Enthalpies of formation of polyhalite: A mineral relevant to salt repository
Guo, Xiaofeng; Xu, Hongwu
2017-06-02
Polyhalite is an important coexisting mineral with halite in salt repositories for nuclear waste disposal, such as Waste Isolation Pilot Plant (WIPP) in Carlsbad, New Mexico. The thermal stability of this mineral is a key knowledge in evaluating the integrity of a salt repository in the long term, as water may release due to thermal decomposition of polyhalite. Previous studies on structural evolution of polyhalite at elevated temperatures laid the basis for detailed calorimetric measurements. Using high-temperature oxide-melt drop-solution calorimetry at 975 K with sodium molybdate as the solvent, we have determined the standard enthalpies of formation from constituent sulfatesmore » (ΔH° f,sul), oxides (ΔH° f,ox) and elements (ΔH° f,ele) of a polyhalite sample with the composition of K 2Ca 2Mg(SO 4) 4·1.95H 2O from the Salado formation at the WIPP site. The obtained results are: ΔH° f,sul = -152.5 ± 5.3 kJ/mol, ΔH° f,ox = -1926.1 ± 10.5 kJ/mol, and ΔH° f,ele = -6301.2 ± 9.9 kJ/mol. Furthermore, based on the estimated formation entropies of polyhalite, its standard Gibbs free energy of formation has been derived to be in the range of -5715.3 ± 9.9 kJ/mol to -5739.3 ± 9.9 kJ/mol. In conclusion, these determined thermodynamic properties provide fundamental parameters for modeling the stability behavior of polyhalite in salt repositories.« less
Thermal behavior of polyhalite: a high-temperature synchrotron XRD study
Xu, Hongwu; Guo, Xiaofeng; Bai, Jianming
2016-09-17
As an accessory mineral in marine evaporites, polyhalite, K 2MgCa 2(SO 4) 4·2H 2O, coexists with halite (NaCl) in salt formations, which have been considered as potential repositories for permanent storage of high-level nuclear wastes. However, because of the heat generated by radioactive decays in the wastes, polyhalite may dehydrate, and the released water will dissolve its neighboring salt, potentially affecting the repository integrity. Thus, studying the thermal behavior of polyhalite is important. In this paper, a polyhalite sample containing a small amount of halite was collected from the Salado formation at the WIPP site in Carlsbad, New Mexico. Tomore » determine its thermal behavior, in situ high-temperature synchrotron X-ray diffraction was conducted from room temperature to 1066 K with the sample powders sealed in a silica-glass capillary. At about 506 K, polyhalite started to decompose into water vapor, anhydrite (CaSO 4) and two langbeinite-type phases, K 2Ca x Mg 2-x (SO 4) 3, with different Ca/Mg ratios. XRD peaks of the minor halite disappeared, presumably due to its dissolution by water vapor. With further increasing temperature, the two langbeinite solid solution phases displayed complex variations in crystallinity, composition and their molar ratio and then were combined into the single-phase triple salt, K 2CaMg(SO 4) 3, at ~919 K. Rietveld analyses of the XRD data allowed determination of structural parameters of polyhalite and its decomposed anhydrite and langbeinite phases as a function of temperature. Finally, from the results, the thermal expansion coefficients of these phases have been derived, and the structural mechanisms of their thermal behavior been discussed.« less
First-principles study of anhydrite, polyhalite and carnallite
NASA Astrophysics Data System (ADS)
Weck, Philippe F.; Kim, Eunja; Jové-Colón, Carlos F.; Sassani, David C.
2014-02-01
We report density functional calculations of the structures and properties of anhydrite (CaSO4), polyhalite (K2SO4·MgSO4·2CaSO4·2H2O) and carnallite (KCl·MgCl2·6H2O). Densities of states are systematically investigated and phonon analysis using density functional perturbation theory is performed at constant equilibrium volume for anhydrite and polyhalite in order to derive their isochoric thermal properties. Thermal properties at constant atmospheric pressure are also calculated using the quasi-harmonic approximation. The computed molar entropy and isobaric heat capacity for anhydrite reproduce experimental data up to 800 K to within 3% and 10%, respectively, while further experimental work is needed to assess our theoretical predictions for polyhalite.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Guo, Xiaofeng; Xu, Hongwu
Polyhalite is an important coexisting mineral with halite in salt repositories for nuclear waste disposal, such as Waste Isolation Pilot Plant (WIPP) in Carlsbad, New Mexico. The thermal stability of this mineral is a key knowledge in evaluating the integrity of a salt repository in the long term, as water may release due to thermal decomposition of polyhalite. Previous studies on structural evolution of polyhalite at elevated temperatures laid the basis for detailed calorimetric measurements. Using high-temperature oxide-melt drop-solution calorimetry at 975 K with sodium molybdate as the solvent, we have determined the standard enthalpies of formation from constituent sulfatesmore » (ΔH° f,sul), oxides (ΔH° f,ox) and elements (ΔH° f,ele) of a polyhalite sample with the composition of K 2Ca 2Mg(SO 4) 4·1.95H 2O from the Salado formation at the WIPP site. The obtained results are: ΔH° f,sul = -152.5 ± 5.3 kJ/mol, ΔH° f,ox = -1926.1 ± 10.5 kJ/mol, and ΔH° f,ele = -6301.2 ± 9.9 kJ/mol. Furthermore, based on the estimated formation entropies of polyhalite, its standard Gibbs free energy of formation has been derived to be in the range of -5715.3 ± 9.9 kJ/mol to -5739.3 ± 9.9 kJ/mol. In conclusion, these determined thermodynamic properties provide fundamental parameters for modeling the stability behavior of polyhalite in salt repositories.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Xu, Hongwu; Guo, Xiaofeng; Bai, Jianming
