Sample records for dawsonite

  1. Solution mining dawsonite from hydrocarbon containing formations with a chelating agent

    DOEpatents

    Vinegar, Harold J [Bellaire, TX

    2009-07-07

    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.

  2. Evidence for dawsonite in Hanford high-level nuclear waste tanks.

    PubMed

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

    2012-03-30

    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.

  3. Continental-scale magmatic carbon dioxide seepage recorded by dawsonite in the Bowen-Gunnedah-Sydney basin system, eastern Australia

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Baker, J.C.; Bai, G.P.; Hamilton, P.J.

    1995-07-03

    Dawsonite, NaAlCO{sub 3}(OH){sub 2}, is widespread as a cement, replacement, and cavity filling in Permo-Triassic sedimentary rocks of the Bowen-Gunnedah-Sydney basin system eastern Australia. The origin of dawsonite in these rocks was studied by petrographic and stable isotope analysis. Dawsonite {delta}{sup 13}C (PDB) values range from {minus}4.0 to +4.1{per_thousand} and are remarkably consistent throughout the Bowen-Gunnedah-Sydney basin system. These values indicate either a marine carbonate or magmatic source for carbon in the dawsonite. A magmatic carbon source is considered more likely on the basis that (1) evidence of and the cause for widespread marine carbonate dissolution in the sedimentary successionsmore » are not apparent, (2) dawsonite is widespread in both marine and nonmarine facies, (3) the region has been the site of major igneous activity, (4) other dawsonite deposits of similar carbon isotopic composition are linked to igneous activity, and (5) magmatic CO{sub 2} accumulations are known in parts of the Bowen-Gunnedah-Sydney basin system. The timing of igneous activity in the Bowen Basin constrains the timing of dawsonite formation in the Bowen-Gunnedah-Sydney basin system to the Tertiary, consistent with textural relationships, which indicate that dawsonite formed late during the burial history of the Permo-triassic sequences. The distribution and interpreted origin of dawsonite implies magmatic CO{sub 2} seepage in the Bowen-Gunnedah-Sydney basin system on a continental scale.« less

  4. Varying heating in dawsonite zones in hydrocarbon containing formations

    DOEpatents

    Vinegar, Harold J [Bellaire, TX; Xie, Xueying [Houston, TX; Miller, David Scott [Katy, TX

    2009-07-07

    A method for treating an oil shale formation comprising dawsonite includes assessing a dawsonite composition of one or more zones in the formation. Heat from one or more heaters is provided to the formation such that different amounts of heat are provided to zones with different dawsonite compositions. The provided heat is allowed to transfer from the heaters to the formation. Fluids are produced from the formation.

  5. Synthesis of Fire-Extinguishing Dawsonites

    NASA Technical Reports Server (NTRS)

    Altman, R. L.

    1982-01-01

    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.

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

    PubMed

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

    2015-02-05

    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 CO3(2-) 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. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    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.

  8. Powder Extinguishants for Jet-Fuel Fires

    NASA Technical Reports Server (NTRS)

    Altman, R. L.; Mayer, L. A.; Ling, A. C.

    1986-01-01

    Mixtures of alkali metal dawsonite and metal halide show superior performance. In tests of new dry powder fire extinguishants, mixtures of potassium dawsonite with either stannous iodide or potassium iodide found effective for extinguishing jet-fuel fires on hot metal surfaces (up to 900 degrees C). Mixtures performed more effectively than either compound alone.

  9. Fire extinguishant materials

    NASA Technical Reports Server (NTRS)

    Altman, R. L.; Mayer, L. A.; Ling, A. C. (Inventor)

    1983-01-01

    Fire extinguishant composition comprising a mixture of a finely divided aluminum compound and alkali metal, stannous or plumbous halide is provided. Aluminum compound may be aluminum hydroxide, alumina or boehmite but preferably it is an alkali metal dawsonite. The metal halide may be an alkali metal, e.g. potassium iodide, bromide or chloride or stannous or plumbous iodide, bromide or chloride. Potassium iodide is preferred.

