description: We have measured the optical constants of montmorillonite and the separated coats and cores of B. subtilis spores over the wavelength interval from 200 nm to 2500 nm. The optical constants of kaolin were obtained over the wavelength interval from 130 nm to 2500 nm. Our results are applicable to the development of systems for detection of airborne biological contaminants. Future work will include measurement of the optical constants of B. cereus spores, B. sub tilts vegetative cells, egg albumin, illite, and a mixture (by weight) of one third kaolin, one third montmorillonite, and one third illite.
Date: December 1, 1997
Creator: Arakawa, E.T.; Tuminello, P.S.; Khare, B.N.; Millham, M.E.; Authier, S. & Pierce, J.
Partner: UNT Libraries Government Documents Department

Caustic Waste-Soil Weathering Reactions and Their Impacts on Trace Contaminant Migration and Sequestration

Description: We are studying Cs, Sr and I uptake and release during clay mineral weathering under conditions representative of caustic tank waste leachate. Cesium sorption after 1 year reaction was the greatest in the order of vermiculite, illite, montmorillonite and kaolinite. Vermiculite showed highest Sr sorption, followed by kaolinite, montmorillonite and illite. Secondary phase products were feldspathoid sodium aluminum nitrate silicate, sodium aluminum nitrate silicate hydrate, Na-Al chabazite and zeolite X. Discrete Sr phases were found in kaolinite and illite systems after at 10{sup -3} M Cs/Sr. Transmission electron microscopy with EDS indicates a high single Sr phase in illite systems. Spheroidal secondary phases are common in all clay consisting of intergrown Na-containing sodalite and cancrinite. In the case of illite, montmorillonite and kaolinite, Cs or Sr are found in association with these neoformed spheroidal secondary phases, but this is not the case in vermiculite systems. In vermiculite, most of Cs and Sr is associated with clay particle, presumably because of its high charge density, rather than secondary phases. For detailed investigations of Cs/Sr coprecipitation with neoformed alumosilicate during the clay weathering process, we are conducting homogeneous nucleation experiments in the absence of clay minerals. Silica is reacted with synthetic tank waste to elucidate sites of Cs, Sr and I uptake in products. We are varying the Si/Al and the initial Cs, Sr and I concentrations to examine effects on mineral formation and uptake rate. To date, we have observed that precipitation kinetics and the nature of reaction products varies with initial Cs, Sr and I concentration. Solid phase products are being investigated by XRD, FTIR, NMR and EXAFS, and are also being subjected to dissolution kinetics studies to assess long term stability.
Date: June 1, 2003
Creator: Chorover, Jon D.
Partner: UNT Libraries Government Documents Department

FINE PARTICAL AND TOXIC METAL EMISSIONS FROM THE COMBUSTION OF SEWAGE SLUDGE/COAL MIXTURES: A SYSTEMATIC ASSESSMENT

Description: This research project focuses on pollutants from the combustion of mixtures of dried municipal sewage sludge (MSS) and pulverized coal. The objective was to determine potential tradeoffs between CO{sub 2} mitigation through using a CO{sub 2} neutral fuel, such as municipal sewage sludge, and the emergence of other potential problems such as the emission of toxic fly ash particles. The work led to new insight into mechanisms governing the partitioning of major and trace metals from the combustion of sewage sludge, and mixtures of coal and sewage sludge. The research also showed that the co-combustion of coal and sewage sludge emitted fine particulate matter that might potentially cause greater lung injury than that from the combustion of either coal alone or municipal sewage sludge alone. The reason appeared to be that the toxicity measured required the presence of large amounts of both zinc and sulfur in particles that were inhaled. MSS provided the zinc while coal provided the sulfur. Additional research showed that the toxic effects could most likely be engineered out of the process, through the introduction of kaolinite sorbent downstream of the combustion zone, or removing the sulfur from the fuel. These results are consequences of applying ''Health Effects Engineering'' to this issue. Health Effects Engineering is a new discipline arising out of this work, and is derived from using a collaboration of combustion engineers and toxicologists to mitigate the potentially bad health effects from combustion of this biomass fuel.
Date: September 21, 2003
Creator: Wendt, Jost O.L.; Seames, Wayne S. & Fernandez, Art
Partner: UNT Libraries Government Documents Department

MINERAL-SURFACTANT INTERACTIONS FOR MINIMUM REAGENTS PRECIPITATION AND ADSORPTION FOR IMPROVED OIL RECOVERY

Description: Significant surfactant loss by adsorption or precipitation on reservoir minerals can cause chemical flooding processes to be less than satisfactory for enhanced oil recovery. This project is aimed towards an understanding of the role of reservoir minerals and their dissolved species in chemical loss by precipitation or adsorption of surfactants/polymers in enhanced oil recovery. Emphasis will be on the type and nature of different minerals in the oil reservoirs. Macroscopic adsorption, precipitation, wettability and nanoscopic orientation/conformation studies for aggregates of various surfactant/polymer mixtures on reservoir rocks systems is planned for exploring the cause of chemical loss by means of precipitation or adsorption, and the effect of rock mineralogy on the chemical loss. During this reporting period, the minerals proposed in this study: sandstone, limestone, gypsum, kaolinite and pyrite, have been characterized to obtain their particle size distribution and surface area, which will be used in the analysis of adsorption and wettability data. The effect of surfactant mixing ratio on the adsorption of mixture of C{sub 12}-C{sub 4}-C{sub 12} Gemini surfactant (synthesized during last period) and sugar-based nonionic surfactant n-dodecyl-{beta}-D-maltoside (DM) has been studied. It was discovered that even trace amounts of Gemini in the mixture is sufficient to force significant adsorption of DM. DM adsorption on silica increased from relatively negligible levels to very high levels. It is clear form analysis of the results that desired adsorption of either surfactant component in the mixtures can be obtained by controlling the mixing ratio, the total mixture concentration, pH etc. Along with these adsorption studies, changes in mineral wettability due to the adsorption of Gemini/DM mixtures were determined under relevant conditions to identify the nano-structure of the adsorbed layers. With increasing total surfactant adsorption, the silica mineral undergoes a wettability change from hydrophilic surface to hydrophobic and then revert to hydrophilic surface. ...
Date: October 30, 2004
Creator: Somasundaran, P.
Partner: UNT Libraries Government Documents Department

