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Sample records for hematite calcite gypsum

  1. Effect of Mica and Hematite (001) Surfaces on the Precipitation of Calcite

    Huifang Xu; Mo Zhou; Yihang Fang; H. Henry Teng

    2018-01-01

    The substrate effect of mica and hematite on the nucleation and crystallization of calcite was investigated using scanning electron microscope (SEM), X-ray diffraction (XRD), and electron backscatter diffraction (EBSD) methods. On mica, we found, in the absence of Mg2+, the substrates’ (001) surfaces with hexagonal and pseudo-hexagonal two-dimensional (2-D) structure can affect the orientation of calcite nucleation with calcite (001) ~// mica (001) and calcite (010) ~// mica (010) to be the m...

  2. Effect of Mica and Hematite (001 Surfaces on the Precipitation of Calcite

    Huifang Xu

    2018-01-01

    Full Text Available The substrate effect of mica and hematite on the nucleation and crystallization of calcite was investigated using scanning electron microscope (SEM, X-ray diffraction (XRD, and electron backscatter diffraction (EBSD methods. On mica, we found, in the absence of Mg2+, the substrates’ (001 surfaces with hexagonal and pseudo-hexagonal two-dimensional (2-D structure can affect the orientation of calcite nucleation with calcite (001 ~// mica (001 and calcite (010 ~// mica (010 to be the major interfacial relationship. On hematite, we did not observe frequent twinning relationship between adjacent calcite gains, but often saw preferentially nucleation of calcite at surface steps on hematite substrate. We suggest that calcite crystals initially nucleate from the Ca2+ layers adsorbed on the surfaces. The pseudo-hexagonal symmetry on mica (001 surface also leads to the observed calcite (001 twinning. A second and less common orientation between calcite {104} and mica (001 was detected but could be due to local structure damage of the mica surface. Results in the presence of Mg2+ show that the substrate surfaces can weaken Mg toxicity to calcite nucleation and lead to a higher level of Mg incorporation into calcite lattice.

  3. Relative Shock Effects in Mixed Powders of Calcite, Gypsum, and Quartz: A Calibration Scheme from Shock Experiments

    Bell, Mary S.

    2009-01-01

    The shock behavior of calcite and gypsum is important in understanding the Cretaceous/Tertiary event and other terrestrial impacts that contain evaporite sediments in their targets. Most interest focuses on issues of devolatilization to quantify the production of CO2 or SO2 to better understand their role in generating a temporary atmosphere and its effects on climate and biota [e.g., papers in 1,2,3,4]. Devolatilization of carbonate is also important because the dispersion and fragmentation of ejecta is strongly controlled by the expansion of large volumes of gas during the impact process as well [5,6]. Shock recovery experiments for calcite yield seemingly conflicting results: early experimental devolatilization studies [7,8,9] suggested that calcite was substantially outgassed at 30 GPa (> 50%). However, the recent petrographic work of [10,11,12] presented evidence that essentially intact calcite is recovered from 60 GPa experiments. [13] reported results of shock experiments on anhydrite, gypsum, and mixtures of those phases with silica. Their observations indicate little or no devolatilization of anhydrite shocked to 42 GPa and that the fraction of sulfur, by mass, that degassed is approx.10(exp -2) of theoretical prediction. In another (preliminary) report of shock experiments on calcite, anhydrite, and gypsum, [14] observe calcite recrystallization when shock loaded at 61 GPa, only intensive plastic deformation in anhydrite shock loaded at 63 GPa, and gypsum converted to anhydrite when shock loaded at 56 GPa. [15] shock loaded anhydrite and quartz to a peak pressure of 60 GPa. All of the quartz grains were trans-formed to glass and the platy anhydrite grains were completely pseudomorphed by small crystallized anhydrite grains. However, no evidence of interaction between the two phases could be observed and they suggest that recrystallization of anhydrite grains is the result of a solid state transformation. [16] reanalyzed the calcite and anhydrite shock

  4. Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution.

    Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami

    2017-03-01

    Calcium carbonate (CaCO 3 ) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO 4 ·2H 2 O and CaSO 4 transformed into calcite, a polymorph of CaCO 3 , while maintaining their macroscopic structure when immersed in 1mol/L Na 2 CO 3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO 4 ·2H 2 O and CaSO 4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO 4 ·2H 2 O and CaSO 4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Late-stage anhydrite-gypsum-siderite-dolomite-calcite assemblages record the transition from a deep to a shallow hydrothermal system in the Schwarzwald mining district, SW Germany

    Burisch, Mathias; Walter, Benjamin F.; Gerdes, Axel; Lanz, Maximilian; Markl, Gregor

    2018-02-01

    The majority of hydrothermal vein systems of economic interest occur at relatively shallow crustal levels, although many of them formed at significantly greater depths. Their present position is a consequence of uplift and erosion. Although, many aspects of their formation are well constrained, the temporal chemical evolution of such systems during uplift and erosion is still poorly understood. These vein minerals comprise calcite, dolomite-ankerite, siderite-magnesite, anhydrite and gypsum forming the last gangue assemblages in Jurassic and Tertiary sulphide-fluorite-quartz-barite veins of the Schwarzwald mining district, SW Germany. Mineral textures of samples from nine localities reveal that in these sequences, mineral precipitation follows a recurring pattern: early calcite is followed by anhydrite or gypsum, siderite and/or dolomite. This succession may repeat up to three times. In-situ (LA-ICP-MS) U-Pb age dating of 15 carbonates from three subsequent generations of the late-stage vein assemblage yield robust ages between 20 and 0.6 Ma. Each mineral sequence forms in a distinctive period of about 2-5 Ma. These ages clearly relate these late-stage mineral phases to the youngest geological episode of the Schwarzwald, which is associated with the Cenozoic Rhine Graben rifting and basement uplift. Based on thermodynamic modelling, the formation of the observed mineral assemblages required an deeply sourced Mg-, Fe- and SO4-rich fluid (b), which was episodically mixed with a shallow crustal HCO3-rich fluid (a). As a consequence of fluid mixing, concentrations of Mg, Fe and SO4 temporarily increased and initiated the formation of the observed sulphate-carbonate mineral sequences. This discontinuous large-scale vertical fluid mixing was presumably directly related to episodes of active tectonics associated with the Cenozoic strike-slip regime of the Upper Rhine Graben. Analogously, episodic fluid mixing is a major key in the formation of older (Jurassic to early

  6. Model of gypsum, calcite and silica solubilities for application to geothermal waters over a wide range of temperature, P/sub CO/sub 2// and ionic strength. Final technical report, October 1, 1983-September 30, 1984

    1984-01-01

    This report describes the construction of a high temperature (25 to 250/sup 0/C), variable P/sub CO/sub 2// (1 to 40 atm), chemical model of mineral (including gypsum, calcite and amorphous silica) solubilities in the system: Na-K-Ca-H-Cl-SO/sub 4/-HCO/sub 3/-CO/sub 3/-CO/sub 2/-SiO/sub 2/-H/sub 2/O. This model was designed to support geothermal energy production needs.

  7. Geothermometry obtained from the calcite twin and fluid inclusions in barite (Irankuh Pb-Zn deposit, Southwest of Isfahan)

    Alijan Aftabi; Hengameh Hosseini-Dinani

    2017-01-01

    The Irankuh mining district is located 20 km southwest of Isfahan and is geologically situated in Sanandaj - Sirjan zone and the lower Cretaceous sequence of Isfahan-Malayer ore mineralization area. The ore minerals are emplaced in the faulted contact of Jurassic shale and Cretaceous carbonates and include pyrite, galena, sphalerite, calcite, barite, dolomite, quartz as well as minor marcasite, smithsonite, cerussite, gypsum, malachite, hematite and goethite. The mineralization is mainly occu...

  8. Geothermometry obtained from the calcite twin and fluid inclusions in barite (Irankuh Pb-Zn deposit, Southwest of Isfahan

    Alijan Aftabi

    2017-03-01

    Full Text Available The Irankuh mining district is located 20 km southwest of Isfahan and is geologically situated in Sanandaj - Sirjan zone and the lower Cretaceous sequence of Isfahan-Malayer ore mineralization area. The ore minerals are emplaced in the faulted contact of Jurassic shale and Cretaceous carbonates and include pyrite, galena, sphalerite, calcite, barite, dolomite, quartz as well as minor marcasite, smithsonite, cerussite, gypsum, malachite, hematite and goethite. The mineralization is mainly occurred as hydrothermal veins and veinlets associated with fractures and faults, suggesting the deposit is likely to be of epigenetic type. A comparison between geothermometric results obtained from calcite twins and fluid inclusions showed a similar temperature range for the mineralization (less than 170ºc. Fluid inclusion studies indicate the temperature, salinity and density ranges of 80-166ºc, 5.39-20.94 wt.% NaCl and 0.95-1.12, respectively. The obtained data share many similarities with those of the MVT deposits

  9. SEDIMENTARY LOW-MANGANESE HEMATITE DEPOSITS OF THE BUKOVICA AREA IN THE NORTHWESTERN MT. PETROVA GORA, CENTRAL CROATIA

    Milivoj Čop

    1998-12-01

    Full Text Available Middle-Permian Gröden deposits crop out on the surface of 0.8 km in the Bukovica area and on the surface of 0.8 km2 in the Mt. Loskun-jska gora in the NW part of the Petrova gora Mountain. One half of the Bukovica Gröden deposits contains in its lowest parts 1 to 5 m (in average 2.5 m thick hematite bed cutted in blocks by NE-SW stretch¬ing vertical, normal and reverse faults. The hematite bed is unconfor-mably underlain by Lower Permian quartz-wackes (subgraywackes intercalated with shales intercalations. Ore deposit is explored by 308 boreholes (10509 m and by numerous adits, inclines and crosscuts on the underground surface of 0.4 km2 . From 1936 to 1941 and from 1953 to 1969 has been exploited 183000 t of ore with (in wt %: 34.0 Si02, 2.9 Al2O3; 59.0 Fe203; 0.15 MnO; 0.7 CaO; 0.4 MgO; 0.1 P, 0.37 S; 1.25 l.o. ign. Proven remaining ore reserves are 250.000 t. Paragenesis is investigated by microscopy of thin and polished sections, XRD, DTA, AAS analyses and by sedimentological analyses. Paragenesis major minerals are of hematite and quartz, with subordinate stable litho-clasts, muscovite (sericite and scarce kaolinite, calcite, dolomite, and barite. Accessories are zircon, rutile, tourmaline, amphibole, garnet, apatite. Epigenetic veinlets and small nests are built up of quartz or calcite as the main neominerals associated with siderite, barite, kaolinite, pyrite, gypsum. Iron from the Bukovica hematite ore origi¬nated by land weathering during hot climate and transported by rivers and underground waters deposited in river beds, in flood plains and in shallow sea. Precipitation of the Bukovica iron ores took place after the Saalic orogenetic phase. At Hrastno (SE Slovenia and at Rude nearby Samobor (Croatia, similar hematite deposits were found.

  10. Hydrogeology of Gypsum formations

    Klimchouk A.

    1996-01-01

    Full Text Available Detailed explanation of hydrogeological characteristics of gypsum aquifers is given in various situations: deep-seated karst-confined conditions, subjacent, entrenched and denuded karst types-semi-confined, phreatic and vadose conditions. The hydrogeological evolution of barren exposed gypsum karst and flow velocities in gypsum karst aquifers is also discussed.

  11. MODIFIED GYPSUM BINDER

    KONDRATEVA N. V.

    2017-02-01

    Full Text Available Summary. Statement of the problem. A disadvantage of the gypsum binder is the limited water resistance of products that historically led to the use of gypsum products mostly for internal construction and finishing works. To regulate the process of hydration and structure formation of the use of chemical additives that are introduced with the mixing water or in the production of the binder. As a rule, substances that increase the solubility of the gypsum binder referred to as the hardening accelerator, and substances which retard the solubility of the inhibitors of hardening of the mixture. Most accelerators and retarders hardening affect adversely on the final strength of the mixture. More effective impact on gypsum binder additives have plasticizers. The purpose of the article. Getting gypsum binder modified with the aim of improving its water resistance and improvement of some technological factors (the time of hardening, water gypsum ratio, etc. would reduce its shortcomings and expand the scope of application of the binder. Conclusion. The result of the research reviewed changes in the basic properties of the gypsum binder with the introduction of additives, plasticizers, and selected the most effective supplements to significantly reduce water gypsum ratio, to improve strength properties and to obtain gypsum binder more dense structure.

  12. Intracrystalline deformation of calcite

    Bresser, J.H.P. de

    1991-01-01

    It is well established from observations on natural calcite tectonites that intracrystalline plastic mechanisms are important during the deformation of calcite rocks in nature. In this thesis, new data are presented on fundamental aspects of deformation behaviour of calcite under conditions where

  13. Model study of initial adsorption of SO{sub 2} on calcite and dolomite

    Malaga-Starzec, Katarina; Panas, Itai; Lindqvist, Oliver

    2004-01-30

    The rate of calcareous stone degradation is to a significant extent controlled by their surface chemistry with SO{sub 2}. Initial surface sulphite is converted to a harmful gypsum upon, e.g. NO{sub 2} catalysed oxidation. However, it has been observed by scanning electron microscopy that the lateral distributions of gypsum crystals differ between calcitic and dolomitic marbles. The first-principles density functional theory is employed to understand the origin of these fundamentally different morphologies. Here, the stability differences of surface sulphite at calcite CaCO{sub 3} (s) and dolomite Ca{sub x}Mg{sub 1-x}CO{sub 3} (s) are determined. A qualitative difference in surface sulphite stability, favouring the former, is reported. This is taken to imply that calcitic micro-crystals embedded in a dolomitic matrix act as sinks in the surface sulphation process, controlled by SO{sub 2} diffusion. The subsequent formation of gypsum under such conditions will not require SO{sub 4}{sup 2-} (aq) ion transport. This explains the homogeneous distribution of gypsum observed on the calcitic micro-crystals in dolomite. In contrast, sulphation on purely calcitic marbles never reaches such high SO{sub 2} coverage. Rather, upon oxidation, SO{sub 4}{sup 2-} (aq) transport to nucleation centres, such as grain boundaries, is required for the growth of gypsum crystals.

  14. Model study of initial adsorption of SO2 on calcite and dolomite

    Malaga-Starzec, Katarina; Panas, Itai; Lindqvist, Oliver

    2004-01-01

    The rate of calcareous stone degradation is to a significant extent controlled by their surface chemistry with SO 2 . Initial surface sulphite is converted to a harmful gypsum upon, e.g. NO 2 catalysed oxidation. However, it has been observed by scanning electron microscopy that the lateral distributions of gypsum crystals differ between calcitic and dolomitic marbles. The first-principles density functional theory is employed to understand the origin of these fundamentally different morphologies. Here, the stability differences of surface sulphite at calcite CaCO 3 (s) and dolomite Ca x Mg 1-x CO 3 (s) are determined. A qualitative difference in surface sulphite stability, favouring the former, is reported. This is taken to imply that calcitic micro-crystals embedded in a dolomitic matrix act as sinks in the surface sulphation process, controlled by SO 2 diffusion. The subsequent formation of gypsum under such conditions will not require SO 4 2- (aq) ion transport. This explains the homogeneous distribution of gypsum observed on the calcitic micro-crystals in dolomite. In contrast, sulphation on purely calcitic marbles never reaches such high SO 2 coverage. Rather, upon oxidation, SO 4 2- (aq) transport to nucleation centres, such as grain boundaries, is required for the growth of gypsum crystals

  15. Compaction of FGD-gypsum

    Stoop, B.T.J.; Larbi, J.A.; Heijnen, W.M.M.

    1996-01-01

    It is shown that it is possible to produce compacted gypsum with a low porosity and a high strength on a laboratory scale by uniaxial compaction of flue gas desulphurization (FGD-) gypsum powder. Compacted FGD-gypsum cylinders were produced at a compaction pres-sure between 50 and 500 MPa yielding

  16. Gypsum accumulation on carbonate stone

    McGee, E.S.; Mossotti, V.G.

    1992-01-01

    The accumulation of gypsum on carbonate stone has been investigated through exposure of fresh samples of limestone and marble at monitored sites, through examination of alteration crusts from old buildings and through laboratory experiments. Several factors contribute to gypsum accumulation on carbonate stone. Marble or limestone that is sheltered from direct washing by rain in an urban environment with elevated pollution levels is likely to accumulate a gypsum crust. Crust development may be enhanced if the stone is porous or has an irregular surface area. Gypsum crusts are a surficial alteration feature; gypsum crystals form at the pore opening-air interface, where evaporation is greatest.

  17. Testing CO2 Sequestration in an Alkaline Soil Treated with Flue Gas Desulfurization Gypsum (FGDG)

    Han, Y.; Tokunaga, T. K.

    2012-12-01

    Identifying effective and economical methods for increasing carbon storage in soils is of interest for reducing soil CO2 fluxes to the atmosphere in order to partially offset anthropogenic CO2 contributions to climate change This study investigates an alternative strategy for increasing carbon retention in soils by accelerating calcite (CaCO3) precipitation and promoting soil organic carbon (SOC) complexation on mineral surfaces. The addition of calcium ion to soils with pH > 8, often found in arid and semi-arid regions, may accelerate the slow process of calcite precipitation. Increased ionic strength from addition of a soluble Ca source also suppresses microbial activity which oxidizes SOC to gaseous CO2. Through obtaining C mass balances in soil profiles, this study is quantifying the efficiency of gypsum amendments for mitigating C losses to the atmosphere. The objective of this study is to identify conditions in which inorganic and organic C sequestration is practical in semi-arid and arid soils by gypsum treatment. As an inexpensive calcium source, we proposed to use flue gas desulfurization gypsum (FGDG), a byproduct of fossil fuel burning electric power plants. To test the hypothesis, laboratory column experiments have been conducted in calcite-buffered soil with addition of gypsum and FGDG. The results of several months of column monitoring are demonstrating that gypsum-treated soil have lowered amounts of soil organic carbon loss and increased inorganic carbon (calcite) production. The excess generation of FGDG relative to industrial and agricultural needs, FGDG, is currently regarded as waste. Thus application of FGDG application in some soils may be an effective and economical means for fixing CO2 in soil organic and inorganic carbon forms.Soil carbon cycle, with proposed increased C retention by calcite precipitation and by SOC binding onto soil mineral surfaces, with both processes driven by calcium released from gypsum dissolution.

  18. Gypsum karst in Great Britain

    Cooper A.H.

    1996-01-01

    Full Text Available In Great Britain the most spectacular gypsum karst development is in the Zechstein gypsum (late Permian mainly in north-eastern England. The Midlands of England also has some karst developed in the Triassic gypsum in the vicinity of Nottingham. Along the north-east coast, south of Sunderland, well-developed palaeokarst, with magnificent breccia pipes, was produced by dissolution of Permian gypsum. In north-west England a small gypsum cave system of phreatic origin has been surveyed and recorded. A large actively evolving phreatic gypsum cave system has been postulated beneath the Ripon area on the basis of studies of subsidence and boreholes. The rate of gypsum dissolution here, and the associated collapse lead to difficult civil engineering and construction conditions, which can also be aggravated by water abstraction.

  19. Mechanism of gypsum hydration

    Pacheco, G.

    1991-06-01

    Full Text Available There is an hypothesis that the mechanism o f gypsum hydration and dehydration is performed through two simultaneous phenomena. In this study we try to clear up this phenomenon using chlorides as accelerators or a mixture of ethanol-methanol as retarders to carry out the gypsum setting. Natural Mexican gypsum samples and a hemihydrate prepared in the laboratory are used. The following analytical techniques are used: MO, DRX, DTA, TG and DTG. In agreement with the obtained results, it can be concluded: that colloid formation depends on the action of accelerators or retarders and the crystals are a consequence of the quantity of hemihydrate formed.

    En el mecanismo de hidratación y deshidratación del yeso existe la hipótesis de que éste se efectúa por dos fenómenos simultáneos. Este estudio intenta esclarecer estos fenómenos, empleando: cloruros como aceleradores o mezcla etanol-metanol como retardadores para efectuar el fraguado del yeso. Se emplean muestras de yeso de origen natural mexicano y hemihydrate preparado en laboratorio; se utilizan técnicas analíticas: MO, DRX, DTA, TG y DTG. De acuerdo a los resultados obtenidos se puede deducir: que la formación del coloide depende de la acción de los agentes aceleradores o retardadores y que los cristales son consecuencia de la cantidad de hemihidrato formado.

  20. Palaeoclimatic significance of gypsum pseudomorphs in the inner shelf sediments off Machalipatnam bay

    Rao, V.P.

    Pseudo-gypsum crystals have been found in the coarse fraction of the sediments from the inner continental shelf off Machilipatnam Bay. They range in size from 3 to 7 mm are elongate and lenticular in shape. Bassanite and calcite are pseudomorphs...

  1. Neutralization of sulfuric acid solutions by calcite dissolution and the application to anoxic limestone drain design

    Huminicki, Danielle M.C.; Rimstidt, J. Donald

    2008-01-01

    Batch reactor (BR) experiments were conducted to measure the effect of hydrodynamics and gypsum coatings on calcite neutralization rates. A factorial array of BR experiments measured the H + concentration change by calcite dissolution over a pH range of 1.5-3.5 and Na 2 SO 4 concentrations of 0-1 M. The rate of H + concentration change with time was determined by numerical differentiation of H + concentration versus time. Regression modeling showed that for uncoated calcite, rates are only significantly affected by pH, r=-10 -2.32 a H + 0.76 . Whereas, for calcite coated with gypsum only time had a significant effect on calcite dissolution rates, r = -10 -1.96 t -0.53 . Because transport-limited dissolution rates for uncoated calcite are a function of the pH and Reynolds number, a model was developed to express the effects of these two variables on the rate of H + consumption for a solution with a Darcy velocity, q, through a porous medium with a particle radius, r p , such that r ' =1.08x10 -3 q 0.31 r p -0.69 m H + 0.87 . This equation was integrated via a numerical model to simulate the performance of an idealized anoxic limestone drain (ALD). This model predicts the pH and alkalinity change along the length of an ALD. The model shows that the efficiency of an ALD is greater when the Darcy velocity is low and the particle radius is small. In addition, the growth of gypsum coatings causes the rate of H + neutralization to decline as the square root of time as they form and block the H + transport to the calcite surface. Supersaturation with respect to gypsum, leading to coating formation, can be avoided by diluting the ALD feed solution or by replacing limestone with dolomite

  2. Light in the darkening on Naica gypsum crystals

    Castillo-Sandoval, I.; Fuentes-Cobas, L. E.; Esparza-Ponce, H. E.; Carreno-Márquez, J.; Montero-Cabrera, M. E., E-mail: elena.montero@cimav.edu.mx [Centro de Investigación en Materiales Avanzados (CIMAV), Miguel de Cervantes 120, Chihuahua, Chih 31109, México (Mexico); Fuentes-Montero, M. E. [Facultad de Ciencias Químicas, Universidad Autónoma de Chihuahua, Campus Universitario#2, Circuito Universitario, C.P.31125, Chihuahua, Chih. México (Mexico); Reyes-Cortes, M. [Facultad de Ingeniería. Universidad Autónoma de Chihuahua, Campus Universitario#2, Circuito Universitario, C.P.31125, Chihuahua, Chih. México (Mexico)

    2015-07-23

    Naica mine is located in a semi-desertic region at the central-south of Chihuahua State. The Cave of Swords was discovered in 1910 and the Cave of Crystals 90 years later at Naica mines. It is expected that during the last century the human presence has changed the microclimatic conditions inside the cave, resulting in the deterioration of the crystals and the deposition of impurities on gypsum surfaces. As a contribution to the clarification of the mentioned issues, the present work refers to the use of synchrotron radiation for the identification of phases on these surfaces. All the experiments were performed at the Stanford Synchrotron Radiation Lightsource. Grazing incidence X-ray diffraction (GIXRD) and radiography-aided X-ray diffraction (RAXRD) experiments were performed at beamline 11-3. X-Ray micro-fluorescence (μ-SXRF) and micro-X-ray absorption (μ-XANES) were measured at beamline 2-3. Representative results obtained may be summarized as follows: a) Gypsum, galena, sphalerite, hematite and cuprite at the surface of the gypsum crystals were determined. b) The samples micro-structure is affected by impurities. c) The elemental distributions and correlations (0.6-0.9) of Cu, K, Fe, Mn, Pb, Zn, Ca and S were identified by μ-SXRF. The correlations among elemental contents confirmed the phase identification, with the exception of manganese and potassium due to the amorphous nature of some impurity compounds in these samples. The compounds hematite (Fe{sub 2}O{sub 3}), β-MnO{sub 2}, Mn{sub 2}O{sub 3}, MnO and/or MnCO{sub 3}, PbS, PbCO{sub 3} and/or PbSO4, ZnO{sub 4}, ZnS and/or smithsonite (ZnCO{sub 3}), CuS + Cu Oxide were identified by XANES. Plausibly, these latter compounds do not form crystalline phases.

  3. Light in the darkening on Naica gypsum crystals

    Castillo-Sandoval, I.; Fuentes-Cobas, L. E.; Esparza-Ponce, H. E.; Carreno-Márquez, J.; Montero-Cabrera, M. E.; Fuentes-Montero, M. E.; Reyes-Cortes, M.

    2015-01-01

    Naica mine is located in a semi-desertic region at the central-south of Chihuahua State. The Cave of Swords was discovered in 1910 and the Cave of Crystals 90 years later at Naica mines. It is expected that during the last century the human presence has changed the microclimatic conditions inside the cave, resulting in the deterioration of the crystals and the deposition of impurities on gypsum surfaces. As a contribution to the clarification of the mentioned issues, the present work refers to the use of synchrotron radiation for the identification of phases on these surfaces. All the experiments were performed at the Stanford Synchrotron Radiation Lightsource. Grazing incidence X-ray diffraction (GIXRD) and radiography-aided X-ray diffraction (RAXRD) experiments were performed at beamline 11-3. X-Ray micro-fluorescence (μ-SXRF) and micro-X-ray absorption (μ-XANES) were measured at beamline 2-3. Representative results obtained may be summarized as follows: a) Gypsum, galena, sphalerite, hematite and cuprite at the surface of the gypsum crystals were determined. b) The samples micro-structure is affected by impurities. c) The elemental distributions and correlations (0.6-0.9) of Cu, K, Fe, Mn, Pb, Zn, Ca and S were identified by μ-SXRF. The correlations among elemental contents confirmed the phase identification, with the exception of manganese and potassium due to the amorphous nature of some impurity compounds in these samples. The compounds hematite (Fe 2 O 3 ), β-MnO 2 , Mn 2 O 3 , MnO and/or MnCO 3 , PbS, PbCO 3 and/or PbSO4, ZnO 4 , ZnS and/or smithsonite (ZnCO 3 ), CuS + Cu Oxide were identified by XANES. Plausibly, these latter compounds do not form crystalline phases

  4. Thermoluminescence from natural calcites

    Calderon, T.; Jaque, F.; Coy-yll, R.

    1984-01-01

    Thermoluminescence (TL) as well as absorption and EPR spectra of x-irradiated natural calcites have been obtained. Irradiation produces UV absorption bands and a decrease of the Mn 2+ EPR spectrum. A correlation of each TL peak with the bleaching steps of UV absorption bands and the recovering in intensity of the Mn 2+ EPR spectrum has been found. These experimental results support a new model for the radiation damage and thermoluminescence process in calcites. The main point in this model is that holes become trapped at impurities, and the electrons are trapped at dislocations in the form of CO 3 3- . (author)

  5. Mineral of the month: gypsum

    Founie, Alan

    2004-01-01

    The earliest known use of gypsum as a building material was in Anatolia (in what is now Turkey) around 6000 B.C. It has been found on the interiors of the great pyramids in Egypt, which were erected in about 3700 B.C. Now an average new American home contains more than 7 metric tons of gypsum in the form of more than 6,000 square feet of wallboard.

  6. Economics of Gypsum Production in Iran

    Esmaeili, Abdoulkarim

    The purpose of this research is to analyze the economics of gypsum production in Iran. The trend in production cost, selling price and profit are used to investigate economics of gypsum production. In addition, the multivariate time series method is used to determine factors affecting gypsum price in domestic market. The results indicated that due to increase in production and inflation, profitability of gypsum production has decreased during recent years. It is concluded that tariff and non-tariff barriers on mines machinery are among reasons for increasing production cost in Iranian gypsum mines. Decreasing such barriers could increase profitability of gypsum production in Iran.

  7. Magnetic properties of hematite nanoparticles

    Bødker, Franz; Hansen, Mikkel Fougt; Bender Koch, Christian

    2000-01-01

    The magnetic properties of hematite (alpha-Fe2O3) particles with sizes of about 16 nm have been studied by use of Mossbauer spectroscopy, magnetization measurements, and neutron diffraction. The nanoparticles are weakly ferromagnetic at temperatures at least down to 5 K with a spontaneous...... magnetization that is only slightly higher than that of weakly ferromagnetic bulk hematite. At T greater than or similar to 100 K the Mossbauer spectra contain a doublet, which is asymmetric due to magnetic relaxation in the presence of an electric field gradient in accordance with the Blume-Tjon model......, Simultaneous fitting of series of Mossbauer spectra obtained at temperatures from 5 K to well above the superparamagnetic blocking temperature allowed the estimation of the pre-exponential factor in Neel's expression for the superparamagnetic relaxation time, tau(0) = (6 +/- 4) X 10(-11) s and the magnetic...

  8. Growth of indoor fungi on gypsum

    Segers, Frank J J; van Laarhoven, Karel A; Wosten, Han; Dijksterhuis, Jan

    2017-01-01

    AIMS: To have a better understanding of fungal growth on gypsum building materials to prevent indoor fungal growth. METHODS AND RESULTS: Gypsum is acquired by mining or as a by-product of flue-gas desulfurization or treatment of phosphate ore for the production of fertilizer. Natural gypsum,

  9. Experimental Shock Transformation of Gypsum to Anhydrite: A New Low Pressure Regime Shock Indicator

    Bell, Mary S.; Zolensky, Michael E.

    2011-01-01

    The shock behavior of gypsum is important in understanding the Cretaceous/Paleogene event and other terrestrial impacts that contain evaporite sediments in their targets (e.g., Mars Exploration Rover Spirit detected sulfate at Gusev crater, [1]). Most interest focuses on issues of devolatilization to quantify the production of SO2 to better understand its role in generating a temporary atmosphere and its effects on climate and biota [2,3]. Kondo and Ahrens [4] measured induced radiation emitted from single crystal gypsum shocked to 30 and 40 GPa. They observed greybody emission spectra corresponding to temperatures in the range of 3,000 to 4,000 K that are a factor of 2 to 10 times greater than calculated pressure-density energy equation of state temperatures (Hugoniot) and are high enough to melt gypsum. Chen et al. [5] reported results of shock experiments on anhydrite, gypsum, and mixtures of these phases with silica. Their observations indicated little or no devolatilization of anhydrite shocked to 42 GPa and that the fraction of sulfur, by mass, that degassed is approx.10(exp -2) of theoretical prediction. In another report of shock experiments on calcite, anhydrite, and gypsum, Badjukov et al. [6] observed only intensive plastic deformation in anhydrite shock loaded at 63 GPa, and gypsum converted to anhydrite when shock loaded at 56 GPa but have not experimentally shocked gypsum in a step-wise manner to constrain possible incipient transformation effects. Schmitt and Hornemann [7] shock loaded anhydrite and quartz to a peak pressure of 60 GPa and report the platy anhydrite grains were completely pseudomorphed by small crystallized anhydrite grains. However, no evidence of interaction between the two phases could be observed and they suggested that recrystallization of anhydrite grains is the result of a solid-state transformation. They concluded that significant decomposition of anhydrite requires shock pressures higher than 60 GPa. Gupta et al. [8

  10. Arsenic uptake in bacterial calcite

    Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco; Lee, Sang Soo; Fenter, Paul; Newville, Matthew; Rimondi, Valentina; Pratesi, Giovanni; Costagliola, Pilario

    2018-02-01

    Bio-mediated processes for arsenic (As) uptake in calcite were investigated by means of X-ray Diffraction (XRD) and X-ray Absorption Spectroscopy (XAS) coupled with X-ray Fluorescence measurements. The environmental bacterial strain Bacillus licheniformis BD5, sampled at the Bullicame Hot Springs (Viterbo, Central Italy), was used to synthesize calcite from As-enriched growth media. Both liquid and solid cultures were applied to simulate planktonic and biofilm community environments, respectively. Bacterial calcite samples cultured in liquid media had an As enrichment factor (Kd) 50 times higher than that from solid media. The XRD analysis revealed an elongation of the crystal lattice along the c axis (by 0.03 Å) for biogenic calcite, which likely resulted from the substitution of larger arsenate for carbonate in the crystal. The XAS data also showed a clear difference in the oxidation state of sorbed As between bacterial and abiotic calcite. Abiotic chemical processes yielded predominantly As(V) uptake whereas bacterial precipitation processes led to the uptake of both As(III) and As(V). The presence of As(III) in bacterial calcite is proposed to result from subsequent reduction of arsenate to arsenite by bacterial activities. To the best of our knowledge, this is the first experimental observation of the incorporation of As(III) in the calcite crystal lattice, revealing a critical role of biochemical processes for the As cycling in nature.

  11. Arsenic uptake in bacterial calcite

    Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco; Lee, Sang Soo; Fenter, Paul; Newville, Matthew G.; Rimondi, Valentina; Pratesi, Giovanni; Costagliola, Pilario

    2018-02-01

    Bio-mediated processes for arsenic (As) uptake in calcite were investigated by means of X-ray Diffraction (XRD) and Xray Absorption Spectroscopy (XAS) coupled with X-ray Fluorescence measurements. The environmental bacterial strain Bacillus licheniformis BD5, sampled at the Bullicame Hot Springs (Viterbo, Central Italy), was used to synthesize calcite from As-enriched growth media. Both liquid and solid cultures were applied to simulate planktonic and biofilm community environments, respectively. Bacterial calcite samples cultured in liquid media had an As enrichment factor (Kd) 50 times higher than that from solid media. The XRD analysis revealed an elongation of the crystal lattice along the c axis (by 0.03Å) for biogenic calcite, which likely resulted from the substitution of larger arsenate for carbonate in the crystal. The XAS data also showed a clear difference in the oxidation state of sorbed As between bacterial and abiotic calcite. Abiotic chemical processes yielded predominantly As(V) uptake whereas bacterial precipitation processes led to the uptake of both As(III) and As(V). The presence of As(III) in bacterial calcite is proposed to result from subsequent reduction of arsenate to arsenite by bacterial activities. To the best of our knowledge, this is the first experimental observation of the incorporation of As(III) in the calcite crystal lattice, revealing a critical role of biochemical processes for the As cycling in nature.

  12. Coprecipitation of cadmium with calcite

    Fujino, Osamu; Kumagai, Tetsu; Shigematsu, Tsunenobu; Matsui, Masakazu

    1976-01-01

    The distribution of cadmium between precipitates of calcite and saturated aqueous solution was measured at 25 0 C to understand the distribution of cadmium in the bivalves. Calcite was precipitated from calcium bicarbonate solution by the gradual release of carbon dioxide. The cadmium ions were coprecipitated in calcite, obeying the logarithmic distribution law. The apparent distribution coefficient was decreased as α, α'-dipyridyl increased, but the true distribution coefficient was found to be an almost constant value, 560. This value is fairly close to the ratio of solubility product constants K sub(calcite)/K sub(CdCO 3 ), 890. This suggests that the deviation of the present solid solution from ideality is not very large. (auth.)

  13. Growth of indoor fungi on gypsum.

    Segers, F J J; van Laarhoven, K A; Wösten, H A B; Dijksterhuis, J

    2017-08-01

    To have a better understanding of fungal growth on gypsum building materials to prevent indoor fungal growth. Gypsum is acquired by mining or as a by-product of flue-gas desulphurization or treatment of phosphate ore for the production of fertilizer. Natural gypsum, flue-gas gypsum and phosphogypsum therefore have different mineral compositions. Here, growth of fungi on these types of gypsum was assessed. Conidia of the indoor fungi Aspergillus niger, Cladosporium halotolerans and Penicillium rubens were inoculated and observed using microscopic techniques including low-temperature scanning electron microscopy. Elemental analysis of gypsum was done using inductively coupled plasma atomic emission spectroscopy and segmented flow analysis. Moisture content of the gypsum was determined using a dynamic vapour sorption apparatus. Aspergillus niger, C. halotolerans and P. rubens hardly germinated on natural gypsum and flue-gas gypsum. The latter two fungi did show germination, outgrowth, and conidiation on phosphogypsum, while A. niger hardly germinated on this substrate. Other experiments show that C. halotolerans and P. rubens can develop in pure water, but A. niger does not. The observations show that the lack of germination of three indoor fungi is explained by the low amount of phosphor in natural, flue-gas and laboratory-grade gypsum. Additionally, C. halotolerans and P. rubens can develop in pure water, while conidia of A. niger do not show any germination, which is explained by the need for organic molecules of this species to induce germination. Indoor fungal growth is a potential threat to human health and causes damage to building materials. This study possibly helps in the application of the right type of gypsum in buildings. © 2017 The Society for Applied Microbiology.

  14. Attenuation characteristics of gypsum wallboard

    Christensen, Ralph C.; Sayeg, Joseph

    1978-01-01

    Increased cost of lead is promoting enhanced usage of common building materials for shielding in diagnostic medical and dental facilities where only a few half value layers (HVLs) are needed. We have measured attenuation of x-rays in gypsum wallboard as a function of kVp, filtration, and wallboard thickness. Our findings, obtained using a Victoreen 555 with an 0.1 DAS probe in poor geometry, are in agreement with the sparse data in the literature (Gross and McCullough (1977), Radiology 122: 825. Moos et al. (1961), Oral Surgery, Oral Medicine, and Oral Pathology 14: 569) but extend to thicker wall configurations and different kVp and filtration parameters. We conclude that gypsum wallboard as sole shielding material should be used with great caution. These findings are of value in maximizing the benefit/cost ratio for diagnostic shielding, and strengthen the conviction that, where used for shielding purposes, common building materials must be installed carefully and HVL-depth dependence considered thoroughly. (author)

  15. Evolution and the Calcite Eye Lens

    Williams, Vernon L.

    2013-01-01

    Calcite is a uniaxial, birefringent crystal, which in its optically transparent form, has been used for animal eye lenses, the trilobite being one such animal. Because of the calcite birefringence there is a difficulty in using calcite as a lens. When the propagation direction of incoming light is not exactly on the c-axis, the mages blur. In this paper, calcite blurring is evaluated, and the non-blurring by a crystallin eye lens is compared to a calcite one.

  16. Calcite Dissolution Kinetics

    Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

    2016-12-01

    A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations 500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral

  17. Gypsum addition to soils contaminated by red mud: implications for aluminium, arsenic, molybdenum and vanadium solubility.

    Lehoux, Alizée P; Lockwood, Cindy L; Mayes, William M; Stewart, Douglas I; Mortimer, Robert J G; Gruiz, Katalin; Burke, Ian T

    2013-10-01

    Red mud is highly alkaline (pH 13), saline and can contain elevated concentrations of several potentially toxic elements (e.g. Al, As, Mo and V). Release of up to 1 million m(3) of bauxite residue (red mud) suspension from the Ajka repository, western Hungary, caused large-scale contamination of downstream rivers and floodplains. There is now concern about the potential leaching of toxic metal(loid)s from the red mud as some have enhanced solubility at high pH. This study investigated the impact of red mud addition to three different Hungarian soils with respect to trace element solubility and soil geochemistry. The effectiveness of gypsum amendment for the rehabilitation of red mud-contaminated soils was also examined. Red mud addition to soils caused a pH increase, proportional to red mud addition, of up to 4 pH units (e.g. pH 7 → 11). Increasing red mud addition also led to significant increases in salinity, dissolved organic carbon and aqueous trace element concentrations. However, the response was highly soil specific and one of the soils tested buffered pH to around pH 8.5 even with the highest red mud loading tested (33 % w/w); experiments using this soil also had much lower aqueous Al, As and V concentrations. Gypsum addition to soil/red mud mixtures, even at relatively low concentrations (1 % w/w), was sufficient to buffer experimental pH to 7.5-8.5. This effect was attributed to the reaction of Ca(2+) supplied by the gypsum with OH(-) and carbonate from the red mud to precipitate calcite. The lowered pH enhanced trace element sorption and largely inhibited the release of Al, As and V. Mo concentrations, however, were largely unaffected by gypsum induced pH buffering due to the greater solubility of Mo (as molybdate) at circumneutral pH. Gypsum addition also leads to significantly higher porewater salinities, and column experiments demonstrated that this increase in total dissolved solids persisted even after 25 pore volume replacements. Gypsum

  18. Nickel adsorption on chalk and calcite

    Belova, Dina Alexandrovna; Lakshtanov, Leonid; Carneiro, J.F.

    2014-01-01

    Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite...... = - 1.12 on calcite and log KNi = - 0.43 and - 0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts...... of polysaccharides and clay nanoparticles on the chalk surface....

  19. Measurement of soil moisture using gypsum blocks

    Friis Dela, B.

    the building. Consequently, measuring the moisture of the surrounding soil is of great importance for detecting the source of moisture in a building. Up till now, information has been needed to carry out individual calibrations for the different types of gypsum blocks available on the market and to account......For the past 50 years, gypsum blocks have been used to determine soil moisture content. This report describes a method for calibrating gypsum blocks for soil moisture measurements. Moisture conditions inside a building are strongly influenced by the moisture conditions in the soil surrounding...

  20. Effects of gypsum on trace metals in soils and earthworms

    Mined gypsum has been beneficially used for many years as an agricultural amendment. Currently a large amount of flue gas desulfurization (FGD) gypsum is produced by removal of SO2 from flue gas streams when fuels with high S content are burned. The FGD gypsum, similar to mined gypsum, can enhance c...

  1. Interactions between cadmium and calcite

    van der Weijden, R.D.

    1995-01-01

    The thesis is composed of five chapters, some of which have been published or have been accepted for publication. The contents in some of the chapters may therefore slightly overlap, also because the subjects are closely related. The first two chapters focus mostly on the sorption of Cd on calcite,

  2. Hematite (U-Th)/He thermochronometry constrains intraplate strike-slip faulting on the Kuh-e-Faghan Fault, central Iran

    Calzolari, Gabriele; Rossetti, Federico; Ault, Alexis K.; Lucci, Federico; Olivetti, Valerio; Nozaem, Reza

    2018-03-01

    The Kuh-e-Faghan strike-slip fault system (KFF), located to the northern edge of the Lut Block in central Iran, developed through a Neogene-Quaternary pulsed history of eastward fault propagation and fault-related exhumation. This system is a consequence of the residual stresses transmitted from the Arabia-Eurasia convergent plate boundary. Here we integrate structural and textural analysis with new and previously published apatite fission-track (AFT) and apatite (U-Th)/He (apatite He) results, chlorite thermomentry, and hematite (U-Th)/He data from hematite-coated brittle fault surfaces to constrain the timing of tectonic activity and refine patterns of late Miocene-Pliocene burial and exhumation associated with the propagation of the KFF. Twenty-nine hematite (U-Th)/He (hematite He) dates from three striated hematite coated slip surfaces from the KFF fault core and damage zone yield individual dates from 12-2 Ma. Petrographic analysis and chlorite thermometry of a polyphase, fossil fluid system in the KFF fault core document that fluid circulation and mineralization transitioned from a closed system characterized by pressure solution and calcite growth to an open system characterized by hot hydrothermal (T = 239 ± 10 °C) fluids and hematite formation. Hematite microtextures and grain size analysis reveal primary and secondary syntectonic hematite fabrics, no evidence of hematite comminution and similar hematite He closure temperatures ( 60-85 °C) in each sample. Integration of these results with thermal history modeling of AFT and apatite He data shows that KFF activity in the late Miocene is characterized by an early stage of fault nucleation, fluid circulation, hematite mineralization, and eastward propagation not associated with vertical movement that lasted from 12 to 7 Ma. Hematite He, AFT, and apatite He data track a second phase of fault system activity involving fault-related exhumation initiating at 7 Ma and continuing until present time. Our new data

  3. Gypsum ground: a new occurrence of gypsum sediment in playas of central Australia

    Xiang Yang Chen; Bowler, James M.; Magee, John W.

    1991-06-01

    There are many playas (dry salt lakes) in arid central Australia (regional rainfall about 250 mm/y and pan evaporation around 3000 mm/y). Highly soluble salts, such as halite, only appear as a thin (several centimetres thick), white, ephemeral efflorescent crust on the dry surface. Gypsum is the major evaporite precipitating both at present and preserved in sediment sequences. One type of gypsum deposit forms a distinctive surface feature, which is here termed "gypsum ground". It consists of a thick (up to 80 cm) gypsum zone which rises from the surrounding smooth white playa surface and is overlain by a heaved brown crust. The gypsum zone, with an average gypsum content above 60%, consists of pure gypsum sublayers and interlayered clastic bands of sandy clay. The gypsum crystals are highly corroded, especially in the direction parallel to the c-axis and on the upper sides where illuviated clay has accumulated in corrosion hollows. Overgrowth parallel to the a- and b-axes is very common, forming highly discoidal habits. These secondary changes (corrosion and overgrowth) are well-developed in the vadose zone and absent from crystals below the long-term watertable (depth around 40 cm). These crystal characteristics indicate a rainwater leaching process. At Lake Amadeus, one of the largest playas (800 km 2) of central Australia, such gypsum ground occupies 16% of the total area. The gypsum ground is interpreted as an alteration of a pre-existing gypsum deposit which probably extended across the whole playa before breaking down, leaving a playa marginal terrace and several terrace islands within the gypsum ground. This pre-existing gypsum deposit, preserved in the residual islands, consists of pure, pale, sand-sized lenticular crystals. It is believed to have been deposited during an episode of high regional watertable, causing active groundwater seepage and more frequent surface brine in the playa. A later fall in watertable, probably resulting from climatic change

  4. Densification of zirconia-hematite nanopowders

    Raming, T.P.; Winnubst, Aloysius J.A.; van Zyl, W.E.; Verweij, H.

    2003-01-01

    The densification of dual-phase yttria-doped tetragonal zirconia polycrystals (Y-TZP) and -Fe2O3 (hematite) composite powders is described. Different powder synthesis methods, different forms of dry compaction processes, and two sinter methods (pressureless sintering and sinterforging) were

  5. GYPSUM DEPOSITS IN THE REPUBLIC OF CROATIA

    Anto Gabrić

    2002-12-01

    Full Text Available The occurences and deposits of gypsum can be found in big karst poljes (Sinjsko, Vrličko, Petrovo, Kosovo and Kninsko as well as in tectonnically predestined river valleys of Zrmanja, Butišnica and Una. There also appear spatially localized occurences on the island of Vis and in the vicinity of Samobor. Evaporites (gypsum and anhydrite with adjoining overlying clastic rocks (red sandstones, siltites and pelites, carbonate rocks (dolomites and limestones and porous carbonate breccias (Rauhwackes were deposited during the period of Upper Permian. The recent position of the Upper Permian beds is a result of complex tectonic, particularly neotectonic, movements and diapiric displacements. Evaporites were deposited in marginal areas of the epicontinental marine basin, in a period of favourable conditions for the sabkha and playa sedimentation due to the continuous shoreline progradation. The Upper Permian age of these sediments in Dalmatio is proved by the characteristic mineral paragenesis and palinological determinations in elastics rocks, as well as by isotope analyses of sulphure in gypsum. Gypsum is a significant ore mineral resource in building, cement production, as well as in a number of tehnological processes used in chemical industry and elsewhere. According to the recent investigations gypsum is predestined to serve as an ore mineral resource of significant perspectives (the paper is published in Croatian.

  6. Gypsum crystals observed in experimental and natural sea ice

    Geilfus, N.-X.; Galley, R. J.; Cooper, M.; Halden, N.; Hare, A.; Wang, F.; Søgaard, D. H.; Rysgaard, S.

    2013-12-01

    gypsum has been predicted to precipitate in sea ice, it has never been observed. Here we provide the first report on gypsum precipitation in both experimental and natural sea ice. Crystals were identified by X-ray diffraction analysis. Based on their apparent distinguishing characteristics, the gypsum crystals were identified as being authigenic. The FREeZing CHEMistry (FREZCHEM) model results support our observations of both gypsum and ikaite precipitation at typical in situ sea ice temperatures and confirms the "Gitterman pathway" where gypsum is predicted to precipitate. The occurrence of authigenic gypsum in sea ice during its formation represents a new observation of precipitate formation and potential marine deposition in polar seas.

  7. Adsorption of aqueous silicate on hematite

    Taylor, P.; Ticknor, K.V.

    1997-08-01

    During radioisotope sorption studies, adsorption of silicate from synthetic groundwaters by synthetic hematite was observed. To further investigate this observation, the adsorption of silicate onto hematite (α-Fe 2 O 3 ) powder from a neutral, aqueous NaC1 solution (0.1 mol/dm 3 ), containing 2.56 x 10 -4 mol/dm 3 of Si added as Na 2 SiO 3 ·9H 2 O, was measured at ∼21 deg C. Equilibrium adsorption of silicate amounted to ∼1.93 μmol/m 2 (one Si(O,OH) 4 moiety per 86 A 2 ). It is important to take this adsorption into account when evaluating the ability of iron oxides to adsorb other species, especially anions, from groundwaters. Silicate adsorption is known to diminish the ability of iron oxides to adsorb other anions. (author)

  8. High-yield synthesis of vaterite microparticles in gypsum suspension system via ultrasonic probe vibration/magnetic stirring

    Wang, Bo; Pan, Zihe; Cheng, Huaigang; Chen, Zuliang; Cheng, Fangqin

    2018-06-01

    Vaterite-type calcium carbonate particles have some unique properties such as high hydrophilicity, large surface areas, and hierarchical structures consisting of primary vaterite particles in comparison with calcite or aragonite-type polymorphs. In this paper, gypsum (CaSO4·2H2O) suspension is used to synthesize micro-sized vaterite CaCO3 through magnetic stirring (MS) and ultrasonic probe vibration (UPV) methods. The effects of ammonia concentration, CO2 flow rate, solid-liquid ratio on the gypsum carbonation process, mineral phase composition, morphology and particle size distribution of CaCO3 are investigated. The results show that the carbonation process is significantly influenced by ammonia concentration, CO2 flow rate and ultrasound. Comparing with magnetic stirring, ultrasonic probe vibration take less time to reach the complete carbonate reaction. Gypsum is transformed to vaterite with the conversion rate about ∼95% when the mole ratio of NH4+/Ca2+ is 2.4 otherwise the carbonation reaction was uncompleted with gypsum residues left. Comparing with MS method, the UPV method resulted in smaller size and narrower size distribution of as-prepared microparticles and approximately 80% reduction of the particle size was achieved. It is established that increasing the solid-liquid ratio resulted in larger particle size in MS system and smaller particle size in UPV system. Increasing CO2 flow rate caused the particle size decreased in MS system and increased in UPV system.

  9. Shock-induced devolatilization of calcite

    Boslough, M. B.; Ahrens, T. J.; Vizgirda, J.; Becker, R. H.; Epstein, S.

    1982-01-01

    Experimental measurements of the release adiabats by Vizgirda (1981) indicate that substantial vaporization takes place upon release from shock pressures of 37 GPa for calcite and 14 GPa for aragonite. The present investigation includes the first controlled partial vaporization experiments on calcite. The experiments were conducted to test the predictions of the release adiabat experiments. The quantities of the gaseous species produced from shocked calcite and their carbon and oxygen isotopic compositions were determined, and the shock-induced effect on the Mn(2+) electron spin resonance spectrum in the shock-recovered calcite was observed. On the basis of the obtained results, it is concluded that shock stresses at the 17-18 GPa level give rise to volatilization of 0.03-0.3 (mole) percent of calcite to CO2 and CO. The devolatilization of calcite occurs at low pressure at significantly lower entropy densities than predicted on the basis of thermodynamic continuum models.

  10. Gypsum karst in Italy: a review

    De Waele, Jo; Chiarini, Veronica; Columbu, Andrea; D'Angeli, Ilenia M.; Madonia, Giuliana; Parise, Mario; Piccini, Leonardo; Vattano, Marco; Vigna, Bartolomeo; Zini, Luca; Forti, Paolo

    2016-04-01

    Although outcropping only rarely in Italy, gypsum karst has been described in detail since the early XXth century (Marinelli, 1917). Gypsum caves are now known from almost all Italian regions (Madonia & Forti, 2003), but are mainly localised along the northern border of the Apennine chain (Emilia Romagna and Marche regions), Calabria, and Sicily, where the major outcrops occur. Recently, important caves have also been discovered in the underground gypsum quarries in Piedmont (Vigna et al., 2010). During the late 80s and 90s several multidisciplinary studies have been carried out in many gypsum areas. All this work converged into a comprehensive overview in 2003 (Madonia & Forti, 2003). Further detailed studies focused on the gypsum areas of Emilia Romagna (Chiesi et al., 2010; Forti & Lucci, 2010; Demaria et al., 2012; De Waele & Pasini, 2013; Ercolani et al., 2013; Columbu et al., 2015; Lucci & Piastra, 2015; Tedeschi et al., 2015) and of Sicily (Madonia & Vattano, 2011). Sinkholes related to Permo-Triassic gypsum have been studied in Friuli Venezia Giulia (Zini et al., 2015). This presentation will review the state of the art regarding different aspects of evaporite karst in Italy focusing on the main new results. References Chiesi M., et al. (2010) - Origin and evolution of a salty gypsum/anhydrite karst spring: the case of Poiano (Northern Apennines, Italy). Hydrogeology Journal, 18, pp. 1111-1124. Columbu A. et al. (2015) - Gypsum caves as indicators of climate-driven river incision and aggradation in a rapidly uplifting region. Geology, 43(6), 539-542. Demaria D. et al. (Eds.) (2012), Le Grotte Bolognesi, GSB-USB, 431 p. De Waele J., Pasini G. (2013) - Intra-messinian gypsum palaeokarst in the northern Apennines and its palaeogeographic implications. Terra Nova 25, pp. 199-205. Ercolani M., et al. (Eds.) (2013), I Gessi e la Cave i Monte Tondo. Studio multidisciplinare di un'area carsica nella Vena del Gesso Romagnola. Memorie Ist. It. Spel. II(26), 559 p

  11. Mechanical properties of gypsum board at elevated temperatures

    S.M. Cramer; O.M. Friday; R.H. White; G. Sriprutkiat

    2003-01-01

    Gypsum board is a common fire barrier used in house and general building construction. Recently, evaluation of the collapses of the World Trade Center Towers highlighted the potential role and failure of gypsum board in containing the fires and resisting damage. The use of gypsum board as primary fire protection of light-flame wood or steel construction is ubiquitous....

  12. Gypsum crystals observed in experimental and natural sea ice

    Geilfus, Nicolas-Xavier; Galley, Ryan; Cooper, Marc

    2013-01-01

    , the gypsum crystals were identified as being authigenic. The FREeZing CHEMistry (FREZCHEM) model results support our observations of both gypsum and ikaite precipitation at typical in situ sea ice temperatures and confirms the “Gitterman pathway” where gypsum is predicted to precipitate. The occurrence...

  13. Comparison of the surface roughness of gypsum models constructed using various impression materials and gypsum products

    Yi-Chih Chang

    2016-03-01

    Conclusion: The surface roughness of stone models was mainly determined by the type of alginate impression material, and was less affected by the type of silicone rubber impression material or gypsum product, or the storage time before repouring.

  14. Characterization of hematite nanoparticles synthesized via two different pathways

    Das, Soumya; Hendry, M. Jim

    2014-08-01

    Hematite is one of the most common and thermodynamically stable iron oxides found in both natural and anthropogenic systems. Owing to its ubiquity, stability, moderate specific surface area, and ability to sequester metals and metalloids from aquatic systems, it has been the subject of a large number of adsorption studies published during the past few decades. Although preparation techniques are known to affect the surface morphology of hematite nanoparticles, the effects of aging under environmentally relevant conditions have yet to be tested with respect to surface morphology, surface area, and adsorptive capacity. We prepared hematite via two different pathways and aged it under highly alkaline conditions encountered in many mill tailings settings. Crystal habits and morphologies of the hematite nanoparticles were analyzed via scanning electron microscopy and transmission electron microscopy. X-ray diffraction, Raman spectroscopy, and Brunauer-Emmett-Teller surface area analyses were also conducted on the hematite nanoparticles before and after aging. The hematite synthesized via an Fe(III) salt solution (average particle size 37 nm) was morphologically and structurally different from the hematite synthesized via ferrihydrite aging (average particle size 144 nm). Overall, our data demonstrate that the crystallinity of hematite produced via ferrihydrite transformation is susceptible to morphological alterations/modifications. In contrast, the hematite formed via hydrolysis of an Fe(III) salt solution remains very stable in terms of structure, size, and morphology even under extreme experimental conditions.

  15. Thickness Dependent on Photocatalytic Activity of Hematite Thin Films

    Yen-Hua Chen

    2012-01-01

    Full Text Available Hematite (Fe2O3 thin films with different thicknesses are fabricated by the rf magnetron sputtering deposition. The effects of film thicknesses on the photocatalytic activity of hematite films have been investigated. Hematite films possess a polycrystalline hexagonal structure, and the band gap decreases with an increase of film thickness. Moreover, all hematite films exhibit good photocatalytic ability under visible-light irradiation; the photocatalytic activity of hematite films increases with the increasing film thickness. This is because the hematite film with a thicker thickness has a rougher surface, providing more reaction sites for photocatalysis. Another reason is a lower band gap of a hematite film would generate more electron-hole pairs under visible-light illumination to enhance photocatalytic efficiency. Experimental data are well fitted with Langmuir-Hinshelwood kinetic model. The photocatalytic rate constant of hematite films ranges from 0.052 to 0.068 min-1. This suggests that the hematite film is a superior photocatalyst under visible-light irradiation.

  16. Magnetic and structural properties of ferrihydrite/hematite nanocomposites

    Pariona, N.; Camacho-Aguilar, K.I.; Ramos-González, R.; Martinez, Arturo I.; Herrera-Trejo, M.; Baggio-Saitovitch, E.

    2016-01-01

    A rich variety of ferrihydrite/hematite nanocomposites (NCs) with specific size, composition and properties were obtained in transformation reactions of 2-line ferrihydrite. Transmission electron microscopy (TEM) observations showed that the NCs consist of clusters of strongly aggregated nanoparticles (NPs) similarly to a “plum pudding”, where hematite NPs “raisins” are surrounded by ferrihydrite “pudding”. Magnetic measurements of the NCs correlate very well with TEM results; i.e., higher coercive fields correspond to greater hematite crystallite size. First order reversal curve (FORC) measurements were used for the characterization of the magnetic components of the NCs. FORC diagrams revealed that the NCs prepared at short times are composed by single domains with low coercivity, and NCs prepared at times larger than 60 min exhibited elongated distribution along the Hc axis. It suggested that these samples consist of mixtures of different kinds of hematite particles, ones with low coercivity and others with coercivity greater than 600 Oe. For NCs prepared at times larger than 60 min, Mossbauer spectroscopy revealed the presence of two sextets, which one was assigned to fine hematite particles and other to hematite particles with hyperfine parameters near to bulk hematite. The correlation of the structural and magnetic properties of the ferrihydrite/hematite NCs revealed important characteristics of these materials which have not been reported elsewhere. - Highlights: • Ferrihydrite/hematite nanocomposites were prepared. • The “plum pudding” morphology of the ferrihydrite/hematite nanocomposites was found. • The FORC diagrams of ferrihydrite/hematite nanocomposites have been measured.

  17. Magnetic and structural properties of ferrihydrite/hematite nanocomposites

    Pariona, N.; Camacho-Aguilar, K.I.; Ramos-González, R. [Center for Research and Advanced Studies of the National Polytechnic Institute, Cinvestav-Saltillo, Av. Industria Metalúrgica 1062, Parque Industrial Ramos Arizpe, Coahuila 25900 (Mexico); Martinez, Arturo I., E-mail: mtz.art@gmail.com [Center for Research and Advanced Studies of the National Polytechnic Institute, Cinvestav-Saltillo, Av. Industria Metalúrgica 1062, Parque Industrial Ramos Arizpe, Coahuila 25900 (Mexico); Herrera-Trejo, M. [Center for Research and Advanced Studies of the National Polytechnic Institute, Cinvestav-Saltillo, Av. Industria Metalúrgica 1062, Parque Industrial Ramos Arizpe, Coahuila 25900 (Mexico); Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Físicas, Río de Janeiro 22290-180 (Brazil)

    2016-05-15

    A rich variety of ferrihydrite/hematite nanocomposites (NCs) with specific size, composition and properties were obtained in transformation reactions of 2-line ferrihydrite. Transmission electron microscopy (TEM) observations showed that the NCs consist of clusters of strongly aggregated nanoparticles (NPs) similarly to a “plum pudding”, where hematite NPs “raisins” are surrounded by ferrihydrite “pudding”. Magnetic measurements of the NCs correlate very well with TEM results; i.e., higher coercive fields correspond to greater hematite crystallite size. First order reversal curve (FORC) measurements were used for the characterization of the magnetic components of the NCs. FORC diagrams revealed that the NCs prepared at short times are composed by single domains with low coercivity, and NCs prepared at times larger than 60 min exhibited elongated distribution along the Hc axis. It suggested that these samples consist of mixtures of different kinds of hematite particles, ones with low coercivity and others with coercivity greater than 600 Oe. For NCs prepared at times larger than 60 min, Mossbauer spectroscopy revealed the presence of two sextets, which one was assigned to fine hematite particles and other to hematite particles with hyperfine parameters near to bulk hematite. The correlation of the structural and magnetic properties of the ferrihydrite/hematite NCs revealed important characteristics of these materials which have not been reported elsewhere. - Highlights: • Ferrihydrite/hematite nanocomposites were prepared. • The “plum pudding” morphology of the ferrihydrite/hematite nanocomposites was found. • The FORC diagrams of ferrihydrite/hematite nanocomposites have been measured.

  18. Hematite nuclear fuel cycle facility decommissioning

    Hayes, K.