  10. Experimental and simulation studies of iron oxides for geochemical fixation of CO2-SO2 gas mixtures

    USGS Publications Warehouse

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

    2011-01-01

    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.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Meznarich, Huei K.; bolling, Stacey D.; Cooke, Gary A.

    2016-10-01

    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 2O], cejkaite [Na 4(UO 2)(CO 3) 3], and an unidentified organic solid, with minor amounts of gibbsite [Al(OH) 3], natrophosphate [Na 7F(PO 4) 2·19H 2O], and traces of unidentified iron-rich and manganese-rich phases. Note that the presencemore » 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.« less

  12. Mineralogical and geochemical consequences of the long-term presence of CO2 in natural reservoirs: An example from the Springerville-St. Johns Field, Arizona, and New Mexico, U.S.A

    USGS Publications Warehouse

    Moore, J.; Adams, M.; Allis, R.; Lutz, S.; Rauzi, S.

    2005-01-01

    The Springerville-St. Johns CO2 field in eastern Arizona and western New Mexico is one of more than a dozen gas fields developed within the Colorado Plateau and Southern Rocky Mountain region. Extensive travertine (CaCO3) deposits record a long history of CO2 migration and leakage to the atmosphere. The oldest travertine deposits may have formed during the initial filling of the CO2 reservoir when groundwaters exsolved CO2 upon reaching the surface. The youngest travertine deposits are associated with springs on the floor of the Little Colorado River valley, but travertine deposition appears to be insignificant today. Older deposits occur up to 325 m above the valley floor. Geologic relationships suggest travertine deposition began in the late Pleistocene after volcanic activity ended at ???0.3 Ma. Most of the CaCO3 could have been derived from dissolution of the underlying limestones and dolomites. Interactions between the reservoir fluids and rocks were observed in core samples from one of the intervals that produced dry gas. These reactions resulted in the dissolution of carbonate cements and detrital feldspars and the formation of dawsonite and kaolinite. Geochemical simulations suggest that the dawsonite could have been deposited when the CO2 fugacity reached 20 bars and that the kaolinite formed as the CO2 fugacity decreased. Corrosion of drill pipe by acidic waters and a pronounced HCO3 anomaly above the CO2 reservoir provide evidence of a continuing flux of CO2 from depth. CO2 storage occurs primarily as dissolved carbonate species and as gas accumulations. Only a small percentage of the CO2 was sequestered in secondary minerals. ?? 2005 Elsevier B.V. All rights reserved.

  13. Spatial and stratigraphic distribution of water in oil shale of the Green River Formation using Fischer Assay, Piceance Basin, northwestern Colorado

    USGS Publications Warehouse

    Johnson, Ronald C.; Mercier, Tracey J.; Brownfield, Michael E.

    2014-01-01

    The spatial and stratigraphic distribution of water in oil shale of the Eocene Green River Formation in the Piceance Basin of northwestern Colorado was studied in detail using some 321,000 Fischer assay analyses in the U.S. Geological Survey oil-shale database. The oil-shale section was subdivided into 17 roughly time-stratigraphic intervals, and the distribution of water in each interval was assessed separately. This study was conducted in part to determine whether water produced during retorting of oil shale could provide a significant amount of the water needed for an oil-shale industry. Recent estimates of water requirements vary from 1 to 10 barrels of water per barrel of oil produced, depending on the type of retort process used. Sources of water in Green River oil shale include (1) free water within clay minerals; (2) water from the hydrated minerals nahcolite (NaHCO3), dawsonite (NaAl(OH)2CO3), and analcime (NaAlSi2O6.H20); and (3) minor water produced from the breakdown of organic matter in oil shale during retorting. The amounts represented by each of these sources vary both stratigraphically and areally within the basin. Clay is the most important source of water in the lower part of the oil-shale interval and in many basin-margin areas. Nahcolite and dawsonite are the dominant sources of water in the oil-shale and saline-mineral depocenter, and analcime is important in the upper part of the formation. Organic matter does not appear to be a major source of water. The ratio of water to oil generated with retorting is significantly less than 1:1 for most areas of the basin and for most stratigraphic intervals; thus water within oil shale can provide only a fraction of the water needed for an oil-shale industry.

