Sample records for dawsonite

  1. Synthesis of Fire-Extinguishing Dawsonites (United States)

    Altman, R. L.


    Simple nonaqueous process synthesizes sodium or potassium, dawsonites effective against hydrocarbon fuel fires. Fire-extinguishing alkali metal dawsonites are prepared using a finely-pulverized equimolar mixture of hydrogen carbonate, or carbonates and aluminum hydroxide heated for 1 to 6 hours under carbon dioxide pressure.

  2. Why is Dawsonite Absent in CO2 Charged Reservoirs?

    International Nuclear Information System (INIS)

    Hellevang, H.; Declercq, J.; Aagaard, P.


    Growth of the sodium-aluminium-hydroxy carbonate dawsonite (NaAl(OH) 2 CO 3 ) after charging saline aquifers with CO 2 has been assumed in a plethora of numerical simulations at different mineralogies, aqueous solutions, pressures and temperatures. It appears however that dawsonite is less abundant than expected in natural CO 2 storage analogues if we take into account the thermodynamic stability alone. We have mapped the thermodynamic stability of dawsonite relative to mineral phases like albite, kaolinite and analcime from 37 to 200 C and performed closed-system batch kinetic simulations using a new kinetic expression including a nucleation term based on classical nucleation theory, and a growth term that was based on BCF growth theory. Using this rate equation, we have performed a sensitivity study on dawsonite growth on mineralogy, temperature, CO 2 pressure, nucleation rate and its dependencies on temperature and affinity, and on the dawsonite precipitation rate coefficient. Simulations with dawsonite growth disabled showed that the maximum over-saturation reached for dawsonite for seawater-like solutions never exceeded 3-4 times over-saturation. The positive effect on dawsonite growth of increasing the CO 2 pressure was mostly neutralized by higher acidity. Decreasing the precipitation rate coefficient by 5 orders of magnitude had a limited effect on the onset of significant growth, but the amount of dawsonite formed at the end of the 1 000 years simulated time was only 37% below the high-rate case. Reducing the nucleation rates had similar effects leading to postponed dawsonite growth. Finally, based on thermodynamic considerations and numerical simulations, we suggest that the potential of dawsonite growth is limited to a medium-temperature window framed by a high thermodynamic stability relative to competing mineral phases at low temperatures, but with rapidly diminishing nucleation and growth rates at lower temperatures constrained by energy barriers

  3. Solution mining dawsonite from hydrocarbon containing formations with a chelating agent (United States)

    Vinegar, Harold J [Bellaire, TX


    A method for treating an oil shale formation comprising dawsonite includes providing heat from one or more heaters to the formation to heat the formation. Hydrocarbon fluids are produced from the formation. At least some dawsonite in the formation is decomposed with the provided heat. A chelating agent is provided to the formation to dissolve at least some dawsonite decomposition products. The dissolved dawsonite decomposition products are produced from the formation.

  4. Why is Dawsonite Absent in CO2 Charged Reservoirs? Pourquoi la dawsonite est-elle absente des réservoirs chargés en CO2 ?


    Hellevang H.; Declercq J.; Aagaard P.


    Growth of the sodiumaluminium-hydroxy carbonate dawsonite (NaAl(OH)2CO3) after charging saline aquifers with CO2 has been assumed in a plethora of numerical simulations at different mineralogies, aqueous solutions, pressures and temperatures. It appears however that dawsonite is less abundant than expected in natural CO2 storage analogues if we take into account the thermodynamic stability alone. We have mapped the thermodynamic stability of dawsonite relative to mineral phases like al...

  5. Evidence for dawsonite in Hanford high-level nuclear waste tanks. (United States)

    Reynolds, Jacob G; Cooke, Gary A; Herting, Daniel L; Warrant, R Wade


    Gibbsite [Al(OH)(3)] and boehmite (AlOOH) have long been assumed to be the most prevalent aluminum-bearing minerals in Hanford high-level nuclear waste sludge. The present study shows that dawsonite [NaAl(OH)(2)CO(3)] is also a common aluminum-bearing phase in tanks containing high total inorganic carbon (TIC) concentrations and (relatively) low dissolved free hydroxide concentrations. Tank samples were probed for dawsonite by X-ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive Spectrometry (SEM-EDS) and Polarized Light Optical Microscopy. Dawsonite was conclusively identified in four of six tanks studied. In a fifth tank (AN-102), the dawsonite identification was less conclusive because it was only observed as a Na-Al bearing phase with SEM-EDS. Four of the five tank samples with dawsonite also had solid phase Na(2)CO(3) · H(2)O. The one tank without observable dawsonite (Tank C-103) had the lowest TIC content of any of the six tanks. The amount of TIC in Tank C-103 was insufficient to convert most of the aluminum to dawsonite (Al:TIC mol ratio of 20:1). The rest of the tank samples had much lower Al:TIC ratios (between 2:1 and 0.5:1) than Tank C-103. One tank (AZ-102) initially had dawsonite, but dawsonite was not observed in samples taken 15 months after NaOH was added to the tank surface. When NaOH was added to a laboratory sample of waste from Tank AZ-102, the ratio of aluminum to TIC in solution was consistent with the dissolution of dawsonite. The presence of dawsonite in these tanks is of significance because of the large amount of OH(-) consumed by dawsonite dissolution, an effect confirmed with AZ-102 samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. SEM, EDS and vibrational spectroscopic study of dawsonite NaAl(CO3)(OH)2 (United States)

    Frost, Ray L.; López, Andrés; Scholz, Ricardo; Sampaio, Ney Pinheiro; de Oliveira, Fernando A. N.