    2004-01-01

    Westinghouse Electric Company LLC ('Westinghouse') acquired a nuclear fuel processing plant at Hematite, Missouri ('Hematite', the 'Facility', or the 'Plant') in April 2000. The plant has subsequently been closed, and its operations have been relocated to a newer, larger facility. Westinghouse has announced plans to complete its clean-up, decommissioning, and license retirement in a safe, socially responsible, and environmentally sound manner as required by internal policies, as well as those of its parent company, British Nuclear Fuels plc. ('BNFL'). Preliminary investigations have revealed the presence of environmental contamination in various areas of the facility and grounds, including both radioactive contamination and various other substances related to the nuclear fuel processing operations. The disparity in regulatory requirements for radiological and nonradiological contaminants, the variety of historic and recent operations, and the number of previous owners working under various contractual arrangements for both governmental and private concerns has resulted in a complex project. This paper discusses Westinghouse's efforts to develop and implement a comprehensive decontamination and decommissioning (D and D) strategy for the facility and grounds. (author)

  19. Surface controlled dissolution rates of gypsum in aqueous solutions exhibit nonlinear dissolution kinetics

    Jeschke, Alexander A.; Vosbeck, Katrin; Dreybrodt, Wolfgang

    2001-01-01

    The effective dissolution rates of gypsum are determined by mixed kinetics, where the rate constants of dissolution at the surface and the transport constant of molecular diffusion of dissolved material are similar. To obtain the surface reaction rate law it is necessary to know the transport constant. We have determined the surface rate law for monocrystalline selenite by using a rotating disc set-up, where the transport coefficients are well known. As a result, up to a calcium concentration of 0.6 · ceq, we find a nearly linear rate law Rs = ksl (1- cs/ ceq) n1, where cs is the total calcium concentration at the surface and ceq the equilibrium concentration with respect to gypsum, n1 = 1.2 ± 0.2, and ksl = 1.1 · 10 -4 mmol cm -2 s -1 ± 15%. We also employed batch-experiments for selenite, alabaster and gypsum rock samples. The result of these experiments were interpreted by using a transport constant determined by NaCl dissolution experiments under similar physical conditions. The batch experiments reveal a dissolution rate law Rs = ksl (1- cs/ ceq) n1, ksl = 1.3 · 10 -4 mmol · cm -2 s -1, n1 = 1.2 ± 0.2 for c ≤ 0.94 · ceq. Close to equilibrium a nonlinear rate law, Rs = ks2 (1- cs/ ceq) n2, is observed, where ks2 is in the order of 10 mmol · cm -2 s -1 and n2 ≈ 4.5. The experimentally observed gypsum dissolution rates from the batch experiments could be accurately fitted, with only minor variations of the surface reaction constant obtained from the rotating disk experiment and the transport coefficient from the NaCl dissolution batch experiment. Batch experiments on pure synthetic gypsum, reveal a linear rate law up to equilibrium. This indicates inhibition of dissolution in natural samples close to equilibrium, as is known also for calcite minerals.

  20. Calcite biomineralization in coccoliths: Evidence from atomic force microscopy (AFM)

    Henriksen, Karen; Stipp, S.L.S.

    2002-01-01

    geochemistry, crystal orientation, coccolith function, biomineralization, biological calcite, atomic force microscopy......geochemistry, crystal orientation, coccolith function, biomineralization, biological calcite, atomic force microscopy...

  1. Tunisian gypsums: Characteristics and use in cement

    Mahmoudi, Salah; Bennour, Ali; Chalwati, Youssef; Souidi, Khouloud; Thabet, Manel; Srasra, Ezzedine; Zargouni, Fouad

    2016-09-01

    Gypsum materials of hundred meters thickness and interbedded with marine claystones and limestones from different paleogeographic sectors in the Tunisian territory are studied to assess their suitability for cement production. For this reason, thirty representative samples are analysed by chemical, physical and geotechnical tests. The obtained results for the studied gypsum materials are compared to Tunisian and European norms and with the local cements, currently marketed and which obey international norms. Indeed, for all samples hydraulic modulus HM, silica modulus SM and alumina modulus AM vary from (2.37-2.44), (2.48-2.68) and (1.45-2.5), respectively; whereas the required values for these modulus are (1.5-2.5), (2-3) and (1.5-2.5). The same behavior is observed for mineralogical analyses of C3S, C2S, C3A and C4AF and compressive strength at different ages. Briefly, Tunisia contains important reserves of gypsum scattered and spread over the Tunisian territory and can be used for cement production.

  2. Reconstructing Holocene hematite and goethite variations in the Indus Canyon to trace changes in the Asian monsoon system

    Koehler, Cornelia; Clift, Peter; Pressling, Nicola; Limmer, David; Giosan, Liviu; Tabrez, Ali

    2010-05-01

    In order to study Holocene Asian monsoon variations, we reconstructed changes in chemical weathering by examining sediments from the Indus Canyon. During the late Holocene, the Asian monsoon system had periods of high and low intensities that influenced the civilisations living in its realm. For example, the demise of the Harappan civilisation has been linked to a weakened monsoon system around 4 ka. The sediments in the Indus Canyon, which originate from the River Indus and its Himalayan tributaries, provide an ideal, natural environmental archive of the South Asian monsoon system. In order to investigate the alternation between arid and humid monsoonal climatic conditions, variations are traced using the magnetic minerals hematite and goethite, which form under distinct environmental conditions: goethite is stable under humid conditions, whereas hematite forms from the dehydration of goethite under arid conditions. The two minerals are characterised and quantified using environmental magnetic measurements, as well as diffuse reflectance spectrometry. Combining both approaches will enable us to reconstruct variations in chemical weathering over time. Furthermore, because this is governed by temperature and the availability of moisture, our weathering record will allow us to understand monsoon variability during the Holocene and test whether summer rain intensity has been decreasing in SW Asia since 8 ka. In addition, the multi-component analysis of colour reflectance spectra identifies different mineral components including hematite/goethite, clay mineral mixtures, calcite and organics. We will present our results from the multi-sensor core logger equipped with a Minolta spectrometer, measuring both magnetic susceptibility and the optical properties of the split sediment cores. Initial results indicate the presence of hematite and goethite in the sediment. There is an increasing hematite content up the cores, indicating an aridification trend during the Holocene

  3. Local structural order in nanostructured hematite

    Florez, J. M.; Mazo-Zuluaga, J.; Restrepo, J.

    2005-01-01

    Nanostructured α-Fe 2 O 3 powders were prepared by high-energy ball milling. The milling process spans grinding times from 30 min to 24 h. The as-milled samples were characterized by means of 57 Fe Moessbauer spectrometry, Rietveld analysis of X-ray diffraction data and particle size analysis. The obtained results evidence the presence of disordered hematite characterized by a hyperfine field distribution with a well-behaved dependence on the mean crystallite size for which the mean hyperfine field decreases asymptotically as the grain size decreases. A new relationship is proposed in order to describe such behavior. Finally the presence of superparamagnetic grains, the occurrence of a partial topotactic phase transformation into a spinel phase and tool induced contamination are also presented and discussed.

  4. Local structural order in nanostructured hematite

    Florez, J. M.; Mazo-Zuluaga, J.; Restrepo, J., E-mail: jrestre@fisica.udea.edu.co [Universidad de Antioquia, Grupo de Estado Solido, Instituto de Fisica (Colombia)

    2005-09-15

    Nanostructured {alpha}-Fe{sub 2}O{sub 3} powders were prepared by high-energy ball milling. The milling process spans grinding times from 30 min to 24 h. The as-milled samples were characterized by means of {sup 57}Fe Moessbauer spectrometry, Rietveld analysis of X-ray diffraction data and particle size analysis. The obtained results evidence the presence of disordered hematite characterized by a hyperfine field distribution with a well-behaved dependence on the mean crystallite size for which the mean hyperfine field decreases asymptotically as the grain size decreases. A new relationship is proposed in order to describe such behavior. Finally the presence of superparamagnetic grains, the occurrence of a partial topotactic phase transformation into a spinel phase and tool induced contamination are also presented and discussed.

  5. Boron adsorption on hematite and clinoptilolite

    Gainer, G.M.

    1993-01-01

    This thesis describes experiments performed to determine the suitability of boron as a potential reactive tracer for use in saturated-zone C-well reactive tracer studies for the Yucca Mountain Project (YMP). Experiments were performed to identify the prevalent sorption mechanism of boron and to determine adsorption of boron on hematite and clinoptilolite as a function of pH. These minerals are present in the Yucca Mountain tuff in which the C-well studies will be conducted. Evaluation of this sorption mechanism was done by determining the equilibration time of boron-mineral suspensions, by measuring changes in equilibrium to titrations, and by measuring electrophoretic mobility. Experiments were performed with the minerals suspended in NaCl electrolytes of concentrations ranging from 0.1 N NaCl to 0.001 N NaCl. Experimentalconditions included pH values between 3 and 12 and temperature of about 38 degrees C

  6. Simulating the structure of gypsum composites using pulverized basalt waste

    Buryanov Аleksandr

    2017-01-01

    Full Text Available This paper examines the possibility of simulating the structure of gypsum composite modified with basalt dust waste to make materials and products based on it. Structural simulating of the topological space in gypsum modified composite by optimizing its grain-size composition highly improves its physical and mechanical properties. Strength and density tests have confirmed the results of the simulation. The properties of modified gypsum materials are improved by obtaining of denser particle packing in the presence of hemihydrate of finely dispersed basalt and plasticizer particles in the system, and by engaging basalt waste in the structuring process of modified gypsum stone.

  7. Efficiency of sulfuric acid, mined gypsum, and two gypsum by-products in soil crusting prevention and sodic soil reclamation

    Amezketa, E.; Aragues, R.; Gazol, R. [Gobierno Navarra, Pamplona (Spain). Agricultural Resources Evaluation Center

    2005-06-01

    We evaluated the efficiency of four amendments (sulfuric acid, mined-gypsum, and the by-products coal-gypsum and lacto-gypsum) in crusting prevention of two calcareous nonsodic and sodic soils and in sodic soil reclamation. Treatments for crust prevention consisted of surface-applied amendments at equivalent rates of 5 Mg pure-gypsum ha{sup -1}. Treatments for sodic soil reclamation consisted of surface-applied acid and soil-incorporated gypsums at rates of 1 pure-gypsum requirement. The efficiency of these amendments was evaluated by comparing the final infiltration rates (FIR) of the amended vs. the nonamended soils measured in disturbed-soil columns pounded with low-salinity irrigation water. Electrical conductivity (EC) and Na in the leachates of the sodic soil were measured. In the crusting prevention experiment, FIRs (mm h{sup -1) of the nonsodic soil were 21 (nonamended), 33 to 35 (gypsum materials), and 53 (sulfuric acid), whereas those for the sodic soil were 0 (nonamended), 9 (lacto-gypsum), 15 to 17 (coal- and mined-gypsum), and 21 (sulfuric acid). In the sodic-soil reclamation experiment, FIRs were 0 (nonamended), 8 to 9 (gypsum-materials), and 17 (sulfuric acid) mm h{sup -1}. All amendments were effective in crusting prevention and soil reclamation, but sulfuric acid was the most efficient due to the fastest EC and Na reductions in the leachates. The three gypsum-materials were equally effective in the reclamation process and in the nonsodic soil crusting-prevention, whereas lacto-gypsum was less efficient in the sodic-soil crusting-prevention.

  8. Dedolomitization Potential of Fluids from Gypsum-to-Anhydrite Conversion: Mass Balance Constraints from the Late Permian Zechstein-2-Carbonates in NW Germany

    M. Hallenberger

    2018-01-01

    Full Text Available The Zechstein-2-Carbonates represent one of the most prolific hydrocarbon systems of Central Europe. Carbonate reservoir quality is primarily controlled by mineralogy, with dolomite representing moderate-to-good porosities and calcite commonly representing low porosities. Current models suggest that this calcite is the result of a basin-wide phase of dedolomitization. The calcium (Ca source for the dedolomites is thought to be derived from the fluids liberated during gypsum-to-anhydrite conversion. We present an easy-to-use and generally applicable template to estimate the dedolomitization potential of these fluids. Depending on reaction stoichiometry, salinity, and temperature, we estimate that between 2.8⁎10−3 m3 and 6.2⁎10−3 m3 of calcite may replace dolomite for each m3 of anhydrite created. Within the constraints dictated by the environment of the late Permian Zechstein basin, we estimate that about 5⁎10−3 m3 of dedolomite is created for each m3 of anhydrite. Mass balance constraints indicate that fluids derived from gypsum-to-anhydrite conversion account for less than 1% of the observed dedolomite in most of the studied industry wells from northern Germany.

  9. Flue gas desulfurization gypsum and fly ash

    1992-05-01

    The Cumberland Fossil Plant (CUF) is located in Stewart County, Tennessee, and began commercial operation in 1972. This is the Tennessee Valley Authority's newest fossil (coal-burning) steam electric generating plant. Under current operating conditions, the plant burns approximately seven million tons of coal annually. By-products from the combustion of coal are fly ash, approximately 428,000 tons annually, and bottom ash, approximately 115,000 tons annually. Based on historical load and projected ash production rates, a study was initially undertaken to identify feasible alternatives for marketing, utilization and disposal of ash by-products. The preferred alternative to ensure that facilities are planned for all by-products which will potentially be generated at CUF is to plan facilities to handle wet FGD gypsum and dry fly ash. A number of different sites were evaluated for their suitability for development as FGD gypsum and ash storage facilities. LAW Engineering was contracted to conduct onsite explorations of sites to develop information on the general mature of subsurface soil, rock and groundwater conditions in the site areas. Surveys were also conducted on each site to assess the presence of endangered and threatened species, wetlands and floodplains, archaeological and cultural resources, prime farmland and other site characteristics which must be considered from an environmental perspective

  10. Soil management and application of agricultural gypsum in a Planosol for soybean cultivation

    Marchesan, Enio; Tonetto, Felipe; Teló, Gustavo Mack; Coelho, Lucas Lopes; Aramburu, Bruno Behenck; Trivisiol, Vinicius Severo

    2017-01-01

    ABSTRACT: This study investigated the effects of soil management systems, tillage, and application of gypsum agricultural to soil, on soybean development in lowland areas. The experiment was carried out on an Alfisol in a randomized complete block design in a factorial arrangement. The two soil tillage practices were without deep tillage and with deep tillage. Gypsum treatments were no gypsum application, 500kg of gypsum ha-1, 1000kg of gypsum ha-1, and 1500kg of gypsum ha-1. Deep tillage res...

  11. Spin orientation in solid solution hematite-ilmenite

    Brok, Erik; Frandsen, Cathrine; Lefmann, Kim

    2017-01-01

    temperature range below the Néel temperature and does not depend systematically on Ti-content. The results indicate that the out-of-plane spin component is an intrinsic feature of hematite itself, with an origin not yet fully understood, but consistent with group theory. This represents a major shift...... spectroscopy. The usually assumed magnetic structure of hematite within this temperature range is antiferromagnetic with the spins confined to the basal plane of the hexagonal structure; however, an out-of-plane spin component is allowed by the symmetry of the system and has been observed in recent studies......The spin orientation in synthetic hematite-ilmenite samples and in a sample of natural hematite was studied from room temperature to above the antiferromagnetic-paramagnetic phase transition (the Néel temperature; TN ≈ 600–950 K) by neutron powder diffraction and at room temperature by Mössbauer...

  12. MARKETING OF BYPRODUCT GYPSUM FROM FLUE GAS DESULFURIZATION

    The report gives results of an evaluation of the 1985 marketing potential of byproduct gypsum from utility flue gas desulfurization (FGD), for the area east of the Rocky Mountains, using the calculated gypsum production rates of 14 selected power plants. The 114 cement plants and...

  13. Mechanical, Hygric and Thermal Properties of Flue Gas Desulfurization Gypsum

    P. Tesárek

    2004-01-01

    Full Text Available The reference measurements of basic mechanical, thermal and hygric parameters of hardened flue gas desulfurization gypsum are carried out. Moisture diffusivity, water vapor diffusion coefficient, thermal conductivity, volumetric heat capacity and linear thermal expansion coefficient are determined with the primary aim of comparison with data obtained for various types of modified gypsum in the future. 

  14. Occurrence and geochemistry of Nafada Gypsum, north-eastern ...

    Gypsum deposits occur in numerous locations within the Senonian Fika Shale at Nafada, northeastern Nigeria. Geologic investigations at Baro Winde and Wuro Dabo mines indicate the occurrence of three varieties of gypsum namely, Balatino laminated, Alabaster and Satin Spar. These are interlayered within shale and ...

  15. Gypsum as a bedding source for broiler chickens

    Three trials examined the feasibility of flue gas desulfurization gypsum as a bedding material for raising broilers. Gypsum was used alone, under or on top of pine shavings and pine bark. Test materials were placed as bedding in pens to simulate commercial broiler production through three growout cy...

  16. Hydrogen sulfide release from dairy manure storages containing gypsum bedding

    Recycled gypsum products can provide a cost-effective bedding alternative for dairy producers. Manufacturers report reduced odors, moisture and bacteria in the stall environment when compared to traditional bedding. Gypsum provides a sulfate source that can be converted to hydrogen sulfide under ana...

  17. Gypsum-anhydrites in 2 Ga Vempalle Formation, Cuddapah basin ...

    69

    In fact high solubility in water leads to removal of gypsum in suficial environment. ... with presence of evaporite gypsum in the upper as well as lower part of the ..... created with shallow inlet or a slightly permeable seal with main water body.

  18. Magnetic clusters in ilmenite-hematite solid solutions

    Frandsen, Cathrine; Burton, B. P.; Rasmussen, Helge Kildahl

    2010-01-01

    We report the use of high-field 57Fe Mössbauer spectroscopy to resolve the magnetic ordering of ilmenite-hematite [xFeTiO3−(1−x)Fe2O3] solid solutions with x>0.5. We find that nanometer-sized hematite clusters exist within an ilmenite-like matrix. Although both phases are antiferromagnetically...

  19. Origin and diagenetic evolution of gypsum and microbialitic carbonates in the Late Sag of the Namibe Basin (SW Angola)

    Laurent, Gindre-Chanu; Edoardo, Perri; Ian, Sharp R.; Peacock, D. C. P.; Roger, Swart; Ragnar, Poulsen; Hercinda, Ferreira; Vladimir, Machado

    2016-08-01

    Ephemeral evaporitic conditions developed within the uppermost part of the transgressive Late Sag sequence in the Namibe Basin (SW Angola), leading to the formation of extensive centimetre- to metre-thick sulphate-bearing deposits and correlative microbialitic carbonates rich in pseudomorphs after evaporite crystals. The onshore pre-salt beds examined in this study are located up to 25 m underneath the major mid-Aptian evaporitic succession, which is typified at the outcrop by gypsiferous Bambata Formation and in the subsurface by the halite-dominated Loeme Formation. Carbonate-evaporite cycles mostly occur at the top of metre-thick regressive parasequences, which progressively onlap and overstep landward the former faulted (rift) topography, or fill major pre-salt palaeo-valleys. The sulphate beds are made up of alabastrine gypsum associated with embedded botryoidal nodules, dissolution-related gypsum breccia, and are cross-cut by thin satin-spar gypsum veins. Nodular and fine-grained fabrics are interpreted as being diagenetic gypsum deposits resulting from the dissolution and recrystallisation of former depositional subaqueous sulphates, whereas gypsum veins and breccia result from telogenetic processes. The carbonates display a broader diversity of facies, characterised by rapid lateral variations along strike. Thin dolomitic and calcitic bacterial-mediated filamentous microbialitic boundstones enclose a broad variety of evaporite pseudomorphs and can pass laterally over a few metres into sulphate beds. Dissolution-related depositional breccias are also common and indicate early dissolution of former evaporite layers embedded within the microbialites. Sulphate and carbonate units are interpreted as being concomitantly deposited along a tide-dominated coastal supra- to intertidal- sabkha and constitute high-frequency hypersaline precursor events, prior to the accumulation of the giant saline mid-Aptian Bambata and Loeme Formations. Petrographic and geochemical

  20. Incorporation of Uranium into Hematite during Crystallization from Ferrihydrite

    2014-01-01

    Ferrihydrite was exposed to U(VI)-containing cement leachate (pH 10.5) and aged to induce crystallization of hematite. A combination of chemical extractions, TEM, and XAS techniques provided the first evidence that adsorbed U(VI) (≈3000 ppm) was incorporated into hematite during ferrihydrite aggregation and the early stages of crystallization, with continued uptake occurring during hematite ripening. Analysis of EXAFS and XANES data indicated that the U(VI) was incorporated into a distorted, octahedrally coordinated site replacing Fe(III). Fitting of the EXAFS showed the uranyl bonds lengthened from 1.81 to 1.87 Å, in contrast to previous studies that have suggested that the uranyl bond is lost altogether upon incorporation into hematite. The results of this study both provide a new mechanistic understanding of uranium incorporation into hematite and define the nature of the bonding environment of uranium within the mineral structure. Immobilization of U(VI) by incorporation into hematite has clear and important implications for limiting uranium migration in natural and engineered environments. PMID:24580024

  1. The transformation of ferrihydrite into goethite or hematite, revisited

    Cudennec, Yannick; Lecerf, Andre

    2006-01-01

    During the oxidation of iron, poorly crystallized phases are firstly formed: 2- and 6-line ferrihydrite, which presents for the last phase, a similarity with wustite FeO but also with hematite α-Fe 2 O 3 . Crystallization increases with time and the solid phase obtained is dependent on temperature and pH. Obviously, high temperature favours the formation of the oxide hematite α-Fe 2 O 3 . As for the pH factor, it is more complicated. Low and high values of pH (2-5 and 10-14) favour the formation of goethite α-FeOOH, while obtaining hematite is favoured at neutral pH (values around 7). Goethite or hematite are obtained either through a dissolution-crystallization process or in the solid state, through a topotactic transformation. Given the structural relationships observed between ferrihydrite and wustite and hematite, it is allowed to think that a structural continuity could exist between wustite Fe (1- x ) O and hematite via ferrihydrite

  2. Bioavailability of nanoparticulate hematite to Arabidopsis thaliana

    Marusenko, Yevgeniy; Shipp, Jessie; Hamilton, George A.; Morgan, Jennifer L.L.; Keebaugh, Michael; Hill, Hansina; Dutta, Arnab; Zhuo, Xiaoding; Upadhyay, Nabin; Hutchings, James; Herckes, Pierre; Anbar, Ariel D.; Shock, Everett; Hartnett, Hilairy E.

    2013-01-01

    The environmental effects and bioavailability of nanoparticulate iron (Fe) to plants are currently unknown. Here, plant bioavailability of synthesized hematite Fe nanoparticles was evaluated using Arabidopsis thaliana (A. thaliana) as a model. Over 56-days of growing wild-type A. thaliana, the nanoparticle-Fe and no-Fe treatments had lower plant biomass, lower chlorophyll concentrations, and lower internal Fe concentrations than the Fe-treatment. Results for the no-Fe and nanoparticle-Fe treatments were consistently similar throughout the experiment. These results suggest that nanoparticles (mean diameter 40.9 nm, range 22.3–67.0 nm) were not taken up and therefore not bioavailable to A. thaliana. Over 14-days growing wild-type and transgenic (Type I/II proton pump overexpression) A. thaliana, the Type I plant grew more than the wild-type in the nanoparticle-Fe treatment, suggesting Type I plants cope better with Fe limitation; however, the nanoparticle-Fe and no-Fe treatments had similar growth for all plant types. -- Highlights: ► Iron nanoparticles were synthesized and assessed for bioavailability to Arabidopsis. ► Arabidopsis grew better in the presence of EDTA-bound iron than nanoparticulate iron. ► Arabidopsis grew the same in the presence of nanoparticulate iron compared to no iron. -- Synthesized iron nanoparticles were not bioavailable to Arabidopsis thaliana in agar nutrient media

  3. Acidization of shales with calcite cemented fractures

    Kwiatkowski, Kamil; Szymczak, Piotr; Jarosiński, Marek

    2017-04-01

    Investigation of cores drilled from shale formations reveals a relatively large number of calcite-cemented fractures. Usually such fractures are reactivated during fracking and can contribute considerably to the permeability of the resulting fracture network. However, calcite coating on their surfaces effectively excludes them from production. Dissolution of the calcite cement by acidic fluids is investigated numerically with focus on the evolution of fracture morphology. Available surface area, breakthrough time, and reactant penetration length are calculated. Natural fractures in cores from Pomeranian shale formation (northern Poland) were analyzed and classified. Representative fractures are relatively thin (0.1 mm), flat and completely sealed with calcite. Next, the morphology evolution of reactivated natural fractures treated with low-pH fluids has been simulated numerically under various operating conditions. Depth-averaged equations for fracture flow and reactant transport has been solved by finite-difference method coupled with sparse-matrix solver. Transport-limited dissolution has been considered, which corresponds to the treatment with strong acids, such as HCl. Calcite coating in reactivated natural fractures dissolves in a highly non-homogeneous manner - a positive feedback between fluid transport and calcite dissolution leads to the spontaneous formation of wormhole-like patterns, in which most of the flow is focused. The wormholes carry reactive fluids deeper inside the system, which dramatically increases the range of the treatment. Non-uniformity of the dissolution patterns provides a way of retaining the fracture permeability even in the absence of the proppant, since the less dissolved regions will act as supports to keep more dissolved regions open. Evolution of fracture morphology is shown to depend strongly on the thickness of calcite layer - the thicker the coating the more pronounced wormholes are observed. However the interaction between

  4. Permeability of gypsum samples dehydrated in air

    Milsch, Harald; Priegnitz, Mike; Blöcher, Guido

    2011-09-01

    We report on changes in rock permeability induced by devolatilization reactions using gypsum as a reference analog material. Cylindrical samples of natural alabaster were dehydrated in air (dry) for up to 800 h at ambient pressure and temperatures between 378 and 423 K. Subsequently, the reaction kinetics, so induced changes in porosity, and the concurrent evolution of sample permeability were constrained. Weighing the heated samples in predefined time intervals yielded the reaction progress where the stoichiometric mass balance indicated an ultimate and complete dehydration to anhydrite regardless of temperature. Porosity showed to continuously increase with reaction progress from approximately 2% to 30%, whilst the initial bulk volume remained unchanged. Within these limits permeability significantly increased with porosity by almost three orders of magnitude from approximately 7 × 10-19 m2 to 3 × 10-16 m2. We show that - when mechanical and hydraulic feedbacks can be excluded - permeability, reaction progress, and porosity are related unequivocally.

  5. Measuring the gypsum content of C&D debris fines.

    Musson, Stephen E; Xu, Qiyong; Townsend, Timothy G

    2008-11-01

    Construction and demolition (C&D) debris recycling facilities often produce a screened material intended for use as alternative daily cover (ADC) at active landfills or for shaping and grading at closed landfills. This product contains soil and small pieces of wood, concrete, gypsum drywall, shingles and other components of C&D debris. Concerns have been raised over the contribution of gypsum drywall in C&D debris fines to odor problems at landfills where the product is used. To address such concerns, limitations may be placed on the percentage of gypsum (or sulfate) that can occur, and standardized testing procedures are required to permit valid compliance testing. A test procedure was developed for measuring the gypsum content in C&D debris fines. The concentration of sulfate leached in an aqueous solution was used to estimate the initial gypsum content of the sample. The impact of sample size and leaching time were evaluated. Precision and accuracy increased with increasing gypsum content. Results from replicate samples had an average relative standard deviation of 9%. The gypsum content of fines obtained from different facilities in the US varied widely from 1% to over 25%. These variations not only occurred between differing facilities, but within batches produced within a single facility.

  6. Impact of welan gum on tricalcium aluminate–gypsum hydration

    Ma Lei; Zhao Qinglin; Yao Chukang; Zhou Mingkai

    2012-01-01

    The retarding effect of welan gum on tricalcium aluminate–gypsum hydration, as a partial system of ordinary Portland cement (OPC) hydration, was investigated with several methods. The tricalcium aluminate–gypsum hydration behavior in the presence or absence of welan gum was researched by field emission gun scanning electron microscopy, X-ray diffraction and zeta potential analysis. Meanwhile, we studied the surface electrochemical properties and adsorption characteristics of welan gum by utilizing a zeta potential analyzer and UV–VIS absorption spectrophotometer. By adding welan gum, the morphology change of ettringite and retardation of hydration stages in tricalcium aluminate–gypsum system was observed. Moreover, we detected the adsorption behavior and zeta potential inversion of tricalcium aluminate and ettringite, as well as a rapid decrease in the zeta potential of tricalcium aluminate–gypsum system. The reduction on nucleation rate of ettringite and hydration activity of C 3 A was also demonstrated. Thus, through the adsorption effect, welan gum induces a retarding behavior in tricalcium aluminate–gypsum hydration. Highlights: ► Adsorption characteristics of welan gum on C 3 A and ettringite have been studied. ► C 3 A–gypsum hydration behavior and the hydration products are examined in L/S = 3. ► Welan gum retards the process of C 3 A–gypsum hydration. ► The addition of welan gum changes the nucleation growth of ettringite.

  7. Interaction of gypsum with lead in aqueous solutions

    Astilleros, J.M.; Godelitsas, A.; Rodriguez-Blanco, J.D.; Fernandez-Diaz, L.; Prieto, M.; Lagoyannis, A.; Harissopulos, S.

    2010-01-01

    Sorption processes on mineral surfaces are a critical factor in controlling the distribution and accumulation of potentially harmful metals in the environment. This work investigates the effectiveness of gypsum (CaSO 4 .2H 2 O) to sequester Pb. The interaction of gypsum fragments with Pb-bearing solutions (10, 100 and 1000 mg/L) was monitored by performing macroscopic batch-type experiments conducted at room temperature. The aqueous phase composition was periodically determined by Atomic Absorption Spectrometry (AAS), Ion Chromatography (IC) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Regardless of the [Pb aq ] initial , a [Pb aq ] final aq ] initial ≥ 100 mg/L and significantly slower (t > 1 week) for [Pb aq ] initial = 10 mg/L. Speciation calculations revealed that after a long time of interaction (1 month), all the solutions reached equilibrium with respect to both gypsum and anglesite. For [Pb aq ] initial ≥ 100 mg/L, sorption takes place mainly via the rapid dissolution of gypsum and the simultaneous formation of anglesite both on the gypsum surface and in the bulk solution. In the case of [Pb aq ] initial = 10 mg/L, no anglesite precipitation was observed, but surface spectroscopy (proton Rutherford Backscattering Spectroscopy, p-RBS) confirmed the formation of Pb-bearing surface layers on the (0 1 0) gypsum surface in this case also. This study shows that the surface of gypsum can play an important role in the attenuation of Pb in contaminated waters.

  8. Electro-oxidation of water on hematite: Effects of surface termination and oxygen vacancies investigated by first-principles

    Hellman, Anders; Iandolo, Beniamino; Wickman, Bjorn

    2015-01-01

    The oxygen evolution reaction on hydroxyl- and oxygen-terminated hematite was investigated using first-principle calculations within a theoretical electrochemical framework. Both pristine hematite and hematite containing oxygen vacancies were considered. The onset potential was determined to be 1...... on hematite occurs on the oxygen-terminated hematite, containing oxygen vacancies. (C) 2015 Elsevier B.V. All rights reserved....

  9. Sustainable Uses of FGD Gypsum in Agricultural Systems: Introduction.

    Watts, Dexter B; Dick, Warren A

    2014-01-01

    Interest in using gypsum as a management tool to improve crop yields and soil and water quality has recently increased. Abundant supply and availability of flue gas desulfurization (FGD) gypsum, a by-product of scrubbing sulfur from combustion gases at coal-fired power plants, in major agricultural producing regions within the last two decades has attributed to this interest. Currently, published data on the long-term sustainability of FGD gypsum use in agricultural systems is limited. This has led to organization of the American Society of Agronomy's Community "By-product Gypsum Uses in Agriculture" and a special collection of nine technical research articles on various issues related to FGD gypsum uses in agricultural systems. A brief review of FGD gypsum, rationale for the special collection, overviews of articles, knowledge gaps, and future research directions are presented in this introductory paper. The nine articles are focused in three general areas: (i) mercury and other trace element impacts, (ii) water quality impacts, and (iii) agronomic responses and soil physical changes. While this is not an exhaustive review of the topic, results indicate that FGD gypsum use in sustainable agricultural production systems is promising. The environmental impacts of FGD gypsum are mostly positive, with only a few negative results observed, even when applied at rates representing cumulative 80-year applications. Thus, FGD gypsum, if properly managed, seems to represent an important potential input into agricultural systems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  10. Calcite precipitates in Slovenian bottled waters.

    Stanič, Tamara Ferjan; Miler, Miloš; Brenčič, Mihael; Gosar, Mateja

    2017-06-01

    Storage of bottled waters in varying ambient conditions affects its characteristics. Different storage conditions cause changes in the initial chemical composition of bottled water which lead to the occurrence of precipitates with various morphologies. In order to assess the relationship between water composition, storage conditions and precipitate morphology, a study of four brands of Slovenian bottled water stored in PET bottles was carried out. Chemical analyses of the main ions and measurements of the physical properties of water samples were performed before and after storage of water samples at different ambient conditions. SEM/EDS analysis of precipitates was performed after elapsed storage time. The results show that the presence of Mg 2+ , SO 4 2- , SiO 2 , Al, Mn and other impurities such as K + , Na + , Ba and Sr in the water controlled precipitate morphology by inhibiting crystal growth and leading to elongated rhombohedral calcite crystal forms which exhibit furrowed surfaces and calcite rosettes. Different storage conditions, however, affected the number of crystallization nuclei and size of calcite crystals. Hollow calcite spheres composed of cleavage rhombohedrons formed in the water with variable storage conditions by a combination of evaporation and precipitation of water droplets during high temperatures or by the bubble templating method.

  11. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    Wilkinson, Bruce H.

    1982-01-01

    Discusses causes of cyclicity in cratonic carbonate sequences and evidence for and potential significance of postulated primary calcite sediment components in past Paleozoic seas, outlining problems, focusing on models explaining existing data, and identifying background. Future sedimentary geologists will need to address these and related areas…

  12. Process for reducing radioactive contamination in waste product gypsum

    Lange, P.H. Jr.

    1979-01-01

    A process is described for reducing the radioactive contamination in waste product gypsum in which waste product gypsum is reacted with a dilute sulfuric acid containing barium sulfate to form an acid slurry at an elevated temperature, the slurry is preferably cooled, the acid component is separated from the solid, and the resulting solid is separated into a fine fraction and a coarse fraction. The fine fraction predominates in barium sulfate and radioactive contamination. The coarse fraction predominates in a purified gypsum product of reduced radioactive contamination

  13. Mechanisms of metasomatism in the calcite-pitchblende system: 2. Replacement of pitchblende by calcite

    Dymkov, Yu.M.

    1996-01-01

    The principal mechanisms of the nasturan replacement by calcite -intrametasomatism, frontal metasomatism, dispersive metasomatism, and transformative metasomatism - are discussed in terms of G.L. Pospelov's (1973) concept. The main chemical condition required by the process is an oxidized environment, in which the tetravalent uranium of pitchblende or transitional reduced phases (coffinite) oxidizes to yield readily soluble uranyl compounds. The latter are replaced by calcite

  14. Sealing process with calcite in the Nojima active fault zone revealed from isotope analysis of calcite

    Arai, Takashi; Tsukahara, Hiroaki; Morikiyo, Toshiro

    2003-01-01

    The Nojima fault appeared on the surface in the northern part of Awaji Island, central Japan as a result of the Hyogo-ken Nanbu earthquake (1995, M=7.2). Active fault drilling was performed by the Disaster Prevention Research Institute (DPRI), Kyoto University, and core samples were retrieved from 1410 to 1710 m, which were composed of intact and fractured granodiorites. We obtained calcite samples and gas samples from the vein in marginal fracture and non-fracture zones. We analyzed the carbon and oxygen isotope ratios of calcite and carbon dioxide to investigate the characteristic isotope ratios of fluids in the active fault zone, to estimate the origins of fluids, and to determine the sealing process of fractures. The analyzed values of carbon and oxygen isotope ratios of calcite were -10.3 to -7.2 per mille, 18 to 23 per mille, respectively, and carbon isotope ratios of CO 2 were -21 to -17 per mille. If carbon isotope ratios of calcite were at equilibrium with those of CO 2 , the precipitation temperature of calcite is calculated to be 30 to 50 deg C. This temperature is consistent with the present temperature of the depth where drilling cores were retrieved. Oxygen isotope ratios of H 2 O that, precipitated calcite were calculated to be -1.8 to -5.5 per mille. These values indicate calcite were precipitated from mixed fluids of sea water and meteoric water. Therefore, the marginal fracture zone of the Nojima fault was sealed with calcite, which was generated from mixing of sea water and meteoric water in situ. (author)

  15. High-Magnesian Calcite Mesocrystals : A Coordination Chemistry Approach

    Lenders, Jos J. M.; Dey, Archan; Bomans, Paul H. H.; Spielmann, Jan; Hendrix, Marco M. R. M.; de With, Gijsbertus; Meldrum, Fiona C.; Harder, Sjoerd; Sommerdijk, Nico A. J. M.

    2012-01-01

    While biogenic calcites frequently contain appreciable levels of magnesium, the pathways leading to such high concentrations remain unclear. The production of high-magnesian calcites in vitro is highly challenging, because Mg-free aragonite, rather than calcite, is the favored product in the

  16. Calcite growth kinetics: Modeling the effect of solution stoichiometry

    Wolthers, M.; Nehrke, G.; Gustafsson, J.P.; Van Cappellen, P.

    2012-01-01

    Until recently the influence of solution stoichiometry on calcite crystal growth kinetics has attracted little attention, despite the fact that in most aqueous environments calcite precipitates from non-stoichiometric solution. In order to account for the dependence of the calcite crystal growth

  17. Assessment of Natural Exposure From Some kinds of Egyptian Gypsum Using Low Background Spectrometer

    Sroor, A.

    2006-01-01

    Radioactivity of natural gypsum and gypsum derived products are examined investigated due to their importance as element of building materials and agricultural gypsum. the natural gypsum and its product may constitute an additional source of radiation exposure to workers and members of public from radiation produced by radioactive decaying. thirty natural gypsum samples from different quarries and 32 fabricated gypsum samples from commercial companies were analyzed using low background HPGe detector. the natural concentration of Ra-226, 232 Th and 40 K activities in all samples were determined in Bq/Kg dry weight. it was found that radioactivity of natural gypsum is less than the fabricated gypsum, so it can be used as agricultural gypsum. fabricated gypsum is suitable for use as an element of building material in egypt

  18. Radium uptake by recrystallized gypsum: an incorporation study

    Lestini, Leslie; Beaucaire, Catherine; Vercouter, Thomas; Descostes, Michael

    2013-01-01

    Batch experiments of 226 Ra uptake by recrystallized gypsum CaSO 4 .2H 2 O(s), monitored over 200 days, have shown that the published value for the distribution coefficient of 226 Ra between gypsum and an aqueous phase, 0.03 (Gnanapragasam and Lewis, 1995), is an upper limit. This suggests that this value needs to be confirmed. A solid solution between gypsum and radium sulfate (Ca,Ra)SO 4 .2H 2 O(s) cannot be considered per se, which is not surprising considering gypsum's high solubility product (lg Ks = -4.58) and the ionic radius of VIII Ra (1.48 A), when compared to that of VIII Ca (1.12 A). (authors)

  19. Uranium-series dating of gypsum speleothems: methodology and examples.

    Sanna Laura

    2010-01-01

    Full Text Available The analytical problems of dating gypsum speleothems with the U-series technique are reviewed. Gypsum speleothems are, in general, very low in U content, challenging the limits of detection methods. Various approaches to dissolving gypsum and isolation of actinides from the matrix include ion-pairing dissolution with magnesium salts and using nitric acid. The most precise dating technique is Thermal Ionization Mass Spectrometry (TIMS, combined with Fe(OH3 scavenging and anionic exchange chromatography. Less satisfactory, but much quicker, is direct retention of actinides from HNO3 by means of TRU resin and MC-ICP-MS detection. We have tested these methods on gypsum speleothems from the Sorbas karst in Spain and from the Naica caves in Mexico.

  20. Gypsum crystals in the inner shelf sediments off Maharashtra, India

    Hashimi, N.H.; Ambre, N.V.

    Gypsum crystals have been found in the inner shelf silty clay/clayey silt off the Maharashtra Coast between Vengurla and Bombay. Generally these occur as euhedral single or twinned crystals of selenite. Very often shells are found embedded within...

  1. Preliminary Estimate of Gypsum Deposit Based on Wenner

    Dogara M. D. and Aloa J. O.

    estimating the quantity of some possible deposits of gypsum. Just ... exploitation is an everyday activity that is currently going on, but, on a 'wild cat' ... important source of wealth for a nation, but before they are harnessed ..... REFERENCES.

  2. Surface Potential of Polycrystalline Hematite in Aqueous Medium

    Tajana Preočanin

    2011-01-01

    Full Text Available The surface potential of polycrystalline hematite in aqueous sodium perchlorate environment as a function of pH was examined. Surface potential of hematite was obtained from measured electrode potential of a nonporous polycrystalline hematite electrode. Acidic solution was titrated with base, and the backward titration with acid was performed. Substantial hysteresis was obtained which enabled location of the point of zero potential and equilibrium values of surface potentials. The theoretical interpretation of the equilibrium data was performed by applying the surface complexation model and the thermodynamic equilibrium constants for the first and the second step of surface protonation was obtained as logK1∘=11.3;logK2∘=2.8.

  3. Non destructive Testing (NDT) of concrete containing hematite

    Mohamad Pauzi Ismail; Noor Azreen Masenwat; Suhairy Sani; Nasharuddin Isa; Mohamad Haniza Mahmud

    2014-01-01

    This paper described the results of Non-destructive ultrasonic and rebound hammer measurements on concrete containing hematite. Local hematite stones were used as aggregates to produce high density concrete for application in X-and gamma shielding. Concrete cube samples (150 mm x 150 mm x 150 mm) containing hematite as coarse aggregates were prepared by changing mix ratio, water to cement ratio (w/c) and types of fine aggregate. All samples were cured in water for 7 days and then tested after 28 days. Density, rebound number(N) and ultrasonic pulse velocity (UPV) of the samples were taken before compressed to failure. The measurement results are explained and discussed. (author)

  4. Memory effect of ball-milled and annealed nanosized hematite

    Bercoff, P.G.; Bertorello, H.R.; Oliva, M.I.

    2007-01-01

    Fine particles of hematite (mean size 55 nm) were produced by ball milling a mixture of hematite and pure Fe and annealing at 1000 o C. X-ray diffraction (XRD) and Moessbauer spectroscopy show that only α-Fe 2 O 3 is present in the final product, with lattice and Moessbauer parameters that correspond to bulk hematite. ZFC and FC magnetization measurements were performed from 5 to 300 K, at different applied fields. Two magnetic regimes were observed: one at low temperatures (≤100 K) that we ascribe to the magnetic moments in the outer shell of the particles that couple to the magnetic moments in the core, and another at higher temperature that corresponds to the Morin transition, finding that the Morin temperature is T M =246 K. The memory effect is clearly observed in magnetic measurements that start from different remanence states and explained as dependent on the ordering of the magnetic moments within the particles

  5. Direct and indirect dating of gypsum occurrences in deserts using luminescence methods

    Nagar, Y.C.; Juyal, N.; Singhyi, A.K.; Kocurek, G.; Wadhawan, S.K.

    2005-01-01

    In the present study we have made an attempt to directly date gypsum or provide indirect age estimate for gypsum formation through dating the associated sediments (quartz) using the luminescence dating technique. In the direct dating of gypsum, we explored the Optically Stimulated Luminescence (OSL) and Thermally Stimulated Luminescence (TL) behaviour of gypsum. The associated sediments (indirect dating) were dated using the traces of quartz extract from gypsum (concentration 0.1% ) and the underlying and overlying quartz sand in playa

  6. Interfacial Precipitation of Phosphate on Hematite and Goethite

    Lijun Wang

    2018-05-01

    Full Text Available Adsorption and subsequent precipitation of dissolved phosphates on iron oxides, such as hematite and goethite, is of considerable importance in predicting the bioavailability of phosphates. We used in situ atomic force microscopy (AFM to image the kinetic processes of phosphate-bearing solutions interacting with hematite or goethite surfaces. The nucleation of nanoparticles (1.0–4.0 nm in height of iron phosphate (Fe(III-P phases, possibly an amorphous phase at the initial stages, was observed during the dissolution of both hematite and goethite at the earliest crystallization stages. This was followed by a subsequent aggregation stage where larger particles and layered precipitates are formed under different pH values, ionic strengths, and organic additives. Kinetic analysis of the surface nucleation of Fe-P phases in 50 mM NH4H2PO4 at pH 4.5 showed the nucleation rate was greater on goethite than hematite. Enhanced goethite and hematite dissolution in the presence of 10 mM AlCl3 resulted in a rapid increase in Fe-P nucleation rates. A low concentration of citrate promoted the nucleation, whereas nucleation was inhibited at higher concentrations of citrate. By modeling using PHREEQC, calculated saturation indices (SI showed that the three Fe(III-P phases of cacoxenite, tinticite, and strengite may be supersaturated in the reacted solutions. Cacoxenite is predicted to be more thermodynamically favorable in all the phosphate solutions if equilibrium is reached with respect to hematite or goethite, although possibly only amorphous precipitates were observed at the earliest stages. These direct observations at the nanoscale may improve our understanding of phosphate immobilization in iron oxide-rich acid soils.

  7. Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

    Reddy, Michael M.

    2012-01-01

    Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10−4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10−4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

  8. Interaction of alcohols with the calcite surface

    Bovet, Nicolas Emile; Yang, Mingjun; Javadi, Meshkat Sadat

    2015-01-01

    . Controlling their growth requires complex polysaccharides. Polysaccharide activity depends on the functionality of OH groups, so to simplify the system in order to get closer to a molecular level understanding, we investigated the interaction of OH from a suite of alcohols with clean, freshly cleaved calcite...... surfaces. X-ray photoelectron spectroscopy (XPS) provided binding energies and revealed the extent of surface coverage. Molecular dynamics (MD) simulations supplemented with information about molecule ordering, orientation and packing density. The results show that all alcohols studied bond...... with the calcite surface through the OH group, with their carbon chains sticking away in a standing-up orientation. Alcohol molecules are closely packed and form a well-ordered monolayer on the surface....

  9. Photosystem I-​based Biophotovoltaics on Nanostructured Hematite

    Ocakoglu, K.; Krupnik, T.; van den Bosch, B.; Harputlu, E.; Gullo, M.P.; Olmos, J.D.J.; Yildirimcan, S.; Gupta, R.K.; Yakuphanoglu, F.; Barbieri, A.; Reek, J.N.H.; Kargul, J.

    2014-01-01

    The electronic coupling between a robust red algal photosystem I (PSI) associated with its light harvesting antenna (LHCI) and nanocrystalline n-​type semiconductors, TiO2 and hematite (α-​Fe2O3) is utilized for fabrication of the biohybrid dye-​sensitized solar cells (DSSC)​. PSI-​LHCI is

  10. Interaction of gypsum with lead in aqueous solutions

    Astilleros, J.M., E-mail: jmastill@geo.ucm.es [Dpto. Cristalografia y Mineralogia, Universidad Complutense de Madrid, Jose Antonio Novais, 2, E-28040 Madrid (Spain); Godelitsas, A. [Department of Mineralogy and Petrology, Faculty of Geology and Geoenvironment, University of Athens, Panepistimioupoli Zographou, 15784 Athens (Greece); Rodriguez-Blanco, J.D. [School of Earth and Environments, Faculty of Environment, University of Leeds, Leeds LS2 9JT (United Kingdom); Fernandez-Diaz, L. [Dpto. Cristalografia y Mineralogia, Universidad Complutense de Madrid, Jose Antonio Novais, 2, E-28040 Madrid (Spain); Prieto, M. [Dpto. de Geologia, Universidad de Oviedo, E-30005 Oviedo (Spain); Lagoyannis, A.; Harissopulos, S. [Tandem Accelerator Laboratory, Institute of Nuclear Physics, NCSR ' Demokritos' , GR-15310 Attiki (Greece)

    2010-07-15

    Sorption processes on mineral surfaces are a critical factor in controlling the distribution and accumulation of potentially harmful metals in the environment. This work investigates the effectiveness of gypsum (CaSO{sub 4}.2H{sub 2}O) to sequester Pb. The interaction of gypsum fragments with Pb-bearing solutions (10, 100 and 1000 mg/L) was monitored by performing macroscopic batch-type experiments conducted at room temperature. The aqueous phase composition was periodically determined by Atomic Absorption Spectrometry (AAS), Ion Chromatography (IC) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Regardless of the [Pb{sub aq}]{sub initial}, a [Pb{sub aq}]{sub final} < 4 mg/L was always reached. The uptake process was fast (t < 1 h) for [Pb{sub aq}]{sub initial} {>=} 100 mg/L and significantly slower (t > 1 week) for [Pb{sub aq}]{sub initial} = 10 mg/L. Speciation calculations revealed that after a long time of interaction (1 month), all the solutions reached equilibrium with respect to both gypsum and anglesite. For [Pb{sub aq}]{sub initial} {>=} 100 mg/L, sorption takes place mainly via the rapid dissolution of gypsum and the simultaneous formation of anglesite both on the gypsum surface and in the bulk solution. In the case of [Pb{sub aq}]{sub initial} = 10 mg/L, no anglesite precipitation was observed, but surface spectroscopy (proton Rutherford Backscattering Spectroscopy, p-RBS) confirmed the formation of Pb-bearing surface layers on the (0 1 0) gypsum surface in this case also. This study shows that the surface of gypsum can play an important role in the attenuation of Pb in contaminated waters.

  11. Unravelling the mechanisms for plant survival on gypsum soils: an analysis of the chemical composition of gypsum plants from Turkey.

    Bolukbasi, A; Kurt, L; Palacio, S

    2016-03-01

    Depending on their specificity to gypsum, plants can be classified as gypsophiles (gypsum exclusive) and gypsovags (non-exclusive). The former may further be segregated into wide and narrow gypsophiles, depending on the breadth of their distribution area. Narrow gypsum endemics have a putative similar chemical composition to plants non-exclusive to gypsum (i.e. gypsovags), which may indicate their similar ecological strategy as stress-tolerant plant refugees on gypsum. However, this hypothesis awaits testing in different regions of the world. We compared the chemical composition of four narrow gypsum endemics, one widely distributed gypsophile and six gypsovags from Turkey. Further, we explored the plasticity in chemical composition of Turkish gypsovags growing on high- and low-gypsum content soils. Differences were explored with multivariate analyses (RDA) and mixed models (REML). Narrow gypsum endemics segregated from gypsovags in their chemical composition according to RDAs (mainly due to higher K and ash content in the former). Nevertheless, differences were small and disappeared when different nutrients were analysed individually. All the gypsovags studied accumulated more S and ash when growing on high-gypsum than on low-gypsum soils. Similar to narrow gypsum endemics from other regions of the world, most local gypsum endemics from Turkey show a similar chemical composition to gypsovags. This may indicate a shared ecological strategy as stress-tolerant plants not specifically adapted to gypsum. Nevertheless, the narrow gypsum endemic Gypsophila parva showed a chemical composition typical of gypsum specialists, indicating that various strategies are feasible within narrowly distributed gypsophiles. © 2015 German Botanical Society and The Royal Botanical Society of the Netherlands.

  12. Synthesis on research results of FGD gypsum briquetting

    Kosturkiewicz Bogdan

    2017-01-01

    Full Text Available FGD gypsum products can be characterized by significant solubility in water and dusting in dry state. These characteristics can cause a considerable pollution of air, water and soil. Among many approaches of preparing utilization of this waste, the process of compaction using briquetting has proved to be very effective. Using FGD gypsum products a new material of fertilizers characteristics has been acquired and this material is resistant to the conditions of transportation. This paper presents results of experimental briquetting of flue gas desulphurisation products in a roll press. The experiments were conducted in a laboratory roll presses LPW 450 and LPW 1100 equipped with two interchangeable forming rings that form material into saddle-shaped briquettes with volume 6,5 cm3 and 85 cm3. The experiments were conducted with various percentage amounts of FGD gypsum moisture. The results provided information regarding influence of moisture and roll press configuration on quality of briquettes. On the basis of obtained results, technological process and a general outline of technological line for FGD gypsum were developed. Two roll presses of own construction with different outputs were identified as appropriate for this purpose. A range of necessary works related to their adaptation for the FGD gypsum briquetting were pointed out.

  13. Converting SDAP into gypsum in a wet limestone scrubber

    Fogh, F [Faelleskemikerne, Elsamprojekt A/S, Fredericia (Denmark)

    1996-12-01

    The ELSAM power pool has an installed electrical capacity of approx. 5 GW{sub e}, mainly firing import coal. The major base load units are equipped with desulphurization units and three different desulphurization technologies are used: the wet limestone gypsum process, the spray dry absorption process and a sulphuric acid process. Gypsum and sulphuric acid are commercialized, whereas it has been difficult to utilize the spray dry absorption product (SDAP). The main constituents of SDAP are calcium sulphide, calcium chloride, hydrated lime and impurities mainly originating from fly ash. Sulphide can be oxidized into sulphate in acidic solution - the reaction is utilized in the wet limestone gypsum process - and the possibility of using any spare capacity in the wet limestone gypsum units to oxidize the sulphide content of SDAP into sulphate and produce usable gypsum has been investigated in the laboratory and in a 400 MW{sub e} equivalent wet limestone unit. The limestone inhibition effect of the addition of SDAP is currently being studied in the laboratory in order to determine the effect of different SDAP types (plant/coal sources) on limestone reactivity before further long-term full-scale tests are performed and permanent use of the process planned. (EG)

  14. [The effect of disinfectant soaking on dental gypsum model size].

    Zhu, Cao-yun; Xu, Yun-wen; Xu, Kan

    2012-12-01

    To study the influence of disinfectant soaking on the dimensional stability of three kinds of dental gypsum model. Three commonly used gypsums ( type III,IV,Vtype) in clinic were used to make 24 specimens for 50 mm×15 mm×10 mm in size. One hour after release, the specimens were placed for 24 h. A digital caliper was used to measure the size of the gypsum model. Distilled water immersion was as used control, glutaraldehyde disinfectant and Metrix CaviCide disinfectant soaking were used for the experimental group. After soaking for 0.5h, the gypsum models were removed and placed for 0.5 h, 1 h, 2 h, 24 h. The size of the models was measured again using the same method. The data was analyzed with SPSS10.0 software package. The initial gypsum model length was (50.07±0.017) mm, (50.048±0.015) mm and (50.027±0.015) mm. After soaking for different times, the size of the model changed little, and the dimensions changed less than 0.01%. The results show that disinfectant soaking has no significant effect on dental model dimensions.

  15. The Influence of Several Doped Ions on Gas Sensitivity of Hematite

    1999-01-01

    The dehydrating activation energies of the hematite with several doped ions used for the alcohol sensor were determinated by thermogravimetric differential thermal analyzer (TG-DTA) and the grain size of the samples were observed with TEM. The hematites with different doping amounts of Sn4 + were investigated by Mossbauer spectrometer. It shows that the different doped ion is of influence for grain growth of the hematite. The decrease of grain size stemmed from the doped ion causes gas sensitivity for alcohol to increase and the dehydrating activation energy to decrease correspondingly. When the different amounts of Sn4 + is doped in hematite, the microstructure of the hematite can be influenced.

  16. Fracture calcites at Olkiluoto. Evidence from quaternary infills for palaeohydrogeology

    Gehoer, S.; Kaerki, A.; Taikina-aho, O.; Karhu, J.; Loefman, J.; Pitkaenen, P.; Ruotsalainen, P.

    2002-02-01

    Recently formed secondary minerals, predominantly calcite, occur in varying amounts as fracture infills, and the calcite types, their chemical compositions and isotope ratios reflect the compositions and physicochemical factors of the groundwater system in which they were formed. Fluid inclusions trapped in calcites give direct evidence of trapping temperatures and past salinities and of the chemical compositions of the palaeo fluids. A wide range of mineralogical and geochemical examinations were carried out within the EQUIP project to examine features of this kind. The fracture calcites at the Olkiluoto site are of various origins and represent several textural types. The exact number of calcite-producing events is unknown, but the duration of the period that was appropriate for the precipitation of low temperature calcite is estimated to have exceeded 1000 Ma. Thus the number of genetically related calcite units is assumed to be considerable. This study was focused on the petrogenesis of calcites crystallized in fractures of high water conductivity during the latest stages of geological evolution. The majority of these late stage calcites form physically homogeneous, scaly layers, and in a few cases thin layers composed of idiomorphic crystals. Chemically these are almost stoichiometric calcites (CaCO 3 ). The MnO content may exceed 1%, while the amounts of other elements present are minor, although the trace element concentrations, particularly those of large ionic trace elements, can be used as distinguishing features for the recognition of individual precipitates representing different calcite generations. Evidence from fluid inclusions, or more correctly from the absence of these in the late stage calcites, can be interpreted as an indication of slow rates of crystallization under cool conditions. Many chemical variables, e.g. oxygen isotope ratios, demonstrate an equilibrium between the latest calcites and water similar to the present groundwater. Older

  17. Fracture calcites at Olkiluoto. Evidence from quaternary infills for palaeohydrogeology

    Gehoer, S.; Kaerki, A.; Taikina-aho, O. [Kivitieto Oy (Finland); Karhu, J. [Helsinki Univ. (Finland); Loefman, J. [VTT Processes, Espoo (Finland); Pitkaenen, P. [VTT Building and Transport, Espoo (Finland); Ruotsalainen, P. [TUKES, Helsinki (Finland)

    2002-02-01

    Recently formed secondary minerals, predominantly calcite, occur in varying amounts as fracture infills, and the calcite types, their chemical compositions and isotope ratios reflect the compositions and physicochemical factors of the groundwater system in which they were formed. Fluid inclusions trapped in calcites give direct evidence of trapping temperatures and past salinities and of the chemical compositions of the palaeo fluids. A wide range of mineralogical and geochemical examinations were carried out within the EQUIP project to examine features of this kind. The fracture calcites at the Olkiluoto site are of various origins and represent several textural types. The exact number of calcite-producing events is unknown, but the duration of the period that was appropriate for the precipitation of low temperature calcite is estimated to have exceeded 1000 Ma. Thus the number of genetically related calcite units is assumed to be considerable. This study was focused on the petrogenesis of calcites crystallized in fractures of high water conductivity during the latest stages of geological evolution. The majority of these late stage calcites form physically homogeneous, scaly layers, and in a few cases thin layers composed of idiomorphic crystals. Chemically these are almost stoichiometric calcites (CaCO{sub 3}). The MnO content may exceed 1%, while the amounts of other elements present are minor, although the trace element concentrations, particularly those of large ionic trace elements, can be used as distinguishing features for the recognition of individual precipitates representing different calcite generations. Evidence from fluid inclusions, or more correctly from the absence of these in the late stage calcites, can be interpreted as an indication of slow rates of crystallization under cool conditions. Many chemical variables, e.g. oxygen isotope ratios, demonstrate an equilibrium between the latest calcites and water similar to the present groundwater. Older

  18. Effect of magnetic starch on the clarification of hematite tailings wastewater

    Yue, Tao; Wu, Xiqing

    2018-02-01

    The magnetic starch solution, synthesized by mixing the caustic starch, the Fe2+ solution (in some cases containing the Zn2+, Cu2+, Mn2+ or Mg2+ ions) and H2O2 solution, was used as the flocculant to investigate its clarification effect on hematite tailings wastewater. Based on the clarification tests and adsorption analysis it was demonstrated that the magnetic starch produced better clarification effect than the caustic starch, and the adsorption of magnetic starch onto hematite tailings particles was also stronger than the caustic starch. AFM found that the magnetic interaction between magnetic seeds and hematite is characteristic of long range force and greatly strengthens the adsorption of magnetic seeds onto fine hematite for agglomeration. FTIR indicates the starch adsorbed onto the surfaces of hematite and magnetic seeds, thus acting as the bridging between hematite particles and magnetic seeds, resulting in an intensified coverage of the starch onto hematite and positive action in the clarification.

  19. Effect of Time on Gypsum-Impression Material Compatibility

    Won, John Boram

    The purpose of this study was to evaluate the compatibility of dental gypsum with three recently introduced irreversible hydrocolloid (alginate) alternatives. The test materials were Alginot® (Kerr™), Position Penta Quick® (3M ESPE™) and Silgimix ® (Sultan Dental™). The irreversible hydrocolloid impression material, Jeltrate Plus antimicrobial® (Dentsply Caulk™) served as the control. Materials and Methods: Testing of materials was conducted in accordance with ANSI/ADA Specification No. 18 for Alginate Impression Materials. Statistical Analysis: The 3-Way ANOVA test was used to analyze measurements between different time points at a significance level of (p Outcome: It was found that there was greater compatibility between gypsum and the alternative materials over time than the traditional irreversible hydrocolloid material that was tested. A statistically significant amount of surface change/incompatibility was found over time with the combination of the dental gypsum products and the control impression material (Jeltrate Plus antimicrobial®).

  20. Green urea synthesis catalyzed by hematite nanowires in magnetic field

    Yahya, Noorhana; Qureshi, Saima; Rehman, Zia ur; Alqasem, Bilal; Fai Kait, Chong

    2017-01-01

    The catalytic activity of hematite (α-Fe 2 O 3 ) nanowires under the influence of magnetic field on urea synthesis is considered green. The adsorption and subsequent dissociative reaction of hydrogen, nitrogen and carbon dioxide gases on the α-Fe 2 O 3 (111) nanowires were investigated using the density functional theory (DFT) method. The average adsorption energy is −4.12 kcal/mole at different sites. The adsorption of gases resulted in a difference in density and net spin of electrons from 68 to 120 and 0–21 respectively. In addition, it induces magnetic moment value of 36.33 µB, which confirms the enhanced magnetic behaviour of hematite. α-Fe 2 O 3 nanowires (NWs) synthesized by heating iron wire in a box furnace at (750−800) °C and as synthesized α-Fe 2 O 3 nanoparticles (NPs) were received to use as a catalyst in the magnetic reaction of urea synthesis. X-ray Diffractometer (XRD) confirms the peaks of rhombohedral structure of α-Fe 2 O 3 and Raman spectrum analyses confirms the α-Fe 2 O 3 peaks at 410 cm −1 , 500 cm −1 and 616 cm −1 . The needle-like shape of hematite nanowires with length ranging from 16–25) μm and diameter from 74 to 145 nm confirmed by Field emission scanning electron microscopy (FESEM). The magnetic properties of the nanowires exhibited different levels of saturation magnetization, for α-Fe 2 O 3 perpendicularly aligned direction (13.18 emu/g) and random direction (10.73 emu/g). Urea synthesis was done under magnetic field ranges from 0.0 to 2.5 T. The activation energy of α-Fe 2 O 3 NWs for urea production is lower than NPs in the range of 0–1 T, whereas it is reversed for higher magnetic induction values. Fourier transform infrared spectroscopy (FTIR) confirmed the formation of urea at the peaks of 1690–1600 cm −1 . This green urea employing magnetically induced method could be a contender to the Haber-Bosch process currently used by the current industry which utilizes high temperature and high pressure

  1. Triple oxygen isotope systematics of structurally bonded water in gypsum

    Herwartz, Daniel; Surma, Jakub; Voigt, Claudia; Assonov, Sergey; Staubwasser, Michael

    2017-07-01

    The triple oxygen isotopic composition of gypsum mother water (gmw) is recorded in structurally bonded water in gypsum (gsbw). Respective fractionation factors have been determined experimentally for 18O/16O and 17O/16O. By taking previous experiments into account we suggest using 18αgsbw-gmw = 1.0037; 17αgsbw-gmw = 1.00195 and θgsbw-gmw = 0.5285 as fractionation factors in triple oxygen isotope space. Recent gypsum was sampled from a series of 10 ponds located in the Salar de Llamara in the Atacama Desert, Chile. Total dissolved solids (TDS) in these ponds show a gradual increase from 23 g/l to 182 g/l that is accompanied by an increase in pond water 18O/16O. Gsbw falls on a parallel curve to the ambient water from the saline ponds. The offset is mainly due to the equilibrium fractionation between gsbw and gmw. However, gsbw represents a time integrated signal biased towards times of strong evaporation, hence the estimated gmw comprises elevated 18O/16O compositions when compared to pond water samples taken on site. Gypsum precipitation is associated with algae mats in the ponds with lower salinity. No evidence for respective vital effects on the triple oxygen isotopic composition of gypsum hydration water is observed, nor are such effects expected. In principle, the array of δ18Ogsbw vs. 17Oexcess can be used to: (1) provide information on the degree of evaporation during gypsum formation; (2) estimate pristine meteoric water compositions; and (3) estimate local relative humidity which is the controlling parameter of the slope of the array for simple hydrological situations. In our case study, local mining activities may have decreased deep groundwater recharge, causing a recent change of the local hydrology.