  14. Spatial and stratigraphic distribution of water in oil shale of the Green River Formation using Fischer assay, Piceance Basin, northwestern Colorado

    USGS Publications Warehouse

    Johnson, Ronald C.; Mercier, Tracey J.; Brownfield, Michael E.

    2014-01-01

    The spatial and stratigraphic distribution of water in oil shale of the Eocene Green River Formation in the Piceance Basin of northwestern Colorado was studied in detail using some 321,000 Fischer assay analyses in the U.S. Geological Survey oil-shale database. The oil-shale section was subdivided into 17 roughly time-stratigraphic intervals, and the distribution of water in each interval was assessed separately. This study was conducted in part to determine whether water produced during retorting of oil shale could provide a significant amount of the water needed for an oil-shale industry. Recent estimates of water requirements vary from 1 to 10 barrels of water per barrel of oil produced, depending on the type of retort process used. Sources of water in Green River oil shale include (1) free water within clay minerals; (2) water from the hydrated minerals nahcolite (NaHCO3), dawsonite (NaAl(OH)2CO3), and analcime (NaAlSi2O6.H20); and (3) minor water produced from the breakdown of organic matter in oil shale during retorting. The amounts represented by each of these sources vary both stratigraphically and areally within the basin. Clay is the most important source of water in the lower part of the oil-shale interval and in many basin-margin areas. Nahcolite and dawsonite are the dominant sources of water in the oil-shale and saline-mineral depocenter, and analcime is important in the upper part of the formation. Organic matter does not appear to be a major source of water. The ratio of water to oil generated with retorting is significantly less than 1:1 for most areas of the basin and for most stratigraphic intervals; thus water within oil shale can provide only a fraction of the water needed for an oil-shale industry.

  15. Site evaluation for U.S. Bureau of Mines experimental oil-shale mine, Piceance Creek basin, Rio Blanco County, Colorado

    USGS Publications Warehouse

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

    1978-01-01

    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 measurement are necessary as measurements were taken in English units, and most of the contracting agencies involved are using predominantly English units.

  16. Mineralogy and geochemistry of a superhigh-organic-sulfur coal, Yanshan Coalfield, Yunnan, China: Evidence for a volcanic ash component and influence by submarine exhalation

    USGS Publications Warehouse

    Dai, S.; Ren, D.; Zhou, Y.; Chou, C.-L.; Wang, X.; Zhao, L.; Zhu, Xudong

    2008-01-01

    The mineralogy and geochemistry of a superhigh-organic-sulfur (SHOS) coal of Late Permian age from the Yanshan Coalfield, Yunnan Province, southwestern China, have been studied using optical microscope, low-temperature ashing plus X-ray diffraction analysis, scanning electron microscope equipped with energy-dispersive X-ray spectrometer, a sequential chemical extraction procedure, and inductively coupled plasma mass spectrometry. The M9 Coal from the Yanshan Coalfield is a SHOS coal that has a total sulfur content of 10.12%-11.30% and an organic sulfur content of 8.77%-10.30%. The minerals in the coal consist mainly of high-temperature quartz, sanidine, albite, muscovite, illite, pyrite, and trace amounts of kaolinite, plagioclase, akermanite, rutile, and dawsonite. As compared with ordinary worldwide (bituminous coals and anthracite) and Chinese coals, the M9 Coal is remarkably enriched in B (268????g/g), F (841????g/g), V (567????g/g), Cr (329????g/g), Ni (73.9????g/g), Mo (204????g/g), and U (153????g/g). In addition, elements including Se (25.2????g/g), Zr (262????g/g), Nb (20.1????g/g), Cd (2.07????g/g), and Tl (2.03????g/g) are also enriched in the coal. Occurrence of high-temperature quartz, sanidine, muscovite, and illite in the M9 Coal is evidence that there is a volcanic ash component in the coal that was derived from acid volcanic ashes fallen into the swamp during peat accumulation. Occurrence of albite and dawsonite in the coal and strong enrichment of some elements, including F, S, V, Cr, Ni, Mo and U, are attributed to the influence by submarine exhalation which invaded along with seawater into the anoxic peat swamp. Abundances of lithophile elements, including rare earth elements, Nb, Y, Zr, and TiO2, indicate that the silicate minerals in the coal were derived from the northern Vietnam Upland to the south of the basin. ?? 2008 Elsevier B.V. All rights reserved.