As an accessory mineral in marine evaporites, polyhalite, K 2MgCa 2(SO 4) 4·2H 2O, coexists with halite (NaCl) in salt formations, which have been considered as potential repositories for permanent storage of high-level nuclear wastes. However, because of the heat generated by radioactive decays in the wastes, polyhalite may dehydrate, and the released water will dissolve its neighboring salt, potentially affecting the repository integrity. Thus, studying the thermal behavior of polyhalite is important. In this paper, a polyhalite sample containing a small amount of halite was collected from the Salado formation at the WIPP site in Carlsbad, New Mexico. Tomore » determine its thermal behavior, in situ high-temperature synchrotron X-ray diffraction was conducted from room temperature to 1066 K with the sample powders sealed in a silica-glass capillary. At about 506 K, polyhalite started to decompose into water vapor, anhydrite (CaSO 4) and two langbeinite-type phases, K 2Ca x Mg 2-x (SO 4) 3, with different Ca/Mg ratios. XRD peaks of the minor halite disappeared, presumably due to its dissolution by water vapor. With further increasing temperature, the two langbeinite solid solution phases displayed complex variations in crystallinity, composition and their molar ratio and then were combined into the single-phase triple salt, K 2CaMg(SO 4) 3, at ~919 K. Rietveld analyses of the XRD data allowed determination of structural parameters of polyhalite and its decomposed anhydrite and langbeinite phases as a function of temperature. Finally, from the results, the thermal expansion coefficients of these phases have been derived, and the structural mechanisms of their thermal behavior been discussed.« less
NASA Astrophysics Data System (ADS)
Mertineit, Michael; Grewe, Wiebke; Schramm, Michael; Hammer, Jörg; Blanke, Hartmut; Patzschke, Mario
2017-04-01
Fractures occur locally in the z2 potash seam (Kaliflöz Staßfurt). Most of them extend several centimeter to meter into the surrounding salt rocks. The fractures are distributed on all levels in an extremely deformed area of the Morsleben salt mine, Northern Germany. The sampling site is located within a NW-SE trending synclinal structure, which was reverse folded (Behlau & Mingerzahn 2001). The samples were taken between the -195 m and - 305 m level at the field of Marie shaft. In this area, more than 200 healed fractures were mapped. Most of them show opening widths of only a few millimeters to rarely 10 cm. The fractures in rock salt are filled with basically polyhalite, halite and carnallite. In the potash seam, the fractures are filled with kainite, halite and minor amounts of carnallite and polyhalite. In some cases the fracture infill changes depending on the type of surrounding rocks. There are two dominant orientations of the fractures, which can be interpreted as a conjugated system. The main orientation is NE-SW trending, the dip angles are steep (ca. 70°, dip direction NW and SE, respectively). Subsequent deformation of the filled fractures is documented by a strong grain shape fabric of kainite, undulatory extinction and subgrain formation in kainite, and several mineral transformations. Subgrain formation in halite occurred in both, the fracture infill and the surrounding salt rocks. The results correlate in parts with investigations which were carried out at the close-by rock salt mine Braunschweig-Lüneburg (Horn et al. 2016). The development of the fractures occurred during compression of clayey salt rocks. However, the results are only partly comparable due to different properties (composition, impurities) of the investigated stratigraphic units. Further investigations will focus on detailed microstructural and geochemical analyses of the fracture infill and surrounding salt rocks. Age dating of suitable minerals, e.g. polyhalite (Leitner et al. 2013), could help to reconstruct the formation conditions. Behlau, J. & Mingerzahn, G. 2001. Geological and tectonic investigations in the former Morsleben salt mine (Germany) as a basis for the safety assessment of a radioactive waste repository. Engineering Geology 61, 83-97. Leitner, C., Neubauer, F., Genser, J., Borojevic-Sostaric, S. & Rantitsch, G. 2013. 40Ar/39Ar ages of crystallization and recrystallization of rock-forming polyhalite in Alpine rocksalt deposits. In: Jourdan, F., Mark, D.F. & Verati, C. (eds.): Advances in 40Ar/39Ar dating from archaeology to planetary sciences. - Geological Society of London, Special Publications 378, 207-224. Horn, M., Barnasch, J., Bode, J., Stanek, K. & Zeibig, S. 2016. Erscheinungsformen der bruchlosen Deformation und Bruchdeformation im Salinar des Steinsalzbergwerkes Braunschweig-Lüneburg. Kali und Steinsalz 02/2016, 30-42.