    In this work we have studied the mineral dawsonite by using a combination of scanning electron microscopy with EDS and vibrational spectroscopy. Single crystals show an acicular habitus forming aggregates with a rosette shape. The chemical analysis shows a phase composed of C, Al, and Na. Two distinct Raman bands at 1091 and 1068 cm-1 are assigned to the CO32- ν1 symmetric stretching mode. Multiple bands are observed in both the Raman and infrared spectra in the antisymmetric stretching and bending regions showing that the symmetry of the carbonate anion is reduced and in all probability the carbonate anions are not equivalent in the dawsonite structure. Multiple OH deformation vibrations centred upon 950 cm-1 in both the Raman and infrared spectra show that the OH units in the dawsonite structure are non-equivalent. Raman bands observed at 3250, 3283 and 3295 cm-1 are assigned to OH stretching vibrations. The position of these bands indicates strong hydrogen bonding of the OH units in the dawsonite structure. The formation of the mineral dawsonite has the potential to offer a mechanism for the geosequestration of greenhouse gases.

  7. Dawsonite and other carbonate veins in the Cretaceous Izumi Group, SW Japan: a natural support for fracture self-sealing in mud-stone cap-rock in CGS?

    Energy Technology Data Exchange (ETDEWEB)

    Okuyama, Yasuko; Funatsu, Takahiro; Fujii, Takashi [Institute for Geo-Resources and environment, GSJ, AISI, 1-1-1 Higashi, Central 7, Tsukuba, ibaraki 305-8567 (Japan); Take, Shuji [Kishiwada Nature Club, c/o Kishiwada City Natural History Museum, Sakai-Machi 5-6, Kishiwada, Osaka 596-0072 (Japan)


    Dawsonite-bearing carbonate veins are abundant in a compact mud-stone layer of the lower part of the Izumi Group, SW Japan. The mode of occurrence of the veins probably indicates fracturing and mineral sealing associated with upwelling of CO{sub 2}-rich fluid evolved in the reservoir beneath. The carbonate veins studied here can be a natural support to fracturing and healing of mud-stone cap-rock in the CO{sub 2} geological storage. (authors)

  8. Synthesis of alumina/YAG 20 vol% composite by co-precipitation

    Directory of Open Access Journals (Sweden)

    Radosław Lach


    Full Text Available Co-precipitation of alumina/YAG precursor from aluminum and yttrium nitrate solution with ammonium carbonate results in dawsonite. Its crystallographic parameters differ from the compound precipitated with no yttrium additive. It suggests that yttrium ions become incorporated into the dawsonite structure. The DSC/TG and X-ray diffraction measurements show decomposition of dawsonite at elevated temperatures resulting in γ-Al2O3 and then δ- and θ-alumina modifications. Full transformation to α-Al2O3 and YAG occurs at temperatures higher than 1230°C. Starting powder for the sintering experiments was prepared using the coprecipitated precursor calcined at 600°C. Seeding of such powder with 5 wt.% α-Al2O3 results in material of 98% density at 1500°C. Much lower densification show compacts of unseeded powder.

  9. Experimental and simulation studies of iron oxides for geochemical fixation of CO2-SO2 gas mixtures (United States)

    Garcia, Susana; Rosenbauer, Robert J.; Palandri, James; Maroto-Valer, M. Mercedes


    Iron-bearing minerals are reactive phases of the subsurface environment and could potentially trap CO2–SO2gas mixtures derived from fossil fuel combustion processes by their conversion to siderite (FeCO3) and dissolved sulfate. Changes in fluid and mineral compositions resulting from reactions, involving the co-injection of SO2 with CO2 were observed both theoretically and experimentally. Experiments were conducted with a natural hematite (α-Fe2O3) sample. A high pressure-high temperature apparatus was used to simulate conditions in geologic formations deeper than 800 m, where CO2 is in the supercritical state. Solid samples were allowed to react with a NaCl–NaOH brine and SO2-bearing CO2-dominated gas mixtures. The predicted equilibrium mineral assemblage at 100 °C and 250 bar became hematite, dawsonite (NaAl(OH)2CO3), siderite (FeCO3) and quartz (SiO2). Experimentally, siderite and dawsonite, derived from the presence of kaolinite (Al2Si2O5(OH)4) in the parent material, were present in residual solids at longer reaction time intervals, which agreed well with results from the modelling work.