  17. How much CO2 is trapped in carbonate minerals of a natural CO2 occurrence?

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

    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 unexpectedly high proportion of total amount of CO2. Further results enlightened that other carbonates, ankerite, calcite and siderite have precipitated in two generations, the first before and the second after the CO2 flooding. Further laboratory analysis and geochemical models allow us to estimate the ratio of these two generations and also to understand how far the reservoir rock is in the CO2 mineral trapping process.

  18. Development of a carbonate crust on alkaline nuclear waste sludge at the Hanford site.

    PubMed

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

    2018-01-15

    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.

  19. A modeling study of the long-term mineral trapping in deep saline marine sands aquifers (Invited)

    NASA Astrophysics Data System (ADS)

    Aagaard, P.; Pham, V.; Hellevang, H.

    2009-12-01

    Simulation of geochemical processes due to CO2 injection and storage are dependent on sediment petrography and the kinetics of mineral fluid reactions. Mineral trapping of CO2 in the Utsira sand and similar marine sand reservoirs have been revisited based on critical review of rate data and geochemical constraints on formation waters. Reaction paths calculations were done with the PHREEQC modeling software at relevant reservoir conditions covering a temperature range of 30-100 °C and corresponding reservoir pressures. Initial CO2 saturation was determined by the fluid fugacity corresponding with reservoir conditions. The mineral dissolution kinetics was expressed with a chemical affinity term (Aagaard & Helgeson,1982) while a critical super-saturation for mineral growth was included in the precipitation rate expression. The redox conditions and the H2S fugacity in the simulations were constrained by the acetic/propionic acid buffer trend and the magnetite-pyrite buffer (Aagaard et al. 2001) respectively. We used a revised mineralogical composition for the Utsira sand also performed a sensitivity analyses with respect to mineral content. The simulations were run over a period of 10000 years. The main simulation results included dissolution of glauconite, smectite, pyrite, muscovite and albite, with precipitation of the carbonates siderite, ankerite, and minor dawsonite, as well as kaolinite, silica (either chalcedony or quartz), and K-feldspar. The uncertainties in the simulations are specially connected with initial mineral abundances. The effect of critical super-saturation and reactive surface area for precipitation needs to be further evaluated and tested. Aagaard, P. and H.C. Helgeson (1982). Thermodynamic and Kinetic Constraints on Reaction Rates among Minerals and Aqueous Solutions. I. Theoretical Considerations. Am. J. Sci., v. 282, p. 257-285. P. Aagaard, J. Jahren & S.N. Ehrenberg (2001) H2S controling reactions in clastic hydrocarbon reservoirs from the Norwegian Shelf and Gulf Coast, in Cidu, R.(ed) Water-Rock Interaction, WRI-10, Balkema, p. 129-132.

  20. Natural CO 2 accumulations in the western Williston Basin: A mineralogical analog for CO 2 injection at the Weyburn site

    DOE PAGES

    Ryerson, F. J.; Lake, John; Whittaker, Steven; ...