Authigenic K-feldspar in salt rock (Haselgebirge Formation, Eastern Alps)
NASA Astrophysics Data System (ADS)
Leitner, Christoph
2015-04-01
The crystallisation of authigenic quartz under low temperature, saline conditions is well known (Grimm, 1962). Also the growth of low temperature authigenic feldspar in sediments is a long known phenomenon (Kastner & Siever, 1979; Sandler et al., 2004). In this study we intend to show that halite (NaCl) is a major catalyser for authigenic mineral growth. During late Permian (c. 255-250 Ma), when the later Eastern Alps were located around north of the equator, the evaporites of the Haselgebirge Formation were deposited (Piller et al., 2004). The Haselgebirge Fm. consists in salt mines of a two-component tectonite of c. 50 % halite and 50 % sedimentary clastic and other evaporite rocks (Spötl 1998). Most of the clastic rocks are mud- to siltstones ("mudrock"). During this study, we investigated rare sandstones embedded in salt rock form four Alpine salt mines. Around 40 polished thin sections were prepared by dry grinding for thin section analysis and scanning electron microscopy. The sandstones consist mainly of quartz, K-feldspar, rock fragments, micas, accessory minerals and halite in the pore space. They are fine grained and well sorted. Mudrock clasts in sandstone were observed locally, and also coal was observed repeatedly. Asymmetric ripples were found only in the dimension of millimeters to centimeters. Euhedral halite crystals in pores indicate an early presence of halite. During early diagenesis, authigenic minerals crystallized in the following chronological order. (1) Where carbonate (mainly magnesite) occurred, it first filled the pore space. Plant remains were impregnated with carbonate. (2) Halite precipitated between the detritic sandstone grains. Carbonate grains can be completely embedded in halite. (3) K-feldspar and quartz grains usually expose a detritic core and a later grown euhedral inclusion free rim. Euhedral rims of K-feldspar often also enclose a halite core. K-feldspar replaced the pre-existing halite along former grain boundaries of halite. Fluid reaction rims with many tiny minerals (hematite, acicular crystals, fluid inclusions etc.) around quartz, K-feldspar and rock fragments probably belong to this stage. (4) Authigenic anhydrite grew over carbonate, halite (halite inclusions in anhydrite), euhedral quartz and euhedral K-feldspar. (5). The sulfate polyhalite [K2Ca2Mg(SO4)4•2H2O] needs three major cation ingredients: potassium, calcium and magnesium. The large granoblastic polyhalite crystals enclose halite, euhedral quartz and euhedral K-feldspar. It formed coevally with the authigenic anhydrite, which proves by their intermediate intergrowth. The age of granoblastic polyhalite was measured between 235-210 Ma on samples from the salt mines of Altaussee, Berchtesgaden and Bad Dürrnberg with 39Ar/40Ar dating (Leitner et al., 2014). Since deposition of the Haselgebirge Fm. was at c. 250 Ma, the primary diagenetic crystallization was completed c. 15-30 Ma after deposition. The overburden at this time was 1000-2000 m at maximum (formation of the large carbonate platforms; Tollmann, 1985) and therefore very low p-T conditions can be assumed for the formation of authigenic quartz and authigenic K-feldspar.
NASA Astrophysics Data System (ADS)
Leitner, Christoph; Hofmann, Peter; Marschallinger, Robert
2014-05-01
Halite hopper crystals are thought to develop by displacive growth in unconsolidated mud (Gornitz & Schreiber, 1984). The Alpine Haselgebirge, but also e.g. the salt deposits of the Rhine graben (mined at the beginning of the 20th century), comprise hopper crystals with shapes of cuboids, parallelepipeds and rhombohedrons (Görgey, 1912). Obviously, they deformed under oriented stress, which had been tried to reconstruct with respect to the sedimentary layering (Leitner et al., 2013). In the present work, deformed halite hopper crystals embedded in mudrock were automated reconstructed. Object based image analysis (OBIA) has been used successfully in remote sensing for 2D images before. The present study represents the first time that the method was used for reconstruction of three dimensional geological objects. First, manually a reference (gold standard) was created by redrawing contours of the halite crystals on each HRXCT scanning slice. Then, for OBIA, the computer program eCognition was used. For the automated reconstruction a rule set was developed. Thereby, the strength of OBIA was to recognize all objects similar to halite hopper crystals and in particular to eliminate cracks. In a second step, all the objects unsuitable for a structural deformation analysis were dismissed using a support vector machine (SVM) (clusters, polyhalite-coated crystals and spherical halites) The SVM simultaneously drastically reduced the number of halites. From 184 OBIA-objects 67 well shaped remained, which comes close to the number of pre-selected 52 objects. To assess the accuracy of the automated reconstruction, the result before and after SVM was compared to the reference, i.e. the gold standard. State-of the art per-scene statistics were extended to a per-object statistics. Görgey R (1912) Zur Kenntnis der Kalisalzlager von Wittelsheim im Ober-Elsaß. Tschermaks Mineral Petrogr Mitt 31:339-468 Gornitz VM, Schreiber BC (1981) Displacive halite hoppers from the dead sea: Some implications for ancient evaporite deposits. J of Sediment Petrol 51:787-794. doi: 10.1306/212F7DAB-2B24-11D7-8648000102C1865D Leitner C, Neubauer F, Marschallinger R, Genser J, Bernroider M (2013) Origin of deformed halite hopper crystals, pseudomorphic anhydrite cubes and polyhalite in Alpine evaporates (Austria, Germany). Int J Earth Sc 102, pp 813-829, doi: 10.1007/s00531-012-0836-6
John, Charles B.; Cheeseman, R.J.; Lorenz, J.C.; Millgate, M.L.