  2. Chemical properties of an Oxisol after gypsum application

    Victor Roncaratti de Moraes

    2016-10-01

    Full Text Available Gypsum utilization is a critical practice in agriculture because of the high solubility and consequent relative neutralization of subsurface toxic aluminum. However, it has been observed that in most cases, gypsum is being randomly utilized without scientifically established parameters or even the need to use it as a soil amendment at all. The objective of this study was to evaluate the chemical composition and electrical conductivity of an Oxisol’s saturation extract under different gypsum doses (0, 1.0, 2.0, 4.0, and 8.0 Mg ha-1. This experiment was conducted in a greenhouse environment. Soil columns (V = 1.57 dm3 were filled with sifted (2 mm soil collected from the upper layer (0-20 cm. The experimental design adopted was completely randomized with five repetitions. The treatments consisted of a 5 × 2 factorial through five gypsum doses (0.0, 1.0, 2.0, 4.0, and 8.0 Mg ha-1 of gypsum consisting of 224.1 g kg-1 S, 314.8 g kg-1 CaO, and 7 g kg-1 P2O5 and two depth evaluations (0-10 and 10-20 cm. After the treatments, soil from both 0-10 cm and 10-20 cm layers was removed from the columns, sifted once (2 mm, and subjected to vacuum extraction to assess the saturation extract. The data acquired was processed and submitted to variance analysis (when due and adjusted to regression equations when statistically relevant. Significant increases were observed for Ca, Mg, K, P, and S, although Al, Si, and pH presented no statistically significant difference. The electrical conductivity value of this soil in particular is directly related to the gypsum dose.

  3. Origin of calcite in the glacigenic Virttaankangas complex

    Nina M. Kortelainen

    2007-01-01

    Full Text Available Groundwaters of the glacigenic Virttaankangas complex in southern Finland are characterized by high pH values ranging up to 9.5. These values are significantly higher than those observed in silicate-rich shallow groundwater formations in crystalline bedrock areas. TheVirttaankangas sediments were discovered to contain small amounts of fine grained, dispersed calcite, which has a high tendency to increase the pH of local groundwaters. The primary goal of this study was to determine the mode of occurrence of calcite and to identifyits sources. The mineralogy of the glacigenic Virttaankangas complex was studied using material from 21 sediment drill cores. Fine-grained calcite is present in trace amounts (<< 1.4 % in the glaciofluvial and glaciolacustrine depositional units of the Virttaankangas complex. The topmost littoral sands were practically devoid of calcite. The isotope records of carbon and oxygen, the angular morphology of the grains and the uniform dispersion of calcite in the complex suggest a clastic origin for calcite, with no evidence for in-situ precipitation. In order to constrain the source of calcite, the isotopic composition of carbon and oxygen in five calcite samples was compared to the isotopic data from five carbonate rock erratics and eight crystalline bedrock samples from the region. Based on carbon and oxygen isotope ratios and chemical compositions, the dispersed calcite grains of the Virttaankangas complex appear to have been derived from the Mesoproterozoic Satakunta Formation, some 30 km NW from the Virttaankangas area. In sandstone, calcite is predominantly present as diagenetic cement in grain interspaces, concretions and interlayers. The source of detrital calcite was unexpected, as prior to this study the Satakunta sandstone hasnot been known to contain calcite.

  4. Examination of TL and optical absorption in calcite's mineral

    Sabikoglu, I.; Can, N.

    2009-01-01

    Calcite which is a form of crystalline of the calcium carbonate composes parent material of chalk stone (limestone) and marble. Calcite which presents in various colors also in our country consists of yellow, blue, transparent and green colors. In this study, green calcite mineral which is taken from the region of Ayvalik, was examined of its thermoluminescence (TL) and optical absorption features in different doses. It has been obtained a large TL peak in 179 degree C and absorption peak in 550 mm.

  5. An investigation of the heterogeneous nucleation of calcite

    House, W.A.; Tutton, J.A.

    1982-01-01

    The heterogeneous precipitation kinetics of calcite from dilute calcium bicarbonate solutions onto pyrex glass seeds is investigated by using a modified form of the Davies and Jones equation. The rate constant is evaluated from experiments using calcite seeds and it is demonstrated that the growth rate does not increase in proportion to the increase in surface area accompanying precipitation. The number of heteronucleated particles is estimated by assuming a constant density of growth sites on the different calcite surfaces. A comparison is made between the specific surface areas of calcite obtained by the calcium-45 isotopic exchange method and other values. (orig.)

  6. Atom-resolved AFM imaging of calcite nanoparticles in water

    Imada, Hirotake; Kimura, Kenjiro [Department of Chemistry, School of Science, Kobe University, Rokko-dai, Nada, Kobe 657-8501 (Japan); Onishi, Hiroshi, E-mail: oni@kobe-u.ac.jp [Department of Chemistry, School of Science, Kobe University, Rokko-dai, Nada, Kobe 657-8501 (Japan)

    2013-06-20

    Highlights: ► An advanced frequency-modulation AFM (FM-AFM) was applied for imaging particles. ► Atom-resolved topography of nano-sized particles of calcite was observed in water. ► Locally ordered structures were found and assigned to a (104) facet of calcite. ► A promising ability of FM-AFM was demonstrated in imaging nano-sized particles. - Abstract: The atom-resolved topography of calcite nanoparticles was observed in water using a frequency-modulation atomic force microscope. Locally ordered structures were found and assigned to a (104) facet of crystalline calcite.

  7. Atom-resolved AFM imaging of calcite nanoparticles in water

    Imada, Hirotake; Kimura, Kenjiro; Onishi, Hiroshi

    2013-01-01

    Highlights: ► An advanced frequency-modulation AFM (FM-AFM) was applied for imaging particles. ► Atom-resolved topography of nano-sized particles of calcite was observed in water. ► Locally ordered structures were found and assigned to a (104) facet of calcite. ► A promising ability of FM-AFM was demonstrated in imaging nano-sized particles. - Abstract: The atom-resolved topography of calcite nanoparticles was observed in water using a frequency-modulation atomic force microscope. Locally ordered structures were found and assigned to a (104) facet of crystalline calcite

  8. Characterization of quality recycled gypsum and plasterboard with maximized recycled content

    Jiménez-Rivero, J.; García-Navarro, J.

    2017-01-01

    The quality of secondary materials is imperative to promote a circular economy. In order to improve the way in which the quality of recycled gypsum is assessed, European guidelines on recycled gypsum (RG) quality criteria have been outlined in the framework of the Life+ Gypsum to Gypsum (GtoG) project. Such GtoG guidelines, along with the European Standard on gypsum plasterboard EN 520, provided the basis for this study. During the GtoG project, gypsum recycling and plasterboard manufacturing processes were monitored by testing the gypsum feedstock and the plasterboard produced. The aim of this paper is to discuss the results obtained on relevant parameters that characterize gypsum as a secondary raw material, as well as the resulting product. The minimum requirements were fulfilled by 56% of the RG samples and 86% of the plasterboard with increased RG. [es

  9. The nature of hematite depression with corn starch in the reverse flotation of iron ore.

    Shrimali, Kaustubh; Atluri, Venkata; Wang, Yan; Bacchuwar, Sanket; Wang, Xuming; Miller, Jan D

    2018-08-15

    The function of corn starch and the significance of the order of addition of corn starch and mono ether amine in the reverse flotation of iron ore has been investigated. Understanding hematite depression with starch and the corresponding hydrophilic state involves consideration of adsorption with amine as well as flocculation of fine hematite. Captive bubble contact angle and micro-flotation experiments indicated that amine has an affinity towards both hematite and quartz, and that the role of starch is to hinder the adsorption of amine at the hematite surface so that flotation is inhibited. Micro-flotation results confirmed that quartz does not have affinity towards starch at pH 10.5. In addition to competitive adsorption, flocculation of fine hematite occurs and images from high resolution X-ray computed tomography (HRXCT) and cryo-SEM reveal further detail regarding floc structure. These results provide substantial evidence that the fine hematite particles are flocculated in the presence of corn starch, and flocculation is dependent on the particle size of hematite, with greater flocculation for finer particles. Thus, starch is playing a dual role in the reverse flotation of iron ore, acting as a depressant by hindering amine adsorption at the hematite surface in order to maintain the hydrophilic surface state of hematite, and acting as a flocculant to aggregate fine hematite particles, which if not flocculated, could diminish the flotation separation efficiency by being transported to the froth phase during reverse flotation. Copyright © 2018 Elsevier Inc. All rights reserved.

  10. Development of gypsum alteration on marble and limestone

    McGee, E.S.

    1996-01-01

    Blackened alteration crusts of gypsum plus particulates that form on sheltered areas on marble and limestone buildings pose a challenge for rehabilitation and cleaning. Fresh marble and limestone samples exposed at monitored exposure sites present conditions of simple geometry and well-documented exposures but have short exposure histories (one to five years). The gypsum alteration crusts that develop on these samples provide insight into the early stages and rate of alteration crust formation. Alteration crusts from buildings give a longer, but less well known exposure history and present much more complex surfaces for gypsum accumulation. Integrated observations and measurements of alteration crusts from exposure samples and from buildings identify four factors that are important in the formation and development of alteration crusts on marble and limestone: (1) pollution levels, (2) exposure to rain or washing, (3) geometry of exposure of the stone surface, and (4) permeability of the stone. The combination of these factors contributes to both the distribution and the physical characteristics of the gypsum crusts which may affect cleaning decisions.

  11. Composite Gypsum Binders with Silica-containing Additives

    Chernysheva, N. V.; Lesovik, V. S.; Drebezgova, M. Yu; Shatalova, S. V.; Alaskhanov, A. H.

    2018-03-01

    New types of fine mineral additives are proposed for designing water-resistant Composite Gypsum Binders (CGB); these additives significantly differ from traditional quartz feed: wastes from wet magnetic separation of Banded Iron Formation (BIF WMS waste), nanodispersed silica powder (NSP), chalk. Possibility of their combined use has been studied as well.

  12. Preparation of gypsum/polymer composites using radiation

    Aji, Z.

    2007-05-01

    Gypsum composites have been prepared with different monomers using Gamma radiation: acrylamide, butyl acrylate, butyl methacrylate, methyl methacrylate, and methyl acrylate. The conversion of polymerization was determined as a function of absorbed dose. The data show that conversion of polymerization increases by increasing the dose.(author)

  13. Influence of gypsum on efflorescence in ceramic tiles

    Monteiro, C.M.O.L.; Nascimento, R.M.; Martinelli, A.E.

    2009-01-01

    The red ceramic industry is recognized as of major importance in Piaui State. The State capital, Teresina, is the greatest producer of this material, which is used mainly for masonry sealing blocks. One of the most frequent problems in this kind of products is the efflorescence.This paper has the main objective of studying the influence of gypsum on tiles, using the local industry production standards. The raw materials were characterized by FRX, DRX, thermal analysis and sulfates. Extruded test specimens were made with the addition of 1%, 3% and 5% of gypsum in the ceramic paste, burned at 850 deg C, 950 deg C and 1050 deg C and submitted to further technological and analysis for MEV. The reference ceramic paste did not show tendency to efflorescence formation after burning for samples with 1% gypsum added to the paste. The reference ceramic paste showed tendency to efflorescence formation after drying and consolidated efflorescence after burning for samples with 5% gypsum added to the paste. (author)

  14. Evaluation of gypsum rates on greenhouse crop production

    This study was to determine the potential of an added value distribution channel for gypsum waste by evaluating various greenhouse crops with captious pH and calcium needs. Three studies consisting of: Zonal geranium (Pelargonium x hortorum) and petunia (Petunia x hybrida); tomato (Solanum lycoper...

  15. Gypsum Formation during the Messinian Salinity Crisis: an Alternative Model

    Grothe, A.; Krijgsman, W.; Sangiorgi, F.; Vasiliev, I.; Baak, C. V.; Wolthers, M.; Stoica, M.; Reichart, G. J.; Davies, G.

    2016-12-01

    During the Messinian Salinity Crisis (MSC; 5.97 - 5.33 Myr ago), thick packages of evaporites (gypsum and halite) were deposited in the Mediterranean Basin. Traditionally, the occurrence of these evaporites is explained by the so-called "desiccation-model", in which evaporites are considered to result from a (partly) desiccated basin. In the last decade, it was thought that changes in the Mediterranean-Atlantic connectivity could explain the formation of gypsum. Stable isotope studies, however, show that the gypsum formed under influence of large freshwater input. Here we present new strontium isotope data from two well-dated Messinian sections in the Black and Caspian Seas. Our Sr isotope records suggest a persistent Mediterranean-Black Sea connection throughout the salinity crisis, which implies a large additional freshwater source to the Mediterranean. We claim that low saline waters from the Black Sea region are a prerequisite for gypsum formation in the Mediterranean and speculate about the mechanisms explaining this apparent paradox.

  16. Sorption and desorption of arsenate and arsenite on calcite

    Sø, Helle Ugilt; Postma, Diederik Jan; Jakobsen, Rasmus

    2008-01-01

    The adsorption and desorption of arsenate (As(V)) and arsenite (As(111)) oil calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic...

  17. Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

    Antia, A. N.; Suffrian, K.; Holste, L.; Müller, M. N.; Nejstgaard, J. C.; Simonelli, P.; Carotenuto, Y.; Putzeys, S.

    2008-01-01

    Independent of the ongoing acidification of surface seawater, the majority of the calcium carbonate produced in the pelagial is dissolved by natural processes above the lysocline. We investigate to what extent grazing and passage of coccolithophorids through the guts of copepods and the food vacuoles of microzooplankton contribute to calcite dissolution. In laboratory experiments where the coccolithophorid Emiliania huxleyi was fed to the rotifer Brachionus plicatilis, the heterotrophic flagellate Oxyrrhis marina and the copepod Acartia tonsa, calcite dissolution rates of 45-55%, 37-53% and 5-22% of ingested calcite were found. We ascribe higher loss rates in microzooplankton food vacuoles as compared to copepod guts to the strongly acidic digestion and the individual packaging of algal cells. In further experiments, specific rates of calcification and calcite dissolution were also measured in natural populations during the PeECE III mesocosm study under differing ambient pCO2 concentrations. Microzooplankton grazing accounted for between 27 and 70% of the dynamic calcite stock being lost per day, with no measurable effect of CO2 treatment. These measured calcite dissolution rates indicate that dissolution of calcite in the guts of microzooplankton and copepods can account for the calcite losses calculated for the global ocean using budget and model estimates.

  18. Emission polarization study on quartz and calcite.

    Vincent, R. K.

    1972-01-01

    Calculation of the spectral emission polarization of quartz and calcite polished plates for observation angles of 20 and 70 deg by the substitution of complex index of refraction values for each mineral into Fresnel's equations. The emission polarization is shown to be quite wavelength-dependent, demonstrating that selected narrow or medium-width spectral bands exhibit a significantly higher percentage of polarization than a broad spectral band for these two minerals. Field measurements with a broadband infrared radiometer yield polarizations on the order of 2% for a coarse-grained granite rock and beach sand (both quartz-rich). This implies that a more sensitive detector with a selected medium-width filter may be capable of measuring emission polarization accurately enough to make this parameter useful as a remote sensing tool for discrimination among rocks on the basis of texture.

  19. The role of silicate surfaces on calcite precipitation kinetics

    Stockmann, Gabrielle J.; Wolff-Boenisch, Domenik; Bovet, Nicolas Emile

    2014-01-01

    The aim of this study is to illuminate how calcite precipitation depends on the identity and structure of the growth substrate. Calcite was precipitated at 25°C from supersaturated aqueous solutions in the presence of seeds of either calcite or one of six silicate materials: augite, enstatite......, labradorite, olivine, basaltic glass and peridotite rock. Calcite saturation was achieved by mixing a CaCl2-rich aqueous solution with a NaHCO3-Na2CO3 aqueous buffer in mixed-flow reactors containing 0.5-2g of mineral, rock, or glass seeds. This led to an inlet fluid calcite saturation index of 0.6 and a p...

  20. The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

    Soler, Josep M. [Institute of Earth Sciences ' Jaume Almera' (CSIC), Lluis Sole i Sabaris s/n, 08028 Barcelona, Catalonia (Spain); Institute of Environmental Assessment and Water Research (CSIC), Jordi Girona 18, 08034 Barcelona, Catalonia (Spain)], E-mail: jsoler@ija.csic.es; Boi, Marco [Institute of Earth Sciences ' Jaume Almera' (CSIC), Lluis Sole i Sabaris s/n, 08028 Barcelona, Catalonia (Spain); Institute of Environmental Assessment and Water Research (CSIC), Jordi Girona 18, 08034 Barcelona, Catalonia (Spain); Mogollon, Jose Luis [Institute of Earth Sciences ' Jaume Almera' (CSIC), Lluis Sole i Sabaris s/n, 08028 Barcelona, Catalonia (Spain); Instituto de Ciencias de la Tierra, Universidad Central de Venezuela, Caracas 1020-A (Venezuela, Bolivarian Republic of); Cama, Jordi; Ayora, Carlos [Institute of Earth Sciences ' Jaume Almera' (CSIC), Lluis Sole i Sabaris s/n, 08028 Barcelona, Catalonia (Spain); Institute of Environmental Assessment and Water Research (CSIC), Jordi Girona 18, 08034 Barcelona, Catalonia (Spain); Nico, Peter S.; Tamura, Nobumichi; Kunz, Martin [Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720 (United States)

    2008-12-15

    Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H{sub 2}SO{sub 4}, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L{sup -1}, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe-oxyhydroxysulfates (Fe(III)-SO{sub 4}-H{sup +} solutions) or Fe-oxyhydroxychlorides (Fe(III)-Cl-H{sup +} solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to {approx}6-7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)-SO{sub 4}-H{sup +} solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)-Cl-H{sup +} solutions.

  1. Physicochemical Properties and Cellular Responses of Strontium-Doped Gypsum Biomaterials

    Pouria, Amir; Bandegani, Hadis; Pourbaghi-Masouleh, Milad; Hesaraki, Saeed; Alizadeh, Masoud

    2012-01-01

    This paper describes some physical, structural, and biological properties of gypsum bioceramics doped with various amounts of strontium ions (0.19–2.23 wt%) and compares these properties with those of a pure gypsum as control. Strontium-doped gypsum (gypsum:Sr) was obtained by mixing calcium sulfate hemihydrate powder and solutions of strontium nitrate followed by washing the specimens with distilled water to remove residual salts. Gypsum was the only phase found in the composition of both pu...

  2. Calcite surface structure and reactivity: molecular dynamics simulations and macroscopic surface modelling of the calcite-water interface

    Wolthers, M.; Di Tommaso, D.; Du, Z.; de Leeuw, N.H.

    2012-01-01

    Calcite–water interactions are important not only in carbon sequestration and the global carbon cycle, but also in contaminant behaviour in calcite-bearing host rock and in many industrial applications. Here we quantify the effect of variations in surface structure on calcite surface reactivity.

  3. Removal of phosphorus, fluoride and metals from a gypsum mining leachate using steel slag filters.

    Claveau-Mallet, Dominique; Wallace, Scott; Comeau, Yves

    2013-03-15

    The objective of this work was to evaluate the capacity of steel slag filters to treat a gypsum mining leachate containing 11-107 mg P/L ortho-phosphates, 9-37 mg/L fluoride, 0.24-0.83 mg/L manganese, 0.20-3.3 zinc and 1.7-8.2 mg/L aluminum. Column tests fed with reconstituted leachates were conducted for 145-222 days and sampled twice a week. Two types of electric arc furnace (EAF) slags and three filter sequences were tested. The voids hydraulic retention time (HRT(v)) of columns ranged between 4.3 and 19.2 h. Precipitates of contaminants present in columns were sampled and analyzed with X-ray diffraction at the end of tests. The best removal efficiencies over a period of 179 days were obtained with sequential filters that were composed of Fort Smith EAF slag operated at a total HRT(v) of 34 h which removed 99.9% of phosphorus, 85.3% of fluoride, 98.0% of manganese and 99.3% of zinc. Mean concentration at this system's effluent was 0.04 mg P/L ortho-phosphates, 4 mg/L fluoride, 0.02 mg/L manganese, 0.02 zinc and 0.5 mg/L aluminum. Thus, slag filters are promising passive and economical systems for the remediation of mining effluents. Phosphorus was removed by the formation of apatite (hydroxyapatite, Ca(5)(PO(4))(3)OH or fluoroapatite, Ca(5)(PO(4))(3)F) as confirmed by visual and X-ray diffraction analyses. The growth rate of apatite was favored by a high phosphorus concentration. Calcite crystals were present in columns and appeared to be competing for calcium and volume needed for apatite formation. The calcite crystal growth rate was higher than that of apatite crystals. Fluoride was removed by precipitation of fluoroapatite and its removal was favored by a high ratio of phosphorus to fluoride in the wastewater. Copyright © 2012 Elsevier Ltd. All rights reserved.

  4. The Gypsum: White gold of Rajasthan, introduction, uses and future prospective

    Sharma, Gayatri

    2013-06-01

    Rajasthan is mineral based state and Bikaner and its surrounding district have been gifted with Gypsum. Mt of Gypsum is available in these districts. Gypsum has multiple uses including basic raw material for POP industry, addition in cement and a natural fertilizer. This mineral has changes the economic scenario in the remote areas of Bikaner, Nagaur, Hanumangarh, Sanchore, Shriganganagar etc. Gypsum and selenite are mined about 3.0 million tons per year. There is huge demand from cement industry as Gypsum is added for improving setting time of cement. Gypsum is a natural fertilizer for alkaline land and it role is vital in state like India where alkaline land is major role. Its high use as fertilizer has potential to change millions of poor farmer families and improving in crop production. Cement Industry has started importing Gypsum from Thailand, Bankong, Pakistan, Iran etc. The mining of gypsum of purity of 70% CaSO4.2H2O is cooperative effort between the land owners and Rajasthan State Mines and Minerals Limited. Gypsum fulfills the demand of POP and Cement industry in Rajasthan and powder gypsum used in agriculture for recon dining of alkaline soil. This paper deals with multiple uses, availability, and future prospective of Gypsum, a white gold of Rajasthan.

  5. Fine hematite particles of Martian interest: absorption spectra and optical constants

    Marra, A C; Blanco, A; Fonti, S; Jurewicz, A; Orofino, V

    2005-01-01

    Hematite is an iron oxide very important for the study of climatic evolution of Mars. It can occur in two forms: red and grey, mainly depending on the granulometry of the samples. Spectra of bright regions of Mars suggest the presence of red hematite particles. Moreover the Thermal Emission Spectrometer (TES), on board the Mars Global Surveyor mission, has discovered a deposit of crystalline grey hematite in Sinus Meridiani. TES spectra of that Martian region exhibit features at about 18, 23 and 33 μm that are consistent with hematite. Coarse grey hematite is considered strong evidence for longstanding water, while it is unknown whether the formation of fine-grained red hematite requires abundant water. Studies are needed in order to further characterize the spectral properties of the two kinds of hematite. For this reason we have analyzed a sample of submicron hematite particles in the 6.25-50 μm range in order to study the influence of particles size and shape on the infrared spectra. The optical constants of a particulate sample have been derived and compared with published data concerning bulk samples of hematite. Our results seem to indicate that particle shape is an important factor to take into account for optical constants derivation

  6. Chemical and Mineralogical Characterization of a Hematite-bearing Ridge on Mauna Kea, Hawaii: A Potential Mineralogical Process Analog for the Mount Sharp Hematite Ridge

    Graff, T. G.; Morris, R. V.; Ming, D. W.; Hamilton, J. C.; Adams, M.; Fraeman, A. A.; Arvidson, R. E.; Catalano, J. G.; Mertzman, S. A.

    2014-01-01

    The Mars Science Laboratory (MSL) rover Curiosity landed in Gale Crater in August 2012 and is currently roving towards the layered central mound known as Mount Sharp [1]. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) hyperspectral data indicate Mount Sharp contains an 5 km stratigraphic sequence including Fe-Mg smectites, hematite, and hydrated sulfates in the lower layers separated by an unconformity from the overlying anhydrous strata [1,2,3]. Hematite was initially detected in CRISM data to occur in the lower sulfate layers on the north side of the mound [2]. [3] further mapped a distinct hematite detection occurring as part of a 200 m wide ridge that extends 6.5 km NE-SW, approximately parallel with the base of Mount Sharp. It is likely a target for in-situ analyses by Curiosity. We document here the occurrence of a stratum of hematite-bearing breccia that is exposed on the Puu Poliahu cinder cone near the summit of Mauna Kea volcano (Hawaii) (Fig.1). The stratum is more resistant to weathering than surrounding material, giving it the appearance of a ridge. The Mauna Kea hematite ridge is thus arguably a potential terrestrial mineralogical and process analog for the Gale Crater hematite ridge. We are acquiring a variety of chemical and mineralogical data on the Mauna Kea samples, with a focus on the chemical and mineralogical information already available or planned for the Gale hematite ridge.

  7. Gypsum and hydrohalite dynamics in sea ice brines

    Butler, Benjamin M.; Papadimitriou, Stathys; Day, Sarah J.; Kennedy, Hilary

    2017-09-01

    Mineral authigenesis from their dissolved sea salt matrix is an emergent feature of sea ice brines, fuelled by dramatic equilibrium solubility changes in the large sub-zero temperature range of this cryospheric system on the surface of high latitude oceans. The multi-electrolyte composition of seawater results in the potential for several minerals to precipitate in sea ice, each affecting the in-situ geochemical properties of the sea ice brine system, the habitat of sympagic biota. The solubility of two of these minerals, gypsum (CaSO4 ·2H2O) and hydrohalite (NaCl · 2H2O), was investigated in high ionic strength multi-electrolyte solutions at below-zero temperatures to examine their dissolution-precipitation dynamics in the sea ice brine system. The gypsum dynamics in sea ice were found to be highly dependent on the solubilities of mirabilite and hydrohalite between 0.2 and - 25.0 ° C. The hydrohalite solubility between - 14.3 and - 25.0 ° C exhibits a sharp change between undersaturated and supersaturated conditions, and, thus, distinct temperature fields of precipitation and dissolution in sea ice, with saturation occurring at - 22.9 ° C. The sharp changes in hydrohalite solubility at temperatures ⩽-22.9 °C result from the formation of an ice-hydrohalite aggregate, which alters the structural properties of brine inclusions in cold sea ice. Favourable conditions for gypsum precipitation in sea ice were determined to occur in the region of hydrohalite precipitation below - 22.9 ° C and in conditions of metastable mirabilite supersaturation above - 22.9 ° C (investigated at - 7.1 and - 8.2 ° C here) but gypsum is unlikely to persist once mirabilite forms at these warmer (>-22.9 °C) temperatures. The dynamics of hydrohalite in sea ice brines based on its experimental solubility were consistent with that derived from thermodynamic modelling (FREZCHEM code) but the gypsum dynamics derived from the code were inconsistent with that indicated by its

  8. Green urea synthesis catalyzed by hematite nanowires in magnetic field

    Yahya, Noorhana, E-mail: noorhana_yahya@petronas.com.my; Qureshi, Saima; Rehman, Zia ur; Alqasem, Bilal; Fai Kait, Chong

    2017-04-15

    The catalytic activity of hematite (α-Fe{sub 2}O{sub 3}) nanowires under the influence of magnetic field on urea synthesis is considered green. The adsorption and subsequent dissociative reaction of hydrogen, nitrogen and carbon dioxide gases on the α-Fe{sub 2}O{sub 3} (111) nanowires were investigated using the density functional theory (DFT) method. The average adsorption energy is −4.12 kcal/mole at different sites. The adsorption of gases resulted in a difference in density and net spin of electrons from 68 to 120 and 0–21 respectively. In addition, it induces magnetic moment value of 36.33 µB, which confirms the enhanced magnetic behaviour of hematite. α-Fe{sub 2}O{sub 3} nanowires (NWs) synthesized by heating iron wire in a box furnace at (750−800) °C and as synthesized α-Fe{sub 2}O{sub 3} nanoparticles (NPs) were received to use as a catalyst in the magnetic reaction of urea synthesis. X-ray Diffractometer (XRD) confirms the peaks of rhombohedral structure of α-Fe{sub 2}O{sub 3} and Raman spectrum analyses confirms the α-Fe{sub 2}O{sub 3} peaks at 410 cm{sup −1}, 500 cm{sup −1} and 616 cm{sup −1}. The needle-like shape of hematite nanowires with length ranging from 16–25) μm and diameter from 74 to 145 nm confirmed by Field emission scanning electron microscopy (FESEM). The magnetic properties of the nanowires exhibited different levels of saturation magnetization, for α-Fe{sub 2}O{sub 3} perpendicularly aligned direction (13.18 emu/g) and random direction (10.73 emu/g). Urea synthesis was done under magnetic field ranges from 0.0 to 2.5 T. The activation energy of α-Fe{sub 2}O{sub 3} NWs for urea production is lower than NPs in the range of 0–1 T, whereas it is reversed for higher magnetic induction values. Fourier transform infrared spectroscopy (FTIR) confirmed the formation of urea at the peaks of 1690–1600 cm{sup −1}. This green urea employing magnetically induced method could be a contender to the Haber-Bosch process

  9. Reductive Dissolution of Goethite and Hematite by Reduced Flavins

    Shi, Zhi; Zachara, John M.; Wang, Zheming; Shi, Liang; Fredrickson, Jim K.

    2013-10-02

    The abiotic reductive dissolution of goethite and hematite by the reduced forms of flavin mononucleotide (FMNH2) and riboflavin (RBFH2), electron transfer mediators (ETM) secreted by the dissimilatory iron-reducing bacterium Shewanella, was investigated under stringent anaerobic conditions. In contrast to the rapid redox reaction rate observed for ferrihydrite and lepidocrocite (Shi et al., 2012), the reductive dissolution of crystalline goethite and hematite was slower, with the extent of reaction limited by the thermodynamic driving force at circumneutral pH. Both the initial reaction rate and reaction extent increased with decreasing pH. On a unit surface area basis, goethite was less reactive than hematite between pH 4.0 and 7.0. AH2DS, the reduced form of the well-studied synthetic ETM anthraquinone-2,6-disulfonate (AQDS), yielded higher rates than FMNH2 under most reaction conditions, despite the fact that FMNH2 was a more effective reductant than AH2DS for ferryhydrite and lepidocrocite. Two additional model compounds, methyl viologen and benzyl viologen, were investigated under similar reaction conditions to explore the relationship between reaction rate and thermodynamic properties. Relevant kinetic data from the literature were also included in the analysis to span a broad range of half-cell potentials. Other conditions being equal, the surface area normalized initial reaction rate (ra) increased as the redox potential of the reductant became more negative. A non-linear, parabolic relationship was observed between log ra and the redox potential for eight reducants at pH 7.0, as predicted by Marcus theory for electron transfer. When pH and reductant concentration were fixed, log ra was positively correlated to the redox potential of four Fe(III) oxides over a wide pH range, following a non-linear parabolic relationship as well.

  10. Uranyl incorporation into calcite and aragonite: XAFS and luminescence studies

    Reeder, R.J.; Nugent, M.; Lamble, G.M.; Tait, C.D.; Morris, D.E.

    2000-01-01

    X-ray absorption, luminescence, and Raman spectroscopic studies of U(VI)-containing calcite and aragonite show that the UO 2 2+ ion, the dominant and mobile form of dissolved uranium in near-surface waters, has a disordered and apparently less stable coordination environment when incorporated into calcite in comparison to aragonite, both common polymorphs of CaCO 3 . Their findings suggest that calcite, a widely distributed authigenic mineral in soils and near-surface sediments and a principal weathering product of concrete-based containment structures, is not likely to be a suitable host for the long-term sequestration of U(VI). The more stable coordination provided by aragonite suggests that its long-term retention should be favored in this phase, until it inverts to calcite. Consequently, future remobilization of U(VI) coprecipitated with calcium carbonate minerals should not be ruled out in assessments of contaminated sites. Their observation of a similar equatorial coordination of UO 2 2+ in aragonite and the dominant aqueous species [UO 2 (CO 3 ) 3 4- ] but a different coordination in calcite indicates that a change in UO 2 2+ coordination is required for its incorporation into calcite. This may explain the observed preferential uptake of U(VI) by aragonite relative to calcite

  11. An inelastic neutron scattering study of hematite nanoparticles

    Hansen, Mikkel Fougt; Klausen, Stine Nyborg; Lefmann, K

    2003-01-01

    We have studied the magnetic dynamics in nanocrystalline hematite by inelastic neutron scattering at the high-resolution time-of-flight spectrometer IRIS at ISIS. Compared to previous inelastic neutron scattering experiments an improvement of the resolution function is achieved and more detailed...... moment at the antiferromagnetic Bragg reflection. We have studied different weightings of the particle size distribution. The data and their temperature dependence can with good agreement be interpreted on the basis of the Neel-Brown theory for superparamagnetic relaxation and a model for the collective...

  12. Magnetic anisotropy and quantized spin waves in hematite nanoparticles

    Klausen, Stine Nyborg; Lefmann, Kim; Lindgård, Per-Anker

    2004-01-01

    We report on the observation of high-frequency collective magnetic excitations, (h) over bar omegaapproximate to1.1 meV, in hematite (alpha-Fe2O3) nanoparticles. The neutron scattering experiments include measurements at temperatures in the range 6-300 K and applied fields up to 7.5 T as well...... as polarization analysis. We give an explanation for the field- and temperature dependence of the excitations, which are found to have strongly elliptical out-of-plane precession. The frequency of the excitations gives information on the magnetic anisotropy constants in the system. We have in this way determined...

  13. Strontium Incorporation into Calcite Generated by Bacterial Ureolysis

    Yoshiko Fujita; George D. Redden; Jani C. Ingram; Marnie M. Cortez; Robert W. Smith

    2004-01-01

    Strontium incorporation into calcite generated by bacterial ureolysis was investigated as part of an assessment of a proposed remediation approach for 90Sr contamination in groundwater. Urea hydrolysis produces ammonium and carbonate and elevates pH, resulting in the promotion of calcium carbonate precipitation. Urea hydrolysis by the bacterium Bacillus pasteurii in a medium designed to mimic the chemistry of the Snake River Plain Aquifer in Idaho resulted in a pH rise from 7.5 to 9.1. Measured average distribution coefficients (DEX) for Sr in the calcite produced by ureolysis (0.5) were up to an order of magnitude higher than values reported in the literature for natural and synthetic calcites (0.02-0.4). They were also higher than values for calcite produced abiotically by ammonium carbonate addition (0.3). The precipitation of calcite in these experiments was verified by X-ray diffraction. Time-of-flight secondary ion mass spectrometry (ToF SIMS) depth profiling (up to 350 nm) suggested that the Sr was not merely sorbed on the surface, but was present at depth within the particles. X-ray absorption near edge spectra showed that Sr was present in the calcite samples as a solid solution. The extent of Sr incorporation appeared to be driven primarily by the overall rate of calcite precipitation, where faster precipitation was associated with greater Sr uptake into the solid. The presence of bacterial surfaces as potential nucleation sites in the ammonium carbonate precipitation treatment did not enhance overall precipitation or the Sr distribution coefficient. Because bacterial ureolysis can generate high rates of calcite precipitation, the application of this approach is promising for remediation of 90Sr contamination in environments where calcite is stable over the long term

  14. Basic Properties of Flue-Gas Desulfurization Gypsum

    Kovacs Ferenc

    2003-03-01

    Full Text Available Several hundred thousand of FGD gypsum is produced annually at the Matra Power Plant (Hungary as a byproduct of generating electricity and protecting the environment. Chemical and mechanical characteristics of this material were studied of the Department of Mining and Geotechnical Engineering, University of Miskolc (Hungary. The material in question was found dead gypsum which can be calcined easily to obtain a relatively high-strength (15-25 MPa and clean binding material. Furthermore, grain composites were made of it by adding fly ash, which the power plant can provide the expected producers with, thus decreasing the energy consumption of calcining and utilizing a small part of coal combustion wastes.

  15. Intermediate Temperature Fuel Cell Using Gypsum Based Electrolyte And Electrodes

    Suzuki, Satoshi; Nagai, Masayuki; Katagiri, Yuji

    2011-01-01

    The proton conductive electrolyte membrane and the electrodes for intermediate temperature fuel cell were made from the phosphoric acid treated gypsum as a proton conductor. The membrane and the electrodes were built into single cell and tested at intermediate temperature region. The power density of the fuel cell was 0.56 mW/cm -2 at 150 deg. C without any humidification and 1.38 mW/cm -2 at 150 deg. C, 5% relative humidity. The open circuit voltage of the cell was increased higher than 0.7 V when the electrodes were annealed at 150 deg. C, 5%R.H., however the reasons for this are still to be further investigated. The results show that the potential of the phosphoric acid treated gypsum for the intermediate temperature proton conductor.

  16. Biological sulfate removal from gypsum contaminated construction and demolition debris.

    Kijjanapanich, Pimluck; Annachhatre, Ajit P; Esposito, Giovanni; van Hullebusch, Eric D; Lens, Piet N L

    2013-12-15

    Construction and demolition debris (CDD) contains high levels of sulfate that can cause detrimental environmental impacts when disposed without adequate treatment. In landfills, sulfate can be converted to hydrogen sulfide under anaerobic conditions. CDD can thus cause health impacts or odor problems to landfill employees and surrounding residents. Reduction of the sulfate content of CDD is an option to overcome these problems. This study aimed at developing a biological sulfate removal system to reduce the sulfate content of gypsum contaminated CDD in order to decrease the amount of solid waste, to improve the quality of CDD waste for recycling purposes and to recover sulfur from CDD. The treatment leached out the gypsum contained in CDD by water in a leaching column. The sulfate loaded leachate was then treated in a biological sulfate reducing Upflow Anaerobic Sludge Blanket (UASB) reactor to convert the sulfate to sulfide. The UASB reactor was operated at 23 ± 3 °C with a hydraulic retention time and upflow velocity of 15.5 h and 0.1 m h(-1), respectively while ethanol was added as electron donor at a final organic loading rate of 3.46 g COD L(-1) reactor d(-1). The CDD leachate had a pH of 8-9 and sulfate dissolution rates of 526.4 and 609.8 mg L(-1) d(-1) were achieved in CDD gypsum and CDD sand, respectively. Besides, it was observed that the gypsum dissolution was the rate limiting step for the biological treatment of CDD. The sulfate removal efficiency of the system stabilized at around 85%, enabling the reuse of the UASB effluent for the leaching step, proving the versatility of the bioreactor for practical applications. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Lime and gypsum application on the wheat crop

    Caires Eduardo Fávero

    2002-01-01

    Full Text Available Root growth and crop yield can be affected by chemical modifications of the soil profile owing to lime and gypsum applications. A field trial was carried out on a dystrophic Clayey Rhodic Hapludox at Ponta Grossa, PR, Brazil, aiming to evaluate lime (without or with incorporation into the soil and gypsum effects on root growth, mineral nutrition and grain yield of wheat (cv. OR 1. A randomized complete block design was used, with three replications, in a split-plot experiment. Treatments with dolomitic limestone (without lime and 4.5 t ha-1 of lime applied on the surface, in total rate and 1/3 of the requirement per year during 3 years, or incorporated into the soil were applied in July 1998 (main plots and the rates of gypsum (0, 3, 6 and 9 t ha-1 in October 1998 (subplots. Wheat was evaluated in the 2000 winter season. In conditions of water deficit absence, there was no limitation in root growth in depth, for exchangeable Ca of 6 mmol c dm-3. Lime incorporation of lime increased the Mg concentration in the leaves, but wheat yield was not influenced by the correction of soil acidity through liming treatments. Gypsum increased the concentrations of Ca and S in wheat leaves, with significant effects on grain yield. The critical level of S-SO4(2- in the 0-20 cm soil layer, extracted by ammonium acetate 0.5 mol L-1 in acetic acid 0.25 mol L-1, was 25.8 mg dm-3.

  18. occurrence and geochemistry of nafada gypsum, north-eastern nigeria

    DJFLEX

    2010-03-18

    Mar 18, 2010 ... The container was placed in a. “HERZOG” palletizing machine for 10 seconds after which a pellet was produced. The procedure was repeated for each gypsum sample. Each pellet was analyzed for SiO2, Al2O3, CaO, MgO, SO3, K2O, Na2O,. MgCO3, combine water and purity, using X-ray spectrometer.

  19. Comparison of Energy Dissipation, Stiffness, and Damage of Structural Oriented Strand Board (OSB, Conventional Gypsum, and Viscoelastic Gypsum Shearwalls Subjected to Cyclic Loads

    Andrew S. Blasetti

    2012-06-01

    Full Text Available A key element in the seismic load resisting system of a wood framed structure is the shear wall which is typically sheathed on one side with plywood or oriented strand board (OSB and gypsum on the other. The shear capacity of gypsum sheathed shear walls is typically neglected in high seismic areas due to the susceptibility of conventional drywall screw connections to damage caused by earthquakes. The earthquake resistance of an innovative viscoelastic (VE gypsum shearwall is evaluated and compared to conventional structural and non-structural walls. Ten 8 ft × 8 ft wood framed wall specimens of three configurations [nailed-OSB, screw-gypsum, and VE polymer-gypsum] were subjected to a cyclic test protocol. The energy dissipation, stiffness, and damage characteristics of all shearwalls are reported herein. Testing results indicate the VE-gypsum walls can dissipate more energy than the OSB structural panels and 500% more energy that the conventional gypsum sheathed walls and contains a constant source of energy dissipation not seen in the structural and non-structural walls. The wall stiffness of the OSB wall degrades at a far greater rate that the VE gypsum wall and at continued cycling degrades below the VE wall stiffness. Unlike both of the conventional wall types, the VE wall showed no visible or audible signs of damage when subjected to shear displacements up to 1.

  20. Manufacturing of calcium phosphate scaffolds by pseudomorphic transformation of gypsum

    Araujo Batista, H. de.; Batista Cardoso, M.; Sales Vasconcelos, A.; Vinicius Lia Fook, M.; Rodriguez Barbero, M. A.; Garcia Carrodeguas, R.

    2016-08-01

    Carbonated hydroxyapatite (CHAp) and β-tricalcium phosphate (β-TCP) have been employed for decades as constituents of scaffolds for bone regeneration because they chemically resemble bone mineral. In this study, the feasibility to manufacture CHAp/β-TCP scaffolds by pseudomorphic transformation of casted blocks of gypsum was investigated. The transformation was carried out by immersing the precursor gypsum block in 1 M (NH{sub 4}){sub 2}HPO{sub 4}/1.33 M NH{sub 4}OH solution with liquid/solid ratio of 10 mL/g and autoclaving at 120 degree centigrade and 203 kPa (2 atm) for 3 h at least. Neither shape nor dimensions significantly changed during transformation. The composition of scaffolds treated for 3 h was 70 wt.% CHAp and 30 wt.% β-TCP, and their compressive and diametral compressive strengths were 6.5 ± 0.7 and 5.3 ±0.7 MPa, respectively. By increasing the time of treatment to 6 h, the composition of the scaffold enriched in β-TCP (60 wt.% CHAp and 40 wt.% β-TCP) but its compressive and diametral compressive strengths were not significantly affected (6.7 ± 0.9 and 5.4 ± 0.6 MPa, respectively). On the basis of the results obtained, it was concluded that this route is a good approach to the manufacturing of biphasic (CHAp/β-TCP) scaffolds from previously shaped pieces of gypsum. (Author)

  1. Sails: a new gypsum speleothem from Naica, Chihuahua, Mexico

    Forti Paolo

    2007-01-01

    Full Text Available The caves of Naica (Chihuahua, Mexico are perhaps the most famous mine caves of the world due to the presence of giganticgypsum crystals. Nevertheless, very little research has been carried out on this karst area until now. A multidisciplinary investigationstarted in 2006 with the aim not only to define the genesis and the age of the Naica gypsum crystals, but also on other scientificaspects of these caves.This paper describes a completely new type of gypsum speleothem: the “sails”, observed only inside the Cueva de las Velas, one ofthe caves of the Naica system. This speleothem consists of extremely thin, elongated skeleton crystals that have grown epitaxiallyonly on the tips of the gypsum crystals pointing upward. The genesis of sails is strictly related to the environmental conditions setup inside the cave just after the artificial lowering of the groundwater by mine dewatering (less than 20 yr ago. In a few years sail speleothems will disappear entirely and therefore this study is fundamental to preserve at least the memory of them.

  2. Crack Coalescence in Molded Gypsum and Carrara Marble

    Wong, N.; Einstein, H. H.

    2007-12-01

    This research investigates the fracturing and coalescence behavior in prismatic laboratory-molded gypsum and Carrara marble specimens, which consist of either one or two pre-existing open flaws, under uniaxial compression. The tests are monitored by a high speed video system with a frame rate up to 24,000 frames/second. It allows one to precisely observe the cracking mechanisms, in particular if shear or tensile fracturing takes place. Seven crack types and nine crack coalescence categories are identified. The flaw inclination angle, the ligament length and the bridging angle between two flaws have different extents of influence on the coalescence patterns. For coplanar flaws, as the flaw inclination angle increases, there is a general trend of variation from shear coalescence to tensile coalescence. For stepped flaws, as the bridging angle changes from negative to small positive, and further up to large positive values, the coalescence generally progresses from categories of no coalescence, indirect coalescence to direct coalescence. For direct coalescence, it generally progresses from shear, mixed shear-tensile to tensile as the bridging angle increases. Some differences in fracturing and coalescence processes are observed in gypsum and marble, particularly the crack initiation in marble is preceded by the development of macroscopic white patches, but not in gypsum. Scanning Electron Microprobe (SEM) study reveals that the white patches consist of zones of microcracks (process zones).

  3. Electrochemical preparation of hematite nanostructured films for solar hydrogen production

    Ebadzadeh T.

    2012-10-01

    Full Text Available Photoelectrochemical water splitting is a clean and promising technique for using a renewable source of energy, i.e., solar energy, to produce hydrogen. In this work electrochemical formation of iron oxyhydroxide and its conversion to hematite (α- Fe2O3 through thermal treatment have been studied. Oxyhydroxide iron compounds have been prepared onto SnO2/F covered glass substrate by potential cycling with two different potential sweep rate values; then calcined at 520 °C in air to obtain α-Fe2O3 nanostrutured films for their implementation as photoanode in a photoelectrochemical cell. X-ray diffraction analysis allowed finding that iron oxides films have nanocrystalline character. Scanning electron microscopy revealed that films have nanostructured morphology. The obtained results are discussed considering the influence of potential sweep rate employed during the preparation of iron oxyhydroxide film on optical, structural and morphological properties of hematite nanostructured films. Results show that films have acceptable characteristics as photoanode in a photoelectrochemical cell for hydrogen generation from water.

  4. Interaction of light with hematite hierarchical structures: Experiments and simulations

    Distaso, Monica; Zhuromskyy, Oleksander; Seemann, Benjamin; Pflug, Lukas; Mačković, Mirza; Encina, Ezequiel; Taylor, Robin Klupp; Müller, Rolf; Leugering, Günter; Spiecker, Erdmann; Peschel, Ulf; Peukert, Wolfgang

    2017-03-01

    Mesocrystalline particles have been recognized as a class of multifunctional materials with potential applications in different fields. However, the internal organization of nanocomposite mesocrystals and its influence on the final properties have not yet been investigated. In this paper, a novel strategy based on electrodynamic simulations is developed to shed light on how the internal structure of mesocrystals influences their optical properties. In a first instance, a unified design protocol is reported for the fabrication of hematite/PVP particles with different morphologies such as pseudo-cubes, rods-like and apple-like structures and controlled particle size distributions. The optical properties of hematite/PVP mesocrystals are effectively simulated by taking their aggregate and nanocomposite structure into consideration. The superposition T-Matrix approach accounts for the aggregate nature of mesocrystalline particles and validate the effective medium approximation used in the framework of the Mie theory and electromagnetic simulation such as Finite Element Method. The approach described in our paper provides the framework to understand and predict the optical properties of mesocrystals and more general, of hierarchical nanostructured particles.

  5. Molecular ordering of ethanol at the calcite surface

    Pasarín, I. S.; Yang, M.; Bovet, Nicolas Emile

    2012-01-01

    To produce biominerals, such as shells, bones, and teeth, living beings create organic compounds that control the growth of the solid phase. Investigating the atomic scale behavior of individual functional groups at the mineral-fluid interface provides fundamental information that is useful...... for constructing accurate predictive models for natural systems. Previous investigations of the activity of coccolith-associated polysaccharides (CAP) on calcite, using atomic force microscopy (AFM) [ Henriksen, K., Young, J. R., Bown, P. R., and Stipp, S. L. S.Palentology 2004, 43 (Part 3), 725...... dynamics (MD) simulations, the structuring on calcite of a layer of the simplest carbon chain molecule that contains an OH group, ethanol (CH 3-CH2-OH). We found evidence that EtOH forms a highly ordered structure at the calcite surface, where the first layer molecules bond with calcite. The ethanol...

  6. Biocementation of Concrete Pavements Using Microbially Induced Calcite Precipitation.

    Jeong, Jin-Hoon; Jo, Yoon-Soo; Park, Chang-Seon; Kang, Chang-Ho; So, Jae-Seong

    2017-07-28

    In this study, the feasibility of introducing calcite-forming bacteria into concrete pavements to improve their mechanical performance was investigated. Lysinibacillus sphaericus WJ-8, which was isolated in a previous study and is capable of exhibiting high urease activity and calcite production, was used. When analyzed via scanning electron microscopy (SEM) and X-ray diffraction, WJ-8 showed a significant amount of calcite precipitation. The compressive strength of cement mortar mixed with WJ-8 cells and nutrient medium (urea with calcium lactate) increased by 10% compared with that of the controls. Energy dispersive x-ray spectroscopy analyses confirmed that the increase in strength was due to the calcite formed by the WJ-8 cells.

  7. Adsorption of ions on hematite (α-Fe2O3) : a colloid-chemical study

    Breeuwsma, A.

    1973-01-01

    This study is primarily intended to provide a better understanding of the adsorption of ions on hematite (α-Fe 2 O 3 ). In addition, due attention is given to the relation between the ionic adsorption and the colloidal stability of hematite sols.

    Chapter 1. is concerned

  8. Immobilization of molecular cobalt electrocatalyst by hydrophobic interaction with hematite photoanode for highly stable oxygen evolution

    Joya, Khurram

    2015-07-15

    A unique modification of a hematite photoanode with perfluorinated Co-phthalocyanine (CoFPc) by strong binding associated with hydrophobic interaction is demonstrated. The resultant molecular electrocatalyst – hematite photoanode hybrid material showed significant onset shift and high stability for photoelectrochemical oxidation evolution reaction (OER).

  9. Residual Energy Harvesting from Light Transients Using Hematite as an Intrinsic Photocapacitor in a Symmetrical Cell

    Blom, Burgert; van Leeuwen, Nicole; Xie, Mengying; Adamaki, Vana; Bowen, Chris R.; de Araujo, Moises A.; Mascaro, Lucia H.; Cameron, Petra J.; Marken, Frank

    2017-01-01

    Hematite as a sustainable photoabsorber material offers a band gap close to 2 eV and photoanode characteristics, but usually requires additional catalysts to enhance surface redox chemistry during steady state light energy harvesting for water splitting. Here, for a highly doped hematite film,

  10. Immobilization of molecular cobalt electrocatalyst by hydrophobic interaction with hematite photoanode for highly stable oxygen evolution

    Joya, Khurram; Morlanes, Natalia; Maloney, Edward; Rodionov, Valentin; Takanabe, Kazuhiro

    2015-01-01

    A unique modification of a hematite photoanode with perfluorinated Co-phthalocyanine (CoFPc) by strong binding associated with hydrophobic interaction is demonstrated. The resultant molecular electrocatalyst – hematite photoanode hybrid material showed significant onset shift and high stability for photoelectrochemical oxidation evolution reaction (OER).

  11. Microbially induced separation of quartz from calcite using Saccharomyces cerevisiae.

    Padukone, S Usha; Natarajan, K A

    2011-11-01

    Cells of Saccharomyces cerevisiae and their metabolites were successfully utilized to achieve selective separation of quartz and calcite through microbially induced flotation and flocculation. S. cerevisiae was adapted to calcite and quartz minerals. Adsorption studies and electrokinetic investigations were carried out to understand the changes in the surface chemistry of yeast cells and the minerals after mutual interaction. Possible mechanisms in microbially induced flotation and flocculation are outlined. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. In situ Ni-doping during cathodic electrodeposition of hematite for excellent photoelectrochemical performance of nanostructured nickel oxide-hematite p-n junction photoanode

    Phuan, Yi Wen; Ibrahim, Elyas; Chong, Meng Nan; Zhu, Tao; Lee, Byeong-Kyu; Ocon, Joey D.; Chan, Eng Seng

    2017-01-01

    Nanostructured nickel oxide-hematite (NiO/α-Fe2O3) p-n junction photoanodes synthesized from in situ doping of nickel (Ni) during cathodic electrodeposition of hematite were successfully demonstrated. A postulation model was proposed to explain the fundamental mechanism of Ni2+ ions involved, and the eventual formation of NiO on the subsurface region of hematite that enhanced the potential photoelectrochemical water oxidation process. Through this study, it was found that the measured photocurrent densities of the Ni-doped hematite photoanodes were highly dependent on the concentrations of Ni dopant used. The optimum Ni dopant at 25 M% demonstrated an excellent photoelectrochemical performance of 7-folds enhancement as compared to bare hematite photoanode. This was attributed to the increased electron donor density through the p-n junction and thus lowering the energetic barrier for water oxidation activity at the optimum Ni dopant concentration. Concurrently, the in situ Ni-doping of hematite has also lowered the photogenerated charge carrier transfer resistance as measured using the electrochemical impedance spectroscopy. It is expected that the fundamental understanding gained through this study is helpful for the rational design and construction of highly efficient photoanodes for application in photoelectrochemical process.

  13. Hematite mining in the ancient Americas: Mina Primavera, A 2,000 year old Peruvian mine

    Vaughn, Kevin J.; Grados, Moises Linares; Eerkens, Jelmer W.; Edwards, Matthew J.

    2007-12-01

    Mina Primavera, a hematite (Fe2O3) mine located in southern Peru, was exploited beginning approximately 2,000 years ago by two Andean civilizations, the Nasca and Wari. Despite the importance of hematite in the material culture of the ancient Americas, few hematite mines have been reported in the New World literature and none have been reported for the Central Andes. An estimated 3,710 tonnes of hematite were extracted from the mine for over 1,400 years at an average rate of 2.65 tonnes per year, suggesting regular and extensive mining prior to Spanish conquest. The hematite was likely used as a pigment for painting pottery, and the mine demonstrates that iron ores were extracted extensively at an early date in the Americas.

  14. Selective Flotation of Calcite from Fluorite: A Novel Reagent Schedule

    Zhiyong Gao

    2016-10-01

    Full Text Available Fluorite is an important strategic mineral. In general, fluorite ores will contain a certain amount of calcite gangue mineral. Thus, they need to be separated from each other. For an economic separation, a reverse flotation process is used to float calcite gangue from fluorite. However, little information on the separation is available. In this study, a novel reagent schedule using citric acid (CA as the depressant, sodium fluoride (NaF as the regulator and sulfoleic acid (SOA as the collector, was developed to separate calcite from fluorite. The results demonstrated a high selectivity for the flotation of calcite from fluorite using this new reagent schedule. The best selective separation for a single mineral and mixed binary minerals was obtained when 200 mg/L of NaF, 50 mg/L of CA, and 6 mg/L of SOA were used at pH 9. In addition, a batch flotation experiment was carried out using a run-of-mine feed material. Selective separation was achieved with 85.18% calcite removal while only 11.2% of fluorite was lost. An attempt was made to understand the effect of the new reagent schedule on the flotation of calcite. The results from both microflotation and bench scale flotation demonstrated a great potential for industrial application using this novel reagent schedule to upgrade fluorite ore.

  15. Ikaite pseudomorphs in the Zaire deep-sea fan: An intermediate between calcite and porous calcite

    Jansen, J. H. F.; Woensdregt, C. F.; Kooistra, M. J.; van der Gaast, S. J.

    1987-03-01

    Translucent brown aggregates of calcium-carbonate crystals have been found in cores from the Zaire deep-sea fan (west equatorial Africa). The aggregates are well preserved but very friable. Upon storage they become yellowish white and cloudy and release water. Chemical, mineralogical (XRD), petrographical, crystal-morphological, and stable-isotope data demonstrate that the crystals have passed through three phases: (1) an authigenic carbonate phase, probably calcium carbonate, which is represented by the external habit of the present crystals; (2) a translucent brown ikaite phase (CaCO3·6H2O), unstable at temperatures above 5 °C; and (3) a phase consisting of calcite microcrystals that are poorly cemented and form a porous mass within the crystal form of the morphologically unchanged first phase. The transformation from the first phase into ikaite was probably a kinetic replacement. The transformation from ikaite into the third phase occurred because of storage at room temperature. The presence of ikaite is indicative of a low-temperature, anaerobic, organic-carbon-rich marine environment. Ikaite is probably the precursor of a great number of porous calcite pseudomorphs, and possibly also of many marine authigenic microcrystalline carbonate nodules.

  16. Spherulitic (c-axis) Growth for Terrestrial (Mauna Kea, Hawaii) and Martian Hematite "blueberries"

    Golden, D. C.; Ming, D. W.; Morris, R. V.

    2006-01-01

    Hematite concentrations observed by Thermal Emission Spectrometer (TES) onboard Mars Global Surveyor were considered a possible indicator for aqueous processes on Mars. Observations made by Opportunity show that the hematite at Meridiani Planum is present as spherules ( blueberries) and their fragments. The internal structure of the hematite spherules is not discernable at the resolution limit (approx.30 m/pixel) of Opportunity s Microscopic Imager (MI). A terrestrial analog for martian hematite spherules are spherules from hydrothermally altered and sulfate-rich tephra from the summit region of Mauna Kea volcano, Hawaii. The objective of this study is to determine the crystal growth fabric of the Mauna Kea hematite spherules using transmission electron microscopy (TEM) techniques and to relate that crystalline fabric to the observed TES signature of Meridiani Planum "blueberries." TEM analysis of Mauna Kea spherules exhibited a radial growth pattern consisting of "fibrous" hematite with the c-axis of hematite particles aligned along the elongation direction of the hematite fibers. The individual fibers appear to be made of coalesced nano-particles of hematite arranged with their c-axis oriented radially to form a spherical structure. Lattice fringes suggest long-range order across particles and along fibers. According to interpretations of thermal emission spectra for Meridian Planum hematite, the absence of a band at approx. 390/cm implies a geometry where c-face emission dominates. Because the c-face is perpendicular to the c-axis, this is precisely the geometry for the Mauna Kea spherules because the c-axis is aligned parallel to their radial growth direction. Therefore, we conclude as a working hypothesis that the martian spherules also have radial, c-axis growth pattern on a scale that is too small to be detected by the MER MI. Furthermore, by analogy with the Mauna Kea spherules, the martian blueberries could have formed during hydrothermal alteration of

  17. Green urea synthesis catalyzed by hematite nanowires in magnetic field

    Yahya, Noorhana; Qureshi, Saima; Rehman, Zia ur; Alqasem, Bilal; Fai Kait, Chong

    2017-04-01

    The catalytic activity of hematite (α-Fe2O3) nanowires under the influence of magnetic field on urea synthesis is considered green. The adsorption and subsequent dissociative reaction of hydrogen, nitrogen and carbon dioxide gases on the α-Fe2O3 (111) nanowires were investigated using the density functional theory (DFT) method. The average adsorption energy is -4.12 kcal/mole at different sites. The adsorption of gases resulted in a difference in density and net spin of electrons from 68 to 120 and 0-21 respectively. In addition, it induces magnetic moment value of 36.33 μB, which confirms the enhanced magnetic behaviour of hematite. α-Fe2O3 nanowires (NWs) synthesized by heating iron wire in a box furnace at (750-800) °C and as synthesized α-Fe2O3 nanoparticles (NPs) were received to use as a catalyst in the magnetic reaction of urea synthesis. X-ray Diffractometer (XRD) confirms the peaks of rhombohedral structure of α-Fe2O3 and Raman spectrum analyses confirms the α-Fe2O3 peaks at 410 cm-1, 500 cm-1 and 616 cm-1. The needle-like shape of hematite nanowires with length ranging from 16-25) μm and diameter from 74 to 145 nm confirmed by Field emission scanning electron microscopy (FESEM). The magnetic properties of the nanowires exhibited different levels of saturation magnetization, for α-Fe2O3 perpendicularly aligned direction (13.18 emu/g) and random direction (10.73 emu/g). Urea synthesis was done under magnetic field ranges from 0.0 to 2.5 T. The activation energy of α-Fe2O3 NWs for urea production is lower than NPs in the range of 0-1 T, whereas it is reversed for higher magnetic induction values. Fourier transform infrared spectroscopy (FTIR) confirmed the formation of urea at the peaks of 1690-1600 cm-1. This green urea employing magnetically induced method could be a contender to the Haber-Bosch process currently used by the current industry which utilizes high temperature and high pressure.

  18. Suitability of Gypsum for the Production of Gypsum Plaster an Example from the Abu-Ruweis Evaporites (Upper Triassic), as Subayhi Area, Northwest Jordan

    Saqqa, W.; Arikat, M.

    2003-01-01

    The gypsum of Abu Ruweis Formation (Upper Triassic) of the northwestern Jordan was chemically, physically and mechanically assessed for likely industrial uses. Chemical results indicate that the investigated gypsum (calcium sulfate dihydrate) is highly pure. This is confirmed by the high ratios of CaO (32-33%) andSO 3 (41-43%) and the very low content of other elements such as Mg, Al and Si. Trace elements are also negligible. The CaSO 4 % (86-88%), purity ratio (CaO/SO 3 ) (0.85) , and combined water (≅5%) for β-hemihydrate gypsum agree well with the jordanian standards for gypsum plaster. Thermal analyses indicate that the temperature required to obtain hemihydrate gypsum falls between 175deg-200deg. A significant mass variation or maximum loss on weight (-20%) was achieved after initial dehydration by heating to 200deg. Heating to 225deg is far enough to evolve all combined water molecules. The results of fineness, consistency, setting time, compressive strength and flexural strength for β-hemilhydrate agree, in most of the case, with the local and international standards intended for gypsum building components. The study showed that the absorption and consistency ratios for final gypsum product are proportional to porosity, whilst the consistency itself decreases with the increase of applied stresses. (author)

  19. Magnetic dynamics of weakly and strongly interacting hematite nanoparticles

    Hansen, Mikkel Fougt; Bender Koch, Christian; Mørup, Steen

    2000-01-01

    The magnetic dynamics of two differently treated samples of hematite nanoparticles from the same batch with a particle size of about 20 nm have been studied by Mossbauer spectroscopy. The dynamics of the first sample, in which the particles are coated and dispersed in water, is in accordance with...... down by interparticle interactions and a magnetically split spectrum is retained at room temperature. The temperature variation or the magnetic hyperfine field, corresponding to different quantiles in the hyperfine field distribution, can be consistently described by a mean field model...... for "superferromagnetism" in which the magnetic anisotropy is included. The coupling between the particles is due to exchange interactions and the interaction strength can be accounted for by just a few exchange bridges between surface atoms in neighboring crystallites....

