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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

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


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


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

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

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

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
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

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

Vadose Zone VOC Mass Transfer Testing At The SRS Miscellaneous Chemical Basin

Description: Active remedial activities have been ongoing since 1996 to address low levels of solvent contamination at the Miscellaneous Chemical Basin at SRS. Contaminant levels in the subsurface may be approaching levels where mass transfer limitations are impacting the efficiency of the remedial action. Rate limited mass transfer effects have been observed at other sites in the vadose zone at the SRS, however, detailed measurements and evaluation has not been undertaken. Anecdotal evidence suggests that the mass transfer rates are very slow from the fine grain sediments. This conclusion is based on the observation that measured soil gas concentrations tend to be low in permeable zones relative to the higher concentrations found in fine grain zones. Decreasing soil gas concentration with depth below the ''upland unit'' at several areas at SRS is also evidence of slow diffusion rates. In addition, due to the length of time since disposal ceased at the MCB, we hypothesize that mobile solvents have migrated downward, and the solvent remaining in the upper fine grain zone (''upland unit'') are trapped in fine grain material and are primarily released by gas diffusion (Riha and Rossabi 2004). Natural weathering and other chemical solutions disposed with the solvents can further enhance this effect by increasing the micro-porosity in the clays (kaolinite). This microporosity can result in increased entrapment of water and solvents by capillary forces (Powers, et. al., 2003). Also supporting this conclusion is the observation that active SVE has proven ineffective on VOC removal from the fine grain zones at the SRS. Adsorption and the very slow release phenomenon have been documented similarly in the literature especially for old solvent spills such as at the SRS (Pavlostathis and Mathavan 1992; Oostrom and Lenhard 2003). Mass transfer relationships need to be developed in order to optimize remediation activities and to ...
Date: October 30, 2005
Creator: Riha, B
Partner: UNT Libraries Government Documents Department

Improved Water Flooding through Injection Brine Modification

Description: Crude oil/brine/rock interactions can lead to large variations in the displacement efficiency of waterflooding, by far the most widely applied method of improved oil recovery. Laboratory waterflood tests show that injection of dilute brine can increase oil recovery. Numerous fields in the Powder River basin have been waterflooded using low salinity brine (about 500 ppm) from the Madison limestone or Fox Hills sandstone. Although many uncertainties arise in the interpretation and comparison of field production data, injection of low salinity brine appears to give higher recovery compared to brine of moderate salinity (about 7,000 ppm). Laboratory studies of the effect of brine composition on oil recovery cover a wide range of rock types and crude oils. Oil recovery increases using low salinity brine as the injection water ranged from a low of no notable increase to as much as 37.0% depending on the system being studied. Recovery increases using low salinity brine after establishing residual oil saturation (tertiary mode) ranged from no significant increase to 6.0%. Tests with two sets of reservoir cores and crude oil indicated slight improvement in recovery for low salinity brine. Crude oil type and rock type (particularly the presence and distribution of kaolinite) both play a dominant role in the effect that brine composition has on waterflood oil recovery.
Date: January 1, 2003
Creator: Robertson, Eric Partridge; Thomas, Charles Phillip; Morrow, Norman & Wyoming), (U of
Partner: UNT Libraries Government Documents Department

Carbonation of Clay Minerals Exposed to scCO2/Water at 200 degrees and 250 degrees C

Description: To clarify the mechanisms of carbonation of clay minerals, such as bentonite, kaolinite, and soft clay, we exposed them to supercritical carbon dioxide (scCO2)/water at temperatures of 200 and 250 C and pressures of 1500 and 2000 psi for 72- and 107-hours. Bentonite, comprising three crystalline phases, montmorillonite (MMT), anorthoclase-type albite, and quartz was susceptible to reactions with ionic carbonic acid yielded by the interactions between scCO2 and water, particularly MMT and anorthoclase-type albite phases. For MMT, the cation-exchangeable ions, such as Na+ and Ca2+, present in its basal interplanar space, were replaced by proton, H+, from ionic carbonic acid; thereafter, the cations leaching from MMT directly reacted with CO32- as a counter ion of H+ to form carbonate compounds. Such in-situ carbonation process in basal space caused the shrinkage and breakage of the spacing structure within MMT. In contrast, the wet carbonation of anorthoclase-type albite, categorized as rock minerals, entailed the formation of three amorphous by-products, such as carbonates, kaolinite-like compounds, and silicon dioxide. Together, these two different carbonations caused the disintegration and corruption of bentonite. Kaolinite clay containing the amorphous carbonates and silicon dioxide was inert to wet carbonation. We noted only a gain in weight due to its water uptake, suggesting that kaolinite-like by-products generated by the wet carbonation of rock minerals might remain unchanged even during extended exposure. Soft clay consisting of two crystalline phases, dolomite and silicon dioxide, also was unaltered by wet carbonation, despite the uptake of water.
Date: November 1, 2010
Creator: Sugama, T.; Ecker, L.; Gill, S.; Butcher, T. (BNL) & Bour, D. (AltaRock Energy, Inc.)
Partner: UNT Libraries Government Documents Department