1978-01-01
The proposed Waste Isolation Pilot Plant (WIPP) area includes about 18,960 acres in Tps. 22 and 23 S., Rs. 30 and 31 E., New Mexico Principal Meridian, Eddy County, southeastern New Mexico. It is located within the Carlsbad Mining District about 25 miles east of Carlsbad. The WIPP area is immediately south of the Capitan Limestone subcrop, which formed the northern margin of the Delaware basin in Permian time. During Late Permian (Ochoan) time, gypsum, anhydrite, and halite were deposited in the seas of the Delaware basin to form the Castile Formation. These deposits have a maximum thickness of about 2,000 feet and grade upward into the more argillaceous beds of the Salado Formation. The Salado Formation contains abundant sulfate minerals, notably anhydrite and polyhalite. The potash ore minerals, langbeinite and sylvite, occur in the upper part of the Salado Formation in the McNutt potash zone, a local name applied to a potassium-rich zone.
A process-sedimentary framework for characterizing recent and ancient sabkhas
Handford, C.R.
1981-01-01
The discovery of sabkha environments during the 1960's, marked the beginning of Recent evaporite sedimentological studies and their perception as models for facies analysis. However, variation among Recent sabkhas, though recognized by the geologic community, has not been duly addressed, which has resulted in overuse of the Trucial Coast model in comparative sedimentological studies. Knowledge of the dominant physical processes which determine sabkha morphology, and of the sedimentary response to those processes, can lead to a fundamental understanding of a sabkha's origin and of how it differs from other sabkhas. Physical processes thought to be most important (besides evaporation) include those operative under: (1) marine-; (2) fluvial-lacustrine-; and (3) eolian-dominated conditions. Dominance of one or more of these in the proper settings give rise to marine coastal sabkhas, continental playas, and interdune sabkhas. Sedimentary responses to dominant physical processes lead to the development of sabkhas consisting of a combination of either: (1) terrigenous clastics; (2) carbonate-sulfate (anhydrite-gypsum) minerals; or (3) soluble salts (halite, sylvite, polyhalite, etc.). Sediment characterization can also allow discrimination of the range or compositional variety in, for example, coastal sabkhas. Where applied to the stratigraphic record, this classification system may help unravel the sedimentary history of an ancient sabkha system, and a determination of the dominant physical processes that ruled its development. ?? 1981.
Isotopic composition of sulfate accumulations, Northern Calcareous Alps, Austria
NASA Astrophysics Data System (ADS)
Bojar, Ana-Voica; Halas, Stanislaw; Bojar, Hans-Peter; Trembaczowski, Andrzej
2015-04-01
The Eastern Alps are characterised by the presence of three main tectonic units, such as the Lower, Middle and Upper Austroalpine, which overlie the Penninicum (Tollmann, 1977). The Upper Austroalpine unit consists of the Northern Calcareous Alps (NCA) overlying the Greywacke zone and corresponding to the Graz Paleozoic, Murau Paleozoic and the Gurktal Nappe. Evaporitic rocks are lacking in the later ones. The Northern Calcareous Alps are a detached fold and thrust belt. The sedimentation started in the Late Carboniferous or Early Permian, the age of the youngest sediments being Eocene. The NCA are divided into the Bajuvaric, Tirolic and Juvavic nappe complexes. The evaporitic Haselgebirge Formation occurs in connection with the Juvavic nappe complex at the base of the Tirolic units (Leitner et al., 2013). The Haselgebirge Formation consists mainly of salt, shales, gypsum and anhydrite and includes the oldest sediments of the NCA. The age of the Haselgebirge Formation, established by using spors and geochronological data, is Permian to Lower Triassic. For the Northern Calcareous Alps, the mineralogy of sulphate accumulations consists mainly of gypsum and anhydrite and subordonates of carbonates. The carbonates as magnesite, dolomite and calcite can be found either as singular crystals or as small accumulations within the hosting gypsum. Sulfides (sphalerite, galena, pyrite), sulfarsenides (enargite, baumhauerite) and native sulphur enrichments are known from several deposits (Kirchner, 1987; Postl, 1990). The investigated samples were selected from various gypsum and halite rich deposits of the Northern Calcareous Alps. A total of over 20 samples were investigated, and both oxygen and sulfur isotopic composition were determined for anhydrite, gyps, polyhalite, blödite and langbeinite. The sulfur isotopic values vary between 10.1 to 14 ‰ (CDT), with three values higher than 14 ‰. The Oxygen isotopic values show a range from 9 to 23 ‰ (SMOW). The sulfur isotopic compositon of 14 sulfides as galena, sphalerite, pyrite and native sulfure were determined as well, with values ranging between -17.5 and 2.8 ‰ (CDT). For the investigated sulfates, the sulfur isotopic values show generally low values, which are characteristic for the late Permian. The broad distribution of sulfide values point toward bacterial reduction, fact also reflected by some higher isotopic values of sulfates. The oxygen values show a larger scatter from 9 to 23‰, which is even larger than that found for the Zechstein anhydrites of northern Germany, north-eastern Italian Alps or western Poland. The associated carbonates, as calcite, dolomite and magnesite are in disequilibrium with the sulfates indicating rather primary marine isotopic signature than re-equlibration with the sulfates at higher temperatures. References Leitner, C., Neubauer, F., Genser, J., Borojevic-Sostaric, B., Rantitsch, G., 2013. 