  20. Nanostructured hematite thin films for photoelectrochemical water splitting

    Maabong, Kelebogile; Machatine, Augusto G. J.; Mwankemwa, Benard S.; Braun, Artur; Bora, Debajeet K.; Toth, Rita; Diale, Mmantsae

    2018-04-01

    Nanostructured hematite thin films prepared by dip coating technique were investigated for their photoelectrochemical activity for generation of hydrogen from water splitting. Structural, morphological and optical analyses of the doped/undoped films were performed by X-ray diffraction, high resolution field emission-scanning electron microscopy, UV-vis spectrophotometry and Raman spectroscopy. The photoelectrochemical measurements of the films showed enhanced photoresponse and cathodic shift of the onset potential upon Ti doping indicating improved transfer of photoholes at the semiconductor-electrolyte interface. Films doped with 1 at% Ti produced 0.72 mA/cm2 at 1.23 V vs RHE which is 2 times higher than current density for the pure film (0.30 mA/cm2, at 1.23 V vs RHE). Gas chromatography analysis of the films also showed enhanced hydrogen evolution at 1 at% Ti with respect to pure film.

  1. Disposal of coal and hematite dusts inhaled successively

    Heppleston, A G

    1958-01-01

    Rabbits and rats were exposed in a chamber to coal (20,000 and 10,000 particles/ml) and hematite (20,000 and 37,000 particles/ml) in succession to follow deposition and clearance by color. Exposures were 5 days/wk, 20 hr/day. Generally, there was dust widely but not uniformly distributed in peripheral alveoli, tending to aggregate and clump in more proximal alveoli with time. There was initial nonuniform distribution more uniform with exposure time. Aggregation mostly through phagocyte activities and more evident in rabbits than rats was observed. There was eventual mixing of two dusts inhaled up to 7 months apart. Dust deposited last is cleared first because of less tortuous route.

  2. Microstructural changes in porous hematite nanoparticles upon calcination

    Johnsen, Rune; Knudsen, Kenneth D.; Molenbroek, Alfons M.

    2011-01-01

    This combined study using small-angle neutron scattering (SANS), X-ray powder diffraction (XRPD), transmission electron microscopy (TEM) and adsorption isotherm techniques demonstrates radical changes in the microstructure of porous hematite (-Fe2O3) nanoparticles upon calcination in air. TEM....... The change in microstructure also causes a reduction in the surface area as calculated by gaseous adsorption. The XRPD and SANS data show that the crystallite and SANS particle sizes are virtually unchanged by calcination at 623 K. Calcination at 973 K induces a significant alteration of the sample. The XRPD...... data reveal that the crystallite size increases significantly, and the SANS and adsorption isotherm studies suggest that the specific surface area decreases by a factor of 5–6. The TEM images show that the particles are sintered into larger agglomerates, but they also show that parts of the porous...

  3. Fixing arsenic contained in a gas phase using solid hematite

    Balladares, E.; Gonzalez, A.; Rarra, R.; Sanchez, M.

    2004-01-01

    Feasibility to obtain ferric arsenate starting from arsenic containing gas in contact with Fe 3 O 3 has been studied. Thermodynamic stability of the system Fe-As-O was analysed in order to verify conditions to form Fe x As y O z type compounds. Experiments were made using a hematite sample suspended in a thermogravimetric device. As 4 O 6 was generated starting from solid As 2 O 3 which was circulating through the iron oxide. Final samples were analysed chemically and by means of DRX, verifying the formation of FeAsO 4 , FeAsO 4 .2h 2 O and FeAsO 4 .(H 2 O) 2 in small quantities. Tests in porous bed and pellets were carried out, studying the effect of: porosity, temperature and oxygen potential. The largest conversion obtained was 10% at 800 degree centigrade, pO 2 =50% and porosity=0.883. (Author) 9 refs

  4. On the complex conductivity signatures of calcite precipitation

    Wu, Yuxin; Hubbard, Susan; Williams, Kenneth Hurst; Ajo-Franklin, Jonathan

    2009-11-01

    Calcite is a mineral phase that frequently precipitates during subsurface remediation or geotechnical engineering processes. This precipitation can lead to changes in the overall behavior of the system, such as flow alternation and soil strengthening. Because induced calcite precipitation is typically quite variable in space and time, monitoring its distribution in the subsurface is a challenge. In this research, we conducted a laboratory column experiment to investigate the potential of complex conductivity as a mean to remotely monitor calcite precipitation. Calcite precipitation was induced in a glass bead (3 mm) packed column through abiotic mixing of CaCl{sub 2} and Na{sub 2}CO{sub 3} solutions. The experiment continued for 12 days with a constant precipitation rate of {approx}0.6 milimole/d. Visual observations and scanning electron microscopy imaging revealed two distinct phases of precipitation: an earlier phase dominated by well distributed, discrete precipitates and a later phase characterized by localized precipitate aggregation and associated pore clogging. Complex conductivity measurements exhibited polarization signals that were characteristic of both phases of calcite precipitation, with the precipitation volume and crystal size controlling the overall polarization magnitude and relaxation time constant. We attribute the observed responses to polarization at the electrical double layer surrounding calcite crystals. Our experiment illustrates the potential of electrical methods for characterizing the distribution and aggregation state of nonconductive minerals like calcite. Advancing our ability to quantify geochemical transformations using such noninvasive methods is expected to facilitate our understanding of complex processes associated with natural subsurface systems as well as processes induced through engineered treatments (such as environmental remediation and carbon sequestration).

  5. Role of Fungi in the Biomineralization of Calcite

    Saskia Bindschedler

    2016-05-01

    Full Text Available In the field of microbial biomineralization, much of the scientific attention is focused on processes carried out by prokaryotes, in particular bacteria, even though fungi are also known to be involved in biogeochemical cycles in numerous ways. They are traditionally recognized as key players in organic matter recycling, as nutrient suppliers via mineral weathering, as well as large producers of organic acids such as oxalic acid for instance, an activity leading to the genesis of various metal complexes such as metal-oxalate. Their implications in the transformation of various mineral and metallic compounds has been widely acknowledged during the last decade, however, currently, their contribution to the genesis of a common biomineral, calcite, needs to be more thoroughly documented. Calcite is observed in many ecosystems and plays an essential role in the biogeochemical cycles of both carbon (C and calcium (Ca. It may be physicochemical or biogenic in origin and numerous organisms have been recognized to control or induce its biomineralization. While fungi have often been suspected of being involved in this process in terrestrial environments, only scarce information supports this hypothesis in natural settings. As a result, calcite biomineralization by microbes is still largely attributed to bacteria at present. However, in some terrestrial environments there are particular calcitic habits that have been described as being fungal in origin. In addition to this, several studies dealing with axenic cultures of fungi have demonstrated the ability of fungi to produce calcite. Examples of fungal biomineralization range from induced to organomineralization processes. More examples of calcite biomineralization related to direct fungal activity, or at least to their presence, have been described within the last decade. However, the peculiar mechanisms leading to calcite biomineralization by fungi remain incompletely understood and more research is

  6. In situ Ni-doping during cathodic electrodeposition of hematite for excellent photoelectrochemical performance of nanostructured nickel oxide-hematite p-n junction photoanode

    Phuan, Yi Wen, E-mail: phuan.yi.wen@monash.edu [School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE 47500 (Malaysia); Ibrahim, Elyas, E-mail: meibr2@student.monash.edu [School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE 47500 (Malaysia); Chong, Meng Nan, E-mail: Chong.Meng.Nan@monash.edu [School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE 47500 (Malaysia); Sustainable Water Alliance, Advanced Engineering Platform, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE 47500 (Malaysia); Zhu, Tao, E-mail: zhu.tao@monash.edu [School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE 47500 (Malaysia); Lee, Byeong-Kyu, E-mail: bklee@ulsan.ac.kr [Department of Civil and Environmental Engineering, University of Ulsan, Nam-gu, Daehakro 93, Ulsan 680-749 (Korea, Republic of); Ocon, Joey D., E-mail: jdocon@up.edu.ph [Laboratory of Electrochemical Engineering (LEE), Department of Chemical Engineering, University of the Philippines Diliman, Quezon City 1101 (Philippines); Chan, Eng Seng, E-mail: chan.eng.seng@monash.edu [School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE 47500 (Malaysia)

    2017-01-15

    Highlights: • NiO-hematite p-n junction photoanodes were fabricated via an in situ Ni-doping. • The fundamental mechanism of Ni{sup 2+} ions involved was elucidated. • The optimum Ni dopant was 25 M% for the highest photocurrent density. • It exhibited an excellent photoelectrochemical performance of 7-folds enhancement. - Abstract: Nanostructured nickel oxide-hematite (NiO/α-Fe{sub 2}O{sub 3}) p-n junction photoanodes synthesized from in situ doping of nickel (Ni) during cathodic electrodeposition of hematite were successfully demonstrated. A postulation model was proposed to explain the fundamental mechanism of Ni{sup 2+} ions involved, and the eventual formation of NiO on the subsurface region of hematite that enhanced the potential photoelectrochemical water oxidation process. Through this study, it was found that the measured photocurrent densities of the Ni-doped hematite photoanodes were highly dependent on the concentrations of Ni dopant used. The optimum Ni dopant at 25 M% demonstrated an excellent photoelectrochemical performance of 7-folds enhancement as compared to bare hematite photoanode. This was attributed to the increased electron donor density through the p-n junction and thus lowering the energetic barrier for water oxidation activity at the optimum Ni dopant concentration. Concurrently, the in situ Ni-doping of hematite has also lowered the photogenerated charge carrier transfer resistance as measured using the electrochemical impedance spectroscopy. It is expected that the fundamental understanding gained through this study is helpful for the rational design and construction of highly efficient photoanodes for application in photoelectrochemical process.

  7. In situ Ni-doping during cathodic electrodeposition of hematite for excellent photoelectrochemical performance of nanostructured nickel oxide-hematite p-n junction photoanode

    Phuan, Yi Wen; Ibrahim, Elyas; Chong, Meng Nan; Zhu, Tao; Lee, Byeong-Kyu; Ocon, Joey D.; Chan, Eng Seng

    2017-01-01

    Highlights: • NiO-hematite p-n junction photoanodes were fabricated via an in situ Ni-doping. • The fundamental mechanism of Ni"2"+ ions involved was elucidated. • The optimum Ni dopant was 25 M% for the highest photocurrent density. • It exhibited an excellent photoelectrochemical performance of 7-folds enhancement. - Abstract: Nanostructured nickel oxide-hematite (NiO/α-Fe_2O_3) p-n junction photoanodes synthesized from in situ doping of nickel (Ni) during cathodic electrodeposition of hematite were successfully demonstrated. A postulation model was proposed to explain the fundamental mechanism of Ni"2"+ ions involved, and the eventual formation of NiO on the subsurface region of hematite that enhanced the potential photoelectrochemical water oxidation process. Through this study, it was found that the measured photocurrent densities of the Ni-doped hematite photoanodes were highly dependent on the concentrations of Ni dopant used. The optimum Ni dopant at 25 M% demonstrated an excellent photoelectrochemical performance of 7-folds enhancement as compared to bare hematite photoanode. This was attributed to the increased electron donor density through the p-n junction and thus lowering the energetic barrier for water oxidation activity at the optimum Ni dopant concentration. Concurrently, the in situ Ni-doping of hematite has also lowered the photogenerated charge carrier transfer resistance as measured using the electrochemical impedance spectroscopy. It is expected that the fundamental understanding gained through this study is helpful for the rational design and construction of highly efficient photoanodes for application in photoelectrochemical process.

  8. Nucleation and growth of the Naica giant gypsum crystals.

    Otálora, Fermín; García-Ruiz, JuanMa

    2014-04-07

    The Cave of Giant Crystals in the Naica mine (Mexico) is one of the most amazing displays of mineral beauty ever created in nature. In addition to the colossal crystals of gypsum, which in some cases exceed eleven meters in length and one meter in thickness, the scenery fashioned by the crystalline beams that thrust through the darkness of the cave from floor to ceiling with a luster like moonlight is a unique example of harmony based on crystal symmetry. We review the crystallogenesis of this remarkable and challenging phenomenon of mineralization near equilibrium that can be used to teach the basics of nucleation and crystal growth.

  9. Cytochrome c interaction with hematite ({alpha}-Fe{sub 2}O{sub 3}) surfaces

    Eggleston, Carrick M. [Department of Geology and Geophysics, University of Wyoming, Laramie, WY 82071 (United States)]. E-mail: carrick@uwyo.edu; Khare, Nidhi [Department of Geology and Geophysics, University of Wyoming, Laramie, WY 82071 (United States); Lovelace, David M. [Department of Geology and Geophysics, University of Wyoming, Laramie, WY 82071 (United States)

    2006-02-15

    The interaction of metalloproteins such as cytochromes with oxides is of interest for a number of reasons, including molecular catalysis of environmentally important mineral-solution electron transfer reactions (e.g., dehalogenations) and photovoltaic applications. Iron reduction by bacteria, thought to be cytochrome mediated, is of interest for geochemical and environmental remediation reasons. As a baseline for understanding cytochrome interaction with ferric oxide surfaces, we report on the interaction of mitochondrial cytochrome c (Mcc), a well-studied protein, with hematite ({alpha}-Fe{sub 2}O{sub 3}) surfaces. Mcc sorbs strongly to hematite from aqueous solution in a narrow pH range corresponding to opposite charge on Mcc and hematite (between pH 8.5 and 10, Mcc is positively charged and hematite surfaces are negatively charged). Cyclic voltammetry of Mcc using hematite electrodes gives redox potentials characteristic of Mcc in a native conformational state, with no evidence for unfolding on the hematite surface. Atomic force microscopy imaging is consistent with a loosely attached adsorbate that is easily deformed by the AFM tip. In phosphate-containing solution, Mcc adhers to the surface more strongly. These results establish hematite as a viable material for electrochemical and spectroscopic characterization of cytochrome-mineral interaction.

  10. Control of Earth-like magnetic fields on the transformation of ferrihydrite to hematite and goethite.

    Jiang, Zhaoxia; Liu, Qingsong; Dekkers, Mark J; Barrón, Vidal; Torrent, José; Roberts, Andrew P

    2016-07-26

    Hematite and goethite are the two most abundant iron oxides in natural environments. Their formation is controlled by multiple environmental factors; therefore, their relative concentration has been used widely to indicate climatic variations. In this study, we aimed to test whether hematite and goethite growth is influenced by ambient magnetic fields of Earth-like values. Ferrihydrite was aged at 95 °C in magnetic fields ranging from ~0 to ~100 μT. Our results indicate a large influence of the applied magnetic field on hematite and goethite growth from ferrihydrite. The synthesized products are a mixture of hematite and goethite for field intensities fields favour hematite formation by accelerating ferrimagnetic ferrihydrite aggregation. Additionally, hematite particles growing in a controlled magnetic field of ~100 μT appear to be arranged in chains, which may be reduced to magnetite keeping its original configuration, therefore, the presence of magnetic particles in chains in natural sediments cannot be used as an exclusive indicator of biogenic magnetite. Hematite vs. goethite formation in our experiments is influenced by field intensity values within the range of geomagnetic field variability. Thus, geomagnetic field intensity could be a source of variation when using iron (oxyhydr-)oxide concentrations in environmental magnetism.

  11. Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters

    Rossi, Carlos; Lozano, Rafael P.

    2016-11-01

    Despite the paleoclimatic relevance of primary calcite to aragonite transitions in stalagmites, the relative role of fluid Mg/Ca ratio, supersaturation and CO32- concentration in controlling such transitions is still incompletely understood. Accordingly, we have monitored the hydrochemistry of 50 drips and 8 pools that are currently precipitating calcite and/or aragonite in El Soplao and Torca Ancha Caves (N. Spain), investigating the mineralogy and geochemistry of the CaCO3 precipitates on the corresponding natural speleothem surfaces. The data reveal that, apart from possible substrate effects, dripwater Mg/Ca is the only obvious control on CaCO3 polymorphism in the studied stalagmites and pools, where calcite- and aragonite-precipitating dripwaters are separated by an initial (i.e. at stalactite tips) Mg/Ca threshold at ≈1.1 mol/mol. Within the analyzed ranges of pH (8.2-8.6), CO32- concentration (1-6 mg/L), supersaturation (SIaragonite: 0.08-1.08; SIcalcite: 0.23-1.24), drip rate (0.2-81 drops/min) and dissolved Zn (6-90 μg/L), we observe no unequivocal influence of these parameters on CaCO3 mineralogy. Despite the almost complete overlapping supersaturations of calcite- and aragonite-precipitating waters, the latter are on average less supersaturated because the waters having Mg/Ca above ∼1.1 have mostly achieved such high ratios by previously precipitating calcite. Both calcite and aragonite precipitated at or near oxygen isotopic equilibrium, and Mg incorporation into calcite was consistent with literature-based predictions, indicating that in the studied cases CaCO3 precipitation was not significantly influenced by strong kinetic effects. In the studied cases, the calcites that precipitate at ∼11 °C from dripwaters with initial Mg/Ca approaching ∼1.1 incorporate ∼5 mol% MgCO3, close to the published value above which calcite solubility exceeds aragonite solubility, suggesting that aragonite precipitation in high-relative-humidity caves is

  12. Impact of environmental conditions on aggregation kinetics of hematite and goethite nanoparticles

    Xu, Chen-yang; Deng, Kai-ying; Li, Jiu-yu; Xu, Ren-kou

    2015-01-01

    Hematite and goethite nanoparticles were used as model minerals to investigate their aggregation kinetics under soil environmental conditions in the present study. The hydrodynamic diameters of hematite and goethite nanoparticles were 34.4 and 66.3 nm, respectively. The positive surface charges and zeta potential values for goethite were higher than for hematite. The effective diameter for goethite was much larger than for hematite due to anisotropic sticking of needle-shaped goethite during aggregation. Moreover, the critical coagulation concentration (CCC) values of nanoparticles in solutions of NaNO 3 , NaCl, NaF, and Na 2 SO 4 were 79.2, 75.0, 7.8, and 0.5 mM for hematite and they were 54.7, 62.6, 5.5, and 0.2 mM for goethite, respectively. The disparity of anions in inducing hematite or goethite aggregation lay in the differences in interfacial interactions. NO 3 − and Cl − could decrease the zeta potential and enhance aggregation mainly through increasing ionic strength and compressing electric double layers of hematite and goethite nanoparticles. F − and SO 4 2− highly destabilized the suspensions of nanoparticles mainly through specific adsorption and then neutralizing the positive surface charges of nanoparticles. Specific adsorption of cations could increase positive surface charges and stabilize hematite and goethite nanoparticles. The Hamaker constants of hematite and goethite nanoparticles were calculated to be 2.87 × 10 −20 and 2.29 × 10 −20 J −1 , respectively. The predicted CCC values based on DLVO theory were consistent well with the experimentally determined CCC values in NaNO 3 , NaCl, NaF, and Na 2 SO 4 systems, which demonstrated that DLVO theory could successfully predict the aggregation kinetics even when specific adsorption of ions occurred

  13. Synthesis of partial stabilized cement-gypsum as new dental retrograde filling material

    Sadhasivam, S. [Institute of Biomedical Engineering, National Taiwan University, Taipei, Taiwan (China); Division of Medical Engineering Research, National Health Research Institute, Zhunan, Miaoli County, Taiwan (China); Chen, Jung-Chih [Institute of Biomedical Engineering, National Taiwan University, Taipei, Taiwan (China); Medical Device Innovation Center, National Cheng Kung University, Tainan,Taiwan (China); Savitha, S. [Institute of Biomedical Engineering, National Taiwan University, Taipei, Taiwan (China); Hsu, Ming-Xiang; Hsu, Chung-King [Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei, Taiwan (China); Lin, Chun-Pin [School of Dentistry and Graduate Institute of Clinical Dentistry, College of Medicine, National Taiwan University and National Taiwan University Hospital, Taipei, Taiwan (China); Lin, Feng-Huei, E-mail: double@ntu.edu.tw [Institute of Biomedical Engineering, National Taiwan University, Taipei, Taiwan (China); Division of Medical Engineering Research, National Health Research Institute, Zhunan, Miaoli County, Taiwan (China)

    2012-10-01

    The study describes the sol-gel synthesis of a new dental retrograde filling material partial stabilized cement (PSC)-gypsum by adding different weight percentage of gypsum (25% PSC + 75% gypsum, 50% PSC + 50% gypsum and 75% PSC + 25% gypsum) to the PSC. The crystalline phase and hydration products of PSC-gypsum were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis. The handling properties such as setting time, viscosity, tensile strength, porosity and pH, were also studied. The XRD and microstructure analysis demonstrated the formation of hydroxyapatite and removal of calcium dihydrate during its immersion in simulated body fluid (SBF) on day 10 for 75% PSC + 25% gypsum. The developed PSC-gypsum not only improved the setting time but also greatly reduced the viscosity, which is very essential for endodontic surgery. The cytotoxic and cell proliferation studies indicated that the synthesized material is highly biocompatible. The increased alkaline pH of the PSC-gypsum also had a remarkable antibacterial activity. - Highlights: Black-Right-Pointing-Pointer A new dental retrograde filling material PSC-gypsum was developed. Black-Right-Pointing-Pointer PSC-gypsum cement has shown excellent initial and final setting time as 15-35 min. Black-Right-Pointing-Pointer It not only improved the setting time but also retain the viscosity, 2 Pa{center_dot}s. Black-Right-Pointing-Pointer High alkaline pH of the cement had a remarkable antibacterial activity. Black-Right-Pointing-Pointer Cytotoxicity studies revealed that the synthesized material is highly biocompatible.

  14. Investigation and dating of gypsum crystals from Sivrihisar region in Eskisehir by ESR and TL techniques

    2011-01-01

    Gypsum crystals taken from Sivrihisar-Eskisehir district were investigated and dated by Electron Spin Resonance (ESR) and Thermoluminescence (TL) techniques. The natural ESR spectra of gypsum samples had also the signals of Mn 2 + in addition to the signal at g=2.009. It was observed that the intensity of ESR signal at g=2.009 increased with gamma irradiation dose. This ESR signal (g=2.009) was used as a dating signal in dating of gypsum samples. The only one TL peak at about 278 degree Celsius was observed in TL glow curves of nonirradiated gypsum sample. In the case of irradiated sample, TL peak at 157 degree Celsius was observed in addition of TL peak at 278 degree Celsius. Gypsum samples were irradiated with a 6 0Co gamma source. The ESR spectra and TL glow curve of gypsum samples were recorded by X-band ESR spectrometer and Risφ TL/OSL reader, respectively. For samples, ESR/TL dose-response curves was constructed. Dose-response curves were fitted with an exponential saturation function. Based on this model, accumulated dose (AD) values for dating are determined. 2 38U, 2 32Th and 4 0K analysis was carried out for gypsum crystals and dolomite which enveloped these gypsum crystals. The internal dose rate was calculated from 2 38U, 2 32Th and 4 0K analysis results of gypsum sample. The external dose rate was calculated by using 2 38U, 2 32Th and 4 0K analysis results of dolomite and cosmic dose rate. Internal and external gamma dose-rate was used for dating calculations. Because of successive recrystallization of gypsum sample after formation, calculated age values of gypsum is smaller than expected formation age.

  15. In-situ deposition of hematite (α-Fe2O3) microcubes on cotton cellulose via hydrothermal method

    Gili, M.; Latag, G.; Balela, M.

    2018-03-01

    Hematite microcubes with truncated edges have been successfully deposited on cotton cellulose via one-step hydrothermal process using anhydrous FeCl3 and glycine as Fe(III) precursor and chelating agent, respectively. The amount of glycine significantly affects the morphology and yield of hematite. The addition of 0.495 g of glycine to 50 ml of 0.1 M FeCl3 solution with 0.400 g of cotton resulted to hematite-deposited cellulose having ∼15% hematite content. The reduction of glycine to 0.247 g increased the amount of hematite on the surface of the cotton cellulose to ∼20% by weight. However, the hematite microcubes have a wide size distribution, with particle size in the range of 0.684 μm to 1.520 μm. Without glycine, hematite cannot be formed in the solution.

  16. Reaction mechanism of reductive decomposition of FGD gypsum with anthracite

    Zheng, Da; Lu, Hailin; Sun, Xiuyun; Liu, Xiaodong; Han, Weiqing; Wang, Lianjun

    2013-01-01

    Highlights: • The reaction mechanism was different if the molar ratio of C/CaSO 4 was different. • The yield of CaO rises with an increase in temperature. • The optimal ratio of C/CaSO 4 = 1.2:1. • The decomposition process is mainly apparent solid–solid reaction with liquid-phase involved. - Abstract: The process of decomposition reaction between flue gas desulfurization (FGD) gypsum and anthracite is complex, which depends on the reaction conditions and atmosphere. In this study, thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA-FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and the experiment in a tubular reactor were used to characterize the decomposition reaction in a nitrogen atmosphere under different conditions. The reaction mechanism analysis showed that the decomposition reaction process and mechanism were different when the molar proportion of C/CaSO 4 was changed. The experiment results showed that appropriate increase in the C/CaSO 4 proportion and higher temperatures were suitable for the formation of the main production of CaO, which can help us to understand the solid state reaction mechanism better. Via kinetic analysis of the reaction between anthracite and FGD gypsum under the optimal molar ratio of C/CaSO 4 , the mechanism model of the reaction was confirmed and the decomposition process was a two-step reaction which was in accordance with apparent solid–solid reaction

  17. Radiological properties of a wax-gypsum compensator material

    Plessis, F.C.P. du; Willemse, C.A.

    2005-01-01

    In this paper the radiological properties of a compensator material consisting of wax and gypsum is presented. Effective attenuation coefficients (EACs) have been determined from transmission measurements with an ion chamber in a Perspex phantom. Measurements were made at 80 and 100 cm source-to-skin distance (SSD) for beam energies of 6, 8, and 15 MV, for field sizes ranging from narrow beam geometries up to 40x40 cm 2 , and at measurement depths of maximum dose build-up, 5 and 10 cm. A parametrization equation could be constructed to predict the EAC values within 4% uncertainty as a function of field size and depth of measurement. The EAC dependence on off-axis position was also quantified at each beam energy and SSD. It was found that the compensator material reduced the required thickness for compensation by 26% at 8 MV when compared to pure paraffin wax for a 10x10 cm 2 field. Relative surface ionization (RSI) measurements have been made to quantify the effect of scattered electrons from the wax-gypsum compensator. Results indicated that for 80 cm SSD the RSI would exceed 50% for fields larger than 15x15 cm 2 . At 100 cm SSD the RSI values were below 50% for all field sizes used

  18. Incorporation of arsenic into gypsum: Relevant to arsenic removal and immobilization process in hydrometallurgical industry

    Zhang, Danni; Yuan, Zidan [Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016 (China); Wang, Shaofeng, E-mail: wangshaofeng@iae.ac.cn [Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016 (China); Jia, Yongfeng, E-mail: yongfeng.jia@iae.ac.cn [Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016 (China); Demopoulos, George P. [Department of Mining and Materials Engineering, McGill University, Montreal, QC H3A 2B2 (Canada)

    2015-12-30

    Highlights: • Quantitatively studied the incorporation of arsenic into the structure of gypsum. • Arsenic content in the solid increased with pH and initial arsenic concentration. • Calcium arsenate phase precipitated in addition to gypsum at higher pH values. • The structure of gypsum and its morphology was altered by the incorporated arsenate. • The incorporated arsenate formed sainfeldite-like local structure in gypsum. - Abstract: Gypsum precipitates as a major secondary mineral during the iron-arsenate coprecipitation process for the removal of arsenic from hydrometallurgical effluents. However, its role in the fixation of arsenic is still unknown. This work investigated the incorporation of arsenic into gypsum quantitatively during the crystallization process at various pHs and the initial arsenic concentrations. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray absorption near edge spectroscopy (XANES) and scanning electron microscopy (SEM) were employed to characterize the coprecipitated solids. The results showed that arsenate was measurably removed from solution during gypsum crystallization and the removal increased with increasing pH. At lower pH where the system was undersaturated with respect to calcium arsenate, arsenate ions were incorporated into gypsum structure, whereas at higher pH, calcium arsenate was formed and constituted the major arsenate bearing species in the precipitated solids. The findings may have important implications for arsenic speciation and stability of the hydrometallurgical solid wastes.

  19. Authigenic gypsum in a deep sea core from Southeastern Arabian Sea

    Guptha, M.V.S.

    Authigenic gypsum has been encountered in a deep sea core RC9-157 from the southeastern Arabian Sea at a depth of 4111 m which is a zone of lysocline. The formation of gypsum in the deep sea region is attributed to the prevailing sulphate rich...

  20. Hydrology of marginal evaporitic basins during the Messinian Salinity Crisis: isotopic investigation of gypsum deposits

    El Kilany, Aida; Caruso, Antonio; Dela Pierre, Francesco; Natalicchio, Marcello; Rouchy, Jean-Marie; Pierre, Catherine; Balter, Vincent; Aloisi, Giovanni

    2016-04-01

    The deposition of gypsum in Messinian Mediterranean marginal basins is controlled by basin restriction and the local hydrological cycle (evaporation/precipitation rates and relative importance of continental vs marine water inputs). We are using the stable isotopic composition of gypsum as a proxy of the hydrological cycle that dominated at the moment of gypsum precipitation. We studied the Messinian Caltanissetta (Sicily) and Tertiary Piedmont (north western Italy) basins where we carried out a high-resolution isotopic study of gypsum layers composing gypsum-marl cycles. These cycles are thought to be the sedimentary expression of astronomical precession cycles, lasting approximately 20 kyr, during which the marginal basins experienced a succession of arid and a wet conditions. We determined the isotopic composition of gypsum hydration water (18O and D), of the sulphate ion (34S, 18O) and of Strontium (87/86Sr), all of which are potentially affected by the hydrological cycle. In our samples, the mother water from which gypsum precipitated is considerably lighter (-4.0 micro-scale. This is an essential step in interpreting the isotopic signals of gypsum because we can expect the 18O and D composition of Messinian continental input to be not too dissimilar from that of modern meteoric waters involved in diagenetic processes.

  1. The Growth of Gypsum in the Presence of Hexavalent Chromium: A Multiscale Study

    Juan Morales

    2016-03-01

    Full Text Available The sorption of dissolved inorganic pollutants into the structure of minerals is an important process that controls the mobility and fate of these pollutants in the Earth’s crust. It also modifies the surface structure and composition of the host mineral, affecting its crystallization kinetics. Here, we investigate the effect of hexavalent chromium, Cr(VI, on the nucleation and growth of gypsum by conducting two types of experiments: (i in situ atomic force microscopy (AFM observations of the growth of gypsum {010} surfaces in the presence of Cr(VI and (ii gypsum precipitation experiments by mixing aqueous solutions containing variable amounts of Cr(VI. Gypsum precipitation is progressively delayed when occurring from solutions bearing increasing Cr(VI concentrations. Chemical analyses of gypsum precipitates show that gypsum incorporates small Cr(VI amounts that correlate with the content of this ion in the aqueous solution. Gypsum cell parameters variation reflects this incorporation. At the molecular scale, Cr(VI induces a slowdown of step advance rates on gypsum {010} surfaces accompanied by the roughening of nanostep edges and the so-called “template effect”. This effect involves the reproduction of the original nanotopography after the completion of individual advancing monolayers and appears as a general nanoscale phenomenon occurring during growth of solid solutions from aqueous solutions even in the case of compositionally-restricted solid solutions.

  2. Pre-contamination of new gypsum wallboard with potentially harmful fungal species

    Andersen, Birgitte; Dosen, Ina; Lewinska, Anna Malgorzata

    2017-01-01

    Gypsum wallboard is a popular building material, but is also very frequently overgrown by Stachybotrys chartarum after severe and/or undetected water damage. The purpose of this study was to determine whether Stachybotrys and other fungi frequently isolated from wet gypsum wallboard are already...

  3. Thermal conductivity of gypsum plasterboards : at ambient temperature and exposed to fire

    Korte, de A.C.J.; Brouwers, H.J.H.; Wald, F.; Kallerova, P.; Chlouba, J.

    2009-01-01

    One of the more complicated thermal properties to calculate for gypsum plasterboard is the thermal conductivity. The thermal conductivity is important because it plays an important role in the fire behaviour of gypsum plasterboards. Plasterboard often protects steel structures of buildings, because

  4. Use of FGD gypsum on a bermudagrass pasture in the Appalachian Plateau Region

    Addition of industrial by-products from coal fired power plants (FGD gypsum and FGD gypsum + fly ash) are thought to increase plant production. Thus, a study was conducted to evaluate the effects of industrial by-products as a soil amendment on bermudagrass (Cynodon dactylon L.) yield. The study was...

  5. Interaction mechanisms of europium and nickel with calcite

    Sabau, Andrea

    2015-01-01

    In the context of the safety assessment of an underground repository for nuclear waste, sorption reactions are one of the main processes to take into account to predict the migration of the radionuclides which might be transferred from the waste canisters to underground waters over geological time scales. Sorption of aqueous species on minerals can include adsorption processes, surface (co)-precipitation, and even incorporation in the bulk of the material, which can lead to the irreversibility of some sorption reactions. This work is focused on two elements: Eu(III) as an analogue of trivalent actinides and Ni(II) as activation product. Calcite was chosen as adsorbent due to its presence in Callovian-Oxfordian clay rocks. Our study combines batch experiments with spectroscopic techniques (TRLFS, RBS and SEM-EDXS) to elucidate the mechanisms occurring at Eu(III)/Ni(II) calcite interface. To obtain a better understanding on the systems, before starting sorption experiments, aqueous chemistry of Eu(III) and Ni(II) was carefully investigated. Macroscopic results showed a strong retention of Eu(III) on calcite, no matter the initial concentration, contact time and CO 2 partial pressure. Ni(II) was also readily sorbed by calcite, but the retention was influenced by contact time and concentration. Time-dependent sorption experiments showed a marked and slow increase of retention upon a long time range (up to 4 months).Desorption results indicated a partly reversible sorption for Ni(II). TRLFS highlighted the influence of initial concentration and contact time on the interaction of Eu(III) with calcite. With the help of RBS and SEM-EDXS, it enabled to discriminate between different mechanisms like surface precipitation, inner-sphere complexation and incorporation. RBS showed incorporation of Eu(III) into calcite up to 250 nm, contrary to Ni(II) which was located at the surface. (author) [fr

  6. Is bicarbonate stable in and on the calcite surface?

    Andersson, M. P.; Rodriguez-Blanco, J. D.; Stipp, S. L. S.

    2016-03-01

    We have used density functional theory with the COSMO-RS implicit solvent model to predict the pKa for the deprotonation of bicarbonate to carbonate, i.e. HCO3- CO32- + H+, when HCO3- is included in, and adsorbed on, a calcite surface. We have used cluster models (80-100 atoms) to represent the flat {10.4} surface, acute steps, obtuse steps, two types of kinks on the acute step and two types of kinks on the obtuse steps. Based on the predicted pKa values, which range from -6.0 to 2.4 depending on the surface site, we conclude that bicarbonate deprotonates to carbonate when it is in calcite even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 < pH < 6.35, where H2CO30 is the dominant dissolved species. When bicarbonate is adsorbed on calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution, 10.35. This means that adsorbed carbonate is stable even when the concentration of dissolved CO32- is several orders of magnitude lower. This has a significant effect on surface charge and thus the behaviour of the calcite surface. Our results help explain the potential determining behaviour of the carbonate species in calcite-water systems, particularly in the pH range where the bicarbonate species dominates in water and where the carbonate species dominates at the surface, i.e. when 7.5 < pH < 10.35. Our atomic scale data for the various calcite surface sites provide the needed input to improve and constrain surface complexation modelling and are especially useful for predicting behaviour in systems where experiments are difficult or impossible, such as at high temperature and pressure.

  7. Surface tension alteration on calcite, induced by ion substitution

    Sakuma, Hiroshi; Andersson, Martin Peter; Bechgaard, Klaus

    2014-01-01

    The interaction of water and organic molecules with mineral surfaces controls many processes in nature and industry. The thermodynamic property, surface tension, is usually determined from the contact angle between phases, but how does one understand the concept of surface tension at the nanoscale...... preferentially as ion pairs at solution-calcite interfaces. Mg2+ incorporation weakens organic molecule adhesion while strengthening water adsorption so Mg2+ substitution renders calcite more water wet. When Mg2+ replaces 10% of surface Ca2+, the contact angle changes dramatically, by 40 to 70, converting...

  8. Diagenetic alteration in low-Mg calcite from macrofossils

    Ullmann, Clemens Vinzenz; Korte, Christoph

    2015-01-01

    microscopy) and chemical (trace element abundances, isotopic ratios) screening techniques used to assess the alteration degree of low-Mg calcite macrofossils and summarize the findings on diagenetic trends observed for elemental and isotopic systems in such materials. For a robust evaluation...... of the preservation state of biogenic calcite, it is advisable to combine a set of complementary techniques. Absolute limiting values of element and isotope ratios for discarding diagenetically altered materials cannot be universally applied, but should rather be evaluated on a case to case basis. The evaluation can...

  9. Utah Marbles and Mars Blueberries: Comparitive Terrestrial Analogs for Hematite Concretions on Mars

    Chan, M. A.; Beitler, B.; Parry, W. T.; Ormö, J.; Komatsu, G.

    2005-03-01

    Compelling comparisons show why Utah iron oxide-cemented "marbles" are a good analog for Mars hematite "blueberries". Terrestrial examples offer valuable models for interpreting the diagenetic history and importance of water on Mars.

  10. Design, Fabrication, and Characterization of Hematite (α-Fe2O3) Nanostructures

    Jansi Rani, B.; Mageswari, R.; Ravi, G.; Ganesh, V.; Yuvakkumar, R.

    2017-12-01

    The influence of processing parameters on the physicochemical properties of hematite α-Fe2O3 nanostructures was investigated. X-ray diffraction results revealed the hematite phase rhombohedral structure. Scanning electron microscope results explored nanospheres, nanohexagonal platelets, nanoellipsoids, distorted nanocubes, and interconnected platelets nanostructures. Rhombohedral single-phase hematite was confirmed through five Raman active modes. 2 P 3/2 (1) → 2 P 1/2 transition in photoluminescence spectra and Fourier-transform infrared spectroscopy band observed at 555 cm-1 revealed the hematite formation. The highest specific capacitance value of 151.09 F/g for scan rate of 10 mV/s was obtained for the hydrothermal-assisted product using an Fe(NO3)2·9H2O precursor in KOH electrolyte solutions.

  11. Efficient removal of trace antimony(III) through adsorption by hematite modified magnetic nanoparticles

    Shan, Chao; Ma, Zhiyao; Tong, Meiping, E-mail: tongmeiping@pku.edu.cn

    2014-03-01

    Graphical abstract: - Highlights: • Sb(III) adsorption capacity of MNP@hematite was twice that of commercial Fe{sub 3}O{sub 4}. • pH, ionic strength, coexisting anions and NOM did not inhibit Sb(III) removal. • MNP@hematite could remove trace Sb(III) and As(III) from water simultaneously. • Efficient removal of Sb(III) from real tap water was achieved. • MNP@hematite could be easily recycled with a magnet and could be used repeatedly. - Abstract: Hematite coated magnetic nanoparticle (MNP@hematite) was fabricated through heterogeneous nucleation technique and used to remove trace Sb(III) from water. Powder X-ray diffraction, transmission electron microscopy (TEM), and alternating gradient magnetometry were utilized to characterize the prepared adsorbent. TEM image showed that MNP@hematite particles were spherical with size of 10–30 nm. With saturation magnetization of 27.0 emu/g, MNP@hematite particles could be easily separated from water with a simple magnetic process in short time (5 min). At initial concentration of 110 μg/L, Sb(III) was rapidly decreased to below 5 μg/L by MNP@hematite in 10 min. Sb(III) adsorption capacity of MNP@hematite was 36.7 mg/g, which was almost twice that of commercial Fe{sub 3}O{sub 4} nanoparticles. The removal of trace Sb(III) was not obviously affected by solution pH (over a wide range from 3 to 11), ionic strength (up to 100 mM), coexisting anions (chloride, nitrate, sulfate, carbonate, silicate, and phosphate, up to 10 mM) and natural organic matters (humic acid and alginate, up to 8 mg/L as TOC). Moreover, MNP@hematite particles were able to remove Sb(III) and As(III) simultaneously. Trace Sb(III) could also be effectively removed from real tap water by MNP@hematite. The magnetic adsorbent could be recycled and used repeatedly.

  12. Efficient removal of trace antimony(III) through adsorption by hematite modified magnetic nanoparticles

    Shan, Chao; Ma, Zhiyao; Tong, Meiping

    2014-01-01

    Graphical abstract: - Highlights: • Sb(III) adsorption capacity of MNP@hematite was twice that of commercial Fe 3 O 4 . • pH, ionic strength, coexisting anions and NOM did not inhibit Sb(III) removal. • MNP@hematite could remove trace Sb(III) and As(III) from water simultaneously. • Efficient removal of Sb(III) from real tap water was achieved. • MNP@hematite could be easily recycled with a magnet and could be used repeatedly. - Abstract: Hematite coated magnetic nanoparticle (MNP@hematite) was fabricated through heterogeneous nucleation technique and used to remove trace Sb(III) from water. Powder X-ray diffraction, transmission electron microscopy (TEM), and alternating gradient magnetometry were utilized to characterize the prepared adsorbent. TEM image showed that MNP@hematite particles were spherical with size of 10–30 nm. With saturation magnetization of 27.0 emu/g, MNP@hematite particles could be easily separated from water with a simple magnetic process in short time (5 min). At initial concentration of 110 μg/L, Sb(III) was rapidly decreased to below 5 μg/L by MNP@hematite in 10 min. Sb(III) adsorption capacity of MNP@hematite was 36.7 mg/g, which was almost twice that of commercial Fe 3 O 4 nanoparticles. The removal of trace Sb(III) was not obviously affected by solution pH (over a wide range from 3 to 11), ionic strength (up to 100 mM), coexisting anions (chloride, nitrate, sulfate, carbonate, silicate, and phosphate, up to 10 mM) and natural organic matters (humic acid and alginate, up to 8 mg/L as TOC). Moreover, MNP@hematite particles were able to remove Sb(III) and As(III) simultaneously. Trace Sb(III) could also be effectively removed from real tap water by MNP@hematite. The magnetic adsorbent could be recycled and used repeatedly

  13. ESR Studies and Dating of Egyptian Gypsum at Ras Mala'ab, Sinai, Egypt

    Abdel-Monem, A. A.; Abdei-Razek, Y. A.; Rasheed, N. M.; Hassan, G.M.; Eissa, H.M.; El-Morsy, M.

    2007-01-01

    A gypsum sample from the famous gypsum-anhydrite evaporitic deposit composing the Ras Mala'ab Formation, Upper Miocene, occurring at Ras Mala'ab, on the east coast of the Gulf of Suez, was subjected to (ESR) dosimetric studies. Also, (ESR) was used to date the formation or most recent recrystallization of that gypsum. The gypsum derivative (ESR) spectrum is characterized by the large broad Fe 2+ signal (g=2.50) and HF-sixtet Mn 2+ signals. Only the characteristic gypsum signal (G l, g=2.0040) was detected between the third and fourth lines of the HF-Mn 2+ which is attributed to the electron-center SO 3 - . This signal was sensitive to artificial γ-irradiation and showed significant enhancement using a γ-dose of 550 Gy. Also, the signal was very stable up to 400 o C. The gypsum sample with a total dose (TD) of 1500 Gy, determined graphically by extrapolating the linear relationship between defect concentration and the artificial γ-doses for (G l, g=2.0040) and an annual dose (D) due to cosmic rays (0.3 mGy), yielded an age of 5.00 Ma. This could mean the age of formation or latest recrystallization of this gypsum deposit. The geologic age assignment of the Ras Mala'ab Group including the evaporitic gypsum unit, is Middle to Late Miocene. It is directly overlain by the Pliocene elastics at the locality of Ras Mala'ab. This might suggest that these evaporitic gypsum facies represent the top of the Miocene in the Gulf of Suez area, since the Miocene-Pliocene boundary is now put at 5.00-5.50 Ma ago. Therefore, the ESR age of the Ras Mala'ab gypsum is consistent with the geologic age assignment

  14. Cretaceous joints in southeastern Canada: dating calcite-filled fractures

    Schneider, David; Spalding, Jennifer; Gautheron, Cécile; Sarda, Philippe; Davis, Donald; Petts, Duane

    2017-04-01

    To resolve the timing of brittle tectonism is a challenge since the classical chronometers required for analyses are not often in equilibrium with the surrounding material or simply absent. In this study, we propose to couple LA-ICP-MS U-Pb and (U-Th)/He dating with geochemical proxies in vein calcite to tackle this dilemma. We examined intracratonic Middle Ordovician limestone bedrock that overlies Mesoproterozoic crystalline basement, which are cut by NE-trending fault zones that have historic M4-5 earthquakes along their trace. E-W to NE-SW vertical joint sets, the relatively youngest stress recorded in the bedrock, possess 1-7 mm thick calcite veins that seal fractures or coat fracture surfaces. The veins possess intragranular calcite that are lined with fine-grained calcite along the vein margin and can exhibit µm- to mm-scale offset (e.g. displaced fossil fragments in host rock). Calcite d18O and d13C values are analogous to the bulk composition of Middle to Late Ordovician limestones, and suggest vein formation from a source dominated by connate fluids. The calcite contain trails of fluid inclusions commonly along fractures, and 3He/4He analyses indicate a primitive, deep fluid signature (R/Ra: 0.5-2.7). Trace element geochemistry of the calcite is highly variable, generally following the elevated HREE and lower LREE of continental crust trends but individual crystals from a single vein may vary by three orders of magnitude. LA-ICP-MS geochemical traverse across veins show elevated concentrations along (sub)grain boundaries and the vein-host rock contact. Despite abundant helium concentrations, (U-Th)/He dating was unsuccessful yielding highly dispersed dates likely from excess helium derived from the fluid inclusions. However, LA-ICP-MS U-Pb dating on calcite separated from the veins yielded model ages of 110.7 ± 6.8 Ma (MSWD: 0.53; n: 16) to 81.4 ± 8.3 Ma (MSWD: 2.6; n: 17). Since all veins are from the same ENE-trend, we regressed all the calcite dates

  15. Termomagnetic investigations influence coal and organic carbon on transformation structure of hematite to magnetite

    Dudchenko N.O.

    2014-12-01

    Full Text Available Thermomagnetic investigations of hematite into magnetite transformations by activated carbon and starch were carried-out using laboratory facility, that allows automatic registration of sample magnetization with the temperature (the rate of sample heating/cooling was 65-80°/min. It was shown, that reduction of hematite by starch occurs by the temperatures up to 650°С and leads to formation of magnetic material with saturation magnetization ~50 А*m2/kg. Reduction of hematite by activated coal in the same temperature range leads to formation of the product with saturation magnetization ~0,5 А*m2/kg. The problem of the development and introduction of new energy-efficient methods of enriching these types of iron ore, which can significantly increase the profitability of using oxidized iron ore in the creation of iron ore and iron ore solve the environmental problems of the regions. Thermomagnetic curves have received in magnetic hematite transformation product using as a reducing agent activated carbon ZL-302 and compare it with starch, proposed a method developed by us. It is shown that reduction of hematite to magnetite using coal ZL-302 is at a much higher temperature compared to starch. Recovery hematite by starch in the temperature range 400 ° -650 ° C results in a product with magnetization ~ 50 A * m2 / kg. Restoration of charcoal hematite in the same temperature range results in a product with magnetization ~ 0.5 A * m2 / kg, and when heated to 800 ° C magnetization increases to ~ 10 * m2 / kg. Thus, hematite ores starch recovery is less energy that can be used to develop new ways to get iron ore concentrates.

  16. Strontium-Doped Hematite as a Possible Humidity Sensing Material for Soil Water Content Determination

    Tulliani, Jean-Marc; Baroni, Chiara; Zavattaro, Laura; Grignani, Carlo

    2013-01-01

    The aim of this work is to study the sensing behavior of Sr-doped hematite for soil water content measurement. The material was prepared by solid state reaction from commercial hematite and strontium carbonate heat treated at 900 °C. X-Ray diffraction, scanning electron microscopy and mercury intrusion porosimetry were used for microstructural characterization of the synthesized powder. Sensors were then prepared by uniaxially pressing and by screen-printing, on an alumina substrate, the prep...

  17. PPF-reinforced, ESP-lightened gypsum plaster

    García Santos, A.

    2009-03-01

    Full Text Available A new construction material has been obtained by adding aggregate to gypsum plaster which, without reducing the bending strength of plain gypsum plaster without aggregates, lowers its density, and consequently the weight of the construction elements made from the agglomerated material, by half.The aggregates used were expanded polystyrene beads and short polypropylene fibre.The new material addresses one of the issues of cardinal interest in construction materials and construction element research, namely the need to lighten materials so as to ease the burden on buildings’ bearing structures while facilitating assembly of construction units, by a single worker wherever possible.With a water / binder ratio of 0.7 and 2% (by weight of plaster of expanded polystyrene and 2% of polypropylene fibre aggregates, the decline in density achieved was 50,88% over plain gypsum plaster and 32.88% over plasterboard.Se ha obtenido un nuevo material de construcción aditivando el yeso o la escayola, mediante la incorporación de agregados, de modo que sin reducir la resistencia a flexotracción de una escayola sin ningún tipo de adición, reduce su densidad a la mitad, y por tanto, el peso de los elementos constructivos que puedan realizarse basándose en él.El material está compuesto por una adición de gránulos de poliestireno expandido y fibras cortadas de polipropileno.El nuevo material incide sobre aquellos aspectos de más interés en el campo de la investigación en construcción, en donde se intenta reducir el peso de los materiales, de modo que se grave lo menos posible la estructura resistente de las edificaciones, a la par que se facilitan los procedimientos de montaje de las unidades constructivas, al poder ser manejadas por un solo operario.La escayola, con relación de agua/conglomerante de 0,7, y con adiciones del 2% en peso (sobre la cantidad de escayola, tanto de poliestireno expandido como de fibras de polipropileno, permite reducir la

  18. Microbially induced separation of quartz from hematite using sulfate reducing bacteria.

    Prakasan, M R Sabari; Natarajan, K A

    2010-07-01

    Cells and metabolic products of Desulfovibrio desulfuricans were successfully used to separate quartz from hematite through environmentally benign microbially induced flotation. Bacterial metabolic products such as extracellular proteins and polysaccharides were isolated from both unadapted and mineral-adapted bacterial metabolite and their basic characteristics were studied in order to get insight into the changes brought about on bioreagents during adaptation. Interaction between bacterial cells and metabolites with minerals like hematite and quartz brought about significant surface-chemical changes on both the minerals. Quartz was rendered more hydrophobic, while hematite became more hydrophilic after biotreatment. The predominance of bacterial polysaccharides on interacted hematite and of proteins on quartz was responsible for the above surface-chemical changes, as attested through adsorption studies. Surface-chemical changes were also observed on bacterial cells after adaptation to the above minerals. Selective separation of quartz from hematite was achieved through interaction with quartz-adapted bacterial cells and metabolite. Mineral-specific proteins secreted by quartz-adapted cells were responsible for conferment of hydrophobicity on quartz resulting in enhanced separation from hematite through flotation. 2010 Elsevier B.V. All rights reserved.

  19. Solution chemistry of carbonate minerals and its effects on the flotation of hematite with sodium oleate

    Li, Dong; Yin, Wan-zhong; Xue, Ji-wei; Yao, Jin; Fu, Ya-feng; Liu, Qi

    2017-07-01

    The effects of carbonate minerals (dolomite and siderite) on the flotation of hematite using sodium oleate as a collector were investigated through flotation tests, supplemented by dissolution measurements, solution chemistry calculations, zeta-potential measurements, Fourier transform infrared (FTIR) spectroscopic studies, and X-ray photoelectron spectroscopy (XPS) analyses. The results of flotation tests show that the presence of siderite or dolomite reduced the recovery of hematite and that the inhibiting effects of dolomite were stronger. Dissolution measurements, solution chemistry calculations, and flotation tests confirmed that both the cations (Ca2+ and Mg2+) and CO3 2- ions dissolved from dolomite depressed hematite flotation, whereas only the CO3 2- ions dissolved from siderite were responsible for hematite depression. The zeta-potential, FTIR spectroscopic, and XPS analyses indicated that Ca2+, Mg2+, and CO3 2- (HCO3 -) could adsorb onto the hematite surface, thereby hindering the adsorption of sodium oleate, which was the main reason for the inhibiting effects of carbonate minerals on hematite flotation.

  20. Use of interfacial layers to prolong hole lifetimes in hematite probed by ultrafast transient absorption spectroscopy

    Paradzah, Alexander T.; Diale, Mmantsae; Maabong, Kelebogile; Krüger, Tjaart P. J.

    2018-04-01

    Hematite is a widely investigated material for applications in solar water oxidation due primarily to its small bandgap. However, full realization of the material continues to be hampered by fast electron-hole recombination rates among other weaknesses such as low hole mobility, short hole diffusion length and low conductivity. To address the problem of fast electron-hole recombination, researchers have resorted to growth of nano-structured hematite, doping and use of under-layers. Under-layer materials enhance the photo-current by minimising electron-hole recombination through suppressing of back electron flow from the substrate, such as fluorine-doped tin oxide (FTO), to hematite. We have carried out ultrafast transient absorption spectroscopy on hematite in which Nb2O5 and SnO2 materials were used as interfacial layers to enhance hole lifetimes. The transient absorption data was fit with four different lifetimes ranging from a few hundred femtoseconds to a few nanoseconds. We show that the electron-hole recombination is slower in samples where interfacial layers are used than in pristine hematite. We also develop a model through target analysis to illustrate the effect of under-layers on electron-hole recombination rates in hematite thin films.

  1. Oxygen vacancy doping of hematite analyzed by electrical conductivity and thermoelectric power measurements

    Mock, Jan; Klingebiel, Benjamin; Köhler, Florian; Nuys, Maurice; Flohre, Jan; Muthmann, Stefan; Kirchartz, Thomas; Carius, Reinhard

    2017-11-01

    Hematite (α -F e2O3 ) is known for poor electronic transport properties, which are the main drawback of this material for optoelectronic applications. In this study, we investigate the concept of enhancing electrical conductivity by the introduction of oxygen vacancies during temperature treatment under low oxygen partial pressure. We demonstrate the possibility of tuning the conductivity continuously by more than five orders of magnitude during stepwise annealing in a moderate temperature range between 300 and 620 K. With thermoelectric power measurements, we are able to attribute the improvement of the electrical conductivity to an enhanced charge-carrier density by more than three orders of magnitude. We compare the oxygen vacancy doping of hematite thin films with hematite nanoparticle layers. Thereby we show that the dominant potential barrier that limits charge transport is either due to grain boundaries in hematite thin films or due to potential barriers that occur at the contact area between the nanoparticles, rather than the potential barrier within the small polaron hopping model, which is usually applied for hematite. Furthermore, we discuss the transition from oxygen-deficient hematite α -F e2O3 -x towards the magnetite F e3O4 phase of iron oxide at high density of vacancies.

  2. Hydrogen Reduction of Hematite Ore Fines to Magnetite Ore Fines at Low Temperatures

    Wenguang Du

    2017-01-01

    Full Text Available Surplus coke oven gases (COGs and low grade hematite ores are abundant in Shanxi, China. Our group proposes a new process that could simultaneously enrich CH4 from COG and produce separated magnetite from low grade hematite. In this work, low-temperature hydrogen reduction of hematite ore fines was performed in a fixed-bed reactor with a stirring apparatus, and a laboratory Davis magnetic tube was used for the magnetic separation of the resulting magnetite ore fines. The properties of the raw hematite ore, reduced products, and magnetic concentrate were analyzed and characterized by a chemical analysis method, X-ray diffraction, optical microscopy, and scanning electron microscopy. The experimental results indicated that, at temperatures lower than 400°C, the rate of reduction of the hematite ore fines was controlled by the interfacial reaction on the core surface. However, at temperatures higher than 450°C, the reaction was controlled by product layer diffusion. With increasing reduction temperature, the average utilization of hydrogen initially increased and tended to a constant value thereafter. The conversion of Fe2O3 in the hematite ore played an important role in the total iron recovery and grade of the concentrate. The grade of the concentrate decreased, whereas the total iron recovery increased with the increasing Fe2O3 conversion.

  3. Sorption of 241Am onto montmorillonite, illite and hematite colloids

    Degueldre, C.; Ulrich, H.J.; Silby, H.

    1994-01-01

    Actinide sorption on colloids may be described as a competition between the formation of complexes in solution and the build up of surface complexes. The role of particle and of carbonate concentrations on the sorption/desorption of 241 Am on montmorillonite, illite and hematite colloids is investigated. Since the partition coefficient (K p ) values are virtually independent of the colloid concentrations, within the range 1 to 300 ppm, no significant aggregation takes place in the sorption/desorption experiment. At pH 8, a slight decrease of K p is observed if the concentration of total carbonate exceeds 10 -2 M. The formation of the carbonato- (and hydroxo-carbonato-) complexes in the solution competes with the formation of surface complexes on the colloids. A relationship between the sorption coefficient and the complexation of 241 Am in the solution has been found. This leads to the conclusion that, besides free americium cation, the hydroxo-, and carbonato- as well as the mixed hydroxo-carbonato-complexes are sorbed. Only when the tricarbonatocomplex [Am(CO 3 ) 3 ] 3- prevails (total carbonate concentration > 10 -2 M), a significant decrease of the distribution coefficient is observed. At pH 10 this decrease disappears because under these conditions the strong hydroxo-complexes dominate. A pragmatic and relatively simple application of surface complexation model describes the observed features. (orig.)

  4. Probing size-dependent electrokinetics of hematite aggregates

    Kedra-Królik, Karolina; Rosso, Kevin M.; Zarzycki, Piotr

    2017-02-01

    Aqueous particle suspensions of many kinds are stabilized by the electrostatic potential developed at their surfaces from reaction with water and ions. An important and less well understood aspect of this stabilization is the dependence of the electrostatic surface potential on particle size. Surface electrostatics are typically probed by measuring particle electrophoretic mobilities and quantified in the electrokinetic potential (f), using commercially available Zeta Potential Analyzers (ZPA). Even though ZPAs provide frequency-spectra (histograms) of electrophoretic mobility and hydrodynamic diameter, typically only the maximal-intensity values are reported, despite the information in the remainder of the spectra. Here we propose a mapping procedure that inter-correlates these histograms to extract additional insight, in this case to probe particle size-dependent electrokinetics. Our method is illustrated for a suspension of prototypical iron (III) oxide (hematite, a-Fe2O3). We found that the electrophoretic mobility and f-potential are a linear function of the aggregate size. By analyzing the distribution of surface site types as a function of aggregate size we show that site coordination increases with increasing aggregate diameter. This observation explains why the acidity of the iron oxide particles decreases with increasing particle size.

  5. Kinetics of Photoelectrochemical Oxidation of Methanol on Hematite Photoanodes

    2017-01-01

    The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on α-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on α-Fe2O3 to formaldehyde with near unity Faradaic efficiency. A rate law analysis under quasi-steady-state conditions of PEC methanol oxidation indicates that rate of reaction is second order in the density of surface holes on hematite and independent of the applied potential. Analogous data on anatase TiO2 photoanodes indicate similar second-order kinetics for methanol oxidation with a second-order rate constant 2 orders of magnitude higher than that on α-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on α-Fe2O3 is retarded ∼20-fold by H/D substitution. Employing these data, we propose a mechanism for methanol oxidation under 1 sun irradiation on these metal oxide surfaces and discuss the implications for the efficient PEC methanol oxidation to formaldehyde and concomitant hydrogen evolution. PMID:28735533

  6. Potential-specific structure at the hematite-electrolyte interface

    McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter; Rosso, Kevin M.

    2018-02-21

    The atomic-scale structure of interfaces between metal oxides and aqueous electrolytes controls their catalytic, geochemical, and corrosion behavior. Measurements that probe these interfaces in situ provide important details of ion and solvent arrangements, but atomically precise structural models do not exist for common oxide-electrolyte interfaces far from equilibrium. Using a novel cell, we measured the structure of the hematite (a-Fe2O3) (110$\\bar{2}$)-electrolyte interface under controlled electrochemical bias using synchrotron crystal truncation rod X ray scattering. At increasingly cathodic potentials, charge-compensating protonation of surface oxygen groups increases the coverage of specifically bound water while adjacent water layers displace outwardly and became disordered. Returning to open circuit potential leaves the surface in a persistent metastable protonation state. The flux of current and ions at applied potential is thus regulated by a unique interfacial electrolyte environment, suggesting that electrical double layer models should be adapted to the dynamically changing interfacial structure far from equilibrium.

  7. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    Madsen, Lene; Grahl-Madsen, Laila; Grøn, Christian

    1996-01-01

    The wettability of hydrocarbon reservoirs depends on how and to what extent the organic compounds are adsorbed onto the surfaces of calcite, quartz and clay. A model system of synthetic call cite, cyclohexane and the three probe molecules: benzoic acid, benzyl alcohol and benzylamine, have been...

  8. Isolation and identification of Pseudomonas azotoformans for induced calcite precipitation.

    Heidari Nonakaran, Siamak; Pazhouhandeh, Maghsoud; Keyvani, Abdullah; Abdollahipour, Fatemeh Zahra; Shirzad, Akbar

    2015-12-01

    Biomineralization is a process by which living organisms produce minerals. The extracellular production of these biominerals by microbes has potential for various bioengineering applications. For example, crack remediation and improvement of durability of concrete is an important goal for engineers and biomineral-producing microbes could be a useful tool in achieving this goal. Here we report the isolation, biochemical characterization and molecular identification of Pseudomonas azotoformans, a microbe that produces calcite and which potentially be used to repair cracks in concrete structures. Initially, 38 bacterial isolates were isolated from soil and cements. As a first test, the isolates were screened using a urease assay followed by biochemical tests for the rate of urea hydrolysis, calcite production and the insolubility of calcite. Molecular amplification and sequencing of a 16S rRNA fragment of selected isolates permitted us to identify P. azotoformans as a good candidate for preparation of biotechnological concrete. This species was isolated from soil and the results show that among the tested isolates it had the highest rate of urea hydrolysis, produced the highest amount of calcite, which, furthermore was the most adhesive and insoluble. This species is thus of interest as an agent with the potential ability to repair cracks in concrete.

  9. Radiation-induced paramagnetic species in natural calcite speleothems

    Rossi, A.M.; Poupeau, G.