  10. Interactions between CO2, saline water and minerals during geological storage of CO2

    International Nuclear Information System (INIS)

    Hellevang, Helge


    The topic of this thesis is to gain a better understanding of interactions between injected CO 2 , aqueous solutions and formation mineralogies. The main focus is concerned with the potential role mineral reactions play in safe long term storage of CO 2 . The work is divided into an experimental part concentrated on the potential of dawsonite (NaAl(OH) 2 CO 3 ) as a permanent storage host of CO 2 , and the development of a new geochemical code ACCRETE that is coupled with the ATHENA multiphase flow simulator. The thesis is composed of two parts: (I) the first part introducing CO 2 storage, geochemical interactions and related work; and (II) the second part that consists of the papers. Part I is composed as follows: Chapter 2 gives a short introduction to geochemical reactions considered important during CO 2 storage, including a thermodynamic framework. Chapter 3 presents objectives of numerical work related to CO 2 -water-rock interactions including a discussion of factors that influence the outcome of numerical simulations. Chapter 4 presents the main results from paper A to E. Chapter 5 give some details about further research that we propose based on the present work and related work in the project. Several new activities have emerged from research on CO 2 -water-rock interaction during the project. Several of the proposed activities are already initiated. Papers A to F are then listed in Part II of the thesis after the citation list. The thesis presents the first data on the reaction kinetics of dawsonite at different pH (Paper A), and comprehensive numerical simulations, both batch- and large scale 3D reactive transport, that illustrate the role different carbonates have for safe storage of CO 2 in geological formations (Papers C to F). The role of dawsonite in CO 2 storage settings is treated throughout the study (Papers A to E) After the main part of the thesis (Part I and II), two appendices are included: Appendix A lists reactions that are included in the

  11. Market analysis of shale oil co-products. Summary report

    Energy Technology Data Exchange (ETDEWEB)


    This study examines the potential for separating, upgrading and marketing sodium mineral co-products together with shale oil production. The co-products investigated are soda ash and alumina which are derived from the minerals nahcolite and dawsonite. Five cases were selected to reflect the variance in mineral and shale oil content in the identified resource. In the five cases examined, oil content of the shale was varied from 20 to 30 gallons per ton. Two sizes of facilities were analyzed for each resource case to determine economies of scale between a 15,000 barrel per day demonstration unit and a 50,000 barrel per day full sized plant. Three separate pieces of analysis were conducted in this study: analysis of manufacturing costs for shale oil and co-products; projection of potential world markets for alumina, soda ash, and nahcolite; and determination of economic viability and market potential for shale co-products.

  12. Final Report of Tank 241-C-105 Dissolution, the Phase 2 Study

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    Meznarich, Huei K. [Washington River Protection Solutions LLC., Richland, WA (United States); bolling, Stacey D. [Washington River Protection Solutions LLC., Richland, WA (United States); Cooke, Gary A. [Washington River Protection Solutions LLC., Richland, WA (United States); Ely, Thomas M. [Washington River Protection Solutions LLC., Richland, WA (United States); Herting, Daniel L. [Washington River Protection Solutions LLC., Richland, WA (United States); Lachut, James S. [Washington River Protection Solutions LLC., Richland, WA (United States); LaMothe, Margaret E. [Washington River Protection Solutions LLC., Richland, WA (United States)


    Three clamshell grab samples were taken from Tank 241-C-105 in October 2015 in accordance with RPP-PLAN-60011. Analytical results of those samples were issued in the report RPP-RPT-59115 by Wastren Advantage, Inc., Hanford Laboratory. Solid phase characterization results were reported separately in LAB-RPT-15-00011 and in RPP-RPT-59147. The major solid phases reported to be present were dawsonite [NaAlCO3(OH)2], trona [Na3(HCO3)(CO3)·2H2O], cejkaite [Na4(UO2)(CO3)3], and an unidentified organic solid, with minor amounts of gibbsite [Al(OH)3], natrophosphate [Na7F(PO4)2·19H2O], and traces of unidentified iron-rich and manganese-rich phases. Note that the presence of dawsonite, trona, and cejkaite requires a relatively low pH, likely around pH 9 to 10. One aliquot of each grab sample was provided to 222-S Laboratory Process Chemistry for dissolution studies. Phase 1 of the dissolution testing followed the approved test plan, WRPS-1404813, Rev. 3, and examined the behavior of the Tank 241-C-105 solids treated with water, 19M sodium hydroxide, 2M nitric acid, and 0.5M oxalic acid/2M nitric acid. Phase 2 of the testing was conducted in accordance with instructions from the client and emphasized treatment with 19M sodium hydroxide followed by water washing. This is the report of the Phase 2 testing.

  13. Final Report of Tank 241-C-105 Dissolution, the Phase 2 Study

    International Nuclear Information System (INIS)

    Meznarich, Huei K.; Bolling, Stacey D.; Cooke, Gary A.; Ely, Thomas M.; Herting, Daniel L.; Lachut, James S.; LaMothe, Margaret E.