40Ar/39Ar ages of recrystallization of rock-forming polyhalite in Alpine rocksalt deposits. In Jordan, F., Mark, D.F., Verati C. (eds.) Advances in 40Ar/39Ar Dating: from Archaeology to Planetary Sciences. Geological Society, London, Special Publications, 378, 207-244. Kirchner, E., 1987: Die Mineral- und Gesteinsvorkommen in den Gipslagerstätten der Lammermasse, innerhalb der Hallstattzone, Salzburg. Jahrbuch Haus der Natur. 10, 156-167. Postl, W., 1990. Enargit und Parnauit aus dem Gips- und Anhydritbergbau Tragöß-Oberort, Steiermark. In: Niedermayr, G. et al. (1990): Neue Mineralfunde aus Österreich XXXIX. Carinthia II, 180/100, 277. Tollmann, A., 1977. Geologie von Österreich. Band 1. Die Zentralalpen. Deuticke, Wien, 766 pp.
Bartsch-Winkler, S.; Sutphin, D.M.; Ball, M.M.; Korzeb, S.L.; Kness, R.F.; Dutchover, J.T.
1993-01-01
In this summary of two comprehensive resource reports produced by the U.S. Bureau of Mines and the U.S. Geological Survey for the U.S. Bureau of Land Management, we discuss the mineral- and energyresource endowment of the 14-millon-acre Roswell Resource Area, New Mexico, managed by the Bureau of Land Management. The Bureau and Survey reports result from separate studies that are compilations of published and unpublished data and integrate new findings on the geology, geochemistry, geophysics, mineral, industrial, and energy commodities, and resources for the seven-county area. The reports have been used by the Bureau of Land Management in preparation of the Roswell Resource Area Resource Management Plan, and will have future use in nationwide mineral- and energy-resource inventories and assessments, as reference and training documents, and as public-information tools. In the Roswell Resource Area, many metals, industrial mineral commodities, and energy resources are being, or have been, produced or prospected. These include metals and high-technology materials, such as copper, gold, silver, thorium, uranium and/or vanadium, rare-earth element minerals, iron, manganese, tungsten, lead, zinc, and molybdenum; industrial mineral resources, including barite, limestone/dolomite, caliche, clay, fluorspar, gypsum, scoria, aggregate, and sand and gravel; and fuels and associated resources, such as oil, gas, tar sand and heavy oil, coal, and gases associated with hydrocarbons. Other commodities that have yet to be identified in economic concentrations include potash, halite, polyhalite, anhydrite, sulfur, feldspar, building stone and decorative rock, brines, various gases associated with oil and gas exploration, and carbon dioxide. ?? 1993 Oxford University Press.
Siegel, M.D.; Anderholm, S.
1994-01-01
The Culebra Dolomite Member of the Rustler Formation, a thin (10 m) fractured dolomite aquifer, lies approximately 450 m above the repository horizon of the Waste Isolation Pilot Plant (WIPP) in southeastern New Mexico, USA. Salinities of water in the Culebra range roughly from 10,000 to 200,000 mg/L within the WIPP site. A proposed model for the post-Pleistocene hydrochemical evolution of the Culebra tentatively identifies the major sources and sinks for many of the groundwater solutes. Reaction-path simulations with the PHRQPITZ code suggest that the Culebra dolomite is a partial chemical equilibrium system whose composition is controlled by an irreversible process (dissolution of evaporites) and equilibrium with gypsum and calcite. Net geochemical reactions along postulated modern flow paths, calculated with the NETPATH code, include dissolution of halite, carbonate and evaporite salts, and ion exchange. R-mode principal component analysis revealed correlations among the concentrations of Si, Mg, pH, Li, and B that are consistent with several clay-water reactions. The results of the geochemical calculations and mineralogical data are consistent with the following hydrochemical model: 1. (1) solutes are added to the Culebra by dissolution of evaporite minerals 2. (2) the solubilities of gypsum and calcite increase as the salinity increases; these minerals dissolve as chemical equilibrium is maintained between them and the groundwater 3. (3) equilibrium is not maintained between the waters and dolomite; sufficient Mg is added to the waters by dissolution of accessory carnallite or polyhalite such that the degree of dolomite supersaturation increases with ionic strength 4. (4) clays within the fractures and rock matrix exert some control on the distribution of Li, B, Mg, and Si via sorption, ion exchange, and dissolution. ?? 1994.