    1989-01-01

    The ESR natural spectrum of humic-free speleothem calcite single crytals in the region of g = 2.0000 is a composite of lines from 4 radiogenic species, in addition to Mn ++ lines. Laboratory irradiation causes appearrance of three more species. Use of isotropic F species (g = 2.0003) for dating is possible if specific cautions are followed. (author) [pt

  10. Removal of trace elements from landfill leachate by calcite precipitation

    Ettler, V.; Zelená, O.; Mihaljevič, M.; Šebek, O.; Strnad, L.; Coufal, P.; Bezdička, Petr

    2006-01-01

    Roč. 88, 1-3 (2006), s. 28-31 ISSN 0375-6742 R&D Projects: GA AV ČR(CZ) KJB3111402 Institutional research plan: CEZ:AV0Z40320502 Keywords : landfill leachate * calcite * scavenging Subject RIV: CA - Inorganic Chemistry Impact factor: 0.922, year: 2006

  11. Immobilization of nanoparticles by occlusion into microbial calcite

    Skuce, Rebecca L.; Tobler, Dominique Jeanette; MacLaren, Ian

    2017-01-01

    systems. In this study, the ureolytic bacteria Sporosarcina pasteurii was used to induce calcium carbonate precipitation in the presence of organo-metallic manufactured nanoparticles. As calcite crystals grew the nanoparticles in the solution became trapped inside these crystals. Capture of NPs within...

  12. Constructive applications of composite gypsum reinforced with Typha Latifolia fibres

    Garcia Santos, A.

    2004-03-01

    Full Text Available The present research analyses the possibility to reinforce gypsum using enea fibres (Typha Latifolia creating a compound material in wich the fibres contribute to increase mechanical resistance, producing as well a reduction of the weight and a possible regulation of the set time.

    La investigación presente analiza la posibilidad de reforzar los morteros de escayola mediante la utilización dé fibras de Typha Latifolia, creando un material compuesto en el que las fibras contribuyen al aumento de resistencia mecánica, a la vez que se produce una reducción del peso y una regulación de los tiempos de fraguado. Las propiedades de estos materiales hacen que, en determinadas aplicaciones, su utilización resulte ventajosa con respecto a materiales tradicionales.

  13. Corrosion of bare and galvanized steel in gypsum

    Gómez, Mercedes

    1988-12-01

    Full Text Available Gypsum is a relatively low-cost building material much abounding in our country. When it is put in contact with steel, it may produce high corrosion rates due to its pH value (close to 7. This work reports the results obtained in studying the corrosion rates of bare and galvanized steel in contact with gypsum and plaster, as well as the influence curing thermal treatment applied to gypsum, enviromental relative humidity and addition of compounds with different natures and purposes may have in such process. In-situ observations, as well as the measurement of the Polarization Resistance and the weight loss have been used as measurement technics. From the results obtained it has been possible to deduce that galvanized steel has better behaviour in dry enviroments than bare steel in the same conditions and moist atmosphere induces proportionally more corrosion in galvanized steel than in bare one. Additions to gypsum do not modified these conclusions, though it may be pointed out that addition of nitrites or lime improves the behaviour of bare steel, while galvanized behaviour is not modified. The addition of lime is not recommended because phenomena of dilated along time expansion may take place.

    El yeso es un material de construcción de relativo bajo coste y que, además, es muy abundante en nuestro país. Debido a su pH cercano a la neutralidad, cuando entra en contacto con el acero, este puede corroerse a elevadas velocidades. En esta comunicación se presentan los resultados de un estudio sobre la velocidad de corrosión del acero desnudo y galvanizado en contacto con yeso y escayola y la influencia que tienen: el tratamiento térmico del curado del yeso, la humedad relativa ambiental y la adición de aditivos de diversa naturaleza y finalidad. Como técnicas de medida se han utilizado la medida de la Resistencia de Polarización y de la pérdida de peso, así como observaciones visuales. De los resultados se puede deducir que en

  14. Optically stimulated luminescence dosimetry with gypsum wallboard (drywall)

    Thompson, J. W.; Burdette, K. E.; Inrig, E. L.; Dewitt, R.; Mistry, R.; Rink, W. J.; Boreham, D. R.

    2010-01-01

    Gypsum wallboard (drywall) represents an attractive target for retrospective dosimetry by optically stimulated luminescence (OSL) in the event of a radiological accident or malicious use of nuclear material. In this study, wallboard is shown to display a radiation-induced luminescence signal (RIS) as well as a natural background signal (NS), which is comparable in intensity to the RIS. Excitation and emission spectra show that maximum luminescence intensity is obtained for stimulation with blue light-emitting diodes (470 nm) and for detection in the ultraviolet region (290-370 nm). It is necessary to decrease the optical stimulation power dramatically in order to adequately separate the RIS from the interfering background signal. The necessary protocols are developed for accurately measuring the absorbed dose as low as 500 mGy and demonstrate that the RIS decays logarithmically with storage time, with complete erasure expected within 1-4 d. (authors)

  15. Preliminary U-Th Dating of Endogenic Gypsum From Lake Petén-Itzá, Guatemala

    Gamble, V. C.; Gallup, C. D.; Hodell, D.; Anselmetti, F.; Brenner, M.; Ariztegui, D.

    2007-05-01

    Uranium-thorium dating of lake sediments can provide accurate ages beyond the range of radiocarbon dating. Many lakes have endogenic precipitation of calcium bearing minerals that allow for substitution by uranium within their crystal structures. The water chemistry of Lake Petén-Itzá, located in northern Guatemala, is dominated by calcium, sulfate and carbonate ions (Deevey et al. 1980; Curtis et al. 1998). Changes in regional climate due to suspected shifts in the ITCZ over the past 85,000 years resulted in both calcite and gypsum deposition, especially during drier periods (Hodell et al. 2006). Both precipitates incorporate uranium from the lake water and can be used for U-Th dating. U-Th dating is problematic in lake systems for several reasons: the potential for 1) diagenetic alteration or dissolution while the endogenic precipitates are settling and after deposition and 2) contamination by detrital thorium. Contamination is a primary issue because of the difficulty of separating the precipitates from the sediment. Despite these concerns, U-Th dating of lake sediments has the potential to be successful with careful selection of precipitates and thorough analysis of the precipitate, the lake system, and the diagenetic environment. Preliminary samples of Lake Petén-Itzá gypsum contain euhedral crystals, indicating a lack of post-depositional alteration. However, the samples have high background thorium levels, indicating the necessity of using the U-Th total sample dissolution isochron dating method (as described by Ku, 2000) to quantify authigenic thorium. Curtis J.H., Brenner M., Hodell D.A., Balser R.A., Islebe G.A., Hooghiemstra H. 1998. A multi-proxy study of Holocene environmental change in the Maya lowlands of Petén, Guatemala. Journal of Paleolimnology 19, 139-159. Deevey E.S., Brenner M., Flannery M.S., Yezdani G.H. 1980. Lakes Yaxha and Scanab, Petén, Guatemala: Limnology and hydrology. Arch. Hydrobiol. 57, 419-460. Hodell D.A., Anselmetti F

  16. Molecular ordering of ethanol at the calcite surface.

    Pasarín, I S; Yang, M; Bovet, N; Glyvradal, M; Nielsen, M M; Bohr, J; Feidenhans'l, R; Stipp, S L S

    2012-02-07

    To produce biominerals, such as shells, bones, and teeth, living beings create organic compounds that control the growth of the solid phase. Investigating the atomic scale behavior of individual functional groups at the mineral-fluid interface provides fundamental information that is useful for constructing accurate predictive models for natural systems. Previous investigations of the activity of coccolith-associated polysaccharides (CAP) on calcite, using atomic force microscopy (AFM) [Henriksen, K., Young, J. R., Bown, P. R., and Stipp, S. L. S. Palentology 2004, 43 (Part 3), 725-743] and molecular dynamics (MD) modeling [Yang, M., Stipp, S. L. S., and Harding, J. H. Cryst. Growth Des. 2008, 8 (11), 4066-4074], have suggested that OH functional groups control polysaccharide attachment. The purpose of this work was to characterize, using X-ray reflectivity (XR) combined with molecular dynamics (MD) simulations, the structuring on calcite of a layer of the simplest carbon chain molecule that contains an OH group, ethanol (CH(3)-CH(2)-OH). We found evidence that EtOH forms a highly ordered structure at the calcite surface, where the first layer molecules bond with calcite. The ethanol molecules stand up perpendicularly at the interface or nearly so. As a consequence, the fatty, CH(3) ends form a new surface, about 6 Å from the termination of the bulk calcite, and beyond that, there is a thin gap where ethanol density is low. Following is a more disordered layer that is two to three ethanol molecules thick, about 14 Å, where density more resembles that of bulk liquid ethanol. The good agreement between theory and experiment gives confidence that a theoretical approach can offer information about behavior in more complex systems.

  17. Influence of gypsum amendment on methane emission from paddy rice soil affected by saline irrigation water

    Ei Ei eTheint

    2016-01-01

    Full Text Available To investigate the influence of gypsum application on methane (CH4 emission from paddy rice soil affected by saline irrigation water, two pot experiments with the rice cultivation were conducted. In pot experiment (I, salinity levels 30 mMNaCl (S30 and 90 mMNaCl (S90, that showed maximum and minimum CH4 production in an incubation experiment, respectively, were selected and studied without and with application of 1 Mg gypsum ha-1(G1. In pot experiment (II, CH4 emission was investigated under different rates of gypsum application: 1 (G1, 2.5 (G2.5 and 5 (G5 Mg gypsum ha-1 under a non-saline and saline condition of 25 mMNaCl (S25. In experiment (I, the smallest CH4 emission was observed in S90. Methane emission in S30 was not significantly different with the non-saline control. The addition of gypsum showed significant lower CH4 emission in saline and non-saline treatments compared with non-saline control. In experiment (II, the CH4 emissions in the saline treatments were not significantly different to the non-saline treatments except S25-G5. However, our work has shown that gypsum can lower CH4 emissions under saline and non-saline conditions. Thus, gypsum can be used as a CH4 mitigation option in non-saline as well as in saline conditions.

  18. Use of gypsum residues as a corrective for saline-sodic soil

    Paulo Medeiros dos Santos

    2014-03-01

    Full Text Available One of the hugest problems faced by the civil construction sector is the final destination of residues, especially gypsum, which presents recycling restrictions. However, these residues present a high amount of calcium in their composition, and can be alternatively used for replacing mined gypsum as a saline-sodic soil corrective. This study aimed at evaluating the efficiency of gypsum residues from the civil construction, when compared to mined gypsum, for correcting a saline-sodic soil. A randomized blocks design was used, in a factorial arrangement consisting of two kinds of corrective (gypsum residue and mined gypsum and five leaching depths (0.5, 1.0, 1.5, 2.0 and 2.5 times the soil pores volume, with three replications. Electric conductivity, soluble cations and sodium adsorption ratio were evaluated in the soil saturation extract. The use of gypsum residue proved to be effective in leaching salts and soluble sodium in saline-sodic soil, and can be recommended as a calcium source for recovering from sodicity.

  19. Initiation and growth of gypsum piercement structures in the Zechstein Basin

    Williams-Stroud, S. C.; Paul, J.

    1997-01-01

    The importance of tectonic processes in initiating halite diapirs has become much better understood in recent years. Less well understood is the development of diapiric structures involving rocks composed predominantly of gypsum. Below about 1000 m, gypsum dehydrates to anhydrite, which often obscures primary sedimentary textures. If the strain associated with diapiric rise in the rock induces the transition to anhydrite, obliteration of primary features in the gypsum can be expected. In our study, we infer that the diapiric movement in the Werra Anhydrite member of cycle 1 of the Zechstein Formation of Europe occurred before the initial transition of gypsum to anhydrite based on the presence of pseudomorphs of bedded primary gypsum crystals, the overburden lithologies and depositional environment, and the mechanical properties of gypsum, anhydrite and carbonate rocks. Faulting and differential loading of a shallow overburden were the key components in initiating the gypsum diapirism. The transition to anhydrite occurred after burial and after cessation of diapirism. In comparison, the diapirism of calcium sulfate of the Leine Anhydrite into the Leine Halite members of cycle 3 of the Zechstein Formation probably occurred much later after burial and appears to have been triggered by halite diapirism, which in turn triggered the dehydration reaction, causing the calcium sulfate to become the incompetent phase relative to the halite. Published by Elsevier Science Ltd.

  20. UTILIZATION OF MINERAL FIBER WASTE IN THE PRODUCTION OF GYPSUM PRODUCTS

    Solov'ev Vitaliy Nikolaevich

    2018-01-01

    Full Text Available Subject: the effectiveness of using compositions with the use of basalt fibers is proven, but the composition must be selected depending on the binder and additives chosen. Research objectives: we examine the possibility of waste recycling of basalt fiber production during manufacturing of modified gypsum composite material with improved characteristics. Materials and methods: as a raw material, a gypsum binder of Samara production was used. As a reinforcement additive, a disperse waste of basalt fiber production of Tver region was used. Studying characteristics of the gypsum binder and modified mixture, and also comparative analysis of these characteristics by average density, total porosity, strength in compression and flexure of the gypsum composite were carried out using standard techniques. Results: dependence of physical and mechanical properties of the modified gypsum material on the content of the basalt fiber additive is established. It was found that an increase in concentration of the additive requires an increased water content or additional use of plasticizer. Conclusions: modification of gypsum stone with a mineral basalt additive will increase the strength, density and durability of thin-walled gypsum products, and, consequently, the demand for products due to ensuring their high quality in transportation and installation.

  1. Structural incorporation of Neptunyl(V) into Calcite: Interfacial Reactions and Kinetics

    Heberling, Frank

    2010-01-01

    In this experimental work the calcite-water interface is characterized by means of zetapotential and surface diffraction measurements. Based on the experimental results a new Basic Stern Surface Complexation model for calcite is developed. Neptunyl(V) adsorption at the calcite surface and incorporation into the calcite structure is studied by batch type adsorption- and mixed flow reactor experiments. Adsorption and incorporation species of Neptunyl are investigated by EXAFS spectroscopy.

  2. Influence of Flue Gas Desulfurization Gypsum Amendments on Heavy Metal Distribution in Reclaimed Sodic Soils

    Chen, Qun; Wang, Shujuan; Li, Yan; Zhang, Ning; Zhao, Bo; Zhuo, Yuqun; Chen, Changhe

    2015-01-01

    Abstract Although flue gas desulfurization (FGD) gypsum has become an effective soil amendment for sodic soil reclamation, it carries extra heavy metal contamination into the soil environment. The fate of heavy metals introduced by FGD gypsum in sodic or saline–alkali soils is still unclear. This work aims to investigate the effects of FGD gypsum addition on the heavy metal distributions in a sodic soil. Original soil samples were collected from typical sodic land in north China. Soil column leaching tests were conducted to investigate the influence of FGD gypsum addition on the soil properties, especially on distribution profiles of the heavy metals (Pb, Cd, Cr, As, and Hg) in the soil layers. Results showed that pH, electrical conductivity, and exchangeable sodium percentage in amended soils were significantly reduced from 10.2 to 8.46, 1.8 to 0.2 dS/m, and 18.14% to 1.28%, respectively. As and Hg concentrations in the soils were found to be positively correlated with FGD gypsum added. The amount of Hg in the leachate was positively correlated with FGD gypsum application ratio, whereas a negative correlation was observed between the Pb concentration in the leachate and the FGD gypsum ratio. Results revealed that heavy metal concentrations in soils complied well with Environmental Quality Standard for Soils in China (GB15618-1995). This work helps to understand the fate of FGD gypsum-introduced heavy metals in sodic soils and provides a baseline for further environmental risk assessment associated with applying FGD gypsum for sodic soil remediation. PMID:26064038

  3. Influence of Flue Gas Desulfurization Gypsum Amendments on Heavy Metal Distribution in Reclaimed Sodic Soils.

    Chen, Qun; Wang, Shujuan; Li, Yan; Zhang, Ning; Zhao, Bo; Zhuo, Yuqun; Chen, Changhe

    2015-06-01

    Although flue gas desulfurization (FGD) gypsum has become an effective soil amendment for sodic soil reclamation, it carries extra heavy metal contamination into the soil environment. The fate of heavy metals introduced by FGD gypsum in sodic or saline-alkali soils is still unclear. This work aims to investigate the effects of FGD gypsum addition on the heavy metal distributions in a sodic soil. Original soil samples were collected from typical sodic land in north China. Soil column leaching tests were conducted to investigate the influence of FGD gypsum addition on the soil properties, especially on distribution profiles of the heavy metals (Pb, Cd, Cr, As, and Hg) in the soil layers. Results showed that pH, electrical conductivity, and exchangeable sodium percentage in amended soils were significantly reduced from 10.2 to 8.46, 1.8 to 0.2 dS/m, and 18.14% to 1.28%, respectively. As and Hg concentrations in the soils were found to be positively correlated with FGD gypsum added. The amount of Hg in the leachate was positively correlated with FGD gypsum application ratio, whereas a negative correlation was observed between the Pb concentration in the leachate and the FGD gypsum ratio. Results revealed that heavy metal concentrations in soils complied well with Environmental Quality Standard for Soils in China (GB15618-1995). This work helps to understand the fate of FGD gypsum-introduced heavy metals in sodic soils and provides a baseline for further environmental risk assessment associated with applying FGD gypsum for sodic soil remediation.

  4. Sorption and catalytic oxidation of Fe(II) at the surface of calcite

    Mettler, S.; Wolthers, M.; Charlet, L.; Von Gunten, U.

    The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps:

  5. Influence of shelf life on the setting time of type IV gypsum

    Hapsari, M. L.; Irawan, B.; Damiyanti, M.

    2017-08-01

    Although expired materials can exhibit a deterioration in their properties, expired type IV gypsum can still be found on the market. In order to evaluate the influence of the shelf life on its setting time, two groups of type IV gypsum (GC Fuji rock EP) with different expiration dates were used in this research. The setting time tests were done in a mold using a Vicat Needle apparatus. The results of the statistical analysis showed a significant difference (pshelf life did influence the setting time of the type IV gypsum.

  6. Investigation of the gypsum quality at three full-scale wet flue gas desulphurisation plants

    Hansen, Brian Brun; Kiil, Søren; Johnsson, Jan Erik

    2011-01-01

    In the present study the gypsum (CaSO4·2H2O) quality at three full-scale wet flue gas desulphurisation (FGD) plants and a pilot plant were examined and compared. Gypsum quality can be expressed in terms of moisture content (particle size and morphology dependent) and the concentration of residual......, low moisture content and low impurity content). An episode concerning a sudden deterioration in the gypsum dewatering properties was furthermore investigated, and a change in crystal morphology, as well as an increased impurity content (aluminium, iron and fluoride), was detected....

  7. Determination of Radium 226 in mexican phosphate fertilizers and gypsum by gamma spectrometry

    Godinez A, M.C.

    1995-01-01

    The 226 Ra isotope was determined in 17, 20 and 46% m/m phosphate fertilizers and gypsum. The samples of the fertilizers were dissolved in 10% v/v nitric acid solutions. The barium sulphate method was used for the precipitation of 226 Ra. On the other hand, alkaline fusion method was used to separate the 226 Ra from gypsum. The results indicated that 226 Ra was present in the phosphate fertilizers and gypsum. The 226 Ra concentrations present in these materials were between 10 -4 - 10 -5 μg g -1 . (Author)

  8. Impact of environmental conditions on aggregation kinetics of hematite and goethite nanoparticles

    Xu, Chen-yang, E-mail: cyxu@issas.ac.cn; Deng, Kai-ying; Li, Jiu-yu, E-mail: jyli@issas.ac.cn; Xu, Ren-kou, E-mail: rkxu@issas.ac.cn [Chinese Academy of Sciences, State Key Laboratory of Soil and Sustainable Agriculture, Institute of Soil Science (China)

    2015-10-15

    Hematite and goethite nanoparticles were used as model minerals to investigate their aggregation kinetics under soil environmental conditions in the present study. The hydrodynamic diameters of hematite and goethite nanoparticles were 34.4 and 66.3 nm, respectively. The positive surface charges and zeta potential values for goethite were higher than for hematite. The effective diameter for goethite was much larger than for hematite due to anisotropic sticking of needle-shaped goethite during aggregation. Moreover, the critical coagulation concentration (CCC) values of nanoparticles in solutions of NaNO{sub 3}, NaCl, NaF, and Na{sub 2}SO{sub 4} were 79.2, 75.0, 7.8, and 0.5 mM for hematite and they were 54.7, 62.6, 5.5, and 0.2 mM for goethite, respectively. The disparity of anions in inducing hematite or goethite aggregation lay in the differences in interfacial interactions. NO{sub 3}{sup −} and Cl{sup −} could decrease the zeta potential and enhance aggregation mainly through increasing ionic strength and compressing electric double layers of hematite and goethite nanoparticles. F{sup −} and SO{sub 4}{sup 2−} highly destabilized the suspensions of nanoparticles mainly through specific adsorption and then neutralizing the positive surface charges of nanoparticles. Specific adsorption of cations could increase positive surface charges and stabilize hematite and goethite nanoparticles. The Hamaker constants of hematite and goethite nanoparticles were calculated to be 2.87 × 10{sup −20} and 2.29 × 10{sup −20} J{sup −1}, respectively. The predicted CCC values based on DLVO theory were consistent well with the experimentally determined CCC values in NaNO{sub 3}, NaCl, NaF, and Na{sub 2}SO{sub 4} systems, which demonstrated that DLVO theory could successfully predict the aggregation kinetics even when specific adsorption of ions occurred.

  9. Utilization of natural hematite as reactive barrier for immobilization of radionuclides from radioactive liquid waste.

    El Afifi, E M; Attallah, M F; Borai, E H

    2016-01-01

    Potential utilization of hematite as a natural material for immobilization of long-lived radionuclides from radioactive liquid waste was investigated. Hematite ore has been characterized by different analytical tools such as Fourier transformer infrared (FTIR), X-ray fluorescence (XRF), powder X-ray diffraction (XRD), thermogravimetry (TG) and differential thermal (DT) analysis, scanning electron microscopy (SEM) and BET-surface area. In this study, europium was used as REEs(III) and as a homolog of Am(III)-isotopes (such as (241)Am of 432.6 y, (242m)Am of 141 y and (243)Am of 7370 y). Micro particles of the hematite ore were used for treatment of radioactive waste containing (152+154)Eu(III). The results indicated that 96% (4.1 × 10(4) Bq) of (152+154)Eu(III) was efficiently retained onto hematite ore. Kinetic experiments indicated that the processes could be simulated by a pseudo-second-order model and suggested that the process may be chemisorption in nature. The applicability of Langmuir, Freundlich and Temkin models was investigated. It was found that Langmuir isotherm exhibited the best fit with the experimental results. It can be concluded that hematite is an economic and efficient reactive barrier for immobilization of long-lived radio isotopes of actinides and REEs(III). Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Synthesis, exploration of energy storage and electrochemical sensing properties of hematite nanoparticles

    Ramasami, Alamelu K. [Centre for Nano and Material Sciences, Jain University, Bangalore 562112 (India); Department of Physics, Advanced Batteries Lab, National University of Singapore, 117542 (Singapore); Ravishankar, T.N.; Sureshkumar, K. [Centre for Nano and Material Sciences, Jain University, Bangalore 562112 (India); Reddy, M.V.; Chowdari, B.V.R. [Department of Physics, Advanced Batteries Lab, National University of Singapore, 117542 (Singapore); Ramakrishnappa, T. [Centre for Nano and Material Sciences, Jain University, Bangalore 562112 (India); Balakrishna, Geetha R., E-mail: br.geetha@jainuniversity.ac.in [Centre for Nano and Material Sciences, Jain University, Bangalore 562112 (India)

    2016-06-25

    Gel-combustion, solution combustion and molten salt methods were used to synthesize hematite nanoparicles. Two weight ratios of precursor (Ferric nitrate) to fuel (Cassava Starch) (1:0.5, 1:1) were used in gel-combustion technique. Ferric nitrate as a precursor and ethylenediamine tetraacetic acid as fuel (in stoichiometric proportions) were used in the solution combustion method. Ferric oxalate was the precursor in molten salt method. The structural parameters of the hematite nanoparticles were studied by X-ray diffraction. The optical properties, including band gap studies were done by UV–Visible spectroscopy. The morphological studies were carried out by Scanning Electron Microscope. The energy storage capacity of the molten salt method-hematite nanoparticles surpassed (920 mAhg{sup −1}) the others while the equal-weight- ratio-hematite nanoparticles synthesized by gel-combustion method exhibited better dopamine sensor properties. - Highlights: • Hematite nanoparticles were synthesized by gel, solution combustion and molten salt methods. • Gel-combustion involved the use of natural fuel extracted from the root tubers of Manihot esculenta. • Two ratios of fuel to precursors were attempted in gel combustion method. • The product formed from the equal weight ratio of fuel to precursor was a very good electrochemical dopamine sensor. • The product formed by molten salt method exhibited good battery behaviour (Li-ion battery).

  11. Synthesis, exploration of energy storage and electrochemical sensing properties of hematite nanoparticles

    Ramasami, Alamelu K.; Ravishankar, T.N.; Sureshkumar, K.; Reddy, M.V.; Chowdari, B.V.R.; Ramakrishnappa, T.; Balakrishna, Geetha R.

    2016-01-01

    Gel-combustion, solution combustion and molten salt methods were used to synthesize hematite nanoparicles. Two weight ratios of precursor (Ferric nitrate) to fuel (Cassava Starch) (1:0.5, 1:1) were used in gel-combustion technique. Ferric nitrate as a precursor and ethylenediamine tetraacetic acid as fuel (in stoichiometric proportions) were used in the solution combustion method. Ferric oxalate was the precursor in molten salt method. The structural parameters of the hematite nanoparticles were studied by X-ray diffraction. The optical properties, including band gap studies were done by UV–Visible spectroscopy. The morphological studies were carried out by Scanning Electron Microscope. The energy storage capacity of the molten salt method-hematite nanoparticles surpassed (920 mAhg"−"1) the others while the equal-weight- ratio-hematite nanoparticles synthesized by gel-combustion method exhibited better dopamine sensor properties. - Highlights: • Hematite nanoparticles were synthesized by gel, solution combustion and molten salt methods. • Gel-combustion involved the use of natural fuel extracted from the root tubers of Manihot esculenta. • Two ratios of fuel to precursors were attempted in gel combustion method. • The product formed from the equal weight ratio of fuel to precursor was a very good electrochemical dopamine sensor. • The product formed by molten salt method exhibited good battery behaviour (Li-ion battery).

  12. Effects of hematite and ferrihydrite nanoparticles on germination and growth of maize

    Nicolaza Pariona

    2017-11-01

    Full Text Available Engineered iron oxide nanoparticles (IO-NPs have been used extensively for environmental remediation. It may cause the release IO-NPs to the environment affecting the functions of ecosystems. Plants are an important component of ecosystems and can be used for the evaluation of overall fate, transport and exposure pathways of IO-NPs in the environment. In this work, the effects of engineered ferrihydrite and hematite NPs on the germination and growth of maize are studied. The germination and growth of maize were done with treatments at different concentrations of hematite and ferrihydrite NPs, namely 1, 2, 4, and 6 g/L. Biological indicators of toxicity or stress in maize seedlings were not observed in treatments with engineered hematite and ferrihydrite NPs. In contrast, the NPs treatments increased the growth of maize and the chlorophyll content, except for hematite NPs at 6 g/L, where non-significant effects were found. The translocation of engineered ferrihydrite and hematite NPs in maize stems was demonstrated using confocal laser scanning microscopy.

  13. Gypsum-induced decay in granite monuments in Northwestern Spain

    Silva Hermo, B.

    2010-03-01

    Full Text Available One of the most common forms of decay in granite monuments is the detachment of the superficial layer of the stone (plaques, plaquettes and scales. Previous studies of granite monuments in the northwest Iberian Peninsula revealed a direct relation between this type of weathering and the presence of calcium sulphate, and a mechanism whereby the salt causes this type of decay was suggested. In the present study, various hypotheses as regards the origin of the gypsum found in granite monuments are proposed. The study involved analysis of the contents of ions soluble in water, the results of X-ray diffraction analyses and the ratios of CaO/SO3 in samples of stone, mortar and deposits collected from different monuments. It was concluded that in most cases the gypsum originated from old paintworks or/and from the joint mortars, although inputs from other sources cannot be discounted, as discussed

    Una de las formas de deterioro más frecuente en los monumentos graníticos es la separación de la capa superficial de la piedra (placas, plaquetas y escamas. En trabajos anteriores centrados en monumentos del noroeste de la Península Ibérica, se constató la relación directa entre esta forma de alteración y la presencia de sulfato de calcio y se propuso el mecanismo a través del cual esta sal provoca este tipo de deterioro. En este trabajo se plantean varias hipótesis acerca del origen del yeso encontrado en monumentos graníticos. Para ello se comparan los contenidos de iones solubilizados en agua, los resultados de difracción de rayos X y las relaciones OCa/SO3 de muestras de piedra, morteros y depósitos recogidas en diferentes monumentos. Se llega a la conclusión de que en la mayor parte de los casos el yeso procede de antiguas pinturas o de revestimientos superficiales y de los morteros de juntas entre sillares, pero no se puede descartar la contribución de otros aportes, los cuales se discuten también en este artículo.

  14. Tuning hardness in calcite by incorporation of amino acids.

    Kim, Yi-Yeoun; Carloni, Joseph D; Demarchi, Beatrice; Sparks, David; Reid, David G; Kunitake, Miki E; Tang, Chiu C; Duer, Melinda J; Freeman, Colin L; Pokroy, Boaz; Penkman, Kirsty; Harding, John H; Estroff, Lara A; Baker, Shefford P; Meldrum, Fiona C

    2016-08-01

    Structural biominerals are inorganic/organic composites that exhibit remarkable mechanical properties. However, the structure-property relationships of even the simplest building unit-mineral single crystals containing embedded macromolecules-remain poorly understood. Here, by means of a model biomineral made from calcite single crystals containing glycine (0-7 mol%) or aspartic acid (0-4 mol%), we elucidate the origin of the superior hardness of biogenic calcite. We analysed lattice distortions in these model crystals by using X-ray diffraction and molecular dynamics simulations, and by means of solid-state nuclear magnetic resonance show that the amino acids are incorporated as individual molecules. We also demonstrate that nanoindentation hardness increased with amino acid content, reaching values equivalent to their biogenic counterparts. A dislocation pinning model reveals that the enhanced hardness is determined by the force required to cut covalent bonds in the molecules.

  15. Primary Evaporites for the Messinian Salinity Crisis: the shallow gypsum vs. deep dolomite formation paradox solved

    De Lange, Gert J.; Krijgsman, Wout

    2014-05-01

    The Messinian Salinity Crisis (MSC) is a dramatic event that took place ~ 5.9 Ma ago, and resulted in the deposition of 0.3-3 km thick evaporites at the Mediterranean seafloor. A considerable and long-lasting controversy existed on the modes of their formation. During the CIESM Almeria Workshop a consensus was reached on several aspects. In addition, remaining issues to be solved were identified, such as for the observed shallow gypsum versus deep dolostone deposits for the early phase of MSC. The onset of MSC is marked by deposition of gypsum/sapropel-like alternations, thought to relate to arid/humid climate conditions. Gypsum precipitation only occurred at marginal settings, while dolomite containing rocks have been reported from deeper settings. A range of potential explanations have been reported, most of which cannot satisfactorily explain all observations. Biogeochemical processes during MSC are poorly understood and commonly neglected. These may, however, explain that different deposits formed in shallow versus deep environments without needing exceptional physical boundary conditions for each. We present here a unifying mechanism in which gypsum formation occurs at all shallow water depths but its preservation is mostly limited to shallow sedimentary settings. In contrast, ongoing anoxic organic matter (OM) degradation processes in the deep basin result in the formation of dolomite. Gypsum precipitation in evaporating seawater takes place at 3-7 times concentrated seawater; seawater is always largely oversaturated relative to dolomite but its formation is thought to be inhibited by the presence of dissolved sulphate. Thus the conditions for formation of gypsum exclude those for the formation of dolomite and vice versa. Another process that links the saturation states of gypsum and dolomite is that of OM degradation by sulphate reduction. In stagnant deep water, oxygen is rapidly depleted through OM degradation, then sulphate becomes the main oxidant for OM

  16. Coal Combustion Residual Beneficial Use Evaluation: Fly Ash Concrete and FGD Gypsum Wallboard

    This page contains documents related to the evaluation of coal combustion residual beneficial use of fly ash concrete and FGD gypsum wallboard including the evaluation itself and the accompanying appendices

  17. Origin of calcite in the glacigenic Virttaankangas complex

    Nina M. Kortelainen; Petri J. Korkeakoski; Juha A. Karhu

    2007-01-01

    Groundwaters of the glacigenic Virttaankangas complex in southern Finland are characterized by high pH values ranging up to 9.5. These values are significantly higher than those observed in silicate-rich shallow groundwater formations in crystalline bedrock areas. TheVirttaankangas sediments were discovered to contain small amounts of fine grained, dispersed calcite, which has a high tendency to increase the pH of local groundwaters. The primary goal of this study was to determine the mode of...

  18. Mineralogical-Chemical Characteristics of Calcite from Zletovo, Sasa and Buchim Deposits

    Shijakova-lvanova, Tena; Paneva-Zajkova, Vesna; Donova, Ilinka

    2006-01-01

    The paper presents mineralogical-chemical characteristics, dependence between some elements and concentration of some calcite elements of Zletovo, Sasa and Buchim deposits. Calcite from Sasa, Zletovo and Buchim occurs in rhombohedral crystals of different size. The colour is white, but in Buchim it is white, pink, and yellow. Their twinning is very common. Chemical composition of calcite was determined by AES-ICP. Results show that in calcite from Buchim the concentration of Ba is much higher in pink calcite from than in white or yellow. The concentration of Zn and Ph is the lowest in white calcite. The calcite from Zletovo contains much higher concentrations of Pb, Zn, Sr, but calcite of Buchim which is pink contains higher amounts of Ba and Co. The concentrations of CaO, MgO, and MnO in all calcite simples are approximately equal. Concentration of all other elements in calcite of Sasa, Zletovo and Buchim is approximately equal. TG and DTA curves out on all simples were recorded.The decompositions of the samples of calcite starts at different temperature and it is not finish until 1000 o C. (Author)

  19. Geobacillus thermoglucosidasius Endospores Function as Nuclei for the Formation of Single Calcite Crystals

    Murai, Rie

    2013-01-01

    Geobacillus thermoglucosidasius colonies were placed on an agar hydrogel containing acetate, calcium ions, and magnesium ions, resulting in the formation of single calcite crystals (calcites) within and peripheral to the plating area or parent colony. Microscopic observation of purified calcites placed on the surface of soybean casein digest (SCD) nutrient medium revealed interior crevices from which bacterial colonies originated. Calcites formed on the gel contained [1-13C]- and [2-13C]acetate, demonstrating that G. thermoglucosidasius utilizes carbon derived from acetate for calcite formation. During calcite formation, vegetative cells swam away from the parent colony in the hydrogel. Hard-agar hydrogel inhibited the formation of calcites peripheral to the parent colony. The calcite dissolved completely in 1 M HCl, with production of bubbles, and the remaining endospore-like particles were easily stained with Brilliant green dye. The presence of DNA and protein in calcites was demonstrated by electrophoresis. We propose that endospores initiate the nucleation of calcites. Endospores of G. thermoglucosidasius remain alive and encapsulated in calcites. PMID:23455343

  20. Design of Cold-Formed Steel Screw Connections with Gypsum Sheathing at Ambient and Elevated Temperatures

    Wei Chen

    2016-09-01

    Full Text Available Load-bearing cold-formed steel (CFS walls sheathed with double layers of gypsum plasterboard on both sides have demonstrated good fire resistance and attracted increasing interest for use in mid-rise CFS structures. As the main connection method, screw connections between CFS and gypsum sheathing play an important role in both the structural design and fire resistance of this wall system. However, studies on the mechanical behavior of screw connections with double-layer gypsum sheathing are still limited. In this study, 200 monotonic tests of screw connections with single- or double-layer gypsum sheathing at both ambient and elevated temperatures were conducted. The failure of screw connections with double-layer gypsum sheathing in shear was different from that of single-layer gypsum sheathing connections at ambient temperature, and it could be described as the breaking of the loaded sheathing edge combined with significant screw tilting and the loaded sheathing edge flexing fracture. However, the screw tilting and flexing fracture of the loaded sheathing edge gradually disappear at elevated temperatures. In addition, the influence of the loaded edge distance, double-layer sheathing and elevated temperatures is discussed in detail with clear conclusions. A unified design formula for the shear strength of screw connections with gypsum sheathing is proposed for ambient and elevated temperatures with adequate accuracy. A simplified load–displacement model with the post-peak branch is developed to evaluate the load–displacement response of screw connections with gypsum sheathing at ambient and elevated temperatures.

  1. Is bicarbonate stable in and on the calcite surface?

    Andersson, Martin Peter; Rodriguez Blanco, Juan Diego; Stipp, Susan Louise Svane

    2016-01-01

    We have used density functional theory with the COSMO-RS implicit solvent model to predict the pKa for the deprotonation of bicarbonate to carbonate, i.e. HCO3− CO32− + H+, when HCO3− is included in, and adsorbed on, a calcite surface. We have used cluster models (80–100 atoms) to represent...... the flat {10.4} surface, acute steps, obtuse steps, two types of kinks on the acute step and two types of kinks on the obtuse steps. Based on the predicted pKa values, which range from −6.0 to 2.4 depending on the surface site, we conclude that bicarbonate deprotonates to carbonate when it is in calcite...... even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 bicarbonate is adsorbed on calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution...

  2. Nucleation, growth and evolution of calcium phosphate films on calcite.

    Naidu, Sonia; Scherer, George W

    2014-12-01

    Marble, a stone composed of the mineral calcite, is subject to chemically induced weathering in nature due to its relatively high dissolution rate in acid rain. To protect monuments and sculpture from corrosion, we are investigating the application of thin layers of hydroxyapatite (HAP) onto marble. The motivation for using HAP is its low dissolution rate and crystal and lattice compatibility with calcite. A mild, wet chemical synthesis route, in which diammonium hydrogen phosphate salt was reacted with marble, alone and with cationic and anionic precursors under different reaction conditions, was used to produce inorganic HAP layers on marble. Nucleation and growth on the calcite substrate was studied, as well as metastable phase evolution, using scanning electron microscopy, grazing incidence X-ray diffraction, and atomic force microscopy. Film nucleation was enhanced by surface roughness. The rate of nucleation and the growth rate of the film increased with cationic (calcium) and anionic (carbonate) precursor additions. Calcium additions also influenced phase formation, introducing a metastable phase (octacalcium phosphate) and a different phase evolution sequence. Copyright © 2014 Elsevier Inc. All rights reserved.

  3. Rate of radiocarbon retention onto calcite by isotope exchange

    Lempinen, Janne; Lehto, Jukka [Helsinki Univ. (Finland). Lab. of Radiochemistry

    2016-11-01

    Radiocarbon ({sup 14}C) is a top priority class radionuclide associated with the long-term safety of spent nuclear fuel disposal. Dissolved inorganic radiocarbon can be retained in bedrock via isotope exchange with calcite (CaCO{sub 3}) at solubility equilibrium with groundwater. In the present study, the rate of the isotope exchange process was investigated on synthetic calcite using batch experiments. Experiments were performed in solutions with a calcium concentration of 0.0002-0.1 M, including two synthetic reference groundwaters. The radiocarbon activity in the solutions decreased exponentially as a function of time, thus following first-order kinetics. The rate of isotope exchange was quantified from an exponential fit to the activity data over time. The rate of radiocarbon retention increased as a function of the calcium activity. The isotope exchange half-life was only 4.3 days at calcium ion activities over 0.01. This half-life is very much shorter than the half-life of {sup 14}C or the time scale of groundwater movements; consequently calcite can effectively retain radiocarbon from brackish and saline groundwaters.

  4. Rate of radiocarbon retention onto calcite by isotope exchange

    Lempinen, Janne; Lehto, Jukka

    2016-01-01

    Radiocarbon ( 14 C) is a top priority class radionuclide associated with the long-term safety of spent nuclear fuel disposal. Dissolved inorganic radiocarbon can be retained in bedrock via isotope exchange with calcite (CaCO 3 ) at solubility equilibrium with groundwater. In the present study, the rate of the isotope exchange process was investigated on synthetic calcite using batch experiments. Experiments were performed in solutions with a calcium concentration of 0.0002-0.1 M, including two synthetic reference groundwaters. The radiocarbon activity in the solutions decreased exponentially as a function of time, thus following first-order kinetics. The rate of isotope exchange was quantified from an exponential fit to the activity data over time. The rate of radiocarbon retention increased as a function of the calcium activity. The isotope exchange half-life was only 4.3 days at calcium ion activities over 0.01. This half-life is very much shorter than the half-life of 14 C or the time scale of groundwater movements; consequently calcite can effectively retain radiocarbon from brackish and saline groundwaters.

  5. Calcite Wettability in the Presence of Dissolved Mg2+ and SO42-

    Generosi, Johanna; Ceccato, Marcel; Andersson, Martin Peter

    2017-01-01

    that potential determining ions in seawater, Mg2+, Ca2+, and SO42–, are responsible for altering the wettability of calcite surfaces. In favorable conditions, e.g., elevated temperature, calcium at the calcite surface can be replaced by magnesium, making organic molecules bind more weakly and water molecules...... bind more strongly, rendering the surface more hydrophilic. We used atomic force microscopy in chemical force mapping mode to probe the adhesion forces between a hydrophobic CH3-terminated AFM tip and a freshly cleaved calcite {10.4} surface to investigate wettability change in the presence of Mg2...... with calcite even after rinsing with CaCO3-saturated deionized water, suggesting sorption on or in calcite. When the calcite-saturated solution of MgSO4 was replaced by calcite-saturated NaCl at the same ionic strength, adhesion force increased again, indicating that the effect is reversible and suggesting Mg...

  6. Effect of thermal treatment on solid–solid interface of hematite thin film synthesized by spin-coating deposition solution

    Bellido-Aguilar, Daniel Angel; Tofanello, Aryane; Souza, Flavio L.; Furini, Leonardo Negri; Constantino, Carlos José Leopoldo

    2016-01-01

    This work describes hematite films prepared by a spin-coating deposition solution (SCDS) method that is a sol–gel method derived technique. Hematite films were prepared at two heat treatment temperatures (500 °C and 800 °C) and the influence of thermal treatment on the photoelectrochemical performance was studied. In addition, since the SCDS method allows an optimal control of stoichiometry and impurity incorporation, hematite films modified with Zn 2+ and Sn 4+ were also prepared. The 800 °C-treated hematite films had a higher wettability and roughness that enabled them to have a better photocatalytic response in comparison with that of 500 °C-treated hematite films. Moreover, modified hematite films demonstrated to have a performance slightly better than that of undoped hematite film as shown in linear sweep voltammetry and chronoamperometry results. Although an improvement in the performance of hematite films was achieved by annealing at higher temperatures and incorporating Zn 2+ or Sn 4+ , the general photocatalytic response of the films was poor. Two plausible hypotheses were discussed related to the (i) dopant segregation at grain boundary, and (ii) poor contact between the hematite and fluorine doped tin oxide layer (from the glass substrate), which was experimentally confirmed by a cross-sectional analysis conducted using scanning electron microscopy (SEM). In fact, additional experiments need to be done in order to improve the hematite deposition and make the SCDS a promise method for industrial application. - Highlights: • High temperature of annealing decreases the hematite adherence and performance. • Zn 2+ and Sn 4+ dopants affected differently the photocurrent onset potentials. • Dopants affected the grain size due to their segregation at grain boundaries.

  7. Effect of thermal treatment on solid–solid interface of hematite thin film synthesized by spin-coating deposition solution

    Bellido-Aguilar, Daniel Angel; Tofanello, Aryane [Centro de Ciências Naturais e Humanas (CCNH), Universidade Federal do ABC, Av. dos Estados N°5001, Bangu, Santo André, São Paulo CEP 09210-580 (Brazil); Souza, Flavio L., E-mail: flavio.souza@ufabc.edu.br [Centro de Ciências Naturais e Humanas (CCNH), Universidade Federal do ABC, Av. dos Estados N°5001, Bangu, Santo André, São Paulo CEP 09210-580 (Brazil); Furini, Leonardo Negri; Constantino, Carlos José Leopoldo [Faculdade de Ciências e Tecnologia (FCT), UNESP Univ Estadual Paulista, Presidente Prudente, São Paulo, 19060-900 (Brazil)

    2016-04-01

    This work describes hematite films prepared by a spin-coating deposition solution (SCDS) method that is a sol–gel method derived technique. Hematite films were prepared at two heat treatment temperatures (500 °C and 800 °C) and the influence of thermal treatment on the photoelectrochemical performance was studied. In addition, since the SCDS method allows an optimal control of stoichiometry and impurity incorporation, hematite films modified with Zn{sup 2+} and Sn{sup 4+} were also prepared. The 800 °C-treated hematite films had a higher wettability and roughness that enabled them to have a better photocatalytic response in comparison with that of 500 °C-treated hematite films. Moreover, modified hematite films demonstrated to have a performance slightly better than that of undoped hematite film as shown in linear sweep voltammetry and chronoamperometry results. Although an improvement in the performance of hematite films was achieved by annealing at higher temperatures and incorporating Zn{sup 2+} or Sn{sup 4+}, the general photocatalytic response of the films was poor. Two plausible hypotheses were discussed related to the (i) dopant segregation at grain boundary, and (ii) poor contact between the hematite and fluorine doped tin oxide layer (from the glass substrate), which was experimentally confirmed by a cross-sectional analysis conducted using scanning electron microscopy (SEM). In fact, additional experiments need to be done in order to improve the hematite deposition and make the SCDS a promise method for industrial application. - Highlights: • High temperature of annealing decreases the hematite adherence and performance. • Zn{sup 2+} and Sn{sup 4+} dopants affected differently the photocurrent onset potentials. • Dopants affected the grain size due to their segregation at grain boundaries.

  8. Oxidation of North Dakota scrubber sludge for soil amendment and production of gypsum. Final report

    Hassett, D.J.; Moe, T.A.

    1997-10-01

    Cooperative Power`s Coal Creek Station (CCS) the North Dakota Industrial Commission, and the US Department of Energy provided funds for a research project at the Energy and Environmental Research Center. The goals of the project were (1) to determine conditions for the conversion of scrubber sludge to gypsum simulating an ex situ process on the laboratory scale; (2) to determine the feasibility of scaleup of the process; (3) if warranted, to demonstrate the ex situ process for conversion on the pilot scale; and (4) to evaluate the quality and handling characteristics of the gypsum produced on the pilot scale. The process development and demonstration phases of this project were successfully completed focusing on ex situ oxidation using air at low pH. The potential to produce a high-purity gypsum on a commercial scale is excellent. The results of this project demonstrate the feasibility of converting CCS scrubber sludge to gypsum exhibiting characteristics appropriate for agricultural application as soil amendment as well as for use in gypsum wallboard production. Gypsum of a purity of over 98% containing acceptable levels of potentially problematic constituents was produced in the laboratory and in a pilot-scale demonstration.

  9. NOx photocatalytic degradation on gypsum plates modified by TiO2-N,C photocatalysts

    Janus Magdalena

    2015-09-01

    Full Text Available In presented studies the photocatalytic decomposition of NOx on gypsum plates modified by TiO2-N,Cphotocatalysts were presented. The gypsum plates were obtained by addition of 10 or 20 wt.% of different types of titanium dioxide, such as: pure TiO2 and carbon and nitrogen co-modified TiO2 (TiO2-N,C to gypsum. TiO2-N,C photocatalysts were obtained by heating up the starting TiO2 (Grupa Azoty Zakłady Chemiczne Police S.A in the atmosphere of ammonia and carbon at the temperature: 100, 300 i 600ºC. Photocatalyst were characterized by FTIR/DRS, UVVis/DR, BET and XRD methods. Moreover the compressive strength tests of modified gypsum were also done. Photocatalytic activity of gypsum plates was done during NOx decomposition. The highest photocatalytic activity has gypsum with 20 wt.% addition of TiO2-N,C obtained at 300ºC.

  10. Field studies with radioactive sulphur-labelled gypsum fertiliser

    Goh, K.M.; Gregg, P.E.H.

    1982-01-01

    Quantitative estimates of the sizes of different sulphur (S) cycling pools in the soil-pasture system have been determined in soils belonging to the recent and yellow-brown earth soil groups. Several field trials were conducted, involving applications of 35 S-labelled gypsum fertiliser. An equilibrium was attained in the specific activity of the pasture herbage at about 240 days after fertiliser application. This was used to estimate pool sizes. At all sites, the amount of S involved in cycling ranged from 105 to 292 kg S/ha, which was sufficiently large to sustain active plant growth if cycled rapidly. However, most of the S was in the inert fraction (80-90% of total soil S) which appeared not to enter the active S cycling pool. At 3 of the sites studied, the major contributor to the cycling S pool was the residues pool of plant residues and soil organisms. No relationship was found between the size of the cycling S pool and topdressing responses of pastures. The significance of the results obtained is discussed in relation to the availability of S to pasture plants. (auth)

  11. PVC mixtures’ mechanical properties with the addition of modified calcite as filler

    Vučinić Dušica R.

    2012-01-01

    Full Text Available In this study mechanical properties of PVC mixtures (PVC, stabilizer, lubricant, filler such as tensile strength, tensile elongation, breaking strength, and breaking elongation were investigated. Unmodified calcite, as well as calcite modified by stearic acid, were used as fillers in wet and dry processes. The PVC mixtures containing the calcite modified by wet procedure have better mechanical properties compared to those with the calcite modified by the dry process. Tensile and breaking strength of the PVC mixture containing the calcite modified with 1.5% stearic acid using wet process, are higher for 2.8% and 5.2%, respectively, compared to the PVC mixture containing the calcite modified with the same amount of acid used in the dry process. The tensile strength difference between the mixtures increases with the increase of the concentration of used stearic acid up to 3%. The strength of PVC mixture with the calcite modified by wet process is 3.1% higher compared to the mixture containing calcite modified by dry process. The results showed that the bonding strength between calcite and the adsorbed organic component affected tensile strength, tensile elongation and breaking strength of the PVC mixtures. The best filler was obtained by wet modification using 1.5% stearic acid solution that provided the formation of a stearate monolayer chemisorbed on calcite. The PVC mixtures containing the calcite modified by wet process using 1.5% stearic acid solution exhibited the best mechanical properties. This calcite was completely hydrophobic with dominant chemically adsorbed surfactant, which means that stearate chemisorbed on calcite provided stronger interaction in the calcite-stearic acid-PVC system.

  12. Surface Forces Apparatus measurements of interactions between rough and reactive calcite surfaces.

    Dziadkowiec, Joanna; Javadi, Shaghayegh; Bratvold, Jon Einar; Nilsen, Ola; Røyne, Anja

    2018-05-28

    Nm-range forces acting between calcite surfaces in water affect macroscopic properties of carbonate rocks and calcite-based granular materials, and are significantly influenced by calcite surface recrystallization. We suggest that the repulsive mechanical effects related to nm-scale surface recrystallization of calcite in water could be partially responsible for the observed decrease of cohesion in calcitic rocks saturated with water. Using the Surface Forces Apparatus (SFA), we simultaneously followed the calcite reactivity and measured the forces in water in two surface configurations: between two rough calcite surfaces (CC), or between rough calcite and a smooth mica surface (CM). We used nm-scale rough, polycrystalline calcite films prepared by Atomic Layer Deposition (ALD). We measured only repulsive forces in CC in CaCO 3 -saturated water, which was related to roughness and possibly to repulsive hydration effects. Adhesive or repulsive forces were measured in CM in CaCO 3 -saturated water depending on calcite roughness, and the adhesion was likely enhanced by electrostatic effects. The pull-off adhesive force in CM became stronger with time and this increase was correlated with a decrease of roughness at contacts, which parameter could be estimated from the measured force-distance curves. That suggested a progressive increase of real contact areas between the surfaces, caused by gradual pressure-driven deformation of calcite surface asperities during repeated loading-unloading cycles. Reactivity of calcite was affected by mass transport across nm to µm-thick gaps between the surfaces. Major roughening was observed only for the smoothest calcite films, where gaps between two opposing surfaces were nm-thick over µm-sized areas, and led to force of crystallization that could overcome confining pressures of the order of MPa. Any substantial roughening of calcite caused a significant increase of the repulsive mechanical force contribution.

  13. Gypsum amendment to soil can reduce selenium uptake by alfalfa grown in the presence of coal fly ash

    Arthur, M.A.; Rubin, G.; Woodbury, P.B.; Weinstein, L.H.

    1993-01-01

    Experiments in the field and greenhouse were conducted in the presence of coal fly ash to determine whether gypsum can reduce Se concentration in alfalfa (Medicago sativa L.). In the field experiment, conducted at a coal fly ash landfill, 11.2 t ha -1 gypsum was applied to soil as a top dressing to test the effect of gypsum in reducing selenium (Se) concentration in aboveground plant tissue. There were four treatment combinations of gypsum over a two year period, 1990, and 1991: (0, 0), (0, 11.2) (11.2, 0) and (11.2, 11.2). In 1991, the Se concentration was lower in alfalfa grown with gypsum, regardless of whether the gypsum was applied in both years or in only one year, indicating that the effect of gypsum application in the first year persisted into the second year. Since there was no increase in aboveground biomass with added gypsum, differences in Se concentration reflect a competitive interaction between S and Se. In the greenhouse experiment, 12 soil treatments were tested: three levels of fly ash (0, 10 and 20%) in combination with each of four levels of gypsum (0, 2.5, 5 and 7.5%). The Se concentration in alfalfa grown in 10% fly ash declined linearly with increasing gypsum dose, resulting in a reduction in Se concentration of 0.04 ± 0.02 μg g -1 for each 1% gypsum added for the first harvest and 0.06 ± 0.03 μg g -1 for each 1% gypsum added in the second harvest. Based on these results, gypsum may prove useful as a management tool to reduce the uptake of Se by plants growing on coal fly ash landfills

  14. Biogenic magnetite, detrital hematite, and relative paleointensity in Quaternary sediments from the Southwest Iberian Margin

    Channell, J. E. T.; Hodell, D. A.; Margari, V.; Skinner, L. C.; Tzedakis, P. C.; Kesler, M. S.

    2013-08-01

    Magnetic properties of late Quaternary sediments on the SW Iberian Margin are dominated by bacterial magnetite, observed by transmission electron microscopy (TEM), with contributions from detrital titanomagnetite and hematite. Reactive hematite, together with low organic matter concentrations and the lack of sulfate reduction, lead to dissimilatory iron reduction and availability of Fe(II) for abundant magnetotactic bacteria. Magnetite grain-size proxies (κARM/κ and ARM/IRM) and S-ratios (sensitive to hematite) vary on stadial/interstadial timescales, contain orbital power, and mimic planktic δ18O. The detrital/biogenic magnetite ratio and hematite concentration are greater during stadials and glacial isotopic stages, reflecting increased detrital (magnetite) input during times of lowered sea level, coinciding with atmospheric conditions favoring hematitic dust supply. Magnetic susceptibility, on the other hand, has a very different response being sensitive to coarse detrital multidomain (MD) magnetite associated with ice-rafted debris (IRD). High susceptibility and/or magnetic grain-size coarsening, mark Heinrich stadials (HS), particularly HS2, HS3, HS4, HS5, HS6 and HS7, as well as older Heinrich-like detrital layers, indicating the sensitivity of this region to fluctuations in the position of the polar front. Relative paleointensity (RPI) records have well-constrained age models based on planktic δ18O correlation to ice-core chronologies, however, they differ from reference records (e.g. PISO) particularly in the vicinity of glacial maxima, mainly due to inefficient normalization of RPI records in intervals of enhanced hematite input.

  15. Magnetite–hematite nanoparticles prepared by green methods for heavy metal ions removal from water

    Ahmed, M.A.; Ali, S.M.; El-Dek, S.I.; Galal, A.

    2013-01-01

    Graphical abstract: The negatively charged cubic magnetite nanoparticles, prepared by the coprecipitation method in N 2 atmosphere, can adsorb up to 99% of the positively charged toxic heavy metal ions at a proper pH value. -- Highlights: • Mixed magnetite–hematite nanoparticles were synthesized via different routes. • Prepared samples were characterized by XRD, HRTEM, BET and magnetic hysteresis. • The material was employed as a sorbent for removal of some heavy metal ions from water. • The effects of pH and the contact time on the adsorption process were studied and optimized. -- Abstract: Mixed magnetite–hematite nanoparticles were synthesized via different routes such as, coprecipitation in air and N 2 atmosphere, citrate–nitrate, glycine–nitrate and microwave-assisted citrate methods. The prepared samples were characterized by X-ray diffraction (XRD), high resolution transmission electron microscope (HRTEM), BET measurements and magnetic hysteresis. XRD data showed the formation of magnetite–hematite mixture with different compositions according to the synthesis method. The particle size was in the range of 4–52 nm for all the prepared samples. From HRTEM micrographs, it was found that, the synthesis method affects the moropholgy of the prepared samples in terms of crystallinity and porosity. The magnetite–hematite mixture was employed as a sorbent material for removal of some heavy metal ions from water such as lead(II), cadmium(II) and chromium(III). The effects of pH value and the contact time on the adsorption process were studied and optimized in order to obtain the highest possible adsorption efficiency of the magnetite–hematite mixture. The effect of the synthesis method of the magnetite–hematite mixture on the adsorption process was also investigated. It was found that samples prepared by the coprecipitation method had better adsorption efficiency than those prepared by other combustion methods

  16. Hydrothermal replacement of calcite by Mg-carbonates

    Jonas, Laura; Mueller, Thomas; Dohmen, Ralf

    2014-05-01

    The transport of heat and mass through the Earth's crust is coupled to mineral reactions and the exchange of isotopes and elements between different phases. Carbonate minerals are a major constituent of the Earth's crust and play an important role in different physical, chemical and even biological processes. In this experimental study, the element exchange reaction between calcite (CaCO3) and a Mg-rich fluid phase is investigated under hydrothermal conditions. Single crystals of calcite (2x2x2 mm) react with 1 ml of a 1 M MgCl2 solution at 200° C in a Teflon-lined steel autoclave for different times between one day and four weeks. The reaction leads to the formation of a porous reaction front and the pseudomorphic replacement of calcite by dolomite [CaMg(CO3)2] and magnesite (MgCO3). Scanning electron microscopy revealed that the reaction rim consists of small Mg-carbonate rhombs closely attached to each other, suggesting that the replacement reaction takes place by a dissolution-precipitation mechanism. Typically, the observed reaction front can be divided into two different domains. The outer part of the reaction rim, i.e. from the mineral surface in contact to the fluid inwards, consists of magnesite, whereas the inner part of the rim surrounding the unreacted calcite core consists of Ca-rich dolomite. The formation of a porous microstructure that varies in different parts of the reaction rim is a direct result of the large molar volume change induced by the replacement of calcite by magnesite and dolomite. The developing porosity therefore creates fluid pathways that promote the progress of the reaction front towards the unreacted core of the single crystal. Compositional profiles measured perpendicular to the mineral surface across the reactions rims using electron microprobe (EMPA) further revealed a compositional gradient within the reaction rim with regard to the structure-forming elements Mg and Ca. Here, the amount of Mg incorporated in both product

  17. Molecular dynamics simulation of siderite-hematite-quartz flotation with sodium oleate

    Li, Lixia; Hao, Haiqing; Yuan, Zhitao; Liu, Jiongtian

    2017-10-01

    Models of sodium oleate adsorption on siderite, hematite and quartz were investigated by molecular dynamic simulation, respectively. Surface energy was calculated to confirm the cleavage plan of hematite and quartz. Both natural cleavage plane of siderite and calculated plane were used to investigate the flotation of the three minerals. Based on the molecular simulation in solution with water as medium, adsorption quantity and interaction capability of oleate ions on the three minerals indicated that siderite could be collected efficiently by sodium oleate at neutral pH. Results of flotation experiments were further demonstrated by analysis of relative concentration of carbon atoms and oxygen atoms.

  18. Transformation of goethite/ferrihydrite to hematite and maghemite under temperate humid conditions in Denmark

    Nørnberg, Per; Finster, Kai; Gunnlaugsson, Haraldur Pall

    2012-01-01

    At a number of sandy soil sites in Mid Jutland, Denmark, with iron content of 1-2%, very red spots (Munsell colour: dusky red 10R 3/4) of a few square meters are found. These spots are most likely due to burning events. After the fire ashes raised pH. This dispersed silt and clay size soil...... particles which were then transported with seepage water down into lower soil horizons. These particles contain hematite and maghemite due to influence of the fire. However, a long-standing unresolved question is how hematite and maghemite can also be present along with goethite and ferrihydrite...

  19. Fabrication of non-aging superhydrophobic surfaces by packing flower-like hematite particles

    Cao, Anmin; Cao, Liangliang; Gao, Di

    2008-03-01

    We demonstrate the fabrication of non-aging superhydrophobic surfaces by packing flower-like micrometer-sized hematite particles. Although hematite is intrinsically hydrophilic, the nanometer-sized protrusions on the particles form textures with overhanging structures that prevent water from entering into the textures and induce a macroscopic superhydrophobic phenomenon. These superhydrophobic surfaces do not age even in extremely oxidative environments---they retain the superhydrophobicity after being stored in ambient laboratory air for 4 months, heated to 800 degree C in air for 10 hours, and exposed to ultraviolet ozone for 10 hours.

  20. A study on the coprecipitation of arsenite and arsenate into calcite coupled with the determination of oxidation states of arsenic both in calcite and water

    Yokoyama, Yuka; Takahashi, Yoshio; Mitsunobu, Satoshi; Tanaka, Kazuya; Itai, Takaaki

    2009-01-01

    It was found that the amount of arsenite incorporated into calcite is much less than that of arsenate. The result suggests that the sequestration of arsenic by coprecipitation with calcite cannot be an important chemical process under reducing conditions such as in groundwater where arsenite is the dominant arsenic species. (author)

  1. Shape Evolution Synthesis of Monodisperse Spherical, Ellipsoidal, and Elongated Hematite (alpha-Fe2O3) Nanoparticles Using Ascorbic Acid

    Tan, W.F.; Yu, Y.T.; Wang, M.X.; Liu, F.; Koopal, L.K.

    2014-01-01

    Spherical, ellipsoidal, and elongated hematite particles have been obtained via a simple chemical precipitation reaction of FeCl3 and NaOH in the presence of ascorbic acid,(AA). The effects of pH, molar ratio of AA/Fe(III), and time on the formation and shape of the hematite particles were

  2. Charge carrier trapping, recombination and transfer in hematite (-Fe2O3) water splitting photoanodes

    Barroso Silva da Cruz, M.; Pendlebury, S.R.; Cowan, A.J.; Durrant, J.R.

    2013-01-01

    Hematite is currently considered one of the most promising materials for the conversion and storage of solar energy via the photoelectrolysis of water. Whilst there has been extensive research and much progress in the development of hematite structures with enhanced photoelectrochemical (PEC)

  3. Thermogravimetric Analysis of Modified Hematite by Methane (CH{sub 4}) for Chemical-Looping Combustion: A Global Kinetics Mechanism

    Monazam, Esmail R; Breault, Ronald W; Siriwardane, Ranjani; Miller, Duane D

    2013-10-01

    Iron oxide (Fe{sub 2}O{sub 3}) or in its natural form (hematite) is a potential material to capture CO{sub 2} through the chemical-looping combustion (CLC) process. It is known that magnesium (Mg) is an effective methyl cleaving catalyst and as such it has been combined with hematite to assess any possible enhancement to the kinetic rate for the reduction of Fe{sub 2}O{sub 3} with methane. Therefore, in order to evaluate its effectiveness as a hematite additive, the behaviors of Mg-modified hematite samples (hematite –5% Mg(OH){sub 2}) have been analyzed with regard to assessing any enhancement to the kinetic rate process. The Mg-modified hematite was prepared by hydrothermal synthesis. The reactivity experiments were conducted in a thermogravimetric analyzer (TGA) using continuous stream of CH{sub 4} (5, 10, and 20%) at temperatures ranging from 700 to 825 {degrees}C over ten reduction cycles. The mass spectroscopy analysis of product gas indicated the presence of CO{sub 2}, H{sub 2}O, H{sub 2} and CO in the gaseous product. The kinetic data at reduction step obtained by isothermal experiments could be well fitted by two parallel rate equations. The modified hematite samples showed higher reactivity as compared to unmodified hematite samples during reduction at all investigated temperatures.