    Three clamshell grab samples were taken from Tank 241-C-105 in October 2015 in accordance with RPP-PLAN-60011. Analytical results of those samples were issued in the report RPP-RPT-59115 by Wastren Advantage, Inc., Hanford Laboratory. Solid phase characterization results were reported separately in LAB-RPT-15-00011 and in RPP-RPT-59147. The major solid phases reported to be present were dawsonite [NaAlCO 3 (OH) 2 ], trona [Na 3 (HCO 3 )(CO 3 )⋅2H 2 O], cejkaite [Na 4 (UO 2 )(CO 3 ) 3 ], and an unidentified organic solid, with minor amounts of gibbsite [Al(OH) 3 ], natrophosphate [Na 7 F(PO 4 ) 2 ⋅19H 2 O], and traces of unidentified iron-rich and manganese-rich phases. Note that the presence of dawsonite, trona, and cejkaite requires a relatively low pH, likely around pH 9 to 10. One aliquot of each grab sample was provided to 222-S Laboratory Process Chemistry for dissolution studies. Phase 1 of the dissolution testing followed the approved test plan, WRPS-1404813, Rev. 3, and examined the behavior of the Tank 241-C-105 solids treated with water, 19M sodium hydroxide, 2M nitric acid, and 0.5M oxalic acid/2M nitric acid. Phase 2 of the testing was conducted in accordance with instructions from the client and emphasized treatment with 19M sodium hydroxide followed by water washing. This is the report of the Phase 2 testing.

  14. Site evaluation for U.S. Bureau of Mines experimental oil-shale mine, Piceance Creek basin, Rio Blanco County, Colorado (United States)

    Ege, John R.; Leavesley, G.H.; Steele, G.S.; Weeks, J.B.


    The U.S. Geological Survey is cooperating with the U.S. Bureau of Mines in the selection of a site for a shaft and experimental mine to be constructed in the Piceance Creek basin, Rio Blanco County, Colo. The Piceance Creek basin, an asymmetric, northwest-trending large structural downwarp, is located approximately 40 km (25 mi) west of the town of Meeker in Rio Blanco County, Colo. The oil-shale, dawsonite, nahcolite, and halite deposits of the Piceance Creek basin occur in the lacustrine Green River Formation of Eocene age. In the basin the Green River Formation comprises three members. In ascending order, they are the Douglas Creek, the Garden Gulch, and the Parachute Creek Members, Four sites are presented for consideration and evaluated on geology and hydrology with respect to shale-oil economics. Evaluated criteria include: (1) stratigraphy, (2) size of site, (3) oil-shale yield, (4) representative quantities of the saline minerals dawsonite and nahcolite, which must be present with a minimum amount of halite, (5) thickness of a 'leached' saline zone, (6) geologic structure, (7) engineering characteristics of rock, (8) representative surface and ground-water conditions, with emphasis on waste disposal and dewatering, and (9) environmental considerations. Serious construction and support problems are anticipated in sinking a deep shaft in the Piceance Creek basin. The two major concerns will be dealing with incompetent rock and large inflow of saline ground water, particularly in the leached zone. Engineering support problems will include stabilizing and hardening the rock from which a certain amount of ground water has been removed. The relative suitability of the four potential oil-shale experimental shaft sites in the Piceance Creek basin has been considered on the basis of all available geologic, hydrologic, and engineering data; site 2 is preferred to sites 1, 3, and 4, The units in this report are presented in the form: metric (English). Both units of

  15. How much CO2 is trapped in carbonate minerals of a natural CO2 occurrence? (United States)

    Király, Csilla; Szabó, Zsuzsanna; Szamosfalvi, Ágnes; Cseresznyés, Dóra; Király, Edit; Szabó, Csaba; Falus, György


    Carbon Capture and Storage (CCS) is a transitional technology to decrease CO2 emissions from human fossil fuel usage and, therefore, to mitigate climate change. The most important criteria of a CO2 geological storage reservoir is that it must hold the injected CO2 for geological time scales without its significant seepage. The injected CO2 undergoes physical and chemical reactions in the reservoir rocks such as structural-stratigraphic, residual, dissolution or mineral trapping mechanisms. Among these, the safest is the mineral trapping, when carbonate minerals such as calcite, ankerite, siderite, dolomite and dawsonite build the CO2 into their crystal structures. The study of natural CO2 occurrences may help to understand the processes in CO2 reservoirs on geological time scales. This is the reason why the selected, the Mihályi-Répcelak natural CO2 occurrence as our research area, which is able to provide particular and highly significant information for the future of CO2 storage. The area is one of the best known CO2 fields in Central Europe. The main aim of this study is to estimate the amount of CO2 trapped in the mineral phase at Mihályi-Répcelak CO2 reservoirs. For gaining the suitable data, we apply petrographic, major and trace element (microprobe and LA-ICP-MS) and stable isotope analysis (mass spectrometry) and thermodynamic and kinetic geochemical models coded in PHREEQC. Rock and pore water compositions of the same formation, representing the pre-CO2 flooding stages of the Mihályi-Répcelak natural CO2 reservoirs are used in the models. Kinetic rate parameters are derived from the USGS report of Palandri and Kharaka (2004). The results of petrographic analysis show that a significant amount of dawsonite (NaAlCO3(OH)2, max. 16 m/m%) precipitated in the rock due to its reactions with CO2 which flooded the reservoir. This carbonate mineral alone traps about 10-30 kg/m3 of the reservoir rock from the CO2 at Mihályi-Répcelak area, which is an