Sorption Energy Maps of Clay Mineral Surfaces

Description: A molecular-level understanding of mineral-water interactions is critical for the evaluation and prediction of the sorption properties of clay minerals that may be used in various chemical and radioactive waste disposal methods. Molecular models of metal sorption incorporate empirical energy force fields, based on molecular orbital calculations and spectroscopic data, that account for Coulombic, van der Waals attractive, and short-range repulsive energies. The summation of the non-bonded energy terms at equally-spaced grid points surrounding a mineral substrate provides a three dimensional potential energy grid. The energy map can be used to determine the optimal sorption sites of metal ions on the exposed surfaces of the mineral. By using this approach, we have evaluated the crystallographic and compositional control of metal sorption on the surfaces of kaolinite and illite. Estimates of the relative sorption energy and most stable sorption sites are derived based on a rigid ion approximation.
Date: July 19, 1999
Creator: Cygan, Randall T. & Kirkpatrick, R. James
Partner: UNT Libraries Government Documents Department

Experimental Determination of Contaminant Metal Mobility as a Function of Temperature, Time, and Solution Chemistry

Description: During the FY96-FY99 funding cycle we examined the uptake of aqueous strontium onto goethite, kaolinite, and amorphous silica surfaces as a function of pH, total strontium, and temperature. Our overall goal was to produce a mechanistic sorption model that can be used in reaction-transport calculations to predict the mobility and attenuation of radioactive strontium (90Sr) in the environment. Our approach was to combine structural information derived from synchrotron-based x-ray absorption spectroscopic analysis together with macroscopic uptake data and surface complexation models to clarify the physical and chemical structure of sorbed complexes. We chose to study these solids because of the prevalence of clays and iron hydroxides in natural systems, and because silica colloids probably form beneath leaking tanks at Hanford as caustic waste is neutralized. We have published the spectroscopic work in two papers in the Journal of Colloid and Interface Science [1, 2], and will soon submit at third manuscript to Geochemical Transactions [3] combining the sorption and spectroscopic data with a mechanistic complexation model.
Date: December 31, 1999
Creator: Carroll, Susan A. & O'Day, Peggy A.
Partner: UNT Libraries Government Documents Department

Caustic Waste-Soil Weathering Reactions and Their Impacts on Trace Contaminant Migration and Sequestration

Description: High pH waste solutions are in gross chemical disequilibrium with the subsurface environment and react with sediment minerals, promoting dissolution and precipitation processes that impact 137Cs, 90Sr, and 129I speciation and migration behavior in the vadose zone. We have conducted long-term kinetic studies, with reaction times ranging from 1 to 369 d, to examine relationships between aluminosilicate weathering in the presence of synthetic tank waste leachate (STWL) and contaminant uptake and release. Our experiments employ a sequence of specimen clay minerals including illite, vermiculite, montmorillonite and kaolinite, which are also important reactive solids in the Hanford sediments. These studies have shown direct coupling between mineral transformation reactions and contaminant sequestration/stabilization.
Date: June 1, 2003
Creator: Chorover, Jon; Mueller, Karl T.; O'Day, Peggy & Serne, R. Jeff
Partner: UNT Libraries Government Documents Department

Geochemistry of Hydrofluoric Acid in Kaolinitic Soils

Description: This document explores the geochemical reactions likely to occur when hydrofluoric acid is spilled on Savannah River Site (SRS) soil. In particular, we evaluate the potential of environmental damage from a one-time release of concentrated hydrofluoric acid into a trench. According to interviews with personnel involved, sometime between 1955 and 1960 drums of 50-60 per cent hydrofluoric acid were disposed in a trench in the Central Shops area. The method of disposal suggests that most of the acid would have been released at the time of burial. No evidence of drum disposal or acidic pH values was found. Therefore, the Soil and Groundwater Closure Projects group requested that we evaluate potential risk by examining the major geochemical interactions expected between hydrofluoric acid and soil. The geochemical calculations in this report were done with The Geochemist's Workbench (Registered). This program uses an extended Debye-Huckel method for calculating activity coefficients. The conclusions of this report are accurate, but some of the intermediate steps may have higher uncertainty. Hydrofluoric acid disposed in a trench in the area would have reacted with soil kaolinite to neutralize the pH to a value of about 4.2. Based on conservative assumptions, this would have occurred within the top 500 cm of soil. This analysis considers only the reaction of the acid with kaolinite. Other processes such as dilution, dispersion, and clogging of permeability would contribute to neutralization of the acid within a shorter distance. When the acid solution reached the water table, dilution would have driven the solution to saturation with gibbsite. A resulting layer enriched in aluminum may be the only remnant of the acid disposal identifiable today. However, any such layer would be difficult to identify because of the normally high aluminum concentrations in the soil. Subtle textural evidence of shallow soil dissolution may be ...
Date: May 11, 2004
Creator: DENHAM, MILES
Partner: UNT Libraries Government Documents Department