  4. CHEMICAL SOIL ATTRIBUTES AS AFFECTED BY LIME AND GYPSUM SURFACE APPLICATION

    A. Mantovani

    2017-10-01

    Full Text Available The gypsum is a soil condition end it has to function contribute to the elimination or reduction of aluminum in the soil in depth. Still, it can contribute to the distribution of nutrients in the soil profile more uniformly and thus increasing the productivity of crops. This study aimed to evaluate the influence of gypsum application, with and without lime, on soil chemical properties and soybean yield, in a no-till system. The experiment was carried in Campos Novos, Santa Catarina State, Brazil, with a randomized block design and split plot design with four replications, the main portion was distributed gypsum doses (1000, 2000, 4000 and 6000 kg ha-1 without incorporation, and the split plot (with and without lime and the liming was 2,000 kg ha-1. We evaluated the performance of components and productivity of soybeans. It was also analyzed the soil pH and Ca, Mg, S and Al at 0-20 and 20-40 cm. The application of gypsum at the rates tested surface with and without lime did not affect the yield components and soybean productivity. At 0-20 cm soil depth lime application increased soil pH by 0.3 units on the average rates of gypsum, but in the 20-40 cm layer was not found effect of lime and gypsum in pH ground due to the short time between application and evaluation. In areas with and without lime contents of Ca and S in the two layers evaluated increased with increasing rates of gypsum, since Mg has difference with the lime application on a 0-20 cm to dose 4000 kg ha-1 and the lime in the gypsum rates and Al decreased with increasing dose gypsum average in the 20-40 cm layer depth. The application of gypsum and limestone softened the negative effects of soil acidity and the increase mainly of calcium and sulfur at 0-20 cm, with less efficient effects in the 20-40 cm layer due to the soil is clayey and the period between the implementation and evaluation be 120 days.

  5. Properties of mortars made by uncalcined FGD gypsum-fly ash-ground granulated blast furnace slag composite binder

    Zhong Shiyun; Ni Kun; Li Jinmei

    2012-01-01

    Highlights: ► The mortar with uncalcined FGD gypsum has suitable workability. ► The strength of mortar with uncalcined FGD gypsum is higher than that of mortar without uncalcined FGD gypsum. ► The dry shrinkage of mortar with uncalcined FGD gypsum is lower than that of mortar without uncalcined FGD gypsum. ► The leaching of sulfate ion of mortar is studied. - Abstract: A series of novel mortars were developed from composite binder of uncalcined FGD gypsum, fly ash (FA) and ground granulated blast furnace slag (GGBFS) for the good utilization of flue gas desulphurization (FGD) gypsum. At a fixed ratio (20%) of GGBFS to the composite binder, keeping consistency of the mortar between 9.5 and 10.0 cm, the properties of the composite mortar were studied. The results show that higher water/binder (W/B) is required to keep the consistency when increasing the percentage of FGD gypsum. No obvious influences of the W/B and content of FGD gypsum on the bleeding of paste were observed which keeps lower than 2% under all experimental conditions tried. The highest compressive and flexural strengths (ratio is 20% FGD gypsum, 20% GGBFS and 60% FA) are 22.6 and 4.3 MPa at 28 days, respectively. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results indicate that massive ettringite crystals and C–S–H gels exist in the hydration products. At 90 days the mortars with FGD gypsum is dramatically smaller drying shrinkage (563–938 micro strain) than that without FGD gypsum (about 2250 micro strain). The release of the SO 4 2- from the mortar was analyzed, indicating that the dissolution of sulfate increases with FGD gypsum. The concentration of SO 4 2- releasing from the mortar with 10% FGD gypsum is almost equal to that obtained from the mortar without FGD gypsum. The release of SO 4 2- from the mortar with 20% FGD gypsum is 9200 mg·m −2 , which is lower than that from the mortar with 95% cement clinker and 5% FGD gypsum.

  6. Speciation of As in calcite by micro-XAFS: Implications for remediation of As contamination in groundwater

    Yokoyama, Y; Takahashi, Y; Iwatsuki, T; Terada, Y

    2013-01-01

    To evaluate the role of calcite as a host phase of arsenic (As) in As-contaminated groundwater, distribution behavior of Asbetween natural calcite and groundwater in deep underground was investigated based on As oxidation state. Speciation analyses of As in natural calcite by μ-XRF-XAFS analyses showed (i) preferentialarsenate uptake by calcite, and (ii) promptness of arsenate uptake by minor iron (Fe) carbonate minerals coprecipitated with calcite. These findings suggest that the effect of calcite on As remediation of the As-contamination systems stronglydepends on arsenite to arsenate ratio (i.e., redox condition) in groundwater, and maybe governed bythe amount of Fe coprecipitated with calcite.

  7. Expediting the chemistry of hematite nanocatalyst for catalytic aquathermolysis of heavy crude oil

    Khalil, Munawar

    In upstream exploration and production of heavy and extra heavy oil, catalytic aquathermolysis is a process where steam (along with catalyst) is injected into the reservoir to improve oil production. The improvement of oil production has been associated with the reduction of heavy oil's viscosity due to the degradation of large hydrocarbon molecules (resin and asphaltene fractions) which mostly the result of desulphurization of organosulphur compounds. In this work, the potential of hematite (alpha-Fe2O3) nanoparticles, a nontoxic, inexpensive and the most stable phase of iron oxide, was investigated for aquathermolysis application. This dissertation encompasses the synthesis, surface modification, catalytic activity, and catalysis mechanism of hematite nanoparticles in aquathermolysis. In the first part of this study, a simple hydrothermal method was successfully developed to synthesize hematite nanoparticles with high purity and good crystallinity. Using this method, the size, crystal's growth rate, shape, and dispersity of the nanoparticles can be controlled by the amount of iron precursor, precipitation agent, temperature and reaction time. Furthermore, the surface chemistry of hematite nanoparticle was modified in order to improve particle dispersibility in hydrocarbon phase. Based on the result, oleic acid (OA) was successfully grafted on the surface of hematite nanoparticles by forming a monodentate interaction and changed the surface property of the nanoparticles from hydrophilic to hydrophobic. As the result, nanoparticles were able to be transferred from aqueous phase to non-polar phase, vice versa, depending on the amount of oleic acid used for modification. In the third part of this work, the catalytic activity and catalytic mechanism of hematite nanoparticles to catalyze desulphurization reaction were studied. It is found that hematite nanoparticles have a good catalytic activity to decompose a highly stable aromatic organosulphur compound, i

  8. Incorporation of Mg and Sr in calcite of cultured benthic foraminifera: impact of calcium concentration and associated calcite saturation state

    M. Raitzsch

    2010-03-01

    Full Text Available We investigated the effect of the calcium concentration in seawater and thereby the calcite saturation state (Ω on the magnesium and strontium incorporation into benthic foraminiferal calcite under laboratory conditions. For this purpose individuals of the shallow-water species Heterostegina depressa (precipitating high-Mg calcite, symbiont-bearing and Ammonia tepida (low-Mg calcite, symbiont-barren were cultured in media under a range of [Ca2+], but similar Mg/Ca ratios. Trace element/Ca ratios of newly formed calcite were analysed with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS and normalized to the seawater elemental composition using the equation DTE=(TE/Cacalcite/(TE/Caseawater. The culturing study shows that DMg of A. tepida significantly decreases with increasing Ω at a gradient of −4.3×10−5 per Ω unit. The DSr value of A. tepida does not change with Ω, suggesting that fossil Sr/Ca in this species may be a potential tool to reconstruct past variations in seawater Sr/Ca. Conversely, DMg of H. depressa shows only a minor decrease with increasing Ω, while DSr increases considerably with Ω at a gradient of 0.009 per Ω unit. The different responses to seawater chemistry of the two species may be explained by a difference in the calcification pathway that is, at the same time, responsible for the variation in the total Mg incorporation between the two species. Since the Mg/Ca ratio in H. depressa is 50–100 times higher than that of A. tepida, it is suggested that the latter exhibits a mechanism that decreases the Mg/Ca ratio of the calcification fluid, while the high-Mg calcite forming species may not have this physiological tool. If the dependency of Mg incorporation on seawater [Ca2+] is also valid for deep

  9. X-ray scattering of calcite thin films deposited by atomic layer deposition: Studies in air and in calcite saturated water solution

    Wang, Peng [Lujan Neutron Scattering Center, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Hudak, Michael R.; Lerner, Allan [Earth and Environmental Sciences Division, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Grubbs, Robert K. [Sandia National Laboratories, P.O. Box 5800, Albuquerque, NM 87185 (United States); Wang, Shanmin [Lujan Neutron Scattering Center, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Zhang, Zhan; Karapetrova, Evguenia [Advance Photon Source, Argonne National Laboratory, 9700S Cass Ave, Argonne, IL 60439 (United States); Hickmott, Donald [Earth and Environmental Sciences Division, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Majewski, Jaroslaw, E-mail: jarek@lanl.gov [Lujan Neutron Scattering Center, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States)

    2014-08-28

    Carbonates are one of the most abundant groups of minerals in earth systems and are important in many geological settings and industrial processes. Calcite (CaCO{sub 3}) thin films produced by atomic layer deposition offer a method to evaluate the surficial properties of carbonates as well as interactions at the carbonate–fluid interface. Using synchrotron X-ray reflectivity and X-ray diffraction, these films are observed to be porous, polycrystalline, and have crystallites oriented with the major (104) calcite cleavage plane parallel to the surface of the z-cut single crystal quartz substrate. An Al{sub 2}O{sub 3} buffer layer, present between quartz and the calcite film, does not affect the as-deposited film, but does influence how the films reorganize in contact with fluid. Without a buffer layer, calcite reorients its crystallites to have populations of (006) and (030) parallel to the substrate, while those with an Al{sub 2}O{sub 3} buffer layer become more amorphous. Amorphous films may represent an analog to amorphous calcium carbonate and provide insights into that material's thermophysical behavior. Due to a higher percentage of pore spaces available for fluid infiltration, films deposited at higher temperature make the calcite thin films more susceptible to amorphization. These films are chemically similar, but structurally dissimilar to bulk natural calcite. Nevertheless, they can be a complementary system to traditional single crystal X-ray surface scattering studies on carbonates, particularly for important but less common minerals, to evaluate mineral–fluid interfacial interactions. - Highlights: • Atomic layer deposition (ALD) used to produce calcite films. • Calcite film orientation and crystallinity depend on ALD parameters. • ALD calcite films can be both crystalline and amorphous. • Interaction of water with films can re-orient or amorphize the films. • ALD calcite films may be useful to study carbonate–fluid interfacial

  10. X-ray scattering of calcite thin films deposited by atomic layer deposition: Studies in air and in calcite saturated water solution

    Wang, Peng; Hudak, Michael R.; Lerner, Allan; Grubbs, Robert K.; Wang, Shanmin; Zhang, Zhan; Karapetrova, Evguenia; Hickmott, Donald; Majewski, Jaroslaw

    2014-01-01

    Carbonates are one of the most abundant groups of minerals in earth systems and are important in many geological settings and industrial processes. Calcite (CaCO 3 ) thin films produced by atomic layer deposition offer a method to evaluate the surficial properties of carbonates as well as interactions at the carbonate–fluid interface. Using synchrotron X-ray reflectivity and X-ray diffraction, these films are observed to be porous, polycrystalline, and have crystallites oriented with the major (104) calcite cleavage plane parallel to the surface of the z-cut single crystal quartz substrate. An Al 2 O 3 buffer layer, present between quartz and the calcite film, does not affect the as-deposited film, but does influence how the films reorganize in contact with fluid. Without a buffer layer, calcite reorients its crystallites to have populations of (006) and (030) parallel to the substrate, while those with an Al 2 O 3 buffer layer become more amorphous. Amorphous films may represent an analog to amorphous calcium carbonate and provide insights into that material's thermophysical behavior. Due to a higher percentage of pore spaces available for fluid infiltration, films deposited at higher temperature make the calcite thin films more susceptible to amorphization. These films are chemically similar, but structurally dissimilar to bulk natural calcite. Nevertheless, they can be a complementary system to traditional single crystal X-ray surface scattering studies on carbonates, particularly for important but less common minerals, to evaluate mineral–fluid interfacial interactions. - Highlights: • Atomic layer deposition (ALD) used to produce calcite films. • Calcite film orientation and crystallinity depend on ALD parameters. • ALD calcite films can be both crystalline and amorphous. • Interaction of water with films can re-orient or amorphize the films. • ALD calcite films may be useful to study carbonate–fluid interfacial interactions

  11. Constraining the origin of the Messinian gypsum deposits using coupled measurement of δ^{18}O$/δD in gypsum hydration water and salinity of fluid inclusions

    Evans, Nicholas P.; Gázquez, Fernando; McKenzie, Judith A.; Chapman, Hazel J.; Hodell, David A.

    2016-04-01

    We used oxygen and hydrogen isotopes of gypsum hydration water (GHW) coupled with salinity deduced from ice melting temperatures of primary fluid inclusions in the same samples (in tandem with 87Sr/86Sr, δ34S and other isotopic measurements) to determine the composition of the mother fluids that formed the gypsum deposits of the Messinian Salinity Crisis from shallow and intermediate-depth basins. Using this method, we constrain the origin of the Messinian Primary Lower Gypsum (PLG) of the Sorbas basin (Betic foreland) and both the Upper Gypsum (UG) and the Lower Gypsum of the Sicilian basin. We then compare these results to measurements made on UG recovered from the deep Ionian and Balearic basins drilled during DSDP Leg 42A. The evolution of GHW δ18O/δD vs. salinity is controlled by mixing processes between fresh and seawater, coupled with the degree of evaporation. Evaporation and subsequent precipitation of gypsum from fluids dominated by freshwater will result in a depressed 87Sr/86Sr values and different trajectory in δ18O/δD vs. salinity space compared to fluids dominated by seawater. The slopes of these regression equations help to define the end-members from which the fluid originated. For example, salinity estimates from PLG cycle 6 in the Sorbas basin range from 18 to 51ppt, and after correction for fractionation factors, estimated δ18O and δD values of the mother water are low (-2.6 meteoric water during gypsum deposition, while 87Sr/86Sr (0.708942 fall below those expected from the evaporation of seawater alone, the slope of the regression equation is similar to that of seawater evaporation. This implies that there is a change up-section from a dominantly marine environment in cycle 2 to a greater influence of meteoric water in cycle 6. The UG from the Sicilian basin display greater δ18O/δD values (2.9 meteoric water that subsequently underwent intense evaporation. This observation concurs with the low values of 87Sr/86Sr from the same UG

  12. Experienced materials in wet limestone-gypsum FGD system

    Hasegawa, S. [Mitsubishi Heavy Industry, Hiroshima (Japan). Hiroshima Research and Development Center; Iwashita, K.; Ochi, E.; Higuchi, T. [Mitsubishi heavy Industry, Yokohama (Japan)

    1998-12-31

    This study was made on the corrosion resistivity evaluation method used for material selection in the Wet Limestone-Gypsum FGD system with examples of various process configuration, their corrosion environment, and the materials used in them. The wet limestone-gypsum process FGD plant is broadly divided into two types-ash-separated (dual-loop) process, and ash-mixed (single-loop) process-depending on whether the flue gas is separated from ash before being led into the absorber or led as it is into the absorber mixed with ash. Presently, the single-loop process has become the mainstream process however. The dual -loop process comprises a dedusting tower (quencher) and an absorption tower (absorber). In the quencher ash is removed with sprayed water where most of the HCl, HF etc., and a part of SO{sub x} and NO{sub x} contained in the flue gas are also removed with absorption. On the contrary, in the single-loop process which is configured of only the absorber, the flue gas is introduced into it as it is contained with ash, SO{sub x}, NO{sub x}, HCl, HF etc. The corrosion environment in these plants largely differs depending on the process type and condition. The absorber recirculated liquid has various ion inclusions among which Cl{sup {minus}} promotes pitting corrosion and crevice corrosion while SO{sub 4}{sup 2{minus}} inhibits these corrosions. Both Cl{sup {minus}} and SO{sub 4}{sup 2{minus}} cover an extremely large range between 25 to 100,000 ppm and 564 to 73,600 ppm respectively, and their influence on the corrosion is related to their activity which is decided by Ca{sup 2+}, Mg{sup 2+}, Na{sup +}, NH{sub 4}{sup +}, H{sup +} and liquid temperature. The balance of these ions is decided by the gas composition, limestone composition, make-up water and wastewater mass balance etc., of individual plants. Accordingly, materials of FGD plant are selected on the basis of evaluated results of corrosion resistivity test made under such simulated process conditions of

  13. The hydrophobic modification of gypsum binder by peat products: physico-chemical and technological basis

    O. Misnikov

    2018-04-01

    Full Text Available Gypsum binder is a quick-setting and fast-hardening material that is used widely in the construction industry for plastering and as an ingredient of concrete, other binding materials, etc. The issue addressed here is its short shelf life (around three months which arises because it is hygroscopic, i.e. it readily absorbs moisture and begins to set during transport and storage. The main methods that are currently available for protecting gypsum binder against unwanted exposure to moisture and water vapour are considered, and hydrophobic modification with the bitumen released during peat thermolysis (a method previously considered for cement is proposed as a promising alternative. Because there is overlap in the temperature ranges used in the manufacture of gypsum binder and those required for the initial stages of thermal decomposition of the organic matter in peat, it is expected that hydrophobisation could be achieved during the established manufacturing process without any changes to plant or procedures. The optimum concentration of organic (peat additive for gypsum rock mined from the Shushokskoye deposit in Russia is derived experimentally. With 0.5–1 % of peat additive, the strength grading of the gypsum plaster is preserved and its storage time without caking and hydration increases, even under adverse conditions (100 % relative humidity. The proposed method is compatible with current gypsum production technology, it does not require any changes in equipment, and the prices of mineral raw materials and semi-finished peat products are approximately the same. Thus, the incorporation of hydrophobic modification using peat into the manufacturing process for gypsum binder is unlikely to increase the cost of the product.

  14. Soil composition and nutritional status of apple as affected by long-term application of gypsum

    Gilberto Nava

    2012-02-01

    Full Text Available Gypsum does not affect the soil negative charges and maintains sulfate in the soil solution, making it one of the cheapest products to increase Ca activity in soil solution, especially in the deeper soil layers. Higher Ca levels in the soil solution can increase the uptake of this nutrient by apple trees, reducing the risk of physiological disorders caused by Ca deficiency. This study assessed the effect of long-term gypsum application on some soil properties and on the chemical composition of leaves and fruits of an apple cultivar susceptible to fruit disorders associated with low Ca. The experiment was conducted in São Joaquim, in the South of Brazil, from 2001 to 2009. Gypsum rates of 0, 1.0, 2.0 and 3.0 t ha-1 were annually broadcast over the soil surface, without incorporation, in an apple orchard with cultivar ´Catarina´, planted in 1997. Gypsum application over eight consecutive years had no effect on soil exchangeable K and Al to a depth of 80 cm, but increased exchangeable Ca in the sampled layers (0-10, 10-20, 40-60 and 60-80 cm, while exchangeable Mg decreased only in the surface layer (0-20 cm. Gypsum did not affect the concentration of any nutrient in the fruits, including Ca. The same was verified in the leaves, except for Mg which decreased with increased gypsum rate. Despite increasing the availability of Ca in the soil profile to a depth of 80 cm, gypsum was not effective to increase the Ca content in leaves and fruits of an apple cultivar susceptible to Ca deficiency grown in an appropriately limed soil.

  15. Surface Coating of Gypsum-Based Molds for Maxillofacial Prosthetic Silicone Elastomeric Material: The Surface Topography.

    Khalaf, Salah; Ariffin, Zaihan; Husein, Adam; Reza, Fazal

    2015-07-01

    This study aimed to compare the surface roughness of maxillofacial silicone elastomers fabricated in noncoated and coated gypsum materials. This study was also conducted to characterize the silicone elastomer specimens after surfaces were modified. A gypsum mold was coated with clear acrylic spray. The coated mold was then used to produce modified silicone experimental specimens (n = 35). The surface roughness of the modified silicone elastomers was compared with that of the control specimens, which were prepared by conventional flasking methods (n = 35). An atomic force microscope (AFM) was used for surface roughness measurement of silicone elastomer (unmodified and modified), and a scanning electron microscope (SEM) was used to evaluate the topographic conditions of coated and noncoated gypsum and silicone elastomer specimens (unmodified and modified) groups. After the gypsum molds were characterized, the fabricated silicone elastomers molded on noncoated and coated gypsum materials were evaluated further. Energy-dispersive X-ray spectroscopy (EDX) analysis of gypsum materials (noncoated and coated) and silicone elastomer specimens (unmodified and modified) was performed to evaluate the elemental changes after coating was conducted. Independent t test was used to analyze the differences in the surface roughness of unmodified and modified silicone at a significance level of p SEM analysis results showed evident differences in surface smoothness. EDX data further revealed the presence of the desired chemical components on the surface layer of unmodified and modified silicone elastomers. Silicone elastomers with lower surface roughness of maxillofacial prostheses can be obtained simply by coating a gypsum mold. © 2014 by the American College of Prosthodontists.

  16. Urea Hydrolysis and Calcium Carbonate Precipitation in Gypsum-Amended Broiler Litter.

    Burt, Christopher D; Cabrera, Miguel L; Rothrock, Michael J; Kissel, D E

    2018-01-01

    Broiler () litter is subject to ammonia (NH) volatilization losses. Previous work has shown that the addition of gypsum to broiler litter can increase nitrogen mineralization and decrease NH losses due to a decrease in pH, but the mechanisms responsible for these effects are not well understood. Therefore, three laboratory studies were conducted to evaluate the effect of gypsum addition to broiler litter on (i) urease activity at three water contents, (ii) calcium carbonate precipitation, and (iii) pH. The addition of gypsum to broiler litter increased ammonium concentrations ( litter pH by 0.43 to 0.49 pH units after 5 d ( litter only increased on Day 0 for broiler litter with low (0.29 g HO g) and high (0.69 g HO g) water contents, and on Day 3 for litter with medium (0.40 g HO g) water content ( litter with gypsum also caused an immediate decrease in litter pH (0.22 pH units) due to the precipitation of calcium carbonate (CaCO) from gypsum-derived calcium and litter bicarbonate. Furthermore, as urea was hydrolyzed, more urea-derived carbon precipitated as CaCO in gypsum-treated litter than in untreated litter ( litter with gypsum favors the precipitation of CaCO, which buffers against increases in litter pH that are known to facilitate NH volatilization. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  17. Differential cellular responses in healthy mice and in mice with established airway inflammation when exposed to hematite nanoparticles

    Gustafsson, Åsa, E-mail: asa.gustafsson@foi.se [Swedish Defence Research Agency, Division of CBRN Defence and Security, Umeå (Sweden); Dept of Public Health and Clinical Medicine, Umeå University (Sweden); Bergström, Ulrika [Swedish Defence Research Agency, Division of CBRN Defence and Security, Umeå (Sweden); Dept of Organismal Biology, Uppsala University, SE-751 Uppsala (Sweden); Ågren, Lina [Swedish Defence Research Agency, Division of CBRN Defence and Security, Umeå (Sweden); Österlund, Lars [Dept of Engineering Sciences, The Ångström Laboratory, Uppsala University, SE-751 Uppsala (Sweden); Sandström, Thomas [Dept of Public Health and Clinical Medicine, Umeå University (Sweden); Bucht, Anders [Swedish Defence Research Agency, Division of CBRN Defence and Security, Umeå (Sweden); Dept of Public Health and Clinical Medicine, Umeå University (Sweden)

    2015-10-01

    The aim of this study was to investigate the inflammatory and immunological responses in airways and lung-draining lymph nodes (LDLNs), following lung exposure to iron oxide (hematite) nanoparticles (NPs). The responses to the hematite NPs were evaluated in both healthy non-sensitized mice, and in sensitized mice with an established allergic airway disease. The mice were exposed intratracheally to either hematite NPs or to vehicle (PBS) and the cellular responses were evaluated on days 1, 2, and 7, post-exposure. Exposure to hematite NPs increased the numbers of neutrophils, eosinophils, and lymphocytes in the airways of non-sensitized mice on days 1 and 2 post-exposure; at these time points the number of lymphocytes was also elevated in the LDLNs. In contrast, exposing sensitized mice to hematite NPs induced a rapid and unspecific cellular reduction in the alveolar space on day 1 post-exposure; a similar decrease of lymphocytes was also observed in the LDLN. The results indicate that cells in the airways and in the LDLN of individuals with established airway inflammation undergo cell death when exposed to hematite NPs. A possible explanation for this toxic response is the extensive generation of reactive oxygen species (ROS) in the pro-oxidative environment of inflamed airways. This study demonstrates how sensitized and non-sensitized mice respond differently to hematite NP exposure, and it highlights the importance of including individuals with respiratory disorders when evaluating health effects of inhaled nanomaterials. - Highlights: • Hematite NPs induce differential responses in airways of healthy and allergic mice. • Hematite induced an airway inflammation in healthy mice. • Hematite induced cellular reduction in the alveolus and lymph nodes of allergic mice. • Cell death is possible due to extensive pro-oxidative environment in allergic mice. • It is important to include sensitive individuals when valuing health effects of NPs.

  18. Properties of mortars made by uncalcined FGD gypsum-fly ash-ground granulated blast furnace slag composite binder.

    Zhong, Shiyun; Ni, Kun; Li, Jinmei

    2012-07-01

    A series of novel mortars were developed from composite binder of uncalcined FGD gypsum, fly ash (FA) and ground granulated blast furnace slag (GGBFS) for the good utilization of flue gas desulphurization (FGD) gypsum. At a fixed ratio (20%) of GGBFS to the composite binder, keeping consistency of the mortar between 9.5 and 10.0 cm, the properties of the composite mortar were studied. The results show that higher water/binder (W/B) is required to keep the consistency when increasing the percentage of FGD gypsum. No obvious influences of the W/B and content of FGD gypsum on the bleeding of paste were observed which keeps lower than 2% under all experimental conditions tried. The highest compressive and flexural strengths (ratio is 20% FGD gypsum, 20% GGBFS and 60% FA) are 22.6 and 4.3 MPa at 28 days, respectively. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results indicate that massive ettringite crystals and C-S-H gels exist in the hydration products. At 90 days the mortars with FGD gypsum is dramatically smaller drying shrinkage (563-938 micro strain) than that without FGD gypsum (about 2250 micro strain). The release of the SO(4)(2-) from the mortar was analyzed, indicating that the dissolution of sulfate increases with FGD gypsum. The concentration of SO(4)(2-) releasing from the mortar with 10% FGD gypsum is almost equal to that obtained from the mortar without FGD gypsum. The release of SO(4)(2-) from the mortar with 20% FGD gypsum is 9200 mg·m(-2), which is lower than that from the mortar with 95% cement clinker and 5% FGD gypsum. Copyright © 2012 Elsevier Ltd. All rights reserved.

  19. Utilization of calcite produced in Turkey for paper coating

    Hüdaverdi Eroğlu

    2002-03-01

    Full Text Available Calcium carbonate is one of the coating pigments widely used in paper industry. Especially, in recent years calcium carbonate filler has gained high importance in alkaline pulping. In Turkey industry actually imports calcium carbonate; whereas, there are rich calcite reservoirs in the country. In this study two different types of domestic ground (GCC calcite samples were used. Physical and chemical properties of calcite samples were tested firstly. CaCO3 percentages of both samples were 97.3 % and 97.6 % (min. 95 % CaCO3. MgCO3 and Fe2O3 percentages were within the desired limits. Brightness values were 95.5 % and 94.5 % and yellowness 1.1 % and 1.5 % elrepho. These values also were within the requested limits. Under 2 microns particle size and over 10 microns particle size fractions were 95 % and 89 % (min. 80 and 1 % and 2 % (max. 2 respectively. Dry matter rates were between 40 %-65 %, for the pilot plant-coating machine. During the preparation of coating color calcium carbonate has been used together with kaolin. The ratios of calcium carbonate to kaolin were 30/70, 40/60, 50/50, 60/40, 70/30, 100/0. In coating color preparation latex was used as a binder because of its wide applications. Latex percentages were 11, 12, and 13 %. Coated papers were glossed and physically tested. As a result, both calcium carbonate samples were found suitable for using in coating color preparation. By the utilization of domestic calcium carbonate in coated paper production, there will be foreign currencies saving.

  20. Calcite production by coccolithophores in the south east Pacific Ocean

    L. Beaufort

    2008-08-01

    Full Text Available BIOSOPE cruise covered an oceanographic transect through the centre of the South Pacific Gyre (SPG from the Marquesas archipelago to the Peru-Chile upwelling (PCU. Water samples from 6 depths in the euphotic zone were collected at 20 stations. The concentrations of suspended calcite particles, coccolithophores cells and detached coccoliths were estimated together with size and weight using an automatic polarizing microscope, a digital camera, and a collection of softwares performing morphometry and pattern recognition. Some of these softwares are new and described here for the first time. The coccolithophores standing stocks were usually low and reached maxima west of the PCU. The coccoliths of Emiliania huxleyi, Gephyrocapsa spp. and Crenalithus spp. (Order Isochrysidales represented more than 30% of all the suspended calcite particles detected in the size range 0.1–46 μm (22% of PIC in term of calcite weight. These species grew preferentially in the Chlorophyll maximum zone. In the SPG their maximum cell concentrations were recorded between depth of 150 and 200 m, which is unusually deep for these taxa. The weight of coccoliths and coccospheres were correlated to their size. Large and heavy coccoliths and coccospheres were found in regions with relatively high fertility in the Marquises Island and in the PCU. Small and light coccoliths and coccospheres were found west of the PCU. This distribution is strongly related to ocean chemistry in particular to alkalinity and to carbonate ions concentration. The biotic (coccolithophores production influence on calcification is mainly driven at the local scale (depth whereas the abiotic (carbonate chemistry plays its most important role at the regional (horizontal level. Here 94% of the variability of coccolith and coccosphere weight can be explained by a change in 7 environmental variables.

  1. Principles of calcite dissolution in human and artificial otoconia.

    Leif Erik Walther

    Full Text Available Human otoconia provide mechanical stimuli to deflect hair cells of the vestibular sensory epithelium for purposes of detecting linear acceleration and head tilts. During lifetime, the volume and number of otoconia are gradually reduced. In a process of degeneration morphological changes occur. Structural changes in human otoconia are assumed to cause vertigo and balance disorders such as benign paroxysmal positional vertigo (BPPV. The aim of this study was to investigate the main principles of morphological changes in human otoconia in dissolution experiments by exposure to hydrochloric acid, EDTA, demineralized water and completely purified water respectively. For comparison reasons artificial (biomimetic otoconia (calcite gelatin nanocomposits and natural calcite were used. Morphological changes were detected in time steps by the use of environmental scanning electron microscopy (ESEM. Under in vitro conditions three main dissolution mechanisms were identified as causing characteristic morphological changes of the specimen under consideration: pH drops in the acidic range, complex formation with calcium ions and changes of ion concentrations in the vicinity of otoconia. Shifts in pH cause a more uniform reduction of otoconia size (isotropic dissolution whereas complexation reactions and changes of the ionic concentrations within the surrounding medium bring about preferred attacks at specific areas (anisotropic dissolution of human and artificial otoconia. Owing to successive reduction of material, all the dissolution mechanisms finally produce fragments and remnants of otoconia. It can be assumed that the organic component of otoconia is not significantly attacked under the given conditions. Artificial otoconia serve as a suitable model system mimicking chemical attacks on biogenic specimens. The underlying principles of calcite dissolution under in vitro conditions may play a role in otoconia degeneration processes such as BPPV.

  2. The promotion effect of coexisting hygroscopic composition on the reaction between oxalic acid and calcite during humidifying process

    Ma, Q.; He, H.

    2012-12-01

    Internally mixed oxalic acid with mineral dust has been frequently detected in field measurements (Sullivan and Prather, 2007; Wang et al., 2012; Yang et al., 2009). Meanwhile, Furukawa and Takahashi (Furukawa and Takahashi, 2011) found that most of the oxalic acid in mineral mixture is present as metal oxalate complexes in the aerosols, however, the formation mechanism of these complexes is not well known. It was reported that cloud process of H2C2O4/CaCO3 mixture could lead to the formation of calcium oxalate (Gierlus et al., 2012). Recently, we used Raman spectroscopy to investigate the hygroscopic behavior of H2C2O4/CaCO3 mixture below saturation condition as well as the effect of coexisting hygroscopic compositions, e.g. Ca(NO3)2, NaCl, NH4NO3, and (NH4)2SO4. It was found that there was no interaction between H2C2O4 and calcite without third component during humidifying process under ambient condition. In contrast, the presence of coexisting Ca(NO)3, NaCl, or NH4NO3 could promote the reaction between H2C2O4 and calcite by providing an aqueous circumstance after deliquescence, resulting in the formation of calcium oxalate hydrates. Moreover, substitution of strong acid (HNO3) by medium acid (H2C2O4) occurred when water vapor was absorbed in Ca(NO3)2/H2C2O4 mixture (Ma and He, 2012). As for (NH4)2SO4, there existed a competition effect between (NH4)2SO4 and H2C2O4 for the reaction with CaCO3. CaCO3 was preferentially reacted with (NH4)2SO4 to form gypsum in the solution, while the residual NH4+ and C2O42- ions were bonded to (NH4)2C2O4 after efflorescence. These results implies a potential formation pathway of metal oxalate complexes in the atmosphere and also suggests that synergistic effect between different constituents in humidifying process of mixed particles should be considered in future hygroscopic behavior studies.

  3. Incorporation of Eu(III) into calcite under recrystallization conditions

    Hellebrandt, S.E. [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology; Jordan, Norbert [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes; Barkleit, Astrid [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Chemistry of the F-Elements; Schmidt, Moritz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). HGF Young Investigator Group; Hofmann, S.

    2017-06-01

    The interaction of three calcite powders with Eu(III) under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). Batch contact studies with reaction times from 1 week up to 3 years revealed that the speciation differs from that observed previously in co-precipitation experiments and is dominated by a newly identified species ''γ''. The speed of formation of this species was found to depend greatly on the recrystallization rate of the studied minerals.

  4. Incorporation of Eu(III) into calcite under recrystallization conditions

    Hellebrandt, S.E.; Jordan, Norbert; Barkleit, Astrid; Schmidt, Moritz; Hofmann, S.

    2017-01-01

    The interaction of three calcite powders with Eu(III) under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). Batch contact studies with reaction times from 1 week up to 3 years revealed that the speciation differs from that observed previously in co-precipitation experiments and is dominated by a newly identified species ''γ''. The speed of formation of this species was found to depend greatly on the recrystallization rate of the studied minerals.

  5. Gallium isotope fractionation during Ga adsorption on calcite and goethite

    Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques

    2018-02-01

    Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its

  6. Comparative study of the shield of concrete blocks with hematite in relation to common concrete blocks

    Costa, Paulo R.; Buerger, Andre A.; Naccache, Veronica K.; Priszkulnik, Simao

    2012-01-01

    The present work shows results of an empirical evaluation of the transmission properties of two radioprotection materials: an ordinary concrete and an ordinary concrete mixed with hematite. It was used techniques of x-ray spectroscopy and measurements of the air-kerma transmitted through these two materials in order to compare the transmission properties for each one. (author)

  7. Synthesis and photo-electrochemical properties of spinel-ferrite-coated hematite for solar water splitting

    Selvaraj, Seenivasan; Moon, Hee; Kim, Do-Heyoung

    2018-01-01

    Photo-electrochemical water splitting with hematite photo-anodes under solar irradiation has attracted considerable attention as regards the production of renewable hydrogen energy. However, many challenges remain unresolved, as the full contribution of the catalytic over-layers has not been fully realized. Herein, we incorporate uniform spinel nickel-ferrite over-layers in hematite photo-anodes to obtain an improved understanding of the associated intrinsic changes. We achieve a 1.5-mA/cm2 photo-current density at 1.23 VRHE (RHE: reversible hydrogen electrode) under one-sun illumination conditions, along with a negative shift of 200 mV in the onset potential, for NiFe2O4-coated Sn-doped hematite photo-anodes. Fundamental electrochemical analyses clearly show that the shift in the onset potential is predominantly due to the enhanced photo-voltage development inside the hematite, rather than being purely caused by the interfacial kinetics. These insights reveal a new direction for fundamental research on photo-anodes towards fabrication of more efficient photo-anode systems.

  8. The colloid hematite particle migration through the unsaturated porous bed at the presence of biosurfactants.

    Pawlowska, Agnieszka; Sznajder, Izabela; Sadowski, Zygmunt

    2017-07-01

    Colloidal particles have an ability to sorb heavy metals, metalloids, and organic compounds (e.g. biosurfactants) present in soil and groundwater. The pH and ionic strength changes may promote release of such particles causing potential contaminant transport. Therefore, it is very important to know how a colloid particle-mineral particle and colloid-mineral-biosurfactant system behaves in the natural environment. They can have negative impact on the environment and human health. This study highlighted the influence of biosurfactants produced by Pseudomonas aeruginosa on the transport of colloidal hematite (α-Fe 2 O 3 ) through porous bed (materials collected from the Szklary and Zloty Stok solid waste heaps from Lower Silesia, Poland). Experiments were conducted using column set in two variants: colloid solution with porous bed and porous bed with adsorbed biosurfactants, in the ionic strengths of 5 × 10 -4 and 5 × 10 -3  M KCl. The zeta potential of mineral materials and colloidal hematite, before and after adsorption of biosurfactant, was determined. Obtained results showed that reduction in ionic strength facilitates colloidal hematite transport through the porous bed. The mobility of colloidal hematite was higher when the rhamnolipid adsorbed on the surface of mineral grain.

  9. Thermal modification of hematite-ilmenite intergrowths in the Ecstall pluton, British Columbia, Canada

    Brownlee, S.J.; Feinberg, J.M.; Harrison, R.J.

    2010-01-01

    In this study, we examine the effects of reheating on finely exsolved hematite-ilmenite intergrowths from the similar to 91 Ma Ecstall pluton using reflected light microscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). As a result of the emplacement of the you......In this study, we examine the effects of reheating on finely exsolved hematite-ilmenite intergrowths from the similar to 91 Ma Ecstall pluton using reflected light microscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). As a result of the emplacement...... of the younger adjacent similar to 52 Ma Quottoon pluton, samples closer to a thermal boundary have experienced greater degrees of thermal alteration. Five main microstructural features characterize hematite-ilmenite intergrowths from the Ecstall: (I) exsolution lamellae of hematite and ilmenite; (II) oxidation....... Higher temperatures also enhanced oxidation in ilmenite. The formation of magnetite altered the bulk magnetic properties of these samples, increasing NRM intensity. This study underscores the need to consider a pluton's post-emplacement thermal history before making tectonic interpretations based...

  10. Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements

    Bargar, John R.; Reitmeyer, Rebecca; Lenhart, John J.; Davis, James A.

    2000-01-01

    We have measured U(VI) adsorption on hematite using EXAFS spectroscopy and electrophoresis under conditions relevant to surface waters and aquifers (0.01 to 10 μM dissolved uranium concentrations, in equilibrium with air, pH 4.5 to 8.5). Both techniques suggest the existence of anionic U(VI)-carbonato ternary complexes. Fits to EXAFS spectra indicate that U(VI) is simultaneously coordinated to surface FeO6 octahedra and carbonate (or bicarbonate) ligands in bidentate fashions, leading to the conclusion that the ternary complexes have an inner-sphere metal bridging (hematite-U(VI)-carbonato) structure. Greater than or equal to 50% of adsorbed U(VI) was comprised of monomeric hematite-U(VI)-carbonato ternary complexes, even at pH 4.5. Multimeric U(VI) species were observed at pH ≥ 6.5 and aqueous U(VI) concentrations approximately an order of magnitude more dilute than the solubility of crystalline β-UO2(OH)2. Based on structural constraints, these complexes were interpreted as dimeric hematite-U(VI)-carbonato ternary complexes. These results suggest that Fe-oxide-U(VI)-carbonato complexes are likely to be important transport-limiting species in oxic aquifers throughout a wide range of pH values.

  11. Ion adsorption on oxides : surface charge formation and cadmium binding on rutile and hematite

    Fokkink, L.G.J.

    1987-01-01

    The adsorption of charge-determining (H +and OH -) and cadmium ions on rutile (TiO 2 ) and hematite (α-Fe

  12. The Distribution of Crystalline Hematite on Mars from the Thermal Emission Spectrometer: Evidence for Liquid Water

    Christensen, P. R.; Malin, M.; Morris, D.; Bandfield, J.; Lane, M.; Edgett, K.

    2000-01-01

    Crystalline hematite on Mars has been mapped using the MGS TES. Two major, and several minor areas of significant accumulation are identified. We favor precipitation models involving Fe-rich water, providing direct mineralogic evidence for large-scale water interactions.

  13. Resolving Iron(II) Sorption and Oxidative Growth on Hematite (001) Using Atom Probe Tomography

    Taylor, Sandra D. [Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States; Liu, Jia [Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States; Arey, Bruce W. [Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States; Schreiber, Daniel K. [Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States; Perea, Daniel E. [Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States; Rosso, Kevin M. [Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States

    2018-02-13

    The distribution of iron resulting from the autocatalytic interaction of aqueous Fe(II) with the hematite (001) surface was directly mapped in three dimensions (3D) for the first time, using iron isotopic labelling and atom probe tomography (APT). Analyses of the mass spectrum showed that natural abundance ratios in 56Fe-dominant hematite are recovered at depth with good accuracy, whereas at the relict interface with 57Fe(II) solution evidence for hematite growth by oxidative adsorption of Fe(II) was found. 3D reconstructions of the isotope positions along the surface normal direction showed a zone enriched in 57Fe, which was consistent with an average net adsorption of 3.2 – 4.3 57Fe atoms nm–2. Statistical analyses utilizing grid-based frequency distribution analyses show a heterogeneous, non-random distribution of oxidized Fe on the (001) surface, consistent with Volmer-Weber-like island growth. The unique 3D nature of the APT data provides an unprecedented means to quantify the atomic-scale distribution of sorbed 57Fe atoms and the extent of segregation on the hematite surface. This new ability to spatially map growth on single crystal faces at the atomic scale will enable resolution to long-standing unanswered questions about the underlying mechanisms for electron and atom exchange involved in a wide variety of redox-catalyzed processes at this archetypal and broadly relevant interface.

  14. Transformation of goethite/ferrihydrite to hematite and maghemite under temperate humid conditions in Denmark

    Nørnberg, P.; Finster, K.; Gunnlaugsson, H. P.; Jensen, S. K.; Merrison, J. P.; Vendelboe, A. L.

    2012-04-01

    At a number of sandy soil sites in Mid Jutland, Denmark, with iron content of 1-2%, very red spots (Munsell colour: dusky red 10R 3/4) of a few square meters are found. These spots are most likely due to burning events. After the fire ashes raised pH. This dispersed silt and clay size soil particles which were then transported with seepage water down into lower soil horizons. These particles contain hematite and maghemite due to influence of the fire. However, a long-standing unresolved question is how hematite and maghemite can also be present along with goethite and ferrihydrite, in the same geographical region, and in extended areas with high iron content (8-40 %) in the topsoil. Hematite and particularly maghemite would normally not be expected to form under the temperate humid Danish climate, but be interpreted as the result of high temperature as found in tropical regions or as seen in soils exposed to fire. The high iron content most likely has its origin in pyrite dissolution in top of the groundwater zone in deeper Miocene deposits. From there Fe2+ is brought to the surface by the groundwater, and in wells oxidized by meeting the atmosphere and precipitated as two line ferrihydrite. This is later transformed into goethite. However, along with these two minerals hematite and maghemite are present in the topsoil around the well area. Forest fires would be a likely explanation to the hematite and maghemite. But a body of evidence argues against these sites having been exposed to fire. 1) The pH in the topsoil is 3.6 - 4.8 and thus not raised by ashes. 2) No charcoal is present. 3) There is no indication of fire outside the high iron content areas. 4) Goethite is present along with hematite and maghemite in microparticles, and the mineralogical zonation produced in a forest fire is not seen. The natural sites contain a uniform mixture of goethite/ferrihydrite, hematite and maghemite down to 20 cm depth. An experimental forest fire left charcoal and ashes at

  15. Messinian Salinity Crisis' Primary Evaporites: the shallow gypsum vs. deep dolomite formation paradox solved

    De Lange, G. J.; Krijgsman, W.

    2015-12-01

    The Messinian Salinity Crisis (MSC) is a dramatic event that took place ~ 5.9 Ma ago, resulting in deposition of 1-3 km thick evaporites at the Mediterranean seafloor. A considerable, long-lasting controversy existed on the modes of their formation, including the observed shallow gypsum versus deep dolostone deposits for the early phase of MSC. The onset of MSC is marked by deposition of gypsum/sapropel-like alternations, thought to relate to arid/humid climate conditions at a precessional rhythm. Gypsum precipitation only occurred at marginal- and dolomite formation at deeper settings. A range of potential explanations was given, most of which cannot satisfactorily explain all observations. Biogeochemical processes during MSC are commonly neglected but may explain that different deposits formed in shallow vs deep environments without exceptional physical boundary conditions for each. A unifying mechanism is presented in which gypsum formation occurs at all shallow water depths but its preservation is limited to shallow sedimentary settings. In contrast, ongoing deep-basin anoxic organic matter (OM) degradation processes result in dolomite formation. Gypsum precipitation in evaporating seawater takes place at 3-7 times concentrated seawater; seawater is always oversaturated relative to dolomite but its formation is inhibited by the presence of dissolved sulphate. Thus conditions for formation of gypsum exclude those for formation of dolomite and vice versa. Another process linking the saturation states of gypsum and dolomite is that of OM degradation by sulphate reduction. In stagnant deep water, ongoing OM-degradation may result in reducing the sulphate and enhancing the dissolved carbonate content. Such low-sulphate / high carbonate conditions in MSC deepwater are. unfavorable for gypsum preservation and favorable for dolomite formation, and always coincide with anoxic, i.e. oxygen-free conditions. Including dynamic biogeochemical processes in the thusfar static

  16. Effects of gypsum and bulk density on neutron probe calibration curves

    Arslan, Awadis; Razzouk, A.K.

    1993-10-01

    The effects of gypsum and bulk density on the neutron probe calibration curve were studied in the laboratory and in the field. The effect of bulk density was negligible for the soil studied in the laboratory, while it was significant for the field calibration. An increase in the slope of moisture content on a volume basis vs. count ratio with increasing gypsum content at the soil was observed in the laboratory calibration. A simple method for correction of the calibration curve for gypsum content was adopted to obtain a specific curve for each layer. The adapted method requires the gypsum fraction to be estimated for each layer and then incorporated in the calibration curve to improve the coefficient of determination. A field calibration showed an improvement of the determination coefficient by introducing bulk density and gypsum fraction, in addition to count ratio using moisture content on a volume basis as a dependent variable in multi linear regression analysis. The same procedure was successful with variable gravel fractions. (author). 18 refs., 3 figs., 2 tabs

  17. Effect of alginate chemical disinfection on bacterial count over gypsum cast.

    Haralur, Satheesh B; Al-Dowah, Omir S; Gana, Naif S; Al-Hytham, Abdullah

    2012-05-01

    To evaluate the efficacy of sodium hypochlorite (1 : 10) and iodophor disinfectants on alginate impressions along with their effect on the survived bacterium count on the gypsum cast. Four alginate impression on each dentate patients were made, of which Group I were not washed or disinfected, Group II impressions were merely washed with water, Group III were disinfected by spraying with sodium hypochlorite (1 : 10), Group IV were disinfected with iodophor (1 : 213). Gypsum cast (type III) were made from all the impression. Impressions and gypsum cast were swabbed in mid palatal region for bacterial culture. Bacterial colony counting done after 3 days of incubation at 37℃ in blood agar media. The data obtained was analyzed by one way ANOVA test at a significant difference level of 0.05. Group I and Group II showed significantly more bacteria compared to Group III and Group IV. Bacterial colonies on the alginate impression and gypsum cast in group disinfected with Sodium hypochlorite (1 : 10) were 0.18, 0.82 respectively compared to group treated with iodophor (1 : 213). There was an increase in bacterial count on dental cast compared to source alginate impressions. Sodium hypochlorite (1 : 10) was found to be better disinfectant for alginate impression. There was an indication of increase in number of bacteria from alginate impression to making of dental cast. Additional gypsum cast disinfectant procedures need to be encouraged to completely eliminate cross infection to dental laboratory.

  18. Gypsum-permineralized microfossils and their relevance to the search for life on Mars.

    Schopf, J William; Farmer, Jack D; Foster, Ian S; Kudryavtsev, Anatoliy B; Gallardo, Victor A; Espinoza, Carola

    2012-07-01

    Orbital and in situ analyses establish that aerially extensive deposits of evaporitic sulfates, including gypsum, are present on the surface of Mars. Although comparable gypsiferous sediments on Earth have been largely ignored by paleontologists, we here report the finding of diverse fossil microscopic organisms permineralized in bottom-nucleated gypsums of seven deposits: two from the Permian (∼260 Ma) of New Mexico, USA; one from the Miocene (∼6 Ma) of Italy; and four from Recent lacustrine and saltern deposits of Australia, Mexico, and Peru. In addition to presenting the first report of the widespread occurrence of microscopic fossils in bottom-nucleated primary gypsum, we show the striking morphological similarity of the majority of the benthic filamentous fossils of these units to the microorganisms of a modern sulfuretum biocoenose. Based on such similarity, in morphology as well as habitat, these findings suggest that anaerobic sulfur-metabolizing microbial assemblages have changed relatively little over hundreds of millions of years. Their discovery as fossilized components of the seven gypsiferous units reported suggests that primary bottom-nucleated gypsum represents a promising target in the search for evidence of past life on Mars. Key Words: Confocal laser scanning microscopy-Gypsum fossils-Mars sample return missions-Raman spectroscopy-Sample Analysis at Mars (SAM) instrument-Sulfuretum.

  19. Photoelectrochemical water splitting with mesoporous hematite prepared by a solution-based colloidal approach.

    Sivula, Kevin; Zboril, Radek; Le Formal, Florian; Robert, Rosa; Weidenkaff, Anke; Tucek, Jiri; Frydrych, Jiri; Grätzel, Michael

    2010-06-02

    Sustainable hydrogen production through photoelectrochemical water splitting using hematite (alpha-Fe(2)O(3)) is a promising approach for the chemical storage of solar energy, but is complicated by the material's nonoptimal optoelectronic properties. Nanostructuring approaches have been shown to increase the performance of hematite, but the ideal nanostructure giving high efficiencies for all absorbed light wavelengths remains elusive. Here, we report for the first time mesoporous hematite photoelectodes prepared by a solution-based colloidal method which yield water-splitting photocurrents of 0.56 mA cm(-2) under standard conditions (AM 1.5G 100 mW cm(-2), 1.23 V vs reversible hydrogen electrode, RHE) and over 1.0 mA cm(-2) before the dark current onset (1.55 V vs RHE). The sintering temperature is found to increase the average particle size, and have a drastic effect on the photoactivity. X-ray photoelectron spectroscopy and magnetic measurements using a SQUID magnetometer link this effect to the diffusion and incorporation of dopant atoms from the transparent conducting substrate. In addition, examining the optical properties of the films reveals a considerable change in the absorption coefficient and onset properties, critical aspects for hematite as a solar energy converter, as a function of the sintering temperature. A detailed investigation into hematite's crystal structure using powder X-ray diffraction with Rietveld refinement to account for these effects correlates an increase in a C(3v)-type crystal lattice distortion to the improved optical properties.

  20. Prediction of calcite Cement Distribution in Shallow Marine Sandstone Reservoirs using Seismic Data

    Bakke, N.E.

    1996-12-31

    This doctoral thesis investigates how calcite cemented layers can be detected by reflection seismic data and how seismic data combined with other methods can be used to predict lateral variation in calcite cementation in shallow marine sandstone reservoirs. Focus is on the geophysical aspects. Sequence stratigraphy and stochastic modelling aspects are only covered superficially. Possible sources of calcite in shallow marine sandstone are grouped into internal and external sources depending on their location relative to the presently cemented rock. Well data and seismic data from the Troll Field in the Norwegian North Sea have been analysed. Tuning amplitudes from stacks of thin calcite cemented layers are analysed. Tuning effects are constructive or destructive interference of pulses resulting from two or more closely spaced reflectors. The zero-offset tuning amplitude is shown to depend on calcite content in the stack and vertical stack size. The relationship is found by regression analysis based on extensive seismic modelling. The results are used to predict calcite distribution in a synthetic and a real data example. It is found that describing calcite cemented beds in shallow marine sandstone reservoirs is not a deterministic problem. Hence seismic inversion and sequence stratigraphy interpretation of well data have been combined in a probabilistic approach to produce models of calcite cemented barriers constrained by a maximum amount of information. It is concluded that seismic data can provide valuable information on distribution of calcite cemented beds in reservoirs where the background sandstones are relatively homogeneous. 63 refs., 78 figs., 10 tabs.

  1. Study of reverse flotation of calcite from scheelite in acidic media

    Deng, Rongdong; Huang, Yuqing; Hu, Yuan; Ku, Jiangang; Zuo, Weiran; Yin, Wanzhong

    2018-05-01

    A new coated-reactive reverse flotation method based on the generation of CO2 bubbles at a calcite surface in acidic solution was used to separate calcite from scheelite. The dissolution kinetics of coated and uncoated calcite were studied in sulfuric acid. The CO2 bubbles generated on the uncoated calcite particle surface are enough to float the particle. However, most of these bubbles left the surface quickly, preventing calcite from floating. Here, a mixture of polyvinyl alcohol polymer and sodium dodecyl sulfonate was used to coat the mineral particles and form a stable membrane, resulting in the formation of a stable foam layer on the calcite surface. After the calcite is coated, the generated bubbles could be successfully captured on the calcite surface, and calcite particles could float to the air-water interface and remain there for more than one hour. Flotation tests indicated that a high-quality tungsten concentrate with a grade of more than 75% and a recovery of more than 99% could be achieved when the particle size was between 0.3 and 1.5 mm. The present results provide theoretical support for the development of a highly efficient flotation separation for carbonate minerals.

  2. Interactions of U(VI), Nd, and Th(IV) at the Calcite-solution interface

    Carroll, S.A.; Dran, J.C.

    1992-01-01

    The interactions of U(VI), Nd, and Th(IV) at the calcite-solution interface at controlled pCO 2 (g) have been investigated by Rutherford backscattering (RBS), scanning electron microscopy (SEM) and energy dispersive (EDS) analyses of reacted calcite. Uranium precipitation at the calcite-solution interface was observed only for those experiments in which the initial [U(VI)] was greater than the solubility of rutherfordine, UO 2 CO 3 (s). At pH 8.0, flat radial uranium and calcium zoned precipitates form at the mineral-solution interface. At pH 4.3, uranium forms an anastomosing precipitate throughout the calcite surface. RBS analyses confirmed the SEM analyses showing that uranium forms a solid phase within the calcite surface, but formation of an uranium-calcium solid solution at depth is limited. In sharp contrast to U(VI), Nd is concentrated in the solid phase as individual neodymium-calcium carbonate crystals. Calcite and pure orthorhombic neodymium carbonate crystals dissolve at the expense of the formation of a more stable neodymium-calcium solid solution. In the presence of calcite, a thorium-calcium solid solution forms by exchanging Th for Ca in the calcite structure. Thorium precipitates in two linear trends which intersect each other at approximately 105deg C and 75deg C, parallel to calcite rhombohedral cleavage faces. (orig.)

  3. Synthesis of sub-millimeter calcite from aqueous solution

    Reimi, M. A.; Morrison, J. M.; Burns, P. C.

    2011-12-01

    A novel aqueous synthesis that leads to the formation of calcite (CaCO3) crystals, up to 500μm in diameter, will be used to facilitate the study of contaminant transport in aqueous environmental systems. Existing processes tend to be complicated and often yield nanometer-sized or amorphous CaCO3. The synthesis method presented here, which involves slow mixing of concentrated solutions of CaCl2 ¬and (NH4)2CO3, produces single crystals of rhombohedral calcite in 2 to 4 days. Variations on the experimental method, including changes in pH and solution concentration, were explored to optimize the synthesis. Scanning Electron Microscope images show the differences in size and purity observed when the crystals are grown at pH values ranging from 2 to 6. The crystals grown from solutions of pH 2 were large (up to 500 micrometers in diameter) with minimal polycrystalline calcium carbonate, while crystals grown from solutions with pH values beyond 4 were smaller (up to 100 micrometers in diameter) with significant polycrystalline calcium carbonate. The synthesis method, materials characterization, and use in future actinide contaminant studies will be discussed.

  4. Inhibiting Effect of Additives on Pressure Solution of Calcite

    Traskine, V.; Skvortsova, Z.; Badun, G.; Chernysheva, M.; Simonov, Ya.; Gazizullin, I.

    2018-05-01

    The task of protection of cultural heritage requires a better understanding of combined effects of mechanical and chemical factors involved in environmental deterioration of monuments. The present paper deals with extending some known physicochemical methods proposed for inhibiting the decay of unstressed materials to their study during water-assisted deformation. The tests have been carried out on natural limestone samples and calcite powders in CaCO3 saturated aqueous solutions under static loads causing measurable pressure solution creep. In the solutions containing 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotriacetic acid, or ethylenediaminetetraacetic acid, the creep rate decreases considerably with increasing concentration of additives. The extent of creep deceleration has been found to be proportional to the independently estimated calcite surface area occupied by adsorbed species. This fact enables us to discriminate the adsorption-induced effect from other variables controlling the pressure solution rate and may be used in screening of compounds able to minimize the environmental impact on marble and limestone objects undergoing mechanical stresses.

  5. Thermoluminescent of induced calcite by gamma and ultraviolet radiation

    Lima, J.F. de.

    1987-01-01

    Samples of brazilian calcite, exposed to gamma radiation in laboratory and heated at constant rate of 2.7 0 C/s, showed three glow peaks at 150, 250 and 350 0 C in their thermoluminescent emission curves. The analysis of these peaks, using different models, indicated that they follow a second order kinetics; it has been obtained, for the activation energy, 1.3, 1.5 and 1.7 eV, and, for the pre-exponential factors, 8.1 x 10 14 , 6.8 x10 13 and 2.4 x 10 12 s -1 . Although the total thermoluminescent emission has stayed constant, the relative height of glow peaks has changed with the temperature of annealing in the range of 400 to 700 0 C. Exposed samples were also illuminated with ultraviolet light and the resultant curves showed partial or total bleaching or some glow peaks and the growth of peaks at lower temperatures. Samples of virgin calcite, submited to increasing exposures of gamma rays, showed a corresponding enhancement of the optical absorption bands in the range of 25000 to 47000 cm -1 A subsequent illumination of these samples with ultraviolet light produced a decrease of the optical absorption bands at the same range. (author) [pt

  6. Geochemical and isotope aspects of calcite deposits and calcitic marbles hosts mineralizations, Serra do Carumbe, Vale do Ribeira, Parana state, Brazil

    Venusso, Gerson Caetano; Andrade e Silva, Antonio C. Gondim de

    2011-01-01

    The calcite deposits and the calcitic marbles hosts occur in Serra do Carumbe, in the Vale do Ribeira region, Parana State, were studied in their geochemical and isotopic aspects viewing the gathering of information about their genesis and economical use. The calcite deposits are constituted by veins and lenses, being three of them concordant and one discordant in relation to the S_0 from the hosting marbles. In these deposits four main types of calcite were recognized: rombohedrical, fibrous, banded and microcrystalline. The calcite reveal themselves having high purity, with CaO concentration above 55.30% and MgO below 0.42%. The lithogeochemical study of the marbles sequence was conducted in various suites revealing an uniformity in their composition, with high values of CaO (above 46.92%) in relation to the MgO values (below 3,37%), what favors their use for cement manufacture, except in sectors that suffered fault influences, where the marbles are impure (siliceous, magnesian, ferruginous and aluminous). Regarding their trace elements content, the hosting calcitic marbles have higher concentrations than the calcite, in the elements Sr, B, Ba and Mg, what makes evident their different formation environments. The δ"1"3C values from calcite range from –9,02 to –12,24 ‰ , referring to PDB, while the values δ"1"8O range from 24,48 to 25,23 ‰, referring to SMOW; meanwhile, for the calcitic marbles, the δ"1"3C values range from –4,03 to 1,42‰ and of δ"1"8O range from 20,71 to 23,00 ‰. The high δ"1"8O values would indicate enrichment referring to the interaction of the calcite's generator fluid with the carbonatic host rock. The δ"1"3C values indicate origin from hydrothermal solution for the calcite, although they would not allow to conclude if their sources would be superficial or profound. As for the hosting calcitic marbles, the isotopic values indicate genesis from pre-cambrian marine limestone. (author)

  7. A DOC coagulant, gypsum treatment can simultaneously reduce As, Cd and Pb uptake by medicinal plants grown in contaminated soil.

    Kim, Hyuck Soo; Seo, Byoung-Hwan; Kuppusamy, Saranya; Lee, Yong Bok; Lee, Jae-Hwang; Yang, Jae-E; Owens, Gary; Kim, Kwon-Rae

    2018-02-01

    The efficiency of gypsum, as a dissolved organic carbon (DOC) coagulator, for the simultaneous immobilization of two heavy metals (Cd and Pb) and one metalloid (As) in agricultural soils near an abandoned mining site was examined. The agricultural soil was defined as long-term contaminated as As (1540mgkg -1 ), Cd (55mgkg -1 ) and Pb (1283mgkg -1 ) concentrations exceeded the Korean guideline values for As (25mgkg -1 ), Cd (4mgkg -1 ), and Pb (200mgkg -1 ). Gypsum was incorporated into the contaminated soil at 3% (w/w). In comparison two commonly using immobilizing agents (lime and compost), together with a mixture (lime+gypsum) were also included in the pot trial for the cultivation of two medical plants (A. gigas and A. macrocephala) and to evaluate the effectiveness of gypsum on As, Cd and Pb immobilization. The results showed that even though pH change-induced immobilizing agents such as lime were more effective than gypsum at immobilizing Cd and Pb, addition of gypsum also effectively reduced heavy metal phytoavailability as indicated by decreases in the concentration of Cd and Pb in medicinal plants. Furthermore, gypsum and gypsum+ lime were also most effective in reducing As concentrations in both plants studied. This was mainly attributed to significant decreases in soil DOC (48-64%) when gypsum and gypsum+lime were applied to the soil. Consequently, it was concluded that enhanced DOC coagulation with gypsum, could be considered as a promising technique for the immobilization of both metals (Cd and Pb) and metalloids (As) in agricultural soils. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. A Ga2O3 underlayer as an isomorphic template for ultrathin hematite films toward efficient photoelectrochemical water splitting.