  16. Extreme alkali bicarbonate- and carbonate-rich fluid inclusions in granite pegmatite from the Precambrian Rønne granite, Bornholm Island, Denmark (United States)

    Thomas, Rainer; Davidson, Paul; Schmidt, Christian


    Our study of fluid and melt inclusions in quartz and feldspar from granite pegmatite from the Precambrian Rønne granite, Bornholm Island, Denmark revealed extremely alkali bicarbonate- and carbonate-rich inclusions. The solid phases (daughter crystals) are mainly nahcolite [NaHCO3], zabuyelite [Li2CO3], and in rare cases potash [K2CO3] in addition to the volatile phases CO2 and aqueous carbonate/bicarbonate solution. Rare melt inclusions contain nahcolite, dawsonite [NaAl(CO3)(OH)2], and muscovite. In addition to fluid and melt inclusions, there are primary CO2-rich vapor inclusions, which mostly contain small nahcolite crystals. The identification of potash as a naturally occurring mineral would appear to be the first recorded instance. From the appearance of high concentrations of these carbonates and bicarbonates, we suggest that the mineral-forming media were water- and alkali carbonate-rich silicate melts or highly concentrated fluids. The coexistence of silicate melt inclusions with carbonate-rich fluid and nahcolite-rich vapor inclusions indicates a melt-melt-vapor equilibrium during the crystallization of the pegmatite. These results are supported by the results of hydrothermal diamond anvil cell experiments in the pseudoternary system H2O-NaHCO3-SiO2. Additionally, we show that boundary layer effects were insignificant in the Bornholm pegmatites and are not required for the origin of primary textures in compositionally simple pegmatites at least.

  17. Development of a carbonate crust on alkaline nuclear waste sludge at the Hanford site. (United States)

    Page, Jason S; Reynolds, Jacob G; Ely, Tom M; Cooke, Gary A


    Hard crusts on aging plutonium production waste have hindered the remediation of the Hanford Site in southeastern Washington, USA. In this study, samples were analyzed to determine the cause of a hard crust that developed on the highly radioactive sludge during 20 years of inactivity in one of the underground tanks (tank 241-C-105). Samples recently taken from the crust were compared with those acquired before the crust appeared. X-ray diffraction and scanning electron microscopy (SEM) indicated that aluminum and uranium phases at the surface had converted from (hydr)oxides (gibbsite and clarkeite) into carbonates (dawsonite and cejkaite) and identified trona as the cementing phase, a bicarbonate that formed at the expense of thermonatrite. Since trona is more stable at lower pH values than thermonatrite, the pH of the surface decreased over time, suggesting that CO 2 from the atmosphere lowered the pH. Thus, a likely cause of crust formation was the absorption of CO 2 from the air, leading to a reduction of the pH and carbonation of the waste surface. The results presented here help establish a model for how nuclear process waste can age and can be used to aid future remediation and retrieval activities. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Corrosion Resistance Properties of Aluminum Coating Applied by Arc Thermal Metal Spray in SAE J2334 Solution with Exposure Periods

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    Han-Seung Lee


    Full Text Available Arc thermal metal spray coating provides excellent corrosion, erosion and wear resistance to steel substrates. This paper incorporates some results of aluminum coating applied by this method on plain carbon steel. Thereafter, coated panels were exposed to an environment known to form stable corrosion products with aluminum. The coated panels were immersed in Society of Automotive Engineers (SAE J2334 for different periods of time. This solution consists of an aqueous solution of NaCl, CaCl2 and NaHCO3. Various electrochemical techniques, i.e., corrosion potential-time, electrochemical impedance spectroscopy (EIS and the potentiodynamic were used to determine the performance of stimulants in improving the properties of the coating. EIS studies revealed the kinetics and mechanism of corrosion and potentiodynamic attributed the formation of a passive film, which stifles the penetration of aggressive ions towards the substrate. The corrosion products that formed on the coating surface, identified using Raman spectroscopy, were Dawsonite (NaAlCO3(OH2 and Al(OH3. These compounds of aluminum are very sparingly soluble in aqueous solution and protect the substrate from pitting and uniform corrosion. The morphology and composition of corrosion products determined by scanning electron microscopy and energy dispersive X-ray analyses indicated that the environment plays a decisive role in improving the corrosion resistance of aluminum coating.

  19. Chemistry which created Green River Formation oil shale

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    Smith, J.W.


    The genesis pattern presented for Green River Formation oil shale explains the major observation. Deposition of relatively large quantities of hydrogen-rich organic matter in the oil shales is a natural consequence of the chemical conditions (basic water and reducing atmosphere) and the physical limitation of clastic materials developed in the stratified ancient Lake Uinta. Stability of the stratification produced the continuous deposition of the organic matter and its uniformity over the deposit. Authigenic formation of the oil-shale minerals proceeds naturally from the lake stratification, and the varve production stems from the seasonable development of organic matter. The lake's stratification produced uniform deposition over the entire area it covered, making the correlatable lateral persistence of the thin laminations a natural consequence. As the lake developed, the attack on aluminosilicates by sodium carbonate in the lower layer produced a silicate skeleton protected by aluminum trihydroxide. On deposition, this aluminum-rich skeleton formed illite in quantity. As the lake became more basic, the protecting aluminum hydroxide coating dissolved amphoterically and illite production dropped at a specific point. Continual build-up of sodium carbonate and aluminate ion in the water of the lake's lower layer reached conditions which precipitated dawsonite and crystallized nahcolite in the sediment as a result of CO/sub 2/ production from organic matter. (JMT)