NASA Astrophysics Data System (ADS)
Stoker, Carol R.; Clarke, Jonathan; Direito, Susana O. L.; Blake, David; Martin, Kevin R.; Zavaleta, Jhony; Foing, Bernard
2011-07-01
We collected and analysed soil cores from four geologic units surrounding Mars Desert Research Station (MDRS) Utah, USA, including Mancos Shale, Dakota Sandstone, Morrison formation (Brushy Basin member) and Summerville formation. The area is an important geochemical and morphological analogue to terrains on Mars. Soils were analysed for mineralogy by a Terra X-ray diffractometer (XRD), a field version of the CheMin instrument on the Mars Science Laboratory (MSL) mission (2012 landing). Soluble ion chemistry, total organic content and identity and distribution of microbial populations were also determined. The Terra data reveal that Mancos and Morrison soils are rich in phyllosilicates similar to those observed on Mars from orbital measurements (montmorillonite, nontronite and illite). Evaporite minerals observed include gypsum, thenardite, polyhalite and calcite. Soil chemical analysis shows sulfate the dominant anion in all soils and SO4>>CO3, as on Mars. The cation pattern Na>Ca>Mg is seen in all soils except for the Summerville where Ca>Na. In all soils, SO4 correlates with Na, suggesting sodium sulfates are the dominant phase. Oxidizable organics are low in all soils and range from a high of 0.7% in the Mancos samples to undetectable at a detection limit of 0.1% in the Morrison soils. Minerals rich in chromium and vanadium were identified in Morrison soils that result from diagenetic replacement of organic compounds. Depositional environment, geologic history and mineralogy all affect the ability to preserve and detect organic compounds. Subsurface biosphere populations were revealed to contain organisms from all three domains (Archaea, Bacteria and Eukarya) with cell density between 3.0×106 and 1.8×107 cells ml-1 at the deepest depth. These measurements are analogous to data that could be obtained on future robotic or human Mars missions and results are relevant to the MSL mission that will investigate phyllosilicates on Mars.
Mineral and energy resources of the BLM Roswell Resource Area, east-central New Mexico
Bartsch-Winkler, Susan B.
1992-01-01
The sedimentary formations of the Roswell Resource Area have significant mineral and energy resources. Some of the pre-Pennsylvanian sequences in the Northwestern Shelf of the Permian Basin are oil and gas reservoirs, and Pennsylvanian rocks in Tucumcari basin are reservoirs of oil and gas as well as source rocks for oil and gas in Triassic rocks. Pre-Permian rocks also contain minor deposits of uranium and vanadium, limestone, and associated gases. Hydrocarbon reservoirs in Permian rocks include associated gases such as carbon dioxide, helium, and nitrogen. Permian rocks are mineralized adjacent to the Lincoln County porphyry belt, and include deposits of copper, uranium, manganese, iron, polymetallic veins, and Mississippi-valley-type (MVT) lead-zinc. Industrial minerals in Permian rocks include fluorite, barite, potash, halite, polyhalite, gypsum, anhydrite, sulfur, limestone, dolomite, brine deposits (iodine and bromine), aggregate (sand), and dimension stone. Doubly terminated quartz crystals, called "Pecos diamonds" and collected as mineral specimens, occur in Permian rocks along the Pecos River. Mesozoic sedimentary rocks are hosts for copper, uranium, and small quantities of gold-silver-tellurium veins, as well as significant deposits of oil and gas, COa, asphalt, coal, and dimension stone. Mesozoic rocks contain limited amounts of limestone, gypsum, petrified wood, dinosaur remains, and clays. Tertiary rocks host ore deposits commonly associated with intrusive rocks, including platinum group elements, iron skarns, manganese, uranium and vanadium, molybdenum, polymetallic vein deposits, gold-silver- tellurium veins, and thorium-rare earth veins. Museum-quality quartz crystals in Lincoln County were formed in association with intrusive rocks in the Lincoln County porphyry belt. Industrial minerals in Tertiary rocks include fluorite, vein- and bedded-barite, caliche, limestone, and aggregate. Tertiary and Quaternary sediments host important placer deposits of gold and titanium, and minor silver, uranium occurrences, as well as important industrial commodities, including caliche, limestone and dolomite, and aggregate (sand). Quaternary basalt contains sub-ore-grade uranium, scoria, and clay deposits.
Mineral and energy resources of the Roswell Resource Area, East-Central New Mexico
Bartsch-Winkler, Susan B.; Donatich, Alessandro J.