Geological Results from Drilling in the Poihipi (Western) Sector of the Wairakei Geothermal Field, NZ

Description: Four wells drilled into the Poihipi Sector on the Western margin of the Wairakei geothermal field have found a similar lithostratigraphy to that encountered in wells previously drilled in the general area. Young pumice breccias overly the Huka Falls Formation, with the latter containing intercalations of the Rautehuia Breccia. This in turn overlies ignimbrites and tuffaceous sediments of the Waiora Formation, which contains flows of Haparangi Rhyolite. This sequence is cut by steeply dipping normal faults which strike to the northeast and for the most part dip towards the northwest. Hydrothermal alteration is virtually limited to the Waiora and Haparangi units where a sequence of interlayered illite-smectite and illite clays are found along with chlorite, quartz, pyrite and calcite. There is a minor occurrence of zeolites. Despite large changes in the area's hydrology in response to exploitation, changes in alteration are limited to a comparatively deep occurrence of kaolinite and minor overprinting of epidote by illitic clay.
Date: January 1, 1995
Creator: Bogie, I.; Lawless, J.V. & MacKenzie, K.M.
Partner: UNT Libraries Government Documents Department

Synthesis of hectorite-TiO2 and kaolinite-TiO2 nanocomposites with photocatalytic activity for the degradation of model air pollutants

Description: We studied the synthesis and photocatalytic activity of small-sized TiO{sub 2} supported on hectorite and kaolinite. Deposition of TiO{sub 2} on the clay mineral surface was conducted by using a sol-gel method with titanium isopropoxide as precursor. Anatase TiO{sub 2} particles formation was achieved by hydrothermal treatment at 180 C. Material characterization was conducted using XRD, SEM, XPS, ICP-OES, BET and porosimetry analysis. Efficiency in synthesizing clay-TiO{sub 2} composites depended strongly on the clay mineral structure. Incorporation of anatase in hectorite, an expandable clay mineral, was found to be very significant (> 36 wt.% Ti) and to be followed by important structural changes at the clay mineral surface. Instead, no major structural modifications of the clay were observed for kaolinite-TiO{sub 2}, as compared with the untreated material. Photocatalytic performance of clay-TiO{sub 2} composites was evaluated with ATR-FTIR following the oxidation of adsorbed toluene and d-limonene, two model air pollutants. In either case, the photocatalytic removal efficiency of these hydrophobic substrates by the synthesized clay-TiO{sub 2} composites was comparable to that observed using pure commercial TiO{sub 2} (Degussa P25).
Date: March 1, 2008
Creator: Destaillats, Hugo; Kibanova, D.; Trejo, M.; Destaillats, H. & Cervini-Silva, J.
Partner: UNT Libraries Government Documents Department

Kaolinite dissolution and precipitation kinetics at 22oC and pH 4

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 flowthrough 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 a 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 ...
Date: April 1, 2008
Creator: Steefel, Carl; Yang, L. & Steefel, C.I.
Partner: UNT Libraries Government Documents Department

Transport and deposition of functionalized CdTe nanoparticles in saturated porous media

Description: Comprehensive understanding of the transport and deposition of engineered nanoparticles (NPs) in subsurface is required to assess their potential negative impact on the environment. We studied the deposition behavior of functionalized quantum dot (QD) NPs (CdTe) in different types of sands (Accusand, ultrapure quartz, and iron-coated sand) at various solution ionic strengths (IS). The observed transport behavior in ultrapure quartz and iron-coated sand was consistent with conventional colloid deposition theories. However, our results from the Accusand column showed that deposition was minimal at the lowest IS (1 mM) and increased significantly as the IS increased. The effluent breakthrough occurred with a delay, followed by a rapid rise to the maximum normalized concentration of unity. Negligible deposition in the column packed with ultrapure quartz sand (100 mM) and Accusand (1 mM) rules out the effect of straining and suggests the importance of surface charge heterogeneity in QD deposition in Accusand at higher IS. Data analyses further show that only a small fraction of sand surface area contributed in QD deposition even at the highest IS (100 mM) tested. The observed delay in breakthrough curves of QDs was attributed to the fast diffusive mass transfer rate of QDs from bulk solution to the sand surface and QD mass transfer on the solid phase. Scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis were used to examine the morphology and elemental composition of sand grains. It was observed that there were regions on the sand covered with layers of clay particles. EDX spectra collected from these regions revealed that Si and Al were the major elements suggesting that the clay particles were kaolinite. Additional batch experiments using gold NPs and SEM analysis were performed and it was observed that the gold NPs were only deposited on clay particles originally on the Accusand surface. ...
Date: October 15, 2010
Creator: Torkzaban, S.; Wan, J.; Kim, Y.; Mulvihill, M. & Tokunaga, T. K.
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