  20. Geochemical Modeling of ILAW Lysimeter Water Extracts

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    Cantrell, Kirk J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)


    Geochemical modeling results of water extracts from simulated immobilized low-activity waste (ILAW) glasses, placed in lysimeters for eight years suggest that the secondary phase reaction network developed using product consistency test (PCT) results at 90°C may need to be modified for field conditions. For sediment samples that had been collected from near the glass samples, the impact of glass corrosion could be readily observed based upon the pH of their water extracts. For unimpacted sediments the pH ranged from 7.88 to 8.11 with an average of 8.04. Sediments that had observable impacts from glass corrosion exhibited elevated pH values (as high as 9.97). For lysimeter sediment samples that appear to have been impacted by glass corrosion to the greatest extent, saturation indices determined for analcime, calcite, and chalcedony in the 1:1 water extracts were near equilibrium and were consistent with the secondary phase reaction network developed using PCT results at 90°C. Fe(OH)3(s) also appears to be essentially at equilibrium in extracts impacted by glass corrosion, but with a solubility product (log Ksp) that is approximately 2.13 units lower than that used in the secondary phase reaction network developed using PCT results at 90°C. The solubilities of TiO2(am) and ZrO2(am) also appear to be much lower than that assumed in the secondary phase reaction network developed using PCT results at 90°C. The extent that the solubility of TiO2(am) and ZrO2(am) were reduced relative to that assumed in the secondary phase reaction network developed using PCT results at 90°C could not be quantified because the concentrations of Ti and Zr in the extracts were below the estimated quantification limit. Gibbsite was consistently highly oversaturated in the extract while dawsonite was at or near equilibrium. This suggests that dawsonite might be a more suitable phase for the secondary phase reaction network

  1. Effect of added zinc on the properties of cobalt-containing ceramic pigments prepared from layered double hydroxides

    International Nuclear Information System (INIS)

    Perez-Bernal, M.E.; Ruano-Casero, R.J.; Rives, V.


    Layered double hydroxides (LDHs) with the hydrotalcite-type structure containing Co and Al, or Zn, Co and Al in the brucite-like layers and carbonate in the interlayer have been prepared by coprecipitation. The Zn/Co molar ratio was kept to 1 in all samples, while the divalent/trivalent molar ratio was varied from 2/1 to 1/2. The samples have been characterised by element chemical analysis, powder X-ray diffraction, differential thermal and thermogravimetric analysis, temperature-programmed reduction and FT-IR spectroscopy. A single hydrotalcite-like phase is formed for samples with molar ratio 2/1, which crystallinity decreases as the Al content is increased, developing small amounts of diaspore and dawsonite and probably an additional amorphous phase. Calcination at 1200 deg. C in air led to formation of spinels; a small amount of NaAlO 2 was observed in the Al-rich samples, which was removed by washing. The nature of the spinels formed (containing Co II , Co III , Al III and Zn II ) strongly depends on the cations molar ratio in the starting materials and the calcination treatment, leading to a partial oxidation of Co II species to Co III ones. Colour properties (L*a*b*) of the original and calcined solids have been measured. While the original samples show a pink colour (lighter for the series containing Zn), the calcined Co,Al samples show a dark blue colour and the Zn,Co,Al ones a green colour. Changes due to the different molar ratios within a given calcined series are less evident than between samples with the same composition in different series. These calcined materials could be usable as ceramic pigments. - Abstract: Mixed oxides from layered double hydroxides (LDHs) with the hydrotalcite-type structure containing Co and Al or Zn, Co and Al in the brucite-like layers are potential candidates for ceramic pigments with tunable colour properties. Display Omitted

  2. Large-scale column experiment: study of CO{sub 2}, pore water rock reactions and model test case; Experimentation de longue duree sur grandes colonnes, dans le contexte du stockage geologique de CO{sub 2}: etude des interactions eau-roche et modelisation

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    Bateman, K.; Turner, G.; Pearce, J.M.; Noy, D.J.; Birchall, D.; Rochelle, C.A. [British Geological Survey, Kingsley Dunham Centre, Keyworth (United Kingdom)