    Hisatomi, Takashi; Brillet, Jérémie; Cornuz, Maurin; Le Formal, Florian; Tétreault, Nicolas; Sivula, Kevin; Grätzel, Michael

    2012-01-01

    Hematite photoanodes for photoelectrochemical (PEC) water splitting are often fabricated as extremely-thin films to minimize charge recombination because of the short diffusion lengths of photoexcited carriers. However, poor crystallinity caused by structural interaction with a substrate negates the potential of ultrathin hematite photoanodes. This study demonstrates that ultrathin Ga2O3 underlayers, which were deposited on conducting substrates prior to hematite layers by atomic layer deposition, served as an isomorphic (corundum-type) structural template for ultrathin hematite and improved the photocurrent onset of PEC water splitting by 0.2 V. The benefit from Ga2O3 underlayers was most pronounced when the thickness of the underlayer was approximately 2 nm. Thinner underlayers did not work effectively as a template presumably because of insufficient crystallinity of the underlayer, while thicker ones diminished the PEC performance of hematite because the underlayer prevented electron injection from hematite to a conductive substrate due to the large conduction band offset. The enhancement of PEC performance by a Ga2O3 underlayer was more significant for thinner hematite layers owing to greater margins for improving the crystallinity of ultrathin hematite. It was confirmed that a Ga2O3 underlayer was applicable to a rough conducting substrate loaded with Sb-doped SnO2 nanoparticles, improving the photocurrent by a factor of 1.4. Accordingly, a Ga2O3 underlayer could push forward the development of host-guest-type nanocomposites consisting of highly-rough substrates and extremely-thin hematite absorbers.

  9. Effect of EDTA and gypsum on self diffusion coefficient of zinc in alkali soil

    Gupta, G.N.; Deb, D.L.

    1981-01-01

    The effect of EDTA and gypsum application on the rate of zinc diffusion was studied in an alkali soil. Gypsum application at the rate of half gypsum requirement (GR) increased the apparent self diffusion coefficient of zinc (DaZn) and decreased the capacity factor (B) of soil. The higher rates (full GR and double GR) depressed the rate of zinc diffusion and increased the B value. Application of EDTA at the rate of 0.77 μeg -1 of soil produced 1600 and 24 fold increase in DaZn and DpZn values respectively and 100 times drop in B value. Addition of 55 ppm Zn to the soil significantly increased the DaZn and DpZn values. (author)

  10. Dimensional accuracy and surface property of titanium casting using gypsum-bonded alumina investment.

    Yan, Min; Takahashi, Hidekazu; Nishimura, Fumio

    2004-12-01

    The aim of the present study was to evaluate the dimensional accuracy and surface property of titanium casting obtained using a gypsum-bonded alumina investment. The experimental gypsum-bonded alumina investment with 20 mass% gypsum content mixed with 2 mass% potassium sulfate was used for five cp titanium castings and three Cu-Zn alloy castings. The accuracy, surface roughness (Ra), and reaction layer thickness of these castings were investigated. The accuracy of the castings obtained from the experimental investment ranged from -0.04 to 0.23%, while surface roughness (Ra) ranged from 7.6 to 10.3microm. A reaction layer of about 150 microm thickness under the titanium casting surface was observed. These results suggested that the titanium casting obtained using the experimental investment was acceptable. Although the reaction layer was thin, surface roughness should be improved.

  11. STRUCTURE AND PROPERTIES OF COMPOSITE MATERIAL BASED ON GYPSUM BINDER AND CARBON NANOTUBES

    CHUMAK Anastasia Gennadievna

    2013-04-01

    Full Text Available The aim of this work is to carry out a number of studies in the area of nanomodi­fication of gypsum binder matrix and to investigate the influence of multilayer carbon nanotubes on the structure, physical and mechanical properties of obtained compos­ites. The study of the gypsum binders structure formation mechanisms with the use of nanoadditives makes it possible to control the production processes of gypsum materi­als and articles with the given set of properties. The main tasks of the binder nanomodification are: even distribution of carbon nanostructures over the whole volume of material and provision of stability for the nanodimensional modifier during production process of the construction composite.

  12. Effect of shelf life on compressive strength of type iv gypsum

    Kusumastuti, K. S.; Irawan, B.; Damiyanti, M.

    2017-08-01

    Type IV gypsum, as a dental material for an indirect restoration’s working model, should have strength and abrasive-resistant properties. These properties depend on the product’s shelf life and its proper storage, which sometimes are easily missed by sellers. The aim of this research was to observe the effect of shelf life on the compressive strength of type IV gypsum with different production dates. Twenty cylindrical specimens were separated into two groups with different production dates and tested with a universal testing with the crosshead speed of 1 mm per minute and a load of 2,500 kgf. The data were analyzed with independent t-tests. There was a significant difference (p<0.05) in the compressive strength between the two groups with an increase in compressive strength seen in the gypsum that was stored longer.

  13. Application of gypsum as shielding against low-energy X-radiation in the radiodiagnosis area

    Lins, J.A.G.; Lima, F.R.A.; Santos, M.A.P. dos; Oliveira, D.N.S. de; Silva, V.H.F.F. da

    2017-01-01

    In recent years, materials such as lead, concrete and iron have been studied for use as shielding for ionizing radiations of different energies in radiative installations. In the radiodiagnosis area, lead and barite are the most used materials as shielding. However, for beams of low energy X-radiation, such as in mammography and dentistry, the gypsum material may be used. This study aims to verify the feasibility of the use of gypsum as shielding for low-energy X-ray using standardized dental X-ray beams in a metrology laboratory. The project will allow a better understanding in the study of gypsum used as shielding, certifying its use as a good attenuator for low-energy X-ray

  14. Analysis of cubic and orthorhombic C3A hydration in presence of gypsum and lime

    Kirchheim, A. P.

    2009-02-26

    Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) have been used to study the microstructural changes and phase development that take place during the hydration of cubic (pure) and orthorhombic (Na-doped) tricalcium aluminate (C3A) and gypsum in the absence and presence of lime. The results demonstrate that important differences occur in the hydration of each C3A polymorph and gypsum when no lime is added; orthorhombic C3A reacts faster with gypsum than the cubic phase, forming longer ettringite needles; however, the presence of lime slows down the formation of ettringite in the orthorhombic sample. Additional rheometric tests showed the possible effects on the setting time in these cementitious mixes.

  15. Analysis of cubic and orthorhombic C3A hydration in presence of gypsum and lime

    Kirchheim, A. P.; Fernà ndez-Altable, V.; Monteiro, P. J. M.; Dal Molin, D. C. C.; Casanova, I.

    2009-01-01

    Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) have been used to study the microstructural changes and phase development that take place during the hydration of cubic (pure) and orthorhombic (Na-doped) tricalcium aluminate (C3A) and gypsum in the absence and presence of lime. The results demonstrate that important differences occur in the hydration of each C3A polymorph and gypsum when no lime is added; orthorhombic C3A reacts faster with gypsum than the cubic phase, forming longer ettringite needles; however, the presence of lime slows down the formation of ettringite in the orthorhombic sample. Additional rheometric tests showed the possible effects on the setting time in these cementitious mixes.

  16. Petroleum Sludge as gypsum replacement in cement plants: Its Impact on Cement Strength

    Benlamoudi, Ali; Kadir, Aeslina Abdul; Khodja, Mohamed

    2017-08-01

    Due to high cost of cement manufacturing and the huge amount of resources exhaustion, companies are trying to incorporate alternative raw materials or by-products into cement production so as to produce alternative sustainable cement. Petroleum sludge is a dangerous waste that poses serious imparts on soil and groundwater. Given that this sludge contains a high percentage of anhydrite (CaSO4), which is the main component of gypsum (CaSO4.2H2O), it may play the same gypsum role in strength development. In this research, a total replacement of gypsum (100%) has been substituted by petroleum sludge in cement production and has led to an increase of 28.8% in UCS values after 28 curing days. Nevertheless, the burning of this waste has emitted a considerable amount of carbon monoxide (CO) gas that needs to be carefully considered prior to use petroleum sludge within cement plants.

  17. The effect of magnesium on partial sulphate removal from mine water as gypsum.

    Tolonen, Emma-Tuulia; Rämö, Jaakko; Lassi, Ulla

    2015-08-15

    The aim of this research was to investigate the effect of magnesium on the removal efficiency of sulphate as gypsum from mine water. The precipitation conditions were simulated with MINEQL + software and the simulation results were compared with the results from laboratory jar test experiments. Both the simulation and the laboratory results showed that magnesium in the mine water was maintaining sulphate in a soluble form as magnesium sulphate (MgSO4) at pH 9.6. Thus magnesium was preventing the removal of sulphate as gypsum (CaSO4·2H2O). However, change in the lime precipitation pH from 9.6 to 12.5 resulted in magnesium hydroxide (Mg(OH)2) precipitation and improved sulphate removal. Additionally, magnesium hydroxide could act as seed crystals for gypsum precipitation or co-precipitate sulphate further enhancing the removal of sulphate from mine water. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Achievement report for fiscal 2000 on development of technology to recycle disintegrated waste gypsum boards; 1999 nendo kaitai haisekko board no saishigenka gijutsu kaihatsu seika hokokusho

    NONE

    2001-03-01

    Investigations and researches have been made on disintegrated waste gypsum boards generated in building demolishing sites, with a target of recycling them as a raw material for boards. In the investigations, the actual status of discarding the disintegrated gypsum boards was identified, whereas the harmful substance contents such as of heavy metals were verified to be below the environmental criteria. As a method to remove impurities and foreign materials from the disintegrated waste gypsum boards, the hydration crushing method was established, in which volumetric change when hemihydrate gypsum returns to gypsum dehydrate is utilized, and bond of gypsum particles with each other and with impurities is destructed to separate them into simple substances. Furthermore, discussions were given on the reforming conditions to reform in an energy saving manner the disintegrated waste gypsum boards into high-quality large-size hemihydrate gypsum by using the wet-type process that utilizes the reversible reaction between hemihydrate gypsum and gypsum dehydrate in the disintegrated waste gypsum boards. A manufacturing process to put the recycled gypsum into practical use was also discussed. Prototype board fabrication and tests were performed by using the reformed gypsum board materials, wherein good results were obtained from all of the practical, chemical, and physical tests. (NEDO)

  19. The solidification of low level radioactive organic fluids with Envirostone Gypsum Cement

    Rosenstiel, T.L.; Lange, R.G.

    1984-01-01

    The primary method for the management of low level radioactive waste (LLW) has been and continues to be the isolation of the waste in a solid mass. Of the four typical LLW streams, organic fluids pose the most significant waste isolation problem. The organic fluids comprised of lubrication oils, hydraulic fluids, sludges, scintillation fluids, etc., result from the operation and maintenance of nuclear power generating stations, research activities, tooling operations, and diagnostic analyses. The United States Gypsum Company developed the patented Envirostone Gypsum Cement system for the solidification of all types of low level radioactive wastes to facilitate handling and transportation to regulated LLW disposal sites. For the solidification of organic fluids, Envirostone Gypsum Cement is used in conjunction with Envirostone Emulsifier, selected for its ability to emulsify a broad range of organic fluids in aqueous solutions. In the solidification process it is theorized that as the crystalline matrix of the gypsum forms, the micelles of the emulsifier behave as a chemical bridge which draws the organic fluid into the crystalline structure via the hydration water. Initial testing of physical properties of solidified waste forms, including leachability, per the requirements and the procedures specified for 10 CFR Part 61 as outlined in the Branch Technical Position Report from the United States Nuclear Regulatory Commission were in progress as of the writing of this paper. Upon completion of this testing a Topical Report will be submitted to the USNRC for review and approval. The presentation reviews field experience in the use of Envirostone Gypsum Cement for the solidification of low level radioactive organic fluids from nuclear power generating stations and makes an economic comparison between Envirostone Gypsum Cement and portland cement systems

  20. Paleotransport of lanthanides and strontium recorded in calcite compositions from tuffs at Yucca Mountain, Nevada, USA

    Vaniman, D.T.; Chipera, S.J.

    1996-01-01

    Secondary calcite occurs in both saturated and unsaturated hydrologic zones (SZ and UZ, respectively) in the tuffs at Yucca Mountain, Nevada, USA. In the upper UZ, the major constituents of the calcite crystal structure (C, O) have surface origins. At greater depth there is a open-quotes barren zone,close quotes straddling the water table, where calcite is rare and mixing of surface and subsurface sources may occur. Deep in the SZ, distinctive Mn calcites reflect deep sources, including Ca released as analcime or albite formed and carbonates derived from underlying Paleozoic rocks. In the UZ and in the barren zone, above the deep Mn calcites, variations in calcite lanthanide chemistry can be used to distinguish rhyolitic from quartz-latitic sources. Lanthanide ratios and Sr contents of calcites record the chemical evolution of waters flowing through the UZ and upper SZ. Variations in calcite chemistry in the UZ and in the barren zone show that (1) Sr, which is readily exchanged with clays or zeolites, is essentially removed from some flowpaths that are in contact with these minerals and (2) traces of Mn oxides found in the tuffs have a significant effect of groundwater chemistry in the UZ and in the barren zone by removing almost all Ce from solution (evidenced by characteristic Ce depletions in calcite throughout this zone). Extreme Ce removal may be a result of Ce oxidation (Ce 3+ → Ce 4+ ) at the surfaces of some Mn oxides, particularly rancieite. Higher Sr contents and lack of Ce depletions in the deeper Mn calcites reflect different ages, origins, and transport systems. The calcite record of lanthanide and Sr transport in the UZ shows that minor minerals (clays and zeolites) and even trace minerals (Mn oxides) will affect the compositions of groundwaters that flow over distances greater than a few tens of meters. 43 refs., 8 figs., 4 tabs

  1. Competition between reaction-induced expansion and creep compaction during gypsum formation: Experimental and numerical investigation

    Skarbek, R. M.; Savage, H. M.; Spiegelman, M. W.; Kelemen, P. B.; Yancopoulos, D.

    2017-12-01

    Deformation and cracking caused by reaction-driven volume increase is an important process in many geological settings, however the conditions controlling these processes are poorly understood. The interaction of rocks with reactive fluids can change permeability and reactive surface area, leading to a large variety of feedbacks. Gypsum is an ideal material to study these processes. It forms rapidly at room temperature via bassanite hydration, and is commonly used as an analogue for rocks in high-temperature, high-pressure conditions. We conducted uniaxial strain experiments to study the effects of applied axial load on deformation and fluid flow during the formation of gypsum from bassanite. While hydration of bassanite to gypsum involves a solid volume increase, gypsum exhibits significant creep compaction when in contact with water. These two volume changing processes occur simultaneously during fluid flow through bassanite. We cold-pressed bassanite powder to form cylinders 2.5 cm in height and 1.2 cm in diameter. Samples were compressed with a static axial load of 0.01 to 4 MPa. Water infiltrated initially unsaturated samples through the bottom face and the height of the samples was recorded as a measure of the total volume change. We also performed experiments on pure gypsum samples to constrain the amount of creep observed in tests on bassanite hydration. At axial loads 1 MPa, creep in the gypsum dominates and samples exhibit monotonic compaction. At intermediate loads, samples exhibit alternating phases of compaction and expansion due to the interplay of the two volume changing processes. We observed a change from net compaction to net expansion at an axial load of 0.250 MPa. We explain this behavior with a simple model that predicts the strain evolution, but does not take fluid flow into account. We also implement a 1D poro-visco-elastic model of the imbibition process that includes the reaction and gypsum creep. We use the results of these models, with

  2. Process for fabrication of dry flue gas gypsum. Verfahren zur Herstellung von trockenem Rauchgasgips

    Wirsching, F.; Hueller, R.; Limmer, B.

    1984-06-20

    According to the invention gypsum from flue gas wet desulfurization is dried without loss of crystallization water by a 1-4% sidestream of the flue gas in a suspended bed dryer and is subsequently separated in a cyclone. The sidestream is removed after the electrostatic precipitator, where the gas temperature is 100-130 degrees, and returned to the main gas stream prior to desulfurization, thus preventing the dehydration of the gypsum and eliminating the energy costs of reheating the gas stream to prevent acid condensation.

  3. GE`s worldwide experience with IFO based gypsum producing flue gas desulfurization systems

    Saleem, A. [GE Environmental Systems, Lebanon, PA (United States)

    1994-12-31

    The In-Situ Forced Oxidation (IFO) process to produce gypsum in a commercial scale flue gas desulfurization (FGD) system was first demonstrated by GE Environmental Systems in 1980 at the Monticello Generating Station of Texas Utilities. Since then, the IFO technology developed and demonstrated by GE has become the industry standard and is used extensively on a world-wide basis to produce both commercial and disposable-grade gypsum. The paper gives an overview of the development, demonstration, commercial design and current status of the IFO technology.

  4. Evaluation of Synthetic Gypsum Recovered via Wet Flue-Gas Desulfurization from Electric Power Plants for Use in Foundries

    R. Biernacki

    2012-09-01

    Full Text Available This article investigates possible use of waste gypsum (synthetic, recovered via flue-gas desulfurization from coal-fired electric powerplants, in foundries. Energy sector, which in Eastern Europe is mostly composed from coal-fired electric power plants, is one of the largestproducers of sulfur dioxide (SO2.In order to protect the environment and reduce the amount of pollution flue-gas desulfurization (FGD is used to remove SO2 fromexhaust flue gases of fossil-fuel power plants. As a result of this process gypsum waste is produced that can be used in practicalapplications.Strength and permeability tests have been made and also in-depth analysis of energy consumption of production process to investigateways of preparing the synthetic gypsum for casting moulds application. This paper also assesses the chemical composition, strength andpermeability of moulds made with synthetic gypsum, in comparison with moulds made with traditional GoldStar XL gypsum and withceramic molds. Moreover examination of structure of synthetic gypsum, the investigations on derivatograph and calculations of energyconsumption during production process of synthetic gypsum in wet flue-gas desulfurization were made.After analysis of gathered data it’s possible to conclude that synthetic gypsum can be used as a material for casting mould. There is nosignificant decrease in key properties, and on the other hand there is many additional benefits including low energy consumption,decreased cost, and decreased environmental impact.

  5. Gypsum and organic matter distribution in a mixed construction and demolition waste sorting process and their possible removal from outputs.

    Montero, A; Tojo, Y; Matsuo, T; Matsuto, T; Yamada, M; Asakura, H; Ono, Y

    2010-03-15

    With insufficient source separation, construction and demolition (C&D) waste becomes a mixed material that is difficult to recycle. Treatment of mixed C&D waste generates residue that contains gypsum and organic matter and poses a risk of H(2)S formation in landfills. Therefore, removing gypsum and organic matter from the residue is vital. This study investigated the distribution of gypsum and organic matter in a sorting process. Heavy liquid separation was used to determine the density ranges in which gypsum and organic matter were most concentrated. The fine residue that was separated before shredding accounted for 27.9% of the waste mass and contained the greatest quantity of gypsum; therefore, most of the gypsum (52.4%) was distributed in this fraction. When this fine fraction was subjected to heavy liquid separation, 93% of the gypsum was concentrated in the density range of 1.59-2.28, which contained 24% of the total waste mass. Therefore, removing this density range after segregating fine particles should reduce the amount of gypsum sent to landfills. Organic matter tends to float as density increases; nevertheless, separation at 1.0 density could be more efficient. (c) 2009 Elsevier B.V. All rights reserved.

  6. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  7. Fluoride ions sorption of the water using natural and modified hematite with aluminium hydroxide

    Teutli S, E. A.

    2011-01-01

    Fluorine is a mineral known for its dental benefits, but fluoride ions can cause fluoro sis in excessive quantities. There are many epidemiological studies on possible adverse effects resulting from prolonged ingestion of fluoride through drinking water. These studies demonstrate that fluoride mainly affects the bone tissue (bones and teeth), may produce an adverse effect on tooth enamel and can cause mild dental fluoro sis at concentrations from 0.9 to 1.2 mg/L in drinking water. In several states of Mexico, water contaminated with fluoride ions can be found, such as Aguascalientes, Chihuahua, Coahuila, Durango, Guanajuato, Sonora, Zacatecas, San Luis Potosi and Jalisco, where the fluoride ions levels are higher than 1.5 mg/L, established by the Mexican Official Standard (NOM-127-Ssa-2000) which sets the permissible limits of water for human use and consumption. Currently, several technologies have been proposed to remove fluoride ions from water such as precipitation methods which are based on the addition of chemicals to water and sorption methods to removed fluoride ions by sorption or ion exchange reactions by some suitable substrate capable of regenerate and reuse. In this work, the sorption of fluoride ions using unmodified and modified hematite with aluminum hydroxide to remove fluoride ions from water by bath experiments was studied. The hematite was modified by treating it with aluminum hydroxide, NaOH and Al 2 (SO 4 ) 3 solutions. The characterization of hematite before and after modification with aluminum hydroxide was studied by X-ray diffraction, scanning electron microscopy, EDS and Bet. The effect of ph, contact time, concentration of fluoride ions, and the dose of sorbent on the sorption of fluoride ions by the modified hematite were studied. Equilibrium was reached within 48 hours of contact time and the maximum sorption of fluoride ions were in the range pH eq between 2.3 and 6.2. Sorption capacities of fluoride ions as a function of dose of

  8. Adsorption of water and carbon dioxide on hematite and consequences for possible hydrate formation.

    Kvamme, Bjørn; Kuznetsova, Tatiana; Kivelae, Pilvi-Helina

    2012-04-07

    The interest in carbon dioxide for enhanced oil recovery is increasing proportional to the decline in naturally driven oil production and also due to the increasing demand for reduced emission of carbon dioxide into the atmosphere. Transport of carbon dioxide in offshore pipelines involves high pressure and low temperatures, conditions which may lead to formation of hydrates from residual water dissolved in carbon dioxide and carbon dioxide. The critical question is whether the water at certain temperatures and pressures will drop out as liquid droplets first, and then form hydrates, or alternatively, adsorb on the pipeline surfaces, and subsequently form hydrates heterogeneously. In this work, we used several different basis sets of density functional theory in ab initio calculations to estimate the charge distribution of hematite (the dominating component of rust) crystals. These rust particles were embedded in water and chemical potential for adsorbed water molecules was estimated through thermodynamic integration and compared to similar estimates for water clusters of the same size. While the generated charges were not unique, the use of high order approximations and different basis sets provides a range of likely charge distributions. Values obtained for the chemical potential of water in different surroundings indicated that it would be thermodynamically favorable for water to adsorb on hematite, and that evaluation of potential carbon dioxide hydrate formation conditions and kinetics should be based on this formation mechanism. Depending on the basis set and approximations, the estimated gain for water to adsorb on the hematite surface rather than condense as droplets varied between -1.7 kJ mole(-1) and -3.4 kJ mole(-1). The partial charge distribution on the hematite surface is incompatible with the hydrate structure, and thus hydrates will be unable to attach to the surface. The behavior of water outside the immediate vicinity of hematite (beyond 3

  9. Biotic control of skeletal growth by scleractinian corals in aragonite-calcite seas.

    Tomihiko Higuchi

    Full Text Available Modern scleractinian coral skeletons are commonly composed of aragonite, the orthorhombic form of CaCO3. Under certain conditions, modern corals produce calcite as a secondary precipitate to fill pore space. However, coral construction of primary skeletons from calcite has yet to be demonstrated. We report a calcitic primary skeleton produced by the modern scleractinian coral Acropora tenuis. When uncalcified juveniles were incubated from the larval stage in seawater with low mMg/Ca levels, the juveniles constructed calcitic crystals in parts of the primary skeleton such as the septa; the deposits were observable under Raman microscopy. Using scanning electron microscopy, we observed different crystal morphologies of aragonite and calcite in a single juvenile skeleton. Quantitative analysis using X-ray diffraction showed that the majority of the skeleton was composed of aragonite even though we had exposed the juveniles to manipulated seawater before their initial crystal nucleation and growth processes. Our results indicate that the modern scleractinian coral Acropora mainly produces aragonite skeletons in both aragonite and calcite seas, but also has the ability to use calcite for part of its skeletal growth when incubated in calcite seas.

  10. Raman spectroscopic study of calcite III to aragonite transformation under high pressure and high temperature

    Liu, Chuanjiang; Zheng, Haifei; Wang, Duojun

    2017-10-01

    In our study, a series of Raman experiments on the phase transition of calcite at high pressure and high temperature were investigated using a hydrothermal diamond anvil cell and Raman spectroscopy technique. It was found that calcite I transformed to calcite II and calcite III at pressures of 1.62 and 2.12 GPa and room temperature. With increasing temperature, the phase transition of calcite III to aragonite occurred. Aragonite was retained upon slowly cooling of the system, indicating that the transition of calcite III to aragonite was irreversible. Based on the available data, the phase boundary between calcite III and aragonite was determined by the following relation: P(GPa) = 0.013 × T(°C) + 1.22 (100°C ≤ T ≤ 170°C). It showed that the transition pressure linearly rose with increasing temperature. A better understanding of the stability of calcite III and aragonite is of great importance to further explore the thermodynamic behavior of carbonates and carbon cycling in the mantle.

  11. Structural evolution of calcite at high temperatures: Phase V unveiled

    Ishizawa, Nobuo; Setoguchi, Hayato; Yanagisawa, Kazumichi

    2013-01-01

    The calcite form of calcium carbonate CaCO3 undergoes a reversible phase transition between Rc and Rm at ~1240 K under a CO2 atmosphere of ~0.4 MPa. The joint probability density function obtained from the single-crystal X-ray diffraction data revealed that the oxygen triangles of the CO3 group in the high temperature form (Phase V) do not sit still at specified positions in the space group Rm, but migrate along the undulated circular orbital about carbon. The present study also shows how the room temperature form (Phase I) develops into Phase V through an intermediate form (Phase IV) in the temperature range between ~985 K and ~1240 K. PMID:24084871

  12. Face-specific Replacement of Calcite by Amorphous Silica Nanoparticles

    Liesegang, M.; Milke, R.; Neusser, G.; Mizaikoff, B.

    2016-12-01

    Amorphous silica, composed of nanoscale spheres, is an important biomineral, alteration product of silicate rocks on the Earth's surface, and precursor material for stable silicate minerals. Despite constant progress in silica sphere synthesis, fundamental knowledge of natural silica particle interaction and ordering processes leading to colloidal crystals is absent so far. To understand the formation pathways of silica spheres in a geologic environment, we investigated silicified Cretaceous mollusk shell pseudomorphs from Coober Pedy (South Australia) using focused ion beam (FIB)-SEM tomography, petrographic microscopy, µ-XRD, and EMPA. The shells consist of replaced calcite crystals (ionic strength remain constant throughout the replacement process, permitting continuous silica nanoparticle formation and diffusion-limited colloid aggregation. Our study provides a natural example of the transformation of an atomic crystal to an amorphous, mesoscale ordered material; thus, links the research fields of natural colloidal crystal formation, carbonate-silica replacement, and crystallization by oriented particle aggregation (CPA).

  13. Age constraints on fluid inclusions in calcite at Yucca Mountain

    Neymark, Leonid A.; Amelin, Yuri V.; Paces, James B.; Peterman, Zell E.; Whelan, Joseph F.

    2001-01-01

    The(sup 207)Pb/(sup 235)U ages for 14 subsamples of opal or chalcedony layers younger than calcite formed at elevated temperature range between 1.88(+-) 0.05 and 9.7(+-) 1.5 Ma with most values older than 6-8 Ma. These data indicate that fluids with elevated temperatures have not been present in the unsaturated zone at Yucca Mountain since about 1.9 Ma and most likely since 6-8 Ma. Discordant U-Pb isotope data for chalcedony subsamples representing the massive silica stage in the formation of the coatings are interpreted using a model of the diffusive loss of U decay products. The model gives an age estimate for the time of chalcedony formation around 10-11 Ma, which overlaps ages of clay minerals formed in tuffs below the water table at Yucca Mountain during the Timber Mountain thermal event

  14. Paleohydrogeological implications from fracture calcites and sulfides in a major hydrogeological zone HZ19 at Olkiluoto

    Sahlstedt, E.; Karhu, J.; Rinne, K.

    2009-08-01

    30 samples of fracture mineral fillings in or near water conducting fractures at Olkiluoto were collected from 10 drill cores for fracture mineral studies. The aim of the study was to obtain information about past hydrogeochemical conditions at Olkiluoto using the calcite morphology, the chemical characteristics and the isotopic composition of carbon and oxygen in calcite. The chemical composition of fracture calcites at Olkiluoto is nearly stoichiometric CaCO 3 . Most variation in the composition of calcite is due to differences in the Mn content, which could indicate variations in groundwater redox conditions. Meaningful REE patterns were obtained for the calcites. REE patterns showed generally negative Eu anomalies, but one fracture calcite specimen had a distinct positive Eu anomaly. This positive anomaly could be related to ancient hydrothermal conditions, although derivation of the anomaly from the host rock cannot be excluded. Preliminary results for calcite U-Th dating of fracture calcites are reported. The isotopic composition of U and Th were analysed by a new multiple collector LA-ICPMS instrument. U and Th concentrations in fracture calcites are generally 18 O values of calcite range from -17 to -7 per mille. Most of the calcites may have been precipitated in the presence of waters with oxygen isotope ratios similar to those in the present-day groundwaters at Olkiluoto. Two samples with an oxygen isotopic composition highly depleted in 18 O were interpreted to have been precipitated at elevated temperatures. The δ 13 C values of calcite showed a wide range of values from -26 to +35 per mille. Multiple sources for carbon are implied. The highest δ 13 C values indicate methanic conditions in the fracture at the time of calcite precipitation. It appears that the methanic environment has earlier extended to shallower depths compared to the location of the methanic environment in the present-day fracture system (> 300 m). Ten pyrite samples were analysed

  15. Iron Isotopes in Spherical Hematite and Goethite Concretions from the Navajo Sandstone (Utah, USA): A Prospective Study for "Martian Blueberries"

    Busigny, V.; Dauphas, N.

    2006-03-01

    Iron isotopes of terrestrial hematite and goethite concretions provide clues on fluid transport, reservoir sizes, redox variations and biotic versus abiotic processes. This opens several avenues of research for future work on Martian blueberries.

  16. Effect of dissolution kinetics on flotation response of calcite with oleate

    D. G. Horta

    Full Text Available Abstract Phosphate flotation performance can be influenced by the dissolution kinetics of the minerals that compose the ore. The purpose of this work was to investigate the effect of dissolution kinetics on flotation response with oleate (collector of calcites from different origins and genesis. The calcite samples were first purified and characterized by x-ray Fluorescence (XRF and the Rietveld method applied to x-ray Diffractometry data (RXD. Experiments of calcite dissolution and microflotationwere performed at pH 8 and pH 10.The pH effect on the calcite dissolution and flotation indicates the possible influence of the carbonate/bicarbonate ions provided by the CO2 present in the air. In addition, the flotation response is greater as the dissolution increases, making more Ca2+ ions available to interact with collector molecules. This result corroborates the surface precipitation mechanism proposed foroleate adsorption on the calcite surface.

  17. Faradaic efficiency of O2 evolution on metal nanoparticle sensitized hematite photoanodes

    Iandolo, Beniamino; Wickman, Björn; Seger, Brian

    2014-01-01

    in several studies, to the best of our knowledge no measurements of the Faradaic efficiency (FE) of the oxygen evolution reaction (OER) have been reported for such systems. This work characterizes the FE on a model system consisting of ultra-thin films of hematite (Fe2O3) sensitized with Ti/Au nanodisks....... Compared to bare hematite references, sensitized samples showed significantly enhanced photocurrents as well as O-2 evolution. Experimental evidence suggests that the observed enhancement was not due to photocatalytic activity of the nanodisks. The FE has been determined to be 100%, within the experimental...... errors, for both sensitized and reference samples. Also, this work demonstrates that the sensitized samples were stable for at least 16 hours photocurrent testing. The concepts shown in this work are generally applicable to any situation in which a semiconductor has its water splitting performance...

  18. Strontium-Doped Hematite as a Possible Humidity Sensing Material for Soil Water Content Determination

    Carlo Grignani

    2013-09-01

    Full Text Available The aim of this work is to study the sensing behavior of Sr-doped hematite for soil water content measurement. The material was prepared by solid state reaction from commercial hematite and strontium carbonate heat treated at 900 °C. X-Ray diffraction, scanning electron microscopy and mercury intrusion porosimetry were used for microstructural characterization of the synthesized powder. Sensors were then prepared by uniaxially pressing and by screen-printing, on an alumina substrate, the prepared powder and subsequent firing in the 800–1,000 °C range. These sensors were first tested in a laboratory apparatus under humid air and then in an homogenized soil and finally in field. The results evidenced that the screen printed film was able to give a response for a soil matric potential from about 570 kPa, that is to say well below the wilting point in the used soil.

  19. Strontium-doped hematite as a possible humidity sensing material for soil water content determination.

    Tulliani, Jean-Marc; Baroni, Chiara; Zavattaro, Laura; Grignani, Carlo

    2013-09-10

    The aim of this work is to study the sensing behavior of Sr-doped hematite for soil water content measurement. The material was prepared by solid state reaction from commercial hematite and strontium carbonate heat treated at 900 °C. X-Ray diffraction, scanning electron microscopy and mercury intrusion porosimetry were used for microstructural characterization of the synthesized powder. Sensors were then prepared by uniaxially pressing and by screen-printing, on an alumina substrate, the prepared powder and subsequent firing in the 800-1,000 °C range. These sensors were first tested in a laboratory apparatus under humid air and then in an homogenized soil and finally in field. The results evidenced that the screen printed film was able to give a response for a soil matric potential from about 570 kPa, that is to say well below the wilting point in the used soil.

  20. Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

    Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

    2018-03-06

    To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

  1. Transformation of Goethite to Hematite Nanocrystallines by High Energy Ball Milling

    O. M. Lemine

    2014-01-01

    Full Text Available α-Fe2O3 nanocrystallines were prepared by direct transformation via high energy ball milling treatment for α-FeOOH powder. X-ray diffraction, Rietveld analysis, TEM, and vibrating sample magnetometer (VSM are used to characterize the samples obtained after several milling times. Phase identification using Rietveld analysis showed that the goethite is transformed to hematite nanocrystalline after 40 hours of milling. HRTEM confirm that the obtained phase is mostly a single-crystal structure. This result suggested that the mechanochemical reaction is an efficient way to prepare some iron oxides nanocrystallines from raw materials which are abundant in the nature. The mechanism of the formation of hematite is discussed in text.

  2. Surfactant-assisted solvothermal preparation of submicrometer-sized hollow hematite particles and their photocatalytic activity

    Lian Suoyuan; Wang Enbo; Gao Lei; Wu Di; Song Yanli; Xu Lin

    2006-01-01

    Submicrometer-sized hollow hematite particles were prepared through a surfactant-assisted solvothermal process. The amount of FeCl 3 .H 2 O and cetyltrimethylammonium bromide, and the acidity of the solution were systematically altered to study their effects on the final results. Hollow hematite particles with shapes from sphere, ellipsoid to peanut were obtained. Their sizes range from 500 nm to 2 μm with shell thickness from 100 to 500 nm. Powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and selected area electron diffraction were applied to investigate the products' crystallinity, purity, morphology, size and structural features. Finally, the study on the photocatalysis of Fe 2 O 3 for the destruction of diethyl phthalate in water was carried out. The result proved that Fe 2 O 3 hollow particles were effective photocatalysts for the degradation of DEP, with 96.8% destruction ratio being obtained within 60 min

  3. High-power pulsed plasma deposition of hematite photoanode for PEC water splitting

    Kment, Š.; Hubička, Zdeněk; Krysa, J.; Olejníček, Jiří; Čada, Martin; Gregora, Ivan; Zlámal, M.; Brunclíková, Michaela; Remeš, Zdeněk; Liu, N.; Wang, L.; Kirchgeorg, R.; Lee, Ch.Y.; Schmuki, P.

    2014-01-01

    Roč. 230, Jul (2014), 8-14 ISSN 0920-5861 R&D Projects: GA ČR GAP108/12/2104; GA MŠk LH12043 Institutional support: RVO:68378271 Keywords : electrical properties * hematite * HiPIMS * hollow cathode plasma jet * photoelectrochemical water splitting * thin films Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 3.893, year: 2014

  4. Stereo soft x-ray microscopy and elemental mapping of hematite and clay suspensions

    Gleber, S.-C.; Thieme, J.; Chao, W.; Fischer, P.

    2008-09-01

    The spatial arrangements of hematite particles within aqueous soil and clay samples are investigated with soft X-ray microscopy, taking advantage of the elemental contrast at the Fe-L edge around E = 707 eV. In combination with stereo microscopy, information about spatial arrangements are revealed and correlated to electrostatic interactions of the different mixtures. Manipulation of a sample mounted to the microscope is possible and particles added while imaging can be detected.

  5. Hematite/silver nanoparticle bilayers on mica--AFM, SEM and streaming potential studies.

    Morga, Maria; Adamczyk, Zbigniew; Oćwieja, Magdalena; Bielańska, Elżbieta

    2014-06-15

    Bilayers of hematite/silver nanoparticles were obtained in the self-assembly process and thoroughly characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), and in situ streaming potential measurements. The hematite nanoparticles, forming a supporting layer, were 22 nm in diameter, exhibiting an isoelectric point at pH 8.9. The silver nanoparticles, used to obtain an external layer, were 29 nm in diameter, and remained negative within the pH range 3 to 11. In order to investigate the particle deposition, mica sheets were used as a model solid substrate. The coverage of the supporting layer was adjusted by changing the bulk concentration of the hematite suspension and the deposition time. Afterward, silver nanoparticle monolayers of controlled coverage were deposited under the diffusion-controlled transport. The coverage of bilayers was determined by a direct enumeration of deposited particles from SEM micrographs and AFM images. Additionally, the formation of the hematite/silver bilayers was investigated by streaming potential measurements carried out under in situ conditions. The effect of the mica substrate and the coverage of a supporting layer on the zeta potential of bilayers was systematically studied. It was established that for the coverage exceeding 0.20, the zeta potential of bilayers was independent on the substrate and the supporting layer coverage. This behavior was theoretically interpreted in terms of the 3D electrokinetic model. Beside significance for basic sciences, these measurements allowed to develop a robust method of preparing nanoparticle bilayers of controlled properties, having potential applications in catalytic processes. Copyright © 2014 Elsevier Inc. All rights reserved.

  6. Transformation of Mg-bearing amorphous calcium carbonate to Mg-calcite - In situ monitoring

    Purgstaller, Bettina; Mavromatis, Vasileios; Immenhauser, Adrian; Dietzel, Martin

    2016-02-01

    The formation of Mg-bearing calcite via an amorphous precursor is a poorly understood process that is of relevance for biogenic and abiogenic carbonate precipitation. In order to gain an improved insight on the controls of Mg incorporation in calcite formed via an Mg-rich amorphous calcium carbonate (Mg-ACC) precursor, the precipitation of Mg-ACC and its transformation to Mg-calcite was monitored by in situ Raman spectroscopy. The experiments were performed at 25.0 ± 0.03 °C and pH 8.3 ± 0.1 and revealed two distinct pathways of Mg-calcite formation: (i) At initial aqueous Mg/Ca molar ratios ⩽ 1:6, Mg-calcite formation occurs via direct precipitation from solution. (ii) Conversely, at higher initial Mg/Ca molar ratios, Mg-calcite forms via an intermediate Mg-rich ACC phase. In the latter case, the final product is a calcite with up to 20 mol% Mg. This Mg content is significant higher than that of the Mg-rich ACC precursor phase. Thus, a strong net uptake of Mg ions from the solution into the crystalline precipitate throughout and also subsequent to ACC transformation is postulated. Moreover, the temporal evolution of the geochemical composition of the reactive solution and the Mg-ACC has no significant effect on the obtained ;solubility product; of Mg-ACC. The enrichment of Mg in calcite throughout and subsequent to Mg-ACC transformation is likely affected by the high aqueous Mg/Ca ratio and carbonate alkalinity concentrations in the reactive solution. The experimental results have a bearing on the formation mechanism of Mg-rich calcites in marine early diagenetic environments, where high carbonate alkalinity concentrations are the rule rather than the exception, and on the insufficiently investigated inorganic component of biomineralisation pathways in many calcite secreting organisms.

  7. Investigating calcite growth rates using a quartz crystal microbalance with dissipation (QCM-D)

    Cao, Bo; Stack, Andrew G.; Steefel, Carl I.; DePaolo, Donald J.; Lammers, Laura N.; Hu, Yandi

    2018-02-01

    Calcite precipitation plays a significant role in processes such as geological carbon sequestration and toxic metal sequestration and, yet, the rates and mechanisms of calcite growth under close to equilibrium conditions are far from well understood. In this study, a quartz crystal microbalance with dissipation (QCM-D) was used for the first time to measure macroscopic calcite growth rates. Calcite seed crystals were first nucleated and grown on sensors, then growth rates of calcite seed crystals were measured in real-time under close to equilibrium conditions (saturation index, SI = log ({Ca2+}/{CO32-}/Ksp) = 0.01-0.7, where {i} represent ion activities and Ksp = 10-8.48 is the calcite thermodynamic solubility constant). At the end of the experiments, total masses of calcite crystals on sensors measured by QCM-D and inductively coupled plasma mass spectrometry (ICP-MS) were consistent, validating the QCM-D measurements. Calcite growth rates measured by QCM-D were compared with reported macroscopic growth rates measured with auto-titration, ICP-MS, and microbalance. Calcite growth rates measured by QCM-D were also compared with microscopic growth rates measured by atomic force microscopy (AFM) and with rates predicted by two process-based crystal growth models. The discrepancies in growth rates among AFM measurements and model predictions appear to mainly arise from differences in step densities, and the step velocities were consistent among the AFM measurements as well as with both model predictions. Using the predicted steady-state step velocity and the measured step densities, both models predict well the growth rates measured using QCM-D and AFM. This study provides valuable insights into the effects of reactive site densities on calcite growth rate, which may help design future growth models to predict transient-state step densities.

  8. Investigation of Parameters Affecting Gypsum Dewatering Properties in a Wet Flue Gas Desulphurization Pilot Plant

    Hansen, Brian Brun; Kiil, Søren

    2012-01-01

    of impurities (0.002 M Al2F6; 50 g quartz/L; 0.02 M Al3+, and 0.040 M Mg2+) were investigated. In addition, slurry from a full-scale wet FGD plant, experiencing formation of flat shaped crystals and poor gypsum dewatering properties, was transferred to the pilot plant to test if the plant would now start...... to time. In this work, the particle size distribution, morphology, and filtration rate of wet FGD gypsum formed in a pilot-scale experimental setup, operated in forced oxidation mode, have been studied. The influence of holding tank residence time (10–408 h), solids content (30–169 g/L), and the presence...... to produce low quality gypsum. The crystals formed in the pilot plant, on the basis of the full-scale slurry did, however, show acceptable filtration rates and crystal morphologies closer to the prismatic crystals from after pilot plant experiments with demineralized water. The gypsum slurry filtration rates...

  9. Use of Flue Gas Desulfurization (FGD) Gypsum as a Heavy Metal Stabilizer in Contaminated Soils

    Flue Gas Desulfurization (FGD) gypsum is a synthetic by-product generated from the flue gas desulfurization process in coal power plants. It has several beneficial applications such as an ingredient in cement production, wallboard production and in agricultural practice as a soil...

  10. Development of a self-compacting gypsum-based lightweight composite

    Yu, Q.; Brouwers, H.J.H.

    2012-01-01

    This article addresses experiments and theories of a self-compacting gypsum-based lightweight composite (SGLC). A ß-hemihydrate is used as binder and lightweight aggregate (LWA, 0–2 mm in different size ranges) is used as aggregate into this composite. The mix of the new composite is designed based

  11. Composition of gypsum from the Koběřice quarry (Czech Republic)

    Konečný, Pavel; Plevová, Eva; Vaculíková, Lenka; Kožušníková, Alena; Peterková, J.; Hundáková, M.

    2011-01-01

    Roč. 8, č. 2 (2011), s. 145-156 ISSN 1214-9705 Institutional research plan: CEZ:AV0Z30860518 Keywords : gypsum * Kobeřice quarry * spectroscopy Subject RIV: DB - Geology ; Mineralogy Impact factor: 0.530, year: 2011 http://www.irsm.cas.cz/abstracts/AGG/02_11/5_Konecny.pdf

  12. Morphology and stability of aggregates of an Oxisol according to tillage system and gypsum application

    Fábio Régis de Souza

    2012-12-01

    Full Text Available Morphological characterization and aggregate stability is an important factor in evaluating management systems. The aim of this paper is to evaluate the stability and morphology of the aggregates of a dystrophic Oxisol managed with no-tillage and conventional tillage with and without the residual action of gypsum. The experimental design was randomized blocks arranged in split-split plot, where the treatments were two soil management systems (plots with 0 and 2000 kg ha-1 of gypsum (subplots and five depths (0-0.05, 0.05-0.10, 0.10-0.15, 0.15-0.20 and 0.20-0.30 m as the subsubplots, with four replications. The aggregate morphology was determined through images and later evaluated by the Quantporo software. Stability was determined by the wet method. The results showed that the no-tillage system, with or without gypsum residual effect, provided the aggregates with the largest geometric diameters. The combination of no-tillage system and the gypsum residual effect provided rougher aggregates.

  13. Two distinctive new species of Commicarpus (Nyctaginaceae) from gypsum outcrops in eastern Ethiopia

    Friis, Ib; Gilbert, Michael G.; Weber, Odile

    2016-01-01

    During field trips in 2013 and 2014, two distinctive plants belonging to the genus Commicarpus were collected in the Lele Hills, Bale Zone, eastern Ethiopia, on outcrops of sedimentary rock belonging to the Gorrahei Formation with high contents of gypsum. The plants are here described as two new...

  14. Microbial Volatile Organic Compound Emissions from Stachybotrys chartarum growing on Gypsum Wallboard and Ceiling tile

    This study compared seven toxigenic strains of S. chartarum found in water-damaged buildings to characterize the microbial volatile organic compound (MVOC) emissions profile while growing on gypsum wallboard (W) and ceiling tile (C) coupons. The inoculated coupons with their sub...

  15. Results using flue gas desulfurization gypsum in soilless substrates for greenhouse crops

    Recent availability of Flue Gas Desulfurization gypsum (FGDG) has led to interested in its possible use in horticulture greenhouse production. Three studies were conducted to determine the effects of increasing rates of FGDG on six greenhouse crops. In the first study, substrates (6:1 pine bark:san...

  16. Seepage Analysis of Upper Gotvand Dam Concerning Gypsum Karstification (2D and 3D Approaches)

    Sadrekarimi, Jamshid; Kiyani, Majid; Fakhri, Behnam

    2011-01-01

    Upper Gotvand Dam is constructed on the Karun River at the south west of Iran. In this paper, 2D and 3D models of the dam together with the foundation and abutments were established, and several seepage analyses were carried out. Then, the gypsum veins that are scattered throughout the foundation...

  17. Gypsum plasterboards enhanced with phase change materials: A fire safety assessment using experimental and computational techniques

    Kolaitis Dionysios I.

    2013-11-01

    Full Text Available Phase Change Materials (PCM can be used for thermal energy storage, aiming to enhance building energy efficiency. Recently, gypsum plasterboards with incorporated paraffin-based PCM blends have become commercially available. In the high temperature environment developed during a fire, the paraffins, which exhibit relatively low boiling points, may evaporate and, escaping through the gypsum plasterboard's porous structure, emerge to the fire region, where they may ignite, thus adversely affecting the fire resistance characteristics of the building. Aiming to assess the fire safety behaviour of such building materials, an extensive experimental and computational analysis is performed. The fire behaviour and the main thermo-physical physical properties of PCM-enhanced gypsum plasterboards are investigated, using a variety of standard tests and devices (Scanning Electron Microscopy, Thermo Gravimetric Analysis, Cone Calorimeter. The obtained results are used to develop a dedicated numerical model, which is implemented in a CFD code. CFD simulations are validated using measurements obtained in a cone calorimeter. In addition, the CFD code is used to simulate an ISO 9705 room exposed to fire conditions, demonstrating that PCM addition may indeed adversely affect the fire safety of a gypsum plasterboard clad building.

  18. Assessment of Mercury in Soils, Crops, Earthworms, and Water when Soil is Treated with Gypsum

    Flue gas desulfurization (FGD) gypsum from fossil fuel combustion has many potential uses in agriculture, but there is concern about the potential environmental effects of its elevated mercury (Hg) concentration. The wet limestone scrubbing process that removes sulfur from flue gas (and produces gyp...

  19. Composting and gypsum amendment of broiler litter to reduce nutrient leaching loss

    Relative to fresh broiler litter, little is known about the dynamics of composted litter derived-nutrient in the ecosystem. In this study, the potential leaching losses of nutrients from compost relative to fresh broiler litter along with flue gas desulfurization (FGD gypsum), as a nutrient immobil...

  20. Characterization of gypsum crystals exposed to a high CO2 concentration fog using x-ray

    Carreño-Márquez, I. J. A.; Castillo-Sandoval, I.; Esparza-Ponce, H. E.; Fuentes-Cobas, L.; Montero-Cabrera, M. E.

    2015-01-01

    In Chihuahua State, a little town called Naica has the largest gypsum single crystals in the world. The growth of these structures has been described as a long and stable process developed over thousands of years. Due to the change in the environmental conditions, these crystals could suffer alterations on their surface. In this project we study the cause of possible deterioration of the giant crystals and intend to suggest measures for their preservation. For this sake, our first experiment consists on several gypsum crystals that have been subjected in a climate chamber to a fog at high CO 2 concentration and 51 °C for a period of time of six months, extracting two crystals every 15 days. Then the crystals have been characterized through Grazing Incidence X-Ray Diffraction using a diffractometer PanAlytical X’PertPro with two different detectors; Xe-filled proportional detector and a Pixel 3D detector. The results were compared to determine which technique is the most suitable to study the degradation of gypsum single crystals. In the two cases, we have identified only the gypsum phase, but with different crystal plane orientations

  1. Inflammatory potential of low doses of airborne fungi from fungal infested damp and dry gypsum boards

    Knudsen, Sofie Marie; Gunnarsen, Lars Bo; Madsen, Anne Mette

    2017-01-01

    chrysogenum. Bacillus infantis and Paenibacillus sp. were found on the gypsum boards, but not recovered in the aerosols. A significant correlation was found between the TIP of diluted and undiluted samples of fungal aerosols. However, diluted samples had a higher TIP than undiluted samples, and no significant...

  2. Flue gas desulfurization gypsum: Its effectiveness as an alternative bedding material for broiler production

    Flue gas desulfurization gypsum (FGDG) may be a viable low-cost alternative bedding material for broiler production. In order to evaluate FGD gypsum’s viability, three consecutive trials were conducted to determine its influence on live performance (body weight, feed consumption, feed efficiency, an...

  3. Adhesion of Escherichia coli onto quartz, hematite and corundum: extended DLVO theory and flotation behavior.

    Farahat, Mohsen; Hirajima, Tsuyoshi; Sasaki, Keiko; Doi, Katsumi

    2009-11-01

    The adhesion of Escherichia coli onto quartz, hematite and corundum was experimentally investigated. A strain of E. coli was used that had the genes for expressing protein for silica precipitation. The maximum cell adhesion was observed at pH mineral adhesion was assessed by the extended DLVO theory approach. The essential parameters for calculation of microbe-mineral interaction energy (Hamaker constants and acid-base components) were experimentally determined. The extended DLVO approach could be used to explain the results of the adhesion experiments. The effect of E. coli on the floatability of three oxide minerals was determined and the results showed that E. coli can act as a selective collector for quartz at acidic pH values, with 90% of the quartz floated at 1.5 x 10(9)cells/ml. However, only 9% hematite and 30% corundum could be floated under similar conditions. By using E. coli and no reagents, it was possible to separate quartz from a hematite-quartz mixture with Newton's efficiency of 0.70. Removal of quartz from the corundum mixture was achieved by E. coli with Newton's efficiency of 0.62.

  4. Synthesis and characterization of hematite pigment obtained from a steel waste industry

    Prim, S.R. [Department of Mechanical Engineering, University of the State of Santa Catarina, Santa Catarina (Brazil); Folgueras, M.V., E-mail: dem2mvf@joinville.udesc.br [Department of Mechanical Engineering, University of the State of Santa Catarina, Santa Catarina (Brazil); Lima, M.A. de [Department of Mechanical Engineering, University of the State of Santa Catarina, Santa Catarina (Brazil); Hotza, D. [Departamento de Engenharia Quimica, Federal University of Santa Catarina, Santa Catarina (Brazil)

    2011-09-15

    Highlights: {yields} The study of using of a industrial waste for the synthesis of hematite pigments. {yields} The nanometer dimension this waste and your behavior as chromophore. {yields} The effect of process variables on the mechanisms of encapsulation sintered pigments. - Abstract: Pigments that meet environmental and technology requirements are the focus of the research in the ceramic sector. This study focuses on the synthesis of ceramic pigment by encapsulation of hematite in crystalline and amorphous silica matrix. Iron oxide from a metal sheet rolling process was used as chromophore. A different content of hematite and silica was homogenized by conventional and high energy milling. The powders obtained after calcinations between 1050 and 1200 {sup o}C for 2 h were characterized by X-ray diffraction and SEM analysis. The pigments were applied to ceramic enamel and porcelain body. The effect of pigment was measured by comparing L*a*b* values of the heated samples. Results showed that the color developed is influenced by variables such as oxide content employed, conditions of milling and processing temperature. The results showed that the use of pigment developed does not interfere in microstructural characteristics of pigmented material. The best hue was obtained from samples with 15 wt% of chromophore, heated at 1200 {sup o}C in amorphous silica matrix.

  5. ADSORPTION OF PARAQUAT DICHLORIDE TO KAOLIN PARTICLES AND TO MIXTURES OF KAOLIN AND HEMATITE PARTICLES

    Dina Alexandra Martins

    2015-03-01

    Full Text Available Deliberate contamination with pesticides is a potential risk to water security, due to the availability of these contaminants and the fact that they do not need special expertise to handle or apply. Adsorption of the herbicide paraquat from an aqueous solution to suspended particles of kaolin and kaolin/hematite mixture was investigated by kinetic and equilibrium assays, taking into consideration several parameters such as initial pH, sorbent dosage and agitation speed. The results showed that the adsorption process is quite fast, reaching an 18% reduction in paraquat concentration in a very short period of time. The addition of hematite particles to kaolin suspension had no apparent effect on the maximum amount of paraquat adsorbed. Kinetic parameters were determined by fitting the pseudo-second order model to the experimental data (correlation coefficients close to 1. Isotherm studies indicate an inhibitory effect, promoted by hematite particles, that was not detected in the adsorption assays. Equilibrium data was best adjusted using the Langmuir model which yielded higher correlation coefficient values and smaller normalized standard deviations.

  6. Impact of water quality parameters on the sorption of U(VI) onto hematite

    Zhao Donglin; Wang Xianbiao; Yang Shitong; Guo Zhiqiang; Sheng Guodong

    2012-01-01

    In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH 6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH 0 , ΔS 0 , and ΔG 0 ) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management. Highlights: ► The sorption of U(VI) was strongly dependent on ionic strength at pH 6.0. ► A positive effect of HA/FA on U(VI) sorption was found at low pH, whereas a negative effect was observed at high pH. ► U(VI) sorption was a spontaneous and endothermic process. ► The results are quite important for the application of hematite in U(VI) pollution management.

  7. Experimental evidence for non-redox transformations between magnetite and hematite under H 2-rich hydrothermal conditions

    Otake, Tsubasa; Wesolowski, David J.; Anovitz, Lawrence M.; Allard, Lawrence F.; Ohmoto, Hiroshi

    2007-05-01

    Transformations of magnetite (Fe IIFe 2IIIO 4) to hematite (Fe 2IIIO 3) (and vice versa) have been thought by many scientists and engineers to require molecular O 2 and/or H 2. Thus, the presence of magnetite and/or hematite in rocks has been linked to a specific oxidation environment. However, the availability of reductants or oxidants in many geologic and industrial environments appears to have been too low to account for the transformations of iron oxides through redox reactions. Here, we report the results of hydrothermal experiments in mildly acidic and H 2-rich aqueous solutions at 150 °C, which demonstrate that transformations of magnetite to hematite, and hematite to magnetite, occur rapidly without involving molecular O 2 or H 2: Fe3O 4(Mt) + 2H (aq)+ ↔ Fe 2O 3(Hm) + Fe (aq)2+ + H 2O. The transformation products are chemically and structurally homogeneous, and typically occur as euhedral single crystals much larger than the precursor minerals. This suggests that, in addition to the expected release of aqueous ferrous species to solution, the transformations involve release of aqueous ferric species from the precursor oxides to the solution, which reprecipitate without being reduced by H 2. These redox-independent transformations may have been responsible for the formation of some iron oxides in natural systems, such as high-grade hematite ores that developed from Banded Iron Formations (BIFs), hematite-rich deposits formed on Mars, corrosion products in power plants and other industrial systems.

  8. Investigation on the Permeability Evolution of Gypsum Interlayer Under High Temperature and Triaxial Pressure

    Tao, Meng; Yechao, You; Jie, Chen; Yaoqing, Hu

    2017-08-01

    The permeability of the surrounding rock is a critical parameter for the designing and assessment of radioactive waste disposal repositories in the rock salt. Generally, in the locations that are chosen for radioactive waste storage, the bedded rock salt is a sedimentary rock that contains NaCl and Na2SO4. Most likely, there are also layers of gypsum ( {CaSO}_{ 4} \\cdot 2 {H}_{ 2} {O)} present in the salt deposit. Radioactive wastes emit a large amount of heat and hydrogen during the process of disposal, which may result in thermal damage of the surrounding rocks and cause a great change in their permeability and tightness. Therefore, it is necessary to investigate the permeability evolution of the gypsum interlayer under high temperature and high pressure in order to evaluate the tightness and security of the nuclear waste repositories in bedded rock salt. In this study, a self-designed rock triaxial testing system by which high temperature and pressure can be applied is used; the μCT225kVFCB micro-CT system is also employed to investigate the permeability and microstructure of gypsum specimens under a constant hydrostatic pressure of 25 MPa, an increasing temperature (ranging from 20 to 650 °C), and a variable inlet gas pressure (1, 2, 4, 6 MPa). The experimental results show: (a) the maximum permeability measured during the whole experiment is less than 10-17 m2, which indicates that the gypsum interlayer has low permeability under high temperature and pressure that meet the requirements for radioactive waste repository. (b) Under the same temperature, the permeability of the gypsum specimen decreases at the beginning and then increases as the pore pressure elevates. When the inlet gas pressure is between 0 and 2 MPa, the Klinkenberg effect is very pronounced. Then, as the pore pressure increases, the movement behavior of gas molecules gradually changes from free motion to forced directional motion. So the role of free movement of gas molecules gradually

  9. A time-resolved laser fluorescence spectroscopy (TRLFS) study of the interaction of trivalent actinides (curium(III)) with calcite

    Stumpf, Th.; Fanghaenel, Th.

    2002-01-01

    Cm(III) interaction with calcite was investigated in the trace concentration range. Two different Cm(III)/calcite sorption species were found. The first Cm(III) sorption species consists of a curium ion that is bonded onto the calcite surface. The second Cm(III) sorption species has lost its complete hydration sphere and is incorporated into the calcite bulk structure /1/. (orig.)

  10. Effect of temperature and concentration principle on gypsum scaling in desalination units

    Ben Ahmed, Samia; Tlili, Mohamed; Ben Amor, Mohamed

    2009-01-01

    Tunisia (North Africa) is currently confronted to the crucial problem of the public, agricultural and industrial feed water supply, in particular in the center and south areas. Production of fresh water by seawater and brackish water desalination has proved to be an alternative for these regions. However, all the desalination processes are based on the concentration principle of waters already presented higher salinity. So, scale problem can occurs by the accumulation of minerals such as CaCO 3 and CaSO 4 . These salts form hard and strongly adhering deposits on the surfaces and their formation is favoured by the decrease of their solubility with increasing temperature. The main object of this investigation is the study and the control of calcium sulphate deposition causes and conditions in the thermal desalination plant. For this purpose, the effect of different water temperatures (30-90 degree) and saturation states (3-10), on homogeneous nucleation and growth of gypsum, variety usually met, was examined. Gypsum was precipitated by mixing aqueous CaCl 2 and Na 2 SO 4 solutions. It was found that, with increasing temperature or supersaturation, the induction time decreases and the growth rate increases. At the same saturation state, the effect of temperature on reducing induction time is more significant for T<50 degree whereas the growth rate of gypsum crystals is more influenced when the temperature exceeds 50 degree. This value can be considered as a critical temperature; once reached the gypsum scaling threat becomes serious. By using classical nucleation theory, the interfacial tension and the nucleation rate values were estimated. It was shown that the interfacial tension is, as well, temperature dependent. The calculation of nucleation rate showed that: i) by increasing temperature, the number of formed nuclei does not change. The effect of this parameter is limited at the kinetic of formation and growth of these nuclei, ii) the water concentration

  11. IMPACT OF NANOMODIFIERS ON MECHANICAL AND PHYSICAL PROPERTIES OF GYPSUM BINDERS

    DEREVIANKO V. N.

    2017-02-01

    Full Text Available Summary. Problem statement. In the next 10 years, more than 90% of materials will be replaced with new materials – nanocomposites [1]. The nanocomponents application will allow manufacture of high-strength materials with reduced production cost and will ensure demand for products [2]. Researches aimed to determination of carbon nanotube type nanomodifier concentration impact on the physical and mechanical properties of gypsum binders are important today and must result in creation of competitive strong nano-materials. Purpose. Research of carbon nanotube (CNT type nanomodifier concentration impact on the physical and mechanical properties of gypsum binders. Conclusion. Sample microstructure analysis revealed that the non-modified gypsum sample structure is dominated by prismatic and lamellar crystals randomly distributed throughout the matrix volume. In this case, loose structure with increased porosity is formed, which results in sample mechanical strength reduction. In the CNT-modified gypsum matrix, well-ordered and homogeneous structure is formed with larger needle-shaped crystals, which results in the phase-contacting area increase, porosity reduction and thus the physical and mechanical characteristics improvement. It is experimentally proved that at the identical nano-modifier content in the gypsum matrix (0.035 %, maximum compression strength gain is achieved with the use of CNT and makes 28- 30%. At the use of initial carbon nanotubes, increase in strength at the same nano-modifier content makes 13-15%. The Ca2+ ions interaction with the graphene-like carbon surface was investigated by the DFT method. Capability is demonstrated of the covalent calcium bonding with the hexagonal carbon surface cell as a result of overlap of Ca2+ valence 3p orbitals and carbon 2р orbitals.