    2013-01-17

    The Devonian carbonates of the Duperow Formation on the western flank of the Williston Basin in southwest Saskatchewan contain natural accumulations of CO 2, and may have done so for as long as 50 million years. These carbonate sediments are characterized by a succession of carbonate cycles capped by anhydrite-rich evaporites that are thought to act as seals to fluid migration. The Weyburn CO 2 injection site lies 400 km to the east in a series of Mississippian carbonates that were deposited in a similar depositional environment. That long-term isolation of natural CO 2 can be accomplished within carbonate stratamore » has motivated the investigation of the Duperow rocks as a potential natural analog for storage of anthropogenic CO 2 in carbonate lithologies. For the Duperow strata to represent a legitimate analog for Midale injection and storage, the similarity in lithofacies, whole rock compositions, mineral compositions and porosity with the Midale Beds must be established. Here we compare lithofacies, whole rock compositions, mineralogy and mineral compositions from both locales. The major mineral phases at both locales are calcite, dolomite and anhydrite. In addition, accessory pyrite, fluorite, quartz and celestine (strontium sulfate) are also observed. Dawsonite, a potential CO 2-trapping mineral, is not observed within the CO 2-bearing horizons of the Duperow Formation, however. The distribution of porosity in the Midale Vuggy units is similar to that of the Duperow Formation, but the Marly units of the Midale have significantly higher porosity. The Duperow Formation is topped by the Dinesmore evaporite that is rich in anhydrite, and often contains authigenic K-feldspar. The chemistry of dolomite and calcite from the two localities also overlaps. Silicate minerals are in low abundance (<3%) within the analyzed Duperow samples, with quartz and K-feldspar the only silicates observed petrographically or in X-ray diffraction patterns. The Midale Beds contain significantly higher silica/silicate concentrations (Durocher et al., 2003), but the paucity of mono- and divalent cations that can be derived from dissolution of these silicate minerals likely precludes significant carbonate mineral formation. Therefore physical and solution trapping are likely to be the primary CO 2 trapping mechanisms at both sites.« less

  1. Supercritical carbon dioxide and sulfur in the Madison Limestone: A natural analog in southwest Wyoming for geologic carbon-sulfur co-sequestration

    NASA Astrophysics Data System (ADS)

    Kaszuba, John P.; Navarre-Sitchler, Alexis; Thyne, Geoffrey; Chopping, Curtis; Meuzelaar, Tom

    2011-09-01

    The Madison Limestone on the Moxa Arch, southwest Wyoming, USA contains large volumes (65-95%) of supercritical CO 2 that it has stored naturally for 50 million years. This reservoir also contains supercritical H 2S, aqueous sulfur complexes (SO 42- and HS -), and sulfur-bearing minerals (anhydrite and pyrite). Although SO 2 is not present, these sulfur-bearing phases are known products of SO 2 disproportionation in other water-rock systems. The natural co-occurrence of SO 42-, S 2-, supercritical CO 2 and brine affords the opportunity to evaluate the fate of a carbon-sulfur co-sequestration scenario. Mineralogic data was obtained from drill core and aqueous geochemical data from wells outside and within the current supercritical CO 2-sulfur-brine-rock system. In addition to dolomite, calcite, and accessory sulfur-bearing minerals, the Madison Limestone contains accessory quartz and the aluminum-bearing minerals feldspar, illite, and analcime. Dawsonite (NaAlCO 3(OH) 2), predicted as an important carbon sink in sequestration modeling studies, is not present. After confirming equilibrium conditions for the Madison Limestone system, reaction path models were constructed with initial conditions based on data from outside the reservoir. Addition of supercritical CO 2 to the Madison Limestone was simulated and the results compared to data from inside the reservoir. The model accurately predicts the observed mineralogy and captures the fundamental changes expected in a Madison Limestone-brine system into which CO 2 is added. pH decreases from 5.7 to 4.5 at 90 °C and to 4.0 at 110 °C, as expected from dissolution of supercritical CO 2, creation of carbonic acid, and buffering by the carbonate rock. The calculated redox potential increases by 0.1 V at 90 °C and 0.15 V at 110 °C due to equilibrium among CO 2, anhydrite, and pyrite. Final calculated Eh and pH match conditions for the co-existing sulfur phases present in produced waters and core from within the reservoir. Total dissolved solids increase with reaction progress, mostly due to dissolution of calcite with an accompanying increase in dissolved bicarbonate. The Madison Limestone is a natural example of the thermodynamic end point that similar fluid-rock systems will develop following emplacement of a supercritical CO 2-sulfur mixture and is a natural analog for geologic carbon-sulfur co-sequestration.