    During underground carbon dioxide (CO{sub 2}) storage operations in deep reservoirs, the CO{sub 2} can be trapped in three ways; - as 'free' CO{sub 2}, most likely as a supercritical phase (physical trapping); - dissolved in formation water (hydrodynamic trapping); - precipitated in carbonate phases such as calcite (mineral trapping). This study focuses on the reactions between CO{sub 2}, pore-water and host rock. The aim of this work was to provide a well-constrained long-term laboratory experiment reacting known quantities of minerals with CO{sub 2}-rich fluids, in order to try and represent situations where CO{sub 2} is being injected into lithologies deep underground. The experimental results can then be used as a test case with which to help validate predictive geochemical computer models. These will help improve our ability to predict the long-term fate of carbon dioxide (CO{sub 2}) stored underground. The experiment, though complex in terms of equipment, ran for approximately 7.5 months. The reacted material was then examined for mineralogical changes and the collected fluids analysed to provide data on the fate of the dissolved species. Changes were readily observable on the carbonates present in the starting material, which matches well with the observed trends in the fluid chemistry. However, although changes in silica concentrations were seen in the fluid chemistry no evidence for pitting or etching was noted in the silica bearing phases. Modelling of the experimental systems was performed using the BGS coupled code, PRECIP. As a general conclusion, the model predictions tend to over estimate the degree of reaction compared with the results from the experiment. In particular, some mineral phases (e.g. dawsonite) that are predicted to form in large quantities by the model are not seen at all in the experimental system. The differences between the model predictions and the experimental observations highlight the need for thermodynamic and kinetic

  3. Final Report For The Initial Solid Phase Characterization Of The 2011 Grab Samples And Composite For The C-109 Hard Heel Study

    International Nuclear Information System (INIS)

    Page, J.S.; Cooke, G.A.; Pestovich, J.A.


    of both the crushed cobble and bulk material. Some of the trace phases were identified as uranium-rich (sodium diuranate and/or clarkeite), sodium aluminum-rich (dawsonite and/or sodium aluminate), and a sludge-like phase with a variable chemistry rich in iron, nickel, and lead. A composite was created from the grab samples and a sample was taken from the composite, labeled S11T009482, for solid phase characterization. In general, the vast majority of the particles and aggregates analyzed in the composite were either gibbsite or natrophosphate. A very minor phase consisting of dispersed small particles was rich in uranium.

  4. Experimental Studies on the Interaction of scCO2 and scCO2-SO2 With Rock Forming Minerals at Conditions of Geologic Carbon Storages - First Results (United States)

    Erzinger, J.; Wilke, F.; Wiersberg, T.; Vasquez Parra, M.


    Co-injection of SO2 (plus possibly NOx and O2) during CO2 storage in deep saline aquifers may cause stronger brine acidification than CO2 alone. Because of that, we investigate chemical corrosion of rocks and rock-forming minerals with impure supercritical CO2 (scCO2) at possible storage conditions of >73.7 bar and >31°C. Contaminates were chosen with respect to the composition of CO2 captured industrially from coal-fired power plants using the oxyfuel technology. The resulting data should build a base for the long-term prediction of the behavior of CO2 in geologic storage reservoirs. Experiments of up to 1000 hrs duration have been performed with 10 natural mineral concentrates (calcite, dolomite, siderite, anhydrite, hematite, albite, microcline, kaolinite, muscovite, biotite) in 3n NaCl solution and pure scCO2 or scCO2+SO2 (99.5+0.5 vol%). The NaCl reaction fluid resembles the average salinity of deep formation waters of the North German Basin and is not free of oxygen. To increase reaction rates all minerals were ground and the reagents agitated either by stirring or shaking in autoclaves of about one liter in volume. The autoclaves consist of Hastelloy™ or ferromagnetic stainless steel fully coated with PTFE. We used in average 15 g of solids, 700 ml liquid, and the vessels were pressurized up to 100 bars with CO2 or CO2-SO2 mixture. Experiments were run at temperatures up to 90°C. Before, during and after the experiments small amounts fluids were sampled and analyzed for dissolved constituents and pH. Solid phases were characterized by XRF, XRD, and EMPA before and after the experiments. Pure scCO2 corrodes all carbonates, reacts only slightly with anhydrite, albite, and microcline at a minimum pH of 4, and does not recognizably interact with the others. After the experiment, albite has gained in a, not yet fully identified, carbonate phase which might be dawsonite. Reaction fluids of the experiments with scCO2+SO2 have mostly lower pH than using scCO2

  5. Numerical modeling of injection and mineral trapping of CO2 withH2S and SO2 in a Sandstone Formation

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tianfu; Apps, John A.; Pruess, Karsten; Yamamoto, Hajime


    Carbon dioxide (CO{sub 2}) injection into deep geologic formations could decrease the atmospheric accumulation of this gas from anthropogenic sources. Furthermore, by co-injecting H{sub 2}S or SO{sub 2}, the products respectively of coal gasification or combustion, with captured CO{sub 2}, problems associated with surface disposal would be mitigated. We developed models that simulate the co-injection of H{sub 2}S or SO{sub 2} with CO{sub 2} into an arkose formation at a depth of about 2 km and 75 C. The hydrogeology and mineralogy of the injected formation are typical of those encountered in Gulf Coast aquifers of the United States. Six numerical simulations of a simplified 1-D radial region surrounding the injection well were performed. The injection of CO{sub 2} alone or co-injection with SO{sub 2} or H{sub 2}S results in a concentrically zoned distribution of secondary minerals surrounding a leached and acidified region adjacent to the injection well. Co-injection of SO{sub 2} with CO{sub 2} results in a larger and more strongly acidified zone, and alteration differs substantially from that caused by the co-injection of H{sub 2}S or injection of CO{sub 2} alone. Precipitation of carbonates occurs within a higher pH (pH > 5) peripheral zone. Significant quantities of CO{sub 2} are sequestered by ankerite, dawsonite, and lesser siderite. The CO{sub 2} mineral-trapping capacity of the formation can attain 40-50 kg/m{sup 3} medium for the selected arkose. In contrast, secondary sulfates precipitate at lower pH (pH < 5) within the acidified zone. Most of the injected SO{sub 2} is transformed and immobilized through alunite precipitation with lesser amounts of anhydrite and minor quantities of pyrite. The dissolved CO{sub 2} increases with time (enhanced solubility trapping). The mineral alteration induced by injection of CO{sub 2} with either SO{sub 2} or H{sub 2}S leads to corresponding changes in porosity. Significant increases in porosity occur in the acidified