  12. Effects of annealing temperature on the physicochemical, optical and photoelectrochemical properties of nanostructured hematite thin films prepared via electrodeposition method

    Phuan, Yi Wen; Chong, Meng Nan; Zhu, Tao; Yong, Siek-Ting; Chan, Eng Seng

    2015-01-01

    Highlights: • Nanostructured hematite thin films were synthesized via electrodeposition method. • Effects of annealing on size, grain boundary and PEC properties were examined. • Photocurrents generation was enhanced when the thin films were annealed at 600 °C. • The highest photocurrent density of 1.6 mA/cm 2 at 0.6 V vs Ag/AgCl was achieved. - Abstract: Hematite (α-Fe 2 O 3 ) is a promising photoanode material for hydrogen production from photoelectrochemical (PEC) water splitting due to its wide abundance, narrow band-gap energy, efficient light absorption and high chemical stability under aqueous environment. The key challenge to the wider utilisation of nanostructured hematite-based photoanode in PEC water splitting, however, is limited by its low photo-assisted water oxidation caused by large overpotential in the nominal range of 0.5–0.6 V. The main aim of this study was to enhance the performance of hematite for photo-assisted water oxidation by optimising the annealing temperature used during the synthesis of nanostructured hematite thin films on fluorine-doped tin oxide (FTO)-based photoanodes prepared via the cathodic electrodeposition method. The resultant nanostructured hematite thin films were characterised using field emission-scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), UV-visible spectroscopy and Fourier transform infrared spectroscopy (FTIR) for their elemental composition, average nanocrystallites size and morphology; phase and crystallinity; UV-absorptivity and band gap energy; and the functional groups, respectively. Results showed that the nanostructured hematite thin films possess good ordered nanocrystallites array and high crystallinity after annealing treatment at 400–600 °C. FE-SEM images illustrated an increase in the average hematite nanocrystallites size from 65 nm to 95 nm when the annealing temperature was varied from 400 °C to 600 °C. As the

  13. Effects of annealing temperature on the physicochemical, optical and photoelectrochemical properties of nanostructured hematite thin films prepared via electrodeposition method

    Phuan, Yi Wen [School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway 46150 Selangor DE (Malaysia); Chong, Meng Nan, E-mail: Chong.Meng.Nan@monash.edu [School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway 46150 Selangor DE (Malaysia); Sustainable Water Alliance, Advanced Engineering Platform, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway 46150 Selangor DE (Malaysia); Zhu, Tao; Yong, Siek-Ting [School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway 46150 Selangor DE (Malaysia); Chan, Eng Seng [School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway 46150 Selangor DE (Malaysia); Sustainable Water Alliance, Advanced Engineering Platform, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway 46150 Selangor DE (Malaysia)

    2015-09-15

    Highlights: • Nanostructured hematite thin films were synthesized via electrodeposition method. • Effects of annealing on size, grain boundary and PEC properties were examined. • Photocurrents generation was enhanced when the thin films were annealed at 600 °C. • The highest photocurrent density of 1.6 mA/cm{sup 2} at 0.6 V vs Ag/AgCl was achieved. - Abstract: Hematite (α-Fe{sub 2}O{sub 3}) is a promising photoanode material for hydrogen production from photoelectrochemical (PEC) water splitting due to its wide abundance, narrow band-gap energy, efficient light absorption and high chemical stability under aqueous environment. The key challenge to the wider utilisation of nanostructured hematite-based photoanode in PEC water splitting, however, is limited by its low photo-assisted water oxidation caused by large overpotential in the nominal range of 0.5–0.6 V. The main aim of this study was to enhance the performance of hematite for photo-assisted water oxidation by optimising the annealing temperature used during the synthesis of nanostructured hematite thin films on fluorine-doped tin oxide (FTO)-based photoanodes prepared via the cathodic electrodeposition method. The resultant nanostructured hematite thin films were characterised using field emission-scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), UV-visible spectroscopy and Fourier transform infrared spectroscopy (FTIR) for their elemental composition, average nanocrystallites size and morphology; phase and crystallinity; UV-absorptivity and band gap energy; and the functional groups, respectively. Results showed that the nanostructured hematite thin films possess good ordered nanocrystallites array and high crystallinity after annealing treatment at 400–600 °C. FE-SEM images illustrated an increase in the average hematite nanocrystallites size from 65 nm to 95 nm when the annealing temperature was varied from 400 °C to 600

  14. Soil fertility, nutrition and yield of maize and barley with gypsum application on soil surface in no-till

    Leandro Michalovicz

    2014-10-01

    Full Text Available Annual crop yield and nutrition have shown differentiated responses to modifications in soil chemical properties brought about by gypsum application. The aim of this study was to evaluate the effect of gypsum application rates on the chemical properties of a Latossolo Bruno (Clayey Oxisol, as well as on the nutrition and yield of a maize-barley succession under no-till. The experiment was set up in November 2009 in Guarapuava, Parana, Brazil, applying gypsum rates of 0.0, 1.5, 3.0, 4.5, and 6.0 Mg ha-1 to the soil surface upon sowing maize, with crop succession of barley. Gypsum application decreased the levels of Al3+ and Mg2+ in the 0.0-0.1 m layer and increased soil pH in the layers from 0.2-0.6 m depth. Gypsum application has increased the levels of Ca2+ in all soil layers up to 0.6 m, and the levels of S-SO4(2- up to 0.8 m. In both crops, the leaf concentrations of Ca and S were increased while Mg concentrations have decreased as a function of gypsum rates. There was also an effect of gypsum rates on grain yield, with a quadratic response of maize and a linear increase for barley. Yield increases were up to 11 and 12 % in relation to control for the maximum technical efficiency (MTE rates of 3.8 and 6.0 Mg ha-1 of gypsum, respectively. Gypsum application improved soil fertility in the profile, especially in the subsurface, as well as plant nutrition, increasing the yields of maize and barley.

  15. Crop Response to Gypsum Application to Subtropical Soils Under No-Till in Brazil: a Systematic Review

    Tales Tiecher

    2018-02-01

    Full Text Available ABSTRACT The use of gypsum to improve the root environment in tropical soils in the southeastern and central-western regions of Brazil is a widespread practice with well-established recommendation criteria. However, only recently gypsum began to be used on subtropical soils in South of Brazil, so available knowledge of its effect on crop yield is incipient and mainly for soils under no-till (NT systems. Avaiable studies span a wide range of responses, from a substantial increase to a slight reduction in crop yield. Also, the specific conditions leading to a favorable effect of gypsum application on crop yield are yet to be accurately identified. The primary objectives of this study were to examine previously reported results to assess the likelihood of a crop response to gypsum and to develop useful recommendation criteria for gypsum application to subtropical soils under NT in Brazil. For this purpose, we examined the results of a total of 73 growing seasons, reported in 20 different scientific publications that assessed grain yield as a function of gypsum rates. Four different scenarios were examined, by the occurrence or not of high subsurface acidity (viz., Al saturation >20 % and/or exchangeable Ca 3 cmolc dm-3 failed to increase crop yield, irrespective of the soil water status. Under these conditions, high gypsum rates (6-15 Mg ha−1 may even reduce grain yield, possibly by inducing K and Mg deficiency. On the other hand, applying gypsum to soils with high subsurface acidity increased yield by 16 % in corn (87 % of cases and by 19 % in winter cereals (83 % of cases, whether or not the soil was water-deficient. By contrast, soybean yield was only increased by gypsum applied in the simultaneous presence of high soil subsurface acidity and water deficiency (average increase 27 %, 100 % of cases.

  16. Formation of complexes between hematite nanoparticles and a non-conventional galactomannan gum. Toward a better understanding on interaction processes.

    Busch, Verónica M; Loosli, Fréderic; Santagapita, Patricio R; Buera, M Pilar; Stoll, Serge

    2015-11-01

    The physicochemical characteristics of hematite nanoparticles related to their size, surface area and reactivity make them useful for many applications, as well as suitable models to study aggregation kinetics. For several applications (such as remediation of contaminated groundwater) it is crucial to maintain the stability of hematite nanoparticle suspensions in order to assure their arrival to the target place. The use of biopolymers has been proposed as a suitable environmentally friendly option to avoid nanoparticle aggregation and assure their stability. The aim of the present work was to investigate the formation of complexes between hematite nanoparticles and a non-conventional galactomannan (vinal gum--VG) obtained from Prosopis ruscifolia in order to promote hematite nanoparticle coating with a green biopolymer. Zeta potential and size of hematite nanoparticles, VG dispersions and the stability of their mixtures were investigated, as well as the influence of the biopolymer concentration and preparation method. DLS and nanoparticle tracking analysis techniques were used for determining the size and the zeta-potential of the suspensions. VG showed a polydispersed size distribution (300-475 nm Z-average diameter, 0.65 Pdi) and a negative zeta potential (between -1 and -12 mV for pH2 and 12, respectively). The aggregation of hematite nanoparticles (3.3 mg/L) was induced by the addition of VG at lower concentrations than 2mg/L (pH5.5). On the other hand, hematite nanoparticles were stabilized at concentrations of VG higher than 2 mg/L. Several phenomena between hematite nanoparticles and VG were involved: steric effects, electrostatic interactions, charge neutralization, charge inversion and polymer bridging. The process of complexation between hematite nanoparticles and the biopolymer was strongly influenced by the preparation protocols. It was concluded that the aggregation, dispersion, and stability of hematite nanoparticles depended on biopolymer

  17. The impact of solution chemistry of electrolyte on the sorption of pentachlorophenol and phenanthrene by natural hematite nanoparticles

    Zeng, Fanfeng; He, Yan, E-mail: yhe2006@zju.edu.cn; Lian, Zhenghua; Xu, Jianming, E-mail: jmxu@zju.edu.cn

    2014-01-01

    Hematite nanoparticles (NPs) were studied as a sorbent for hydrophobic organic contaminants (OCs) under natural ambient conditions through specially designed contrasting solution chemistry of electrolyte. Ionizable pentachlorophenol (PCP) and non-ionizable phenanthrene (PHE) were selected as representative OCs. The sorption capacities of PCP and PHE were pH-dependent, and a larger amount of PCP was sorbed at pH values below its pK{sub a} (4.75). However, the PHE sorption capacity was higher at relatively high or low pHs (e.g. below 4.0 and above 10.0), possibly due to the larger available surface area of the hematite NPs, caused by the higher values of net charges and charge density. Changes in pH might thus affect the sorption of OCs by hematite NPs, through modification of the surface characteristics of the sorbent and the electronic properties of the sorbate molecules. The influence of different ionic strengths indicated that the amounts of PCP and PHE sorbed by hematite NPs decreased as a concentration function of different types of ions (e.g. Na{sup +}, K{sup +}, Mg{sup 2 +} and Ca{sup 2 +}), with the underlying mechanism possibly being due to four interactions i.e. hydrogen-bonding, competitive sorption by ions in the ambient solution, screening effects and aggregation effects. The results confirmed that the surface chemistry of hematite NPs, the chemical properties of PCP and PHE, and solution chemistry (e.g. pH and ionic strength) of the electrolyte all played an important role in PCP and PHE sorption by hematite NPs. By comparison of both sorption capacity and ecologic advantages, our results suggested that natural hematite NPs would be more competitive and efficient for PCP and PHE sorption than engineered NPs. This finding increases our knowledge regarding the environmental function of natural NPs (such as hematite NPs) for OC remediation through manipulating their interfacial behavior. - Highlights: •Hematite NPs was tested for PCP/PHE sorption under

  18. An XRPD and EPR spectroscopy study of microcrystalline calcite bioprecipitated by Bacillus subtilis

    Perito, B.; Romanelli, M.; Buccianti, A.; Passaponti, M.; Montegrossi, G.; Di Benedetto, F.

    2018-05-01

    We report in this study the first XRPD and EPR spectroscopy characterisation of a biogenic calcite, obtained from the activity of the bacterium Bacillus subtilis. Microcrystalline calcite powders obtained from bacterial culture in a suitable precipitation liquid medium were analysed without further manipulation. Both techniques reveal unusual parameters, closely related to the biological source of the mineral, i.e., to the bioprecipitation process and in particular to the organic matrix observed inside calcite. In detail, XRPD analysis revealed that bacterial calcite has slightly higher c/a lattice parameters ratio than abiotic calcite. This correlation was already noticed in microcrystalline calcite samples grown by bio-mineralisation processes, but it had never been previously verified for bacterial biocalcites. EPR spectroscopy evidenced an anomalously large value of W 6, a parameter that can be linked to occupation by different chemical species in the next nearest neighbouring sites. This parameter allows to clearly distinguish bacterial and abiotic calcite. This latter achievement was obtained after having reduced the parameters space into an unbiased Euclidean one, through an isometric log-ratio transformation. We conclude that this approach enables the coupled use of XRPD and EPR for identifying the traces of bacterial activity in fossil carbonate deposits.

  19. Evaluation of Various Synthesis Methods for Calcite-Precipitated Calcium Carbonate (PCC) Formation

    Ramakrishna, Chilakala; Thenepalli, Thriveni; Ahn, Ji Whan

    2017-01-01

    This review paper evaluates different kinds of synthesis methods for calcite precipitated calcium carbonates by using different materials. The various processing routes of calcite with different compositions are reported and the possible optimum conditions required to synthesize a desired particle sizes of calcite are predicted. This paper mainly focuses on that the calcite morphology and size of the particles by carbonation process using loop reactors. In this regard, we have investigated various parameters such as CO 2 flow rate, Ca (OH) 2 concentration, temperature, pH effect, reaction time and loop reactor mechanism with orifice diameter. The research results illustrate the formation of well-defined and pure calcite crystals with controlled crystal growth and particle size, without additives or organic solvents. The crystal growth and particle size can be controlled, and smaller sizes are obtained by decreasing the Ca (OH) 2 concentration and increasing the CO 2 flow rate at lower temperatures with suitable pH. The crystal structure of obtained calcite was characterized by using X-ray diffraction method and the morphology by scanning electron microscope (SEM). The result of x-ray diffraction recognized that the calcite phase of calcium carbonate was the dominating crystalline structure.

  20. Influence of surface conductivity on the apparent zeta potential of calcite.

    Li, Shuai; Leroy, Philippe; Heberling, Frank; Devau, Nicolas; Jougnot, Damien; Chiaberge, Christophe

    2016-04-15

    Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz-Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime. We show that the HS equation seriously underestimates the zeta potential of calcite, particularly when the electrolyte is diluted (ionic strength ⩽ 0.01 M) because of calcite surface conductivity. The basic Stern model successfully predicted the corrected zeta potential by assuming that the zeta potential is located at the outer Helmholtz plane, i.e. without considering a stagnant diffuse layer at the calcite-water interface. The surface conductivity of calcite crystals was inferred from electrical conductivity measurements and computed using our basic Stern model. Surface conductivity was also successfully predicted by our surface complexation model. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. Evaluation of Various Synthesis Methods for Calcite-Precipitated Calcium Carbonate (PCC) Formation

    Ramakrishna, Chilakala [Hanil Cement Corporation, Danyang (Korea, Republic of); Thenepalli, Thriveni; Ahn, Ji Whan [Korea Institute of Geoscience and Mineral Resources, Daejeon (Korea, Republic of)

    2017-06-15

    This review paper evaluates different kinds of synthesis methods for calcite precipitated calcium carbonates by using different materials. The various processing routes of calcite with different compositions are reported and the possible optimum conditions required to synthesize a desired particle sizes of calcite are predicted. This paper mainly focuses on that the calcite morphology and size of the particles by carbonation process using loop reactors. In this regard, we have investigated various parameters such as CO{sub 2} flow rate, Ca (OH){sub 2} concentration, temperature, pH effect, reaction time and loop reactor mechanism with orifice diameter. The research results illustrate the formation of well-defined and pure calcite crystals with controlled crystal growth and particle size, without additives or organic solvents. The crystal growth and particle size can be controlled, and smaller sizes are obtained by decreasing the Ca (OH){sub 2} concentration and increasing the CO{sub 2} flow rate at lower temperatures with suitable pH. The crystal structure of obtained calcite was characterized by using X-ray diffraction method and the morphology by scanning electron microscope (SEM). The result of x-ray diffraction recognized that the calcite phase of calcium carbonate was the dominating crystalline structure.

  2. The coprecipitation of Sr2+ with calcite at 250C and 1 atm

    Pingitore, N.E. Jr.; Eastman, M.P.

    1986-01-01

    The incorporation of Sr 2+ into calcite at earth surface aqueous conditions is affected by the absolute concentration of Sr 2+ , the presence of Ba 2+ and NaCl in the solution and the rate of precipitation. At solution ratios (molar) of Sr 2+ to Ca 2+ in the low 10 -3 range, which yield calcites with several hundred ppm Sr 2+ , kappasub(calcite) sup(Sr) typically assumes a value between 0.10 and 0.20. Above these concentrations the value of kappasub(calcite) sup(Sr) drops to approximately 0.06. Furthermore, if minor amounts of Ba 2+ or large amounts of Na + (0.48 M) are added to a dilute Sr 2+ solution, a value around 0.06 for kappasub(calcite)sup(Sr) is found. This 'strontium concentration effect' and the associated 'competitive cation effect' suggest that small amounts of Sr 2+ may be incorporated into a limited number of nonlattice sites in calcite. Incorporation of Sr 2+ into these sites, presumably defects, noticeably affects kappasub(calcite)sup(Sr) only at low Sr 2+ concentrations and in the absence of competition from other large cations. An increase in kappasub(calcite)sup(Sr) with rate of precipitation, qualitatively similar to that found in other studies, was observed only when precipitation times were decreased from days to hours. For many geologic settings a partition coefficient for Sr 2+ into calcite of 0.06 appears appropriate, but there are situations - very low Sr 2+ concentrations, the presence of Mg 2+ , and fast precipitation rates - in which a larger value might better approximate natural partitioning. (author)

  3. Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein*

    Rahman, M. Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-01-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that –OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature. PMID:21768106

  4. The potential for phosphorus pollution remediation by calcite precipitation in UK freshwaters

    C. Neal

    2001-01-01

    Full Text Available This paper examines the potential for calcium carbonate to reduce phosphate pollution in freshwaters by co-precipitation, a process known as a "self cleansing mechanism". Calcium carbonate saturation levels and phosphate concentrations (SRP - soluble reactive phosphate across the major eastern UK river basins are examined to test for solubility controls. The study shows that calcite saturation varies for each catchment as a function of flow and biological activity rather than by direct regulation by SRP. Indeed, there is no evidence, for any of the rivers studied, that calcite solubility controls hold. However, for groundwater and groundwater-fed springs in the Chalk of the Thames basin, calcite saturation is observed with associated low SRP levels. A self-cleansing mechanism may well be operative within the Chalk due to two factors. Firstly, there is a high potential for nucleation on the calcite micro-crystals in the aquifer. Secondly, there are within aquifer reactions that remove the calcite nucleating inhibitors (SRP and dissolved organic carbon, DOC to levels lower than those occurring within the rivers do. These inhibitors enter the catchment at very high concentrations in association with agricultural pollution (fertilizer application and animal slurry and household contamination (e.g. sewage sources from septic tanks. Under low flow conditions, when the saturation index for calcite is at its highest, so too is the concentration of the nucleation inhibitor SRP. Companion work shows that calcite precipitation can occur at the water-sediment interface of the river and this may involve SRP removal. The data, as a whole, define an apparent bound for calcite solubility control where in the presence of nucleating centres, SRP must be less than 4 mM-P l-1 and DOC must be less than 150 mM-C l-1: a condition that does not seem to pertain within most UK rivers. Keywords: calcite, calcium carbonate, phosphate, soluble reactive phosphate, dissolved

  5. Effect of amino acids on the precipitation kinetics and Ca isotopic composition of gypsum

    Harouaka, Khadouja; Kubicki, James D.; Fantle, Matthew S.

    2017-12-01

    Stirred gypsum (CaSO4 · 2H2O) precipitation experiments (initial Ωgypsum = 2.4 ± 0.14, duration ≈ 1.0-1.5 h) were conducted in the presence of the amino acids glycine (190 μM), L-alanine (190 μM), D- and L-arginine (45 μM), and L-tyrosine (200 μM) to investigate the effect of simple organic compounds on both the precipitation kinetics and Ca isotopic composition of gypsum. Relative to abiotic controls, glycine, tyrosine, and alanine inhibited precipitation rates by ∼22%, 27%, and 29%, respectively, while L- and D-arginine accelerated crystal growth by ∼8% and 48%, respectively. With the exception of tyrosine, amino acid induced inhibition resulted in fractionation factors (αs-f) associated with precipitation that were no more than 0.3‰ lower than amino acid-free controls. In contrast, the tyrosine and D- and L-arginine experiments had αs-f values associated with precipitation that were similar to the controls. Our experimental results indicate that Ca isotopic fractionation associated with gypsum precipitation is impacted by growth inhibition in the presence of amino acids. Specifically, we propose that the surface-specific binding of amino acids to gypsum can change the equilibrium fractionation factor of the bulk mineral. We investigate the hypothesis that amino acids can influence the growth of gypsum at specific crystal faces via adsorption and that different faces have distinct fractionation factors (αface-fluid). Accordingly, preferential sorption of amino acids at particular faces changes the relative, face-specific mass fluxes of Ca during growth, which influences the bulk isotopic composition of the mineral. Density functional theory (DFT) calculations suggest that the energetic favorability of glycine sorption onto gypsum crystal faces occurs in the order: (1 1 0) > (0 1 0) > (1 2 0) > (0 1 1), while glycine sorption onto the (-1 1 1) face was found to be energetically unfavorable. Face-specific fractionation factors constrained by

  6. Pressure response of vacancy ordered maghemite (γ-Fe2O3) and high pressure transformed hematite (α-Fe2O3)

    Hearne, Giovanni; Pischedda, Vittoria

    2012-03-01

    Combined XRD and Mössbauer effect spectroscopy studies to high pressures of ˜30 GPa of vacancy ordered maghemite are presented. The vacancy ordered superstructure is robust and remains intact up to the pressure-induced onset transition to hematite at 13-16 GPa. The pressure transformed hematite is shown to be crystallographically textured, unlike the randomised low pressure maghemite phase. This arises out of a pressure or stress instigated topotactic transformation of the cubic-spinel to hexagonal-corundum structure. The textured sample permits us to obtain information on the spin reorientation behavior of the pressure transformed hematite in compression and decompression sequences. Spin reorientation is restricted to ˜15° over wide pressure ranges, attributable to the effect of entrapped vacancies in the high pressure structure. Thus there are structural and magnetic peculiarities specific to pressure transformed hematite not evident in pressurized hematite starting material. These are triggered by the maghemite→hematite transformation.

  7. Distribution of Minor Elements in Calcite From the Unsaturated Zone at Yucca Mountain, Nevada

    Marshall, B. D.; Whelan, J. F.

    2001-12-01

    Calcite is sporadically distributed in fractures and cavities in the volcanic rocks that form the 500- to 700-m-thick unsaturated zone at Yucca Mountain. Previous work has shown that the calcite precipitated from water moving downward through the unsaturated zone since the volcanic rocks were emplaced approximately 13 Ma. Calcite thus serves as a proxy for the chemistry and amounts of past percolation, two parameters that are important in predictions of the future behavior of the potential radioactive waste repository at Yucca Mountain. Latest calcite, which began forming between approximately 5 and 2 Ma, typically displays fine-scale growth zoning defined by distributions of Mn (inferred from cathodoluminescence), Mg, and Sr. Electron microprobe (EPMA) mapping of outermost calcite reveals Mg growth zoning1 and higher overall concentrations of Mg in late calcite than in older calcite. Micro X-ray fluorescence (micro-XRF) maps were obtained by slow rastering of the samples over a 100-watt X-ray source collimated through a final aperture of 100 μ m. Although the spatial resolution of the micro-XRF mapping is much less than that of EPMA, this technique reveals distributions of some elements to which EPMA is less sensitive. Micro-XRF maps show that Sr is spatially correlated with Mg; Sr concentrations range to 500 μ g/g at the resolution of the 100-μ m collimator. Because both Mg and Sr have similar calcite-water distribution coefficients much less than one, the Mg/Sr in calcite reflects the Mg/Sr of the water that precipitated the calcite. The distribution coefficient for Mn is greater than one and variations in Mn are not correlated with Mg and Sr. Covariation of Mg and Sr in the percolating water may be explained by reactions that affect the rate of uptake of chemical constituents from the overlying rock and soil, and/or evaporation. Late calcite has lower δ 13C values, probably due to a regional change from wetter to drier climate conditions. The higher Mg and

  8. Paleohydrogeological implications from fracture calcites in fissures of low transmissivity. A report of investigations in 2011

    Sahlstedt, E.; Karhu, J.

    2014-07-01

    Samples of fracture fillings were collected from 26 bedrock fractures at Olkiluoto. Special attention was paid to fractures having low transmissivities of <1E-8 m 2 /s. The chemical composition and the C and O isotopic composition of the fracture filling calcite were analysed. In addition, fluid inclusions were studied and microthermometric measurements conducted on fracture filling calcite. The most common minor element in calcite fillings was Mn, having concentrations up to 3.4 wt-%. The δ13C values had a wide range, from -13.0 to 14.5 per mille, and the δ18O values a narrower range, from -13.4 to -7.3 per mille. The δ18O values of late-stage calcite appear to be independent of the transmissivity of the fractures, ranging from -11.2 to -7.3 per mille over a T range from 3E -6 to 1.6E -1 1 m 2 /s. The δ13C values of late-stage calcite appear to have more variation at high transmissivities of >1E-8 m 2 /s. Unusually low and high δ13C values in late-stage calcite fillings occur in the upper ∼ 400 m of the bedrock and are probably related to microbial reduction processes, at near surface (<60 m) conditions to oxidation of organic matter resulting in low δ13C values and at ∼ 55-400 m to methanogenesis, causing high δ 13C values. A relatively low spread in the δ 13C values of late-stage calcite precipitates in low transmissivity (<1E-8 m 2 /s) fractures is most likely caused by stable conditions in the areas of low conductivity in the bedrock, reflecting slow dissolution/reprecipitation of older carbonate fillings. Fluid inclusion data indicate variation in fracture water types from high temperature, ∼ 200 deg C, low salinity fluid with < 4 wt-% of NaCl eq to low temperature, <100 deg C, high salinity fluid with 17-29 wt-% of NaCl eq . The high temperature fluid is associated with Group 5 calcite fillings and the low temperature fluid with Group 3 calcite. The composition of fluids related to Group 4 calcite falls roughly between the compositions

  9. Monitoring of Calcite Precipitation in Hardwater Lakes with Multi-Spectral Remote Sensing Archives

    Iris Heine

    2017-01-01

    Full Text Available Calcite precipitation is a common phenomenon in calcium-rich hardwater lakes during spring and summer, but the number and spatial distribution of lakes with calcite precipitation is unknown. This paper presents a remote sensing based method to observe calcite precipitation over large areas, which are an important prerequisite for a systematic monitoring and evaluation of restoration measurements. We use globally archived satellite remote sensing data for a retrospective systematic assessment of past multi-temporal calcite precipitation events. The database of this study consists of 205 data sets that comprise freely available Landsat and Sentinel 2 data acquired between 1998 and 2015 covering the Northeast German Plain. Calcite precipitation is automatically identified using the green spectra and the metric BGR area, the triangular area between the blue, green and red reflectance value. The validation is based on field measurements of CaCO3 concentrations at three selected lakes, Feldberger Haussee, Breiter Luzin and Schmaler Luzin. The classification accuracy (0.88 is highest for calcite concentrations ≥0.7 mg/L. False negative results are caused by the choice of a conservative classification threshold. False positive results can be explained by already increased calcite concentrations. We successfully transferred the developed method to 21 other hardwater lakes in Northeast Germany. The average duration of lakes with regular calcite precipitation is 37 days. The frequency of calcite precipitation reaches from single time detections up to detections nearly every year. False negative classification results and gaps in Landsat time series reduce the accuracy of frequency and duration monitoring, but in future the image density will increase by acquisitions of Sentinel-2a (and 2b. Our study tested successfully the transfer of the classification approach to Sentinel-2 images. Our study shows that 15 of the 24 lakes have at least one phase of

  10. Ocre, hematites y óxido de hierro: el problema terminológico = Ochre, Hematite and Iron Oxid: The Terminological Issue

    Alfredo Cortell Nicolau

    2016-12-01

    Full Text Available Los óxidos de hierro son prácticamente omnipresentes al analizar contextos, no solo referentes al arte rupestre, sino también en relación con toda una serie de actividades que podríamos considerar cotidianas en ambientes prehistóricos. Sin embargo, su estudio sistemático no ha comenzado hasta tiempos muy recientes. Fruto de ello, podría decirse que una parte de la literatura arqueológica no especializada en el campo de la pigmentología muestra, en ocasiones, cierta inexactitud terminológica. Con este documento pretendemos, a través de un análisis tanto de su funcionamiento, como de las propiedades geoquímicas y mineralógicas del ocre, la hematites y los propios óxidos de hierro, exponer la necesidad de propiedad en su nomenclatura, así como los problemas que podrían derivarse de la falta de precisión. Por último, establecemos algunas propuestas que tal vez pudieran ayudar en esta normativización. Iron oxides are virtually omnipresent when analyzing contexts, not only referring to rock art, but also related to a whole series of activities, which we could consider as quotidian for prehistoric environments. Nevertheless, a systematic study of these has not started until recent times. As a result, it could be argued that a part of archaeological literature, not specialized on pigmentology, shows sometimes a certain lack of terminological accurateness. With this document we mean to, through an analysis both of the functioning and the geochemical and mineralogical properties of ochre, hematite and iron oxides themselves, expose the need for an appropriate terminology, as well as to show the problems derived from an inadequate naming. Finally, we bring some proposals, which could maybe help on an appropriate terminological standardization.

  11. In Situ Observation of Gypsum-Anhydrite Transition at High Pressure and High Temperature

    LIU Chuan-Jiang; ZHENG Hai-Fei

    2012-01-01

    An in-situ Raman spectroscopic study of gypsum-anhydrite transition under a saturated water condition at high pressure and high temperature is performed using a hydrothermal diamond anvil cell (HDAC).The experimental results show that gypsum dissolvs in water at ambient temperature and above 496 MPa.With increasing temperature,the anhydrite (CaSO4) phase precipitates at 250 320℃ in the pressure range of 1.0 1.5 GPa,indicating that under a saturated water condition,both stable conditions of pressure and temperature and high levels of Ca and SO4 ion concentrations in aqueous solution are essential for the formation of anhydrite.A linear relationship between the pressure and temperature for the precipitation of anhydrite is established as P(GPa) =0.0068T - 0.7126 (250℃≤T≤320℃).Anhydrite remained stable during rapid cooling of the sample chamber,showing that the gypsum-anhydrite transition involving both dissolution and precipitation processes is irreversible at high pressure and high temperature.%An in-situ Raman spectroscopic study of gypsum-anhydrite transition under a saturated water condition at high pressure and high temperature is performed using a hydrothermal diamond anvil cell (HDAC). The experimental results show that gypsum dissolvs in water at ambient temperature and above 496 Mpa. With increasing temperature, the anhydrite (CaSO4) phase precipitates at 250-320℃ in the pressure range of 1.0-1.5 Gpa, indicating that under a saturated water condition, both stable conditions of pressure and temperature and high levels of Ca and SO4 ion concentrations in aqueous solution are essential for the formation of anhydrite. A linear relationship between the pressure and temperature for the precipitation of anhydrite is established as P(Gpa) = 0.0068T - 0.7126 (250℃≤T≤320℃). Anhydrite remained stable during rapid cooling of the sample chamber, showing that the gypsum-anhydrite transition involving both dissolution and precipitation processes is

  12. Conditions of uranium-bearing calcite formation in ore-enclosing sediments of the Semizbaj deposit (Kazakhstan)

    Kondrat'eva, I.A.; Maksimova, I.G.; Dojnikova, O.I.

    1995-01-01

    Consideration is given to results of investigation into uranium-bearing calcite, forming the cement of gravelly-sandy rocks of the Semizbaj uranium deposit. Core sampling in prospecting boreholes were used to establish geological conditions, place and time of uranium-bearing calcite formation. Calcite was investigated by optical, electron-microscope and radiographic methods. It is shown that uranium in calcite doesn't form its own mineral phase and exists in scattered state. Uranium in calcite-bearing minerals is present in isomorphic form. Uranium content in calcite was equal to 0.009-0.15 %. It is proposed that mineralization, formed in sedimentary rocks by processes of ground-stratum oxidation, is the source of uranium, enriching calcite. refs., 5 figs., 2 tabs

  13. Gypsum (CaSO42H2O) scaling on polybenzimidazole and cellulose acetate hollow fiber membranes under forward osmosis

    Chen, Si Cong; Su, Jincai; Fu, Feng-Jiang; Mi, Baoxia; Chung, Neal Tai-Shung

    2013-01-01

    We have examined the gypsum (CaSO42H2O) scaling phenomena on membranes with different physicochemical properties in forward osmosis (FO) processes. Three hollow fiber membranes made of (1) cellulose acetate (CA), (2) polybenzimidazole (PBI

  14. High School Forum: "Invitations to Enquiry": The Calcite/Acid Reaction.

    Herron, J. Dudley, Ed.; Driscoll, D. R.

    1979-01-01

    Describes a high school chemistry experiment which involves the reaction between calcite and hydrochloric and sulfuric acids. This reaction can be carried out as a projected demonstration and on an individual basis. (HM)

  15. Calcite dissolution along a transect in the western tropical Indian Ocean: A multiproxy approach

    Naik, S.S.; Naidu, P.D.

    Three paleocarbonate ion proxies, size index, planktonic foraminifera shell weight, and calcite crystallinity, have been employed here to a set of core top samples from the western tropical Indian Ocean in the water depth ranges from 1086 to 4730 m...

  16. Morphological changes of calcite single crystals induced by graphene-biomolecule adducts

    Calvaresi, Matteo; Di Giosia, Matteo; Ianiro, Alessandro; Valle, Francesco; Fermani, Simona; Polishchuk, Iryna; Pokroy, Boaz; Falini, Giuseppe

    2017-01-01

    Calcite has the capability to interact with a wide variety of molecules. This usually induces changes in shape and morphology of crystals. Here, this process was investigated using sheets of graphene-biomolecule adducts. They were prepared and made dispersible in water through the exfoliation of graphite by tip sonication in the presence tryptophan or N-acetyl-D-glucosamine. The crystallization of calcium carbonate in the presence of these additives was obtained by the vapor diffusion method and only calcite formed. The analysis of the microscopic observations showed that the graphene-biomolecule adducts affected shape and morphology of rhombohedral {10.4} faced calcite crystals, due to their stabilization of additional {hk.0} faces. The only presence of the biomolecule affected minimally shape and morphology of calcite crystals, highlighting the key role of the graphene sheets as 2D support for the adsorption of the biomolecules.

  17. Crystallisation of Gypsum and Prevention of Foaming in Wet Flue Gas Desulphurisation (FGD) Plants

    Hansen, Brian Brun

    The aim of this project is to investigate two operational problems, which have been experienced during wet flue gas desulphurisation (FGD) operation, i.e. poor gypsum dewatering properties and foaming. The results of this work can be used for the optimization of wet FGD-plants in terms of reliabi......The aim of this project is to investigate two operational problems, which have been experienced during wet flue gas desulphurisation (FGD) operation, i.e. poor gypsum dewatering properties and foaming. The results of this work can be used for the optimization of wet FGD-plants in terms....... Experiments in a falling film wet FGD pilot plant have shown a strong non-linear behaviour (in a ln(n(l)) vs. l plot) at the lower end of the particle size range, compared to the well-known linear “mixed suspension mixed product removal (MSMPR)” model. A transient population balance model, fitted...

  18. Visible and Mid-Infrared Gypsum Optical Constants for Modeling of Martian Deposits

    Roush, Ted L.; Esposito, Francesca; Rossmann, George R.; Colangeli, Luigi

    2007-08-01

    Introduction: Recent and on-going remote and in situ observations indicate that sulfates are present in significant abundances at various locations on Mars [1-7]. The Mars Reconnaissance Orbiter (MRO) imaging spectrometer (CRISM) is returning hyperspectral data at higher spatial resolution [8] than the OMEGA instrument on the Mars Express Mission [3]. Data from both OMEGA and CRISM have provided spectral evidence for the presence of gypsum and various hydrated sulfates on the Martian surface [e.g. 3-7] Thus, the optical properties of sulfates, in general, are of interest to quantitative interpretation of this increasing volume of remotely sensed data. This is because optical constants describe how a material interacts with electromagnetic radiation and represent the fundamental values used in radiative transfer calculations describing a variety of physical environments. Such environments include atmospheres where aerosols are present, planetary and satellite regoliths, and circumstellar dust clouds. Here we focus upon gypsum because of its applicability due to its identification on Mars. Also, gypsum is a mineral that is readily available in samples sizes that are suitable for study using a variety of spectral measurements. In the infrared (>5 μm) several studies reporting the optical constants of gypsum can be used in evaluating the approach used here. Most importantly, there is a general lack of data regarding the optical constants for gypsum at visible and mid-infrared wavelengths (0.4-5 μm) that are being observed by OMEGA and CRISM. Background: In the infrared, there have been several studies focused at determining the optical constants of gypsum using classical dispersion models [9-11]. These have used a variety of samples including; crystals, compressed pellets of pure materials, and grains suspended in a KBr matrix. Spectral measurements of gypsum, and other sulfates, have existed for about 100 years at visible and mid-infrared wavelengths (0.4-5 μm) [e

  19. Dehydration reactions of gypsum: A neutron and X-ray diffraction study

    Abriel, W.; Reisdorf, K.; Pannetier, J.

    1990-03-01

    The kinetics of the dehydration of gypsum was investigated by powder diffraction methods. Using the incoherent scattering effect of H with the neutron beam, the background intensity as a measure of the water content was checked in the temperature range 295-623 K. The superposed Bragg peaks yielded four major phases: Gypsum, subhydratesCaSO 4(H 2O) x (1 > x > 0),AIII-CaSO 4, AII-CaSO 4. For the subhydrates a maximum water content of x > = 0.74was determined. A different kinetic was found using Guinier X-ray technique with the heated sample prepared on a thin foil. Only with high local H 2O steam pressure, produced in the comparable larger sample container of the neutron diffraction experiment, could this high H 2O occupation of the subhydrate tunnel structure be found. A topotactic mechanism can describe the phase transitions for this reaction.

  20. Radioecology of and radiation dose from Dutch waste gypsum released into the environment

    Koster, H.W.; Weers, A.W. van; Netherlands Energy Research Foundation, Petten)

    1985-11-01

    The Dutch industries release 9 kinds of waste gypsum, 90% of the total quantity is phosphogypsum. Only waste gypsums from the phosphate industries show increased radioactivity, the strongest in phosphogypsum. All phosphogypsum, 2 Tg.a -1 , is disposed of into the Rhine at Rotterdam. This leads to an increase of radionuclides, from the U-238 chain, along the Dutch coast. The calculated increase of activity concentrations in sea food causes an increase of the individual radiation dose of maximal 150 μSv.a -1 and of the Dutch population dose of 170 manSv.a -1 . Stacking of the phosphogypsum would result in a dose increase of one order of magnitude lower. The need for environmental disposal or stacking of at least the fine and coarse fractions of the phosphogypsum, which are difficult to recycle, will remain. (Auth.)

  1. Thermal Dehydration Kinetics of Gypsum and Borogypsum under Non-isothermal Conditions

    I.Y.Elbeyli; S.Piskin

    2004-01-01

    Thermal dehydration of gypsum and borogypsum was investigated under nonisothermal conditions in air by using simultaneous thermogravimetric-differential thermal analyzer. Nonisothermal experiments were carried out at various linear heating rates. Kinetics of dehydration in the temperature range of 373-503 K were evaluated from the DTA (differential thermal analysis)-TGA (thermogravimetric analysis) data by means of Coats-Redfern,Kissinger and Doyle Equations. Values of the activation energy and the pre-exponential factor of the dehydration were calculated. The results of thermal experiments and kinetic parameters indicated that borogypsum is similar to gypsum from dehydration mechanism point of view although it consists of boron and small amount of alkali metal oxides.

  2. Influence of the gypsum dehydration temperature and alkali additives on the properties of anhydrite cement

    Leskeviciene V.

    2010-01-01

    Full Text Available While dehydrating gypsum with additives at the temperatures of 800°C and 900°C the influence of alkali additives on both the crystalline structure of anhydrite and properties of anhydrite binder was investigated. The industrial and household wastes including other lowcost materials were used as additives. Having heated them with gypsum the anhydrite with alkali activation properties was obtained. The properties of such substances were evaluated using the methods of chemical, diffractive X-ray scanning and scanning electron microscopy (SEM analyses. Some additives, e.g. 5 % ground glass waste, were found to increase crystal agglomerate formation of anhydrite binder, accelerate the hydration process of anhydrite and double the compressive strength of hydrated samples compared to samples without additives.

  3. What concentration of actinides can be packed into calcite? Hints from rare earth element (REE) composition

    Christiansen, J.; Stipp, S.L.S.; Waight, T.; Baker, J.A.

    2005-01-01

    Full text of publication follows: For reliable modelling of actinide mobility in the event of spent fuel repository failure, we need data describing the uptake capacity of the minerals likely to find themselves in the transport path. Calcite (CaCO 3 ) is a common secondary mineral in fractures and pore fillings, especially downstream from degrading concrete facilities, so it is a likely candidate for incorporation. Investigations made under ACTAF, a 5. Framework EURATOM integrated project, as well as some other research studies, have shown that actinides are successfully incorporated as substituting ions within the calcite mineral structure. The question remaining, is how much can calcite take up. Geologists routinely use relative concentrations of rare Earth elements (REE's), the lanthanides, for interpreting rock genesis and history. One can also adopt them as analogues for the radioactive elements because their f-orbital electron configuration makes them behave very much like actinides. We collected and analysed a suite of 70 calcite samples from a great number of possible formation environments, geological ages and geographical locations, for the purpose of finding the range and maximum of total f-orbital substitution possible in calcite, under natural conditions. We analysed them using Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). The maximum concentration found was about 5 x 10 -3 mole/kg total REE in a sample that had a geological history of formation where REE fluids played a role. Over the whole suite, total REE ranged from less than 10 -4 moles/kg for limestone samples formed from biogenic calcite where REE-enriched fluids would have played a negligible role. Thus, in natural calcite, REE's are present and all evidence points to a structural incorporation within the mineral rather than as a separate REE-rich phase. These data compare favourably with mole fractions from calcite grown synthetically, where as much as 6 x 10 -3

  4. Fabrication of hematite (α-Fe{sub 2}O{sub 3}) nanoparticles using electrochemical deposition

    Meng, Qingling; Wang, Zuobin, E-mail: wangz@cust.edu.cn; Chai, Xiangyu; Weng, Zhankun; Ding, Ran; Dong, Litong

    2016-04-15

    Graphical abstract: - Highlights: • Cathodic electrochemical deposition proposed to fabricate hematite nanoparticles. • Hematite nanoparticles were fabricated on indium-tin-oxide coated glass substrates. • The size and shape of nanoparticles were determined by deposition conditions. • The nanoparticles were well decentralized for different potential applications. • Electrochemical deposition is a useful approach in fabricating nanoparticles. - Abstract: In this work, cathodic electrochemical deposition was proposed to fabricate reproducible and homogeneous hematite (α-Fe{sub 2}O{sub 3}) nanoparticles on indium-tin-oxide (ITO) films. The α-Fe{sub 2}O{sub 3} nanoparticles, which were quasi-hexagonally shaped, were deposited in an aqueous mixture of FeCl{sub 2} and FeCl{sub 3} at the temperatures 16.5 °C, 40 °C and 60 °C. The electrochemically deposited α-Fe{sub 2}O{sub 3} nanoparticles showed excellent stability and good crystallinity. The α-Fe{sub 2}O{sub 3} nanoparticles were characterized by Raman spectroscope and X-ray diffractometer (XRD). A scanning electron microscope (SEM) was used to measure the size and shape of the nanoparticles. The experiment results have shown that the size and shape of nanoparticles were determined by electrochemical deposition conditions including the deposition time, current density, reaction temperature and solution concentration. The proposed electrochemical deposition method has been proven to be a cost-effective, environment friendly and highly efficient approach in fabricating well decentralized α-Fe{sub 2}O{sub 3} nanoparticles for different potential applications.

  5. Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

    Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

    2001-01-01

    Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

  6. Isothermal Oxidation of Magnetite to Hematite in Air and Cyclic Reduction/Oxidation Under Carbon Looping Combustion Conditions

    Simmonds, Tegan; Hayes, Peter C.

    2017-12-01

    In the carbon looping combustion process the oxygen carrier is regenerated through oxidation in air; this process has been simulated by the oxidation of dense synthetic magnetite for selected temperatures and times. The oxidation of magnetite in air is shown to occur through the formation of dense hematite layers on the particle surface. This dense hematite forms through lath type shear transformations or solid-state diffusion through the product layer. Cyclic reduction in CO-CO2/oxidation in air of hematite single crystals has been carried out under controlled laboratory conditions at 1173 K (900 °C). It has been shown that the initial reduction step is critical to determining the product microstructure, which consists of gas pore dendrites in the magnetite matrix with blocky hematite formed on the pore surfaces. The progressive growth of the magnetite layer with the application of subsequent cycles appears to continue until no original hematite remains, after which physical disintegration of the particles takes place.

  7. Synthesis of Ru doped hematite nanorods for application as photo-anode material in a photoelectrochemical cell (PEC)

    Ndlangamandla, C. L. [University of Zululand, Department of Physics and Engineering (South Africa); Bharuth-Ram, K., E-mail: kbr@tlabs.ac.za [Durban University of Technology, Physics Department (South Africa); Ngom, B. D.; Maaza, M. [iThemba LABS, Materials Research Department (South Africa)

    2017-11-15

    Nanostructured thin films of hematite doped with different concentrations of ruthenium were grown on fluorine doped tin oxide glass substrates using the aqueous chemical growth method. On further heat treatment at 500 {sup ∘}C the structures morphed into hematite nanorods (NRs). The Ru concentration in the NRs was controlled by varying the Ru concentration in the RuCl {sub 3}⋅H{sub 2}O precursors. Scanning Electron Microscopy confirmed the formation of the hematite nanorods, while. X-ray diffraction and Mössbauer spectroscopy (MS) data provided clear evidence of the crystallinity of the nanorods and incorporation of ruthenium in the hematite nanorod structure. The band gap of the Ru-doped hematite NRs, estimated from UV-Vis optical absorption intensity vs photon energy curves, were found to be directly related to the Ru concentration. For concentrations in the range 6–30 mg the band gaps are in the range well suited to drive the water splitting process in a photoelectrochemical cell without application of an external bias.

  8. Effect of defects on the small polaron formation and transport properties of hematite from first-principles calculations.

    Smart, Tyler J; Ping, Yuan

    2017-10-04

    Hematite (α-Fe 2 O 3 ) is a promising candidate as a photoanode material for solar-to-fuel conversion due to its favorable band gap for visible light absorption, its stability in an aqueous environment and its relatively low cost in comparison to other prospective materials. However, the small polaron transport nature in α-Fe 2 O 3 results in low carrier mobility and conductivity, significantly lowering its efficiency from the theoretical limit. Experimentally, it has been found that the incorporation of oxygen vacancies and other dopants, such as Sn, into the material appreciably enhances its photo-to-current efficiency. Yet no quantitative explanation has been provided to understand the role of oxygen vacancy or Sn-doping in hematite. We employed density functional theory to probe the small polaron formation in oxygen deficient hematite, N-doped as well as Sn-doped hematite. We computed the charged defect formation energies, the small polaron formation energy and hopping activation energies to understand the effect of defects on carrier concentration and mobility. This work provides us with a fundamental understanding regarding the role of defects on small polaron formation and transport properties in hematite, offering key insights into the design of new dopants to further improve the efficiency of transition metal oxides for solar-to-fuel conversion.

  9. Precipitation of Calcite during the Deposition of Paleogene Sangkarewang Oil Shale, Ombilin Basin, West Sumatra, Indonesia

    Agus Haris Widayat

    2015-09-01

    Full Text Available DOI: 10.17014/ijog.2.3.185-197Geochemical and petrographical analyses were carried out to investigate the occurrence of calcite in theformer Ombilin lacustrine lake. The study involves eight samples taken from a 56 m long drill core of Sangkarewangoil shale. Geochemical investigation showed that the samples consist of varied terrigenous input represented by Si, Al, K, and Ti, and autochthonous input represented by S, total organic carbon (TOC, and d13C of bulk organic matter. Along the drill core profile the abundance of autochthonous input decreases upwards, while that of terrigenous input oppositely increases upwards. Petrographical analysis revealed that calcite is a major mineral in the samples. In this study, the abundance of calcite could be represented by the abundance of Ca, as calcite is the only significant Ca containing mineral. Ca is abundant in the samples (8.4% in average and its concentration varies similarly with those of S, TOC, and d13C, suggesting that the element as well as calcite incorporates the autochthonous input. Thevariation of calcite abundance in the drill core profile is considered to be related with primary productivity changes during the development of the former lake. Higher primary productivity represented by more positive of d13C value(-24.8‰ during the deposition of the lower part of the drill core profile promoted the higher amount of deposited organic matter. In such environment, the supersaturation of carbonate ion in lake water was also reached and significant precipitation of authigenic calcite occurred. As the lake developed, the primary productivity decreased as indicated by more negative of d13C value (eventually -26.8‰. This condition led to the decreases of deposited organic matterand calcite in the lake sediments.

  10. Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

    Bindschedler, S.; Cailleau, G.; Braissant, O.; Millière, L.; Job, D.; Verrecchia, E. P.

    2014-05-01

    Calcitic nanofibres are ubiquitous habits of secondary calcium carbonate (CaCO3) accumulations observed in calcareous vadose environments. Despite their widespread occurrence, the origin of these nanofeatures remains enigmatic. Three possible mechanisms fuel the debate: (i) purely physicochemical processes, (ii) mineralization of rod-shaped bacteria, and (iii) crystal precipitation on organic templates. Nanofibres can be either mineral (calcitic) or organic in nature. They are very often observed in association with needle fibre calcite (NFC), another typical secondary CaCO3 habit in terrestrial environments. This association has contributed to some confusion between both habits, however they are truly two distinct calcitic features and their recurrent association is likely to be an important fact to help understanding the origin of nanofibres. In this paper the different hypotheses that currently exist to explain the origin of calcitic nanofibres are critically reviewed. In addition to this, a new hypothesis for the origin of nanofibres is proposed based on the fact that current knowledge attributes a fungal origin to NFC. As this feature and nanofibres are recurrently observed together, a possible fungal origin for nanofibres which are associated with NFC is investigated. Sequential enzymatic digestion of the fungal cell wall of selected fungal species demonstrates that the fungal cell wall can be a source of organic nanofibres. The obtained organic nanofibres show a striking morphological resemblance when compared to their natural counterparts, emphasizing a fungal origin for part of the organic nanofibres observed in association with NFC. It is further hypothesized that these organic nanofibres may act as templates for calcite nucleation in a biologically influenced mineralization process, generating calcitic nanofibres. This highlights the possible involvement of fungi in CaCO3 biomineralization processes, a role still poorly documented. Moreover, on a global

  11. The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

    Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

    2017-01-01

    Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

  12. Influence of Flue Gas Desulfurization Gypsum on Reducing Soluble Phosphorus in Successive Runoff Events from a Coastal Plain Bermudagrass Pasture.

    Watts, Dexter B; Torbert, H Allen

    2016-05-01

    Controlling the threat that pastures intensively managed with poultry litter (PL) pose to accelerating eutrophication is a major issue in the southeastern United States. Gypsum (CaSO) has been identified as a promising management tool for ameliorating litter P losses to runoff. Thus, research was conducted to elucidate gypsum's residual effects on P losses from a bermudagrass ( L.) pasture. Runoff events (60 min) were created using rainfall simulations. Treatments consisted of applying four flue gas desulfurization (FGD) gypsum rates (0, 2.2, 4.4, and 8.9 Mg ha) to bermudagrass fertilized with 13.4 Mg ha PL plus a nonfertilized check (no litter or gypsum) and 8.9 Mg ha FGD gypsum only as controls. Rainfall simulations (∼ 85 mm h) were conducted immediately, 5 wk, and 6 mo (i.e., at the end of growing season) after PL application to determine gypsum's effectiveness at controlling P loss over successive runoff events. The greatest dissolved P (DP) in runoff occurred immediately after PL application. Gypsum effectively reduced cumulative DP concentration losses (54%) compared with PL alone in initial runoff events. Gypsum reduced DP concentrations in succeeding runoff events also regardless of timing, suggesting that its effect is persistent and will not diminish over a growing season. Generally, maximum DP reductions were achieved with 8.9 Mg ha. However, it was surmised from this study that optimal P reduction in a bermudagrass pasture can be achieved with 4.4 Mg ha. Information ascertained from this study may be useful in aiding land managers making prescriptions for management practices that reduce DP losses from agricultural fields. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  13. Metalliferous sediment and a silica-hematite deposit within the Blanco fracture zone, Northeast Pacific

    Hein, J.R.; Clague, D.A.; Koski, R.A.; Embley, R.W.; Dunham, R.E.

    2008-01-01

    A Tiburon ROV dive within the East Blanco Depression (EBD) increased the mapped extent of a known hydrothermal field by an order of magnitude. In addition, a unique opal-CT (cristobalite-tridymite)-hematite mound was discovered, and mineralized sediments and rock were collected and analyzed. Silica-hematite mounds have not previously been found on the deep ocean floor. The light-weight rock of the porous mound consists predominantly of opal-CT and hematite filaments, rods, and strands, and averages 77.8% SiO2 and 11.8% Fe2O3. The hematite and opal-CT precipitated from a low-temperature (???115?? C), strongly oxidized, silica- and iron-rich, sulfur-poor hydrothermal fluid; a bacterial mat provided the framework for precipitation. Samples collected from a volcaniclastic rock outcrop consist primarily of quartz with lesser plagioclase, smectite, pyroxene, and sulfides; SiO2 content averages 72.5%. Formation of these quartz-rich samples is best explained by cooling in an up-flow zone of silica-rich hydrothermal fluids within a low permeability system. Opal-A, opal-CT, and quartz mineralization found in different places within the EBD hydrothermal field likely reflects decreasing silica saturation and increasing temperature of the mineralizing fluid with increasing silica crystallinity. Six push cores recovered gravel, coarse sand, and mud mineralized variously by Fe or Mn oxides, silica, and sulfides. Total rare-earth element concentrations are low for both the rock and push core samples. Ce and Eu anomalies reflect high and low temperature hydrothermal components and detrital phases. A remarkable variety of types of mineralization occur within the EBD field, yet a consistent suite of elements is enriched (relative to basalt and unmineralized cores) in all samples analyzed: Ag, Au, S, Mo, Hg, As, Sb, Sr, and U; most samples are also enriched in Cu, Pb, Cd, and Zn. On the basis of these element enrichments, the EBD hydrothermal field might best be described as a base

  14. The effect of gypsum products and separating materials on the typography of denture base materials.

    Firtell, D N; Walsh, J F; Elahi, J M

    1980-09-01

    The typography of polymethyl methacrylate processed against various gypsum products coated with various separating materials was studied under an SEM. Tinfoil and two commercial tin foil substitutes were used as separating material during processing, and the surfaces of the resulting acrylic resin forms were studied for topographical differences. Tinfoil and alpha 2 hemihydrates produced the smoothest surfaces. As a practical solution, a good quality tinfoil substitute and alpha 1 hemihydrate could be used when processing polymethyl methacrylate resin.

  15. Elementary characterization of samples of Portland cement, natural gypsum and phosphogypsum mortars from Brazil

    Narloch, Danielle Cristine; Paschuk, Sergei Anatolyevich; Corrêa, Janine Nicolosi; Torres, Catarina Alzira Peddis; Mazer, Wellington; Macioski, Gustavo [Universidade Tecnologica Federal do Parana (UTFPR), PR (Brazil); Lara, Alessandro [Universidade de Sao Paulo (USP), SP (Brazil). Departamento de Fisica; Casali, Juliana Machado, E-mail: janine_nicolosi@hotmail.com, E-mail: alellara@hotmail.com, E-mail: jucasali@gmail.com [Instituto Federal de Santa Catarina (IFSC), Florianópolis, SC (Brazil)

    2017-07-01

    Portland cement, the basic ingredient of concrete and is manufactured by crushing, milling and proportioning limestone, sand, clay, iron ore and secondary materials such as shells, chalk or marl combined with shale slate or blast furnace slag, fly ash, gypsum, phosphogypsum, and some others. Evaluating the physical and mineralogical characteristics of the cement and its chemical composition is essential to establish the quality of the product. Therefore, the objective of this work was to characterize and quantify the most common chemical elements in the samples of Brazilian Portland cement, natural gypsum, and phosphogypsum mortars by means of X-ray dispersive energy spectroscopy (EDXRF), as well as to evaluate the strength of these mortars. For analysis of the compressive strength, initially prepared samples were submitted to a destructive mechanical test. Subsequently samples were milled and compacted to form thin tablets, which were submitted to the EDXRF analysis. The qualitative and quantitative analyzes showed that for phosphogypsum mortar the largest mass fractions were found of 49.8±2.5% (Si), 24.66±0.96% (S) and 22.10±0.42% (Ca). For gypsum mortar those values were found of 43.41±0.45% (Ca), 33.8 ± 0.8% (S) and 18.9±1.2% (Si), respectively; and for Portland cement mortar, the predominant elements in those samples have the mass fractions of 64.20±0.52% (Ca) and 27.3±1.5% (Si). The results showed that obtained values of mass fraction of the elements Si, S, K, Ca, Ti, Fe are in rather good agreement with quantities indicated for manufacture. Besides, gypsum and phosphogypsum presented almost the same composition and compressive strength. (author)

  16. Accuracy of Gypsum Casts after Different Impression Techniques and Double Pouring.

    Stephania Caroline Rodolfo Silva

    Full Text Available This study evaluated the accuracy of gypsum casts after different impression techniques and double pouring. Ten patients were selected and for each one it was obtained 5 partial putty/wash impressions with vinyl polysiloxane (VPS material from teeth #13 to #16 with partial metal stock trays. The following techniques were performed: (1 one-step; two-step relief with: (2 PVC film; (3 slow-speed tungsten carbide bur and scalpel blade, (4 small movements of the tray and (5 without relief-negative control. The impressions were disinfected with 0.5% sodium hypochlorite for 10 minutes and stored during 110 and 230 minutes for the first and second pouring, respectively, with type IV gypsum. Three intra-oral lateral photographs of each patient were taken using a tripod and a customized radiographic positioner. The images were imported into ImageJ software and the total area of the buccal surface from teeth #13 to #16 was measured. A 4.0% coefficient of variance was criterion for using these measurements as Baseline values. The casts were photographed and analyzed using the same standardization for the clinical images. The area (mm2 obtained from the difference between the measurements of each gypsum cast and the Baseline value of the respective patient were calculated and analyzed by repeated-measures two way-ANOVA and Mauchly's Sphericity test (α = 0.05. No significant effect was observed for Impression technique (P = 0.23, Second pouring (P = 0.99 and their interaction (P = 0.25. The impression techniques and double pouring did not influence the accuracy of the gypsum casts.

  17. Effect of alginate chemical disinfection on bacterial count over gypsum cast

    Haralur, Satheesh B.; Al-Dowah, Omir S.; Gana, Naif S.; Al-Hytham, Abdullah

    2012-01-01

    PURPOSE To evaluate the efficacy of sodium hypochlorite (1 : 10) and iodophor disinfectants on alginate impressions along with their effect on the survived bacterium count on the gypsum cast. MATERIALS AND METHODS Four alginate impression on each dentate patients were made, of which Group I were not washed or disinfected, Group II impressions were merely washed with water, Group III were disinfected by spraying with sodium hypochlorite (1 : 10), Group IV were disinfected with iodophor (1 : 21...

  18. Elementary characterization of samples of Portland cement, natural gypsum and phosphogypsum mortars from Brazil

    Narloch, Danielle Cristine; Paschuk, Sergei Anatolyevich; Corrêa, Janine Nicolosi; Torres, Catarina Alzira Peddis; Mazer, Wellington; Macioski, Gustavo; Lara, Alessandro

    2017-01-01

    Portland cement, the basic ingredient of concrete and is manufactured by crushing, milling and proportioning limestone, sand, clay, iron ore and secondary materials such as shells, chalk or marl combined with shale slate or blast furnace slag, fly ash, gypsum, phosphogypsum, and some others. Evaluating the physical and mineralogical characteristics of the cement and its chemical composition is essential to establish the quality of the product. Therefore, the objective of this work was to characterize and quantify the most common chemical elements in the samples of Brazilian Portland cement, natural gypsum, and phosphogypsum mortars by means of X-ray dispersive energy spectroscopy (EDXRF), as well as to evaluate the strength of these mortars. For analysis of the compressive strength, initially prepared samples were submitted to a destructive mechanical test. Subsequently samples were milled and compacted to form thin tablets, which were submitted to the EDXRF analysis. The qualitative and quantitative analyzes showed that for phosphogypsum mortar the largest mass fractions were found of 49.8±2.5% (Si), 24.66±0.96% (S) and 22.10±0.42% (Ca). For gypsum mortar those values were found of 43.41±0.45% (Ca), 33.8 ± 0.8% (S) and 18.9±1.2% (Si), respectively; and for Portland cement mortar, the predominant elements in those samples have the mass fractions of 64.20±0.52% (Ca) and 27.3±1.5% (Si). The results showed that obtained values of mass fraction of the elements Si, S, K, Ca, Ti, Fe are in rather good agreement with quantities indicated for manufacture. Besides, gypsum and phosphogypsum presented almost the same composition and compressive strength. (author)

  19. 18O and 34S in the Upper Bartonium gypsum deposits of the Paris basin

    Fontes, J.C.; Letolle, R.

    1976-01-01

    Isotopic analyses ( 18 O and 34 S) of the Eocene gypsum from the Paris basin show a range beyond the normal Tertiary marine values. The possibility of a reduction process during diagenesis is discussed. A hypothesis of continental origin by leaching of Permotriassic deposits is proposed for this formation on the basis of a comparison of the isotopic contents recorded from Germany and eastern France

  20. Kinetics of Inorganic Calcite Dissolution in Seawater under Pressure

    Dong, S.; Subhas, A.; Rollins, N.; Berelson, W.; Adkins, J. F.

    2016-02-01

    While understanding calcium carbonate dissolution is vital in constructing global carbon cycles and predicting the effect of seawater acidification as a result of increasing atmospheric CO2, there is still a major debate over the basic formulation of a dissolution rate law. The kinetics of calcium carbonate dissolution are typically described by the equation: Rate=k(1-Ω)n, while Ω=[Ca2+][CO32-]/Ksp. In this study, 13C-labeled calcite is dissolved in unlabeled seawater and the evolving d13C composition of the fluid is traced over time to establish dissolution rate. Instead of changing ion concentration to obtain varying Ω (as in our previous study; Subhas et al. 2015), we changed Ksp by conducting experiments under different pressures (described in theory as ∂lnKsp/∂P=-ΔV/RT, where ΔV is partial molal volume). This involved the construction of a pressure vessel that could hold our sample bag and provide aliquots while remaining pressurized. Pressure experiments were conducted between 0-2000PSI. Results support the conclusion in our previous study that near-equilibrium dissolution rates are highly nonlinear, but give a disparate relationship between undersaturation and dissolution rate if Ω is calculated assuming the specific ΔV embedded in CO2SYS. A revised ΔV from -37cm3 to -65cm3 would make the dissolution formulation equation agree, but clearly appears unreasonable. Our results are explained by a pressure effect on carbonate dissolution kinetics over and above the influence of pressure on Ω. If this is a phenomenon that occurs in nature, then we would predict that dissolution should be occurring shallower in the water column (as sometimes observed) than indicated by standard Ω calculations.

  1. Calcite/aragonite-biocoated artificial coral reefs for marine parks

    Volodymyr Ivanov

    2017-08-01

    Full Text Available Natural formation of the