  2. Geological and geophysical properties of cap rock in a natural CO2 occurrence, Mihályi-Répcelak area, Western Hungary

    NASA Astrophysics Data System (ADS)

    Király, Csilla; Szamosfalvi, Ágnes; Sendula, Eszter; Páles, Mariann; Kovács, István; Kónya, Péter; Falus, György; Szabó, Csaba

    2015-04-01

    The physical and geochemical consistency of the cap rock is primarily important for safe geological storage of CO2.. As a consequence of CO2 injection reactions took place between the minerals of the reservoir, the cap rock and CO2 saturated pore water. These reactions may change the mineral composition and petrophysical properties of the storage reservoir as well as the cap rock that provides the only physical barrier that retains carbon dioxide in the target reservoir formation. Study of the natural CO2 occurrences delivers information to understand which properties of a cap rock provide the sustainable closure and retainment. Knowledge of the long term effect of CO2 on the behavior of the cap rock is an important input in the selection procedure of a potential CO2 injection site. Yet, very few data exist on geochemical properties and reactivity of the cap rocks. During normal commercial operations the reservoir is typically cored, but not the cap rock. This study may enhance our knowledge about possible mineralogical reactions, which can occur in clayey-aleuritic cap rocks. The Mihályi-Répcelak natural CO2 occurrence is believed to be leakage safe. There is no known seepage on the surface. It is suggested that the aleuritic clay rich cap rock occurring at the natural reservoir can stop CO2 migration into other reservoirs or to the surface. The most important characteristics of cap rocks that they have low permeability (<0.1 mD) and porosity (eff.por. = 4%) and high clayeyness (approx. 80%). However, we demonstrate that in addition to these parameters the geochemical properties of cap rock is also important. In order to characterize the natural CO2 occurrence, we applied the following analysis, like XRD, FTIR, SEM. The petrophysical properties are determined from the interpretation of geophysical well-logs and grain size distribution. The most important result of this study that adequate petrophysical properties do not completely define the suitability of a cap rock. The effective porosity (~4 %), permeability (0.026 mD) and clayeyness (~80%) data imply that the studied aleurolites are good cap rocks. The mineral composition of cap rock is similar to that of reservoir rock, however, the ratio of components is different. The mineralogical analysis and petrography yield to the reaction between CO2 and the cap rocks. The most visible effect of CO2 presence is the dawsonite precipitation after albite dissolution within the cap rocks. Therefore, the CO2 may migrate through the cap rocks in geological time scale, however the total system could be leakage safe.

  3. Geochemical modelling of worst-case leakage scenarios at potential CO2-storage sites - CO2 and saline water contamination of drinking water aquifers

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

    Carbon Capture and Storage is a transitional technology to reduce greenhouse gas emissions and to mitigate climate change. Following the implementation and enforcement of the 2009/31/EC Directive in the Hungarian legislation, the Geological and Geophysical Institute of Hungary is required to evaluate the potential CO2 geological storage structures of the country. Basic assessment of these saline water formations has been already performed and the present goal is to extend the studies to the whole of the storage complex and consider the protection of fresh water aquifers of the neighbouring area even in unlikely scenarios when CO2 injection has a much more regional effect than planned. In this work, worst-case scenarios are modelled to understand the effects of CO2 or saline water leaks into drinking water aquifers. The dissolution of CO2 may significantly change the pH of fresh water which induces mineral dissolution and precipitation in the aquifer and therefore, changes in solution composition and even rock porosity. Mobilization of heavy metals may also be of concern. Brine migration from CO2 reservoir and replacement of fresh water in the shallower aquifer may happen due to pressure increase as a consequence of CO2 injection. The saline water causes changes in solution composition which may also induce mineral reactions. The modelling of the above scenarios has happened at several methodological levels such as equilibrium batch, kinetic batch and kinetic reactive transport simulations. All of these have been performed by PHREEQC using the PHREEQC.DAT thermodynamic database. Kinetic models use equations and kinetic rate parameters from the USGS report of Palandri and Kharaka (2004). Reactive transport modelling also considers estimated fluid flow and dispersivity of the studied formation. Further input parameters are the rock and the original ground water compositions of the aquifers and a range of gas-phase CO2 or brine replacement ratios. Worst-case scenarios 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.

  4. Coupled Reactive Transport Modeling of CO2 Injection in Mt. Simon Sandstone Formation, Midwest USA

    NASA Astrophysics Data System (ADS)

    Liu, F.; Lu, P.; Zhu, C.; Xiao, Y.