  6. A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Chen Zhu


    Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory measured and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between laboratory and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO2 injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the second year of the project, we completed CO{sub 2}-Navajo sandstone interaction batch and flow-through experiments and a Navajo sandstone dissolution experiment without the presence of CO{sub 2} at 200 C and 250-300 bars, and initiated dawsonite dissolution and solubility experiments. We also performed additional 5-day experiments at the

  7. Characterization of Solids in Residual Wastes from Single-Shell Tanks at the Hanford Site, Washington, USA - 9277

    International Nuclear Information System (INIS)

    Krupka, Kenneth M.; Cantrell, Kirk J.; Schaef, Herbert T.; Arey, Bruce W.; Heald, Steve M.; Deutsch, William J.; Lindberg, Michael J.


    Solid-phase characterization methods have been used in an ongoing study of residual wastes (i.e., waste remaining after final retrieval operations) from the underground single-shell storage tanks 241-C-103, 241-C-106, 241-C-202, 241-C-203, and 241-S-112 at the U.S. Department of Energy's Hanford Site in Washington State. The results of studies completed to date show significant variability in the compositions of those residual wastes and the compositions, morphologies, and crystallinities of the individual phases that make up these wastes. These differences undoubtedly result from the various waste types stored and transferred in and out each tank and the sluicing and retrieval operations used for waste retrieval. Our studies indicate that these residual wastes are chemically-complex assemblages of crystalline and amorphous solids that contain contaminants as discrete phases and/or co-precipitated within oxide phases. Depending on the specific tank, various solids (e.g., gibbsite; boehmite; dawsonite; cancrinite; Fe oxides such as hematite, goethite, and maghemite; rhodochrosite; lindbergite; whewellite; nitratine; and numerous amorphous or poorly crystalline phases) have been identified by X-ray diffraction and scanning electron microscopy/energy dispersive X-ray spectroscopy in residual wastes studied to date. Our studies also show that contact of residual wastes with Ca(OH)2- and CaCO3-saturated aqueous solutions, which were used as surrogates for the compositions of pore-fluid leachants derived from young and aged cements respectively, may alter the compositions of solid phases present in the contacted wastes. Fe oxides/hydroxides have been identified in all residual wastes studied to date. They occur in these wastes as discrete particles, particles intergrown within a matrix of other phases, and surface coatings on other particles or particle aggregates. These Fe oxides/hydroxides typically contain trace concentrations of other transition metals, such Cr, Mn

  8. Geochemical modelling of worst-case leakage scenarios at potential CO2-storage sites - CO2 and saline water contamination of drinking water aquifers (United States)

    Szabó, Zsuzsanna; Edit Gál, Nóra; Kun, Éva; Szőcs, Teodóra; Falus, György


    at seven potential CO2-storage areas have been modelled. The visualization of results has been automatized by R programming. The three types of models (equilibrium, kinetic batch and reactive transport) provide different type but overlapping information. All modelling output of both scenarios (CO2/brine) indicate the increase of ion-concentrations in the fresh water, which might exceed drinking water limit values. Transport models provide a possibility to identify the most suitable chemical parameter in the fresh water for leakage monitoring. This indicator parameter may show detectable and early changes even far away from the contamination source. In the CO2 models potassium concentration increase is significant and runs ahead of the other parameters. In the rock, the models indicate feldspar, montmorillonite, dolomite and illite dissolution whereas calcite, chlorite, kaolinite and silica precipitates, and in the case of CO2-inflow models, dawsonite traps a part of the leaking gas.

  9. Simulation of a Potential CO2 Storage in the West Paris Basin: Site Characterization and Assessment of the Long-Term Hydrodynamical and Geochemical Impacts Induced by the CO2 Injection

    Directory of Open Access Journals (Sweden)

    Estublier Audrey


    conditions. This approach succeeded to improve the simulation results of the pressure field and the CO2 plume as well as the geochemical behavior of the rock. These ones showed that the CO2 plume tends to stabilize thanks to the carbonation in calcite and dawsonite and no significant porosity change appears over 1,050 years. The CO2 mass balance per trapping type gives a CO2 carbonation rate of about 78% at 1,050 years that seemed to be excessive compared to the simulation study of other storage sites. Thus, an additional work dealing with both the kinetic data base and the textural models would be necessary in order to reduce the uncertainty of the injected CO2 mineralization.