1995-01-01
The sedimentary formations of the Roswell Resource Area have significant mineral and energy resources. Some of the pre-Pennsylvanian sequences in the Northwestern Shelf of the Permian Basin are oil and gas reservoirs, and Pennsylvanian rocks in Tucumcari Basin are reservoirs of oil and gas as well as source rocks for oil and gas in Triassic rocks. Pre-Permian rocks also contain minor deposits of uranium and vanadium, limestone, and gases. Hydrocarbon reservoirs in Permian rocks include associated gases such as carbon dioxide, helium, and nitrogen. Permian rocks are mineralized adjacent to the Lincoln County porphyry belt, and include deposits of copper, uranium, manganese, iron, polymetallic veins, and Mississippi-Valley-type lead-zinc. Industrial minerals in Permian rocks include fluorite, barite, potash, halite, polyhalite, gypsum, anhydrite, sulfur, limestone, dolomite, brine deposits (iodine and bromine), aggregate (sand), and dimension stone. Doubly terminated quartz crystals, called 'Pecos diamonds' and collected as mineral specimens, occur in Permian rocks along the Pecos River. Mesozoic sedimentary rocks are hosts for copper, uranium, and small quantities of gold-silver-tellurium veins, as well as significant deposits of oil and gas, carbon dioxide, asphalt, coal, and dimension stone. Mesozoic rocks contain limited amounts of limestone, gypsum, petrified wood, and clay. Tertiary rocks host ore deposits commonly associated with intrusive rocks, including platinum-group elements, iron skarns, manganese, uranium and vanadium, molybdenum, polymetallic vein deposits, gold-silver-tellurium veins, and thorium-rare-earth veins. Museum-quality quartz crystals are associated with Tertiary intrusive rocks. Industrial minerals in Tertiary rocks include fluorite, vein- and bedded-barite, caliche, limestone, and aggregate. Tertiary and Quaternary sediments host important placer deposits of gold and titanium, and occurrences of silver and uranium. Important industrial commodities include caliche, limestone and dolomite, and aggregate. Quaternary basalt contains sub-ore-grade uranium, scoria, and clay deposits.
NASA Astrophysics Data System (ADS)
Xiong, Y.; Deng, H.; Nemer, M. B.; Johnsen, S.
2009-12-01
MgO (bulk, pure MgO corresponding to the mineral periclase) is the only engineered barrier certified by the Environmental Protection Agency for emplacement in the Waste Isolation Pilot Plant (WIPP) in the US, and an Mg(OH)2-based engineered barrier (bulk, pure Mg(OH)2 corresponding to brucite) is to be employed in the Asse repository in Germany. Both the WIPP and the Asse are located in salt formations. The WIPP is a U.S. Department of Energy geological repository being used for the permanent disposal of defense-related transuranic waste (TRU waste). The repository is 655 m below the surface, and is situated in the Salado Formation, a Permian salt bed mainly composed of halite, and of lesser amounts of polyhalite, anhydrite, gypsum, magnesite, clays and quartz. The WIPP Generic Weep Brine (GWB), a Na-Mg-Cl dominated brine, is associated with the Salado Formation. The previous vendor for MgO for the WIPP was Premier Chemicals and the current vendor is Martin Marietta Materials. Experimental studies of both Premier MgO and Martin Marietta MgO with the GWB at SNL indicate the formation of magnesium chloride hydroxide hydrate, Mg3Cl(OH)5:4H2O, termed as phase 5. However, this important phase is lacking in the existing thermodynamic database. In this study, the solubility constant of phase 5 is determined from a series of solubility experiments in MgCl2-NaCl solutions. The solubility constant at 25 oC for the following reaction, Mg3Cl(OH)5:4H2O + 5H+ = 3Mg2+ + 9H2O(l) + Cl- is recommended as 43.21±0.33 (2σ) based on the Specific Interaction Theory (SIT) model for extrapolation to infinite dilution. The log K obtained via the Pitzer equations is identical to the above value within the quoted uncertainty. The Gibbs free energy and enthalpy of formation for phase 5 at 25 oC are derived as -3384±2 (2σ) kJ mol-1 and -3896±6 (2σ) kJ mol-1, respectively. The standard entropy and heat capacity of phase 5 at 25 oC are estimated as 393±20 J mol-1 K-1 and 374±19 J mol-1 K-1, respectively. Phase 5, and its similar phase, phase 3 (Mg2Cl(OH)3:4H2O), could have a significant role in influencing the geochemical conditions in geological repositories for nuclear waste in salt formations where MgO or brucite is employed as engineered barriers, when Na-Mg-Cl dominated brines react with MgO or brucite. Based on our solubility constant for phase 5 in combination with the literature value for phase 3, we predict that the composition for the invariant point of phase 5 and phase 3 would be mMg = 1.70 and pmH = 8.93 in the Mg-Cl binary system. The recent WIPP Compliance Recertification Application PA Baseline Calculations indicate that phase 5 instead of phase 3 is indeed a stable phase when GWB equilibrates with actinide-source-term phases, brucite, magnesium carbonates, halite and anhydrite. 1. This research is funded by WIPP programs administered by the U.S. Department of Energy. 2. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.