    2009-12-01

    CO2 sequestration in deep geological formations is one of the promising options for CO2 emission reduction. While several large scale CO2 injections in saline aquifers have shown to be successful for the short-term, there is still a lack of fundamental understanding on key issues such as CO2 storage capacity, injectivity, and security over multiple spatial and temporal scales that need to be addressed. To advance these understandings, we applied multi-phase coupled reactive mass transport modeling to investigate the fate of injected CO2 and reservoir responses to the injection into Mt. Simon Formation. We developed both 1-D and 2-D reactive transport models in a radial region of 10,000 m surrounding a CO2 injection well to represent the Mt. Simon sandstone formation, which is a major regional deep saline reservoir in the Midwest, USA. Supercritical CO2 is injected into the formation for 100 years, and the modeling continues till 10,000 years to monitor both short-term and long-term behavior of injected CO2 and the associated rock-fluid interactions. CO2 co-injection with H2S and SO2 is also simulated to represent the flue gases from coal gasification and combustion in the Illinois Basin. The injection of CO2 results in acidified zones (pH ~3 and 5) adjacent to the wellbore, causing progressive water-rock interactions in the surrounding region. In accordance with the extensive dissolution of authigenic K-feldspar, sequential precipitations of secondary carbonates and clay minerals are predicted in this zone. The vertical profiles of CO2 show fingering pattern from the top of the reservoir to the bottom due to the density variation of CO2-impregnated brine, which facilitate convection induced mixing and solubility trapping. Most of the injected CO2 remains within a radial distance of 2500 m at the end of 10,000 years and is sequestered and immobilized by solubility and residual trapping. Mineral trapping via secondary carbonates, including calcite, magnesite, ankerite and dawsonite, is predicted, but only constituting a minor component as compared to other trapping mechanisms. The mineral alteration induced by CO2 injection results in changes in porosity/permeability due to these complex mineral dissolution and precipitation reactions. Increases in porosity (from 15% to 16.2%) occur in the low-pH zones due to the acidic dissolution of minerals. However, within the carbonate mineral trapping zone, porosity reduction occurs. Co-injection of H2S causes relatively limited modification from the CO2 alone case while significantly higher water-rock reactivity is associated with the SO2 co-injection. Although co-injection of CO2 with H2S and SO2 could potentially reduce separation and injection cost, it may lead to some uncertainty and risks and therefore require further investigation.

  5. Experimental Studies on the Interaction of scCO2 and scCO2-SO2 With Rock Forming Minerals at Conditions of Geologic Carbon Storages - First Results

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

    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 alone, at which those with silicate phases have a lower pH (between 2 and 3) than experiments with carbonates. Fluid-mineral-interactions using scCO2-SO2 are thus much stronger and the concentrations of SO4 and cations in the reacting fluids are generally much higher, especially for Fe, Si and Al of silicates. However, intensity and rate of reactions are controlled by the availability of SO2 and apparently buffered by dissolution and precipitation processes. EMPA and Raman spectroscopy analyses are in progress to identify possible precipitated secondary products on mineral surfaces.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen Zhu

    2006-08-31

    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 measuredmore » 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 same conditions as alkali-feldspar dissolution experiments with and without the presence of CO{sub 2} performed in the first year to check the validation of the experiments and analysis. The changes of solution chemistry as dissolution experiments progressed were monitored with on-line sampling of the aqueous phase at the constant temperature and pressure. These data allow calculating overall apparent mineral (feldspars and sandstones) dissolution rates and secondary mineral precipitation rates as a function of saturation states. State-of-the-art atomic resolution transmission electron microscopy (TEM), scanning electron microscopy (SEM), and electron microprobe was used to characterize the products and reactants. Reaction-path geochemical modeling was used to interpret the experimental results of alkali-feldspar dissolution experiments without the presence of CO{sub 2}. Two manuscripts are near completion. Also during the second year, our education goal of graduate student training has been advanced. A Ph. D. student at Indiana University is progressing well in the degree program and has taken geochemical modeling, SEM, and TEM courses, which will facilitate research in the third year. A Ph. D. student at University of Minnesota had graduated. With the success of training of graduate students and excellent experimental data in the second year, we anticipate a more fruitful year in the third year.« less

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