Cocker, Mark D.; Orris, Greta J.; Dunlap, Pamela; Lipin, Bruce R.; Ludington, Steve; Ryan, Robert J.; Słowakiewicz, Mirosław; Spanski, Gregory T.; Wynn, Jeff; Yang, Chao
2017-08-03
Undiscovered potash resources in the Pripyat Basin, Belarus, and Dnieper-Donets Basin, Ukraine, were assessed as part of a global mineral resource assessment led by the U.S. Geological Survey (USGS). The Pripyat Basin (in Belarus) and the Dnieper-Donets Basin (in Ukraine and southern Belarus) host stratabound and halokinetic Upper Devonian (Frasnian and Famennian) and Permian (Cisuralian) potash-bearing salt. The evaporite basins formed in the Donbass-Pripyat Rift, a Neoproterozoic continental rift structure that was reactivated during the Late Devonian and was flooded by seawater. Though the rift was divided, in part by volcanic deposits, into the separate Pripyat and Dnieper-Donets Basins, both basins contain similar potash‑bearing evaporite sequences. An Early Permian (Cisuralian) sag basin formed over the rift structure and was also inundated by seawater resulting in another sequence of evaporite deposition. Halokinetic activity initiated by basement faulting during the Devonian continued at least into the Permian and influenced potash salt deposition and structural evolution of potash-bearing salt in both basins.Within these basins, four areas (permissive tracts) that permit the presence of undiscovered potash deposits were defined by using geological criteria. Three tracts are permissive for stratabound potash-bearing deposits and include Famennian (Upper Devonian) salt in the Pripyat Basin, and Famennian and Cisuralian (lower Permian) salt in the Dnieper-Donets Basin. In addition, a tract was delineated for halokinetic potash-bearing Famennian salt in the Dnieper-Donets Basin.The Pripyat Basin is the third largest source of potash in the world, producing 6.4 million metric tons of potassium chloride (KCl) (the equivalent of about 4.0 million metric tons of potassium oxide or K2O) in 2012. Potash production began in 1963 in the Starobin #1 mine, near the town of Starobin, Belarus, in the northwestern corner of the basin. Potash is currently produced from six potash mines in the Starobin area. Published reserves in the Pripyat Basin area are about 7.3 billion metric tons of potash ore (about 1.3 billion metric tons of K2O) mostly from potash-bearing salt horizons in the Starobin and Petrikov mine areas. The 15,160-square-kilometer area of the Pripyat Basin underlain by Famennian potash-bearing salt contains as many as 60 known potash-bearing salt horizons. Rough estimates of the total mineral endowment associated with stratabound Famennian salt horizons in the Pripyat Basin range from 80 to 200 billion metric tons of potash-bearing salt that could contain 15 to 30 billion metric tons of K2O.Parameters (including the number of economic potash horizons, grades, and depths) for these estimates are not published so the estimates are not easily confirmed. Historically, reserves have been estimated above a depth of 1,200 meters (m) (approximately the depths of conventional underground mining). Additional undiscovered K2O resources could be significantly greater in the remainder of the Fammenian salt depending on the extents and grades of the 60 identified potash horizons above the USGS assessment depth of 3,000 m in the remainder of the tract. Increasing ambient temperatures with increasing depths in the eastern parts of the Pripyat Basin may require a solution mining process which is aided by higher temperatures.No resource or reserve data have been published and little is known about stratabound Famennian and Frasnian salt in the Dnieper-Donets Basin. These Upper Devonian salt units dip to the southeast and extend to depths of 15–19 kilometers (km) or greater. The tract of stratabound Famennian salt that lies above a depth of 3 km, the depth above which potash is technically recoverable by solution mining, underlies an area of about 15,600 square kilometers (km2). If Upper Devonian salt units in the Dnieper-Donets Basin contain potash-bearing strata similar to salt of the same age in the Pripyat Basin, then the stratabound Famennian tract in the Dnieper-Donets Basin could contain significant undiscovered potash resources.The Cisuralian evaporite sequence in the Dnieper-Donets Basin consists of 10 evaporite cycles with the upper 3 cycles containing potash-bearing salt (mainly as sylvite and carnallite) in several subbasins and polyhalite in the sulfate bearing parts of the identified tract. The area of the Cisuralian tract is 62,700 km2. Potash-bearing cycles are as much as 40 m thick. One subbasin is reported to contain 794 million metric tons of “raw or crude” potash-bearing salt which could contain 50 to 150 million metric tons of K2O, depending on the grade. Undiscovered potash resources in the remainder of this permissive tract may be significantly greater. Depths to the Permian salt range from less than 100 to about 1,500 m.Undiscovered resources of halokinetic potash-bearing salt in the Dnieper-Donets Basin were assessed quantitatively for this study by using the standard USGS three-part form of mineral resource assessment (Singer, 2007a; Singer and Menzie, 2010). Delineation of the permissive tract was based on distributions of mapped halokinetic salt structures. This tract contains at least 248 diapiric salt structures with a total area of 7,840 km2 that occupies approximately 8 percent of the basin area. The vertical extent of these salt structures is hundreds of meters to several kilometers. This assessment estimated that a total mean of 11 undiscovered deposits contain an arithmetic mean estimate of about 840 million metric tons of K2O in the halokinetic salt structures of the Dnieper-Donets Basin for which the probabilistic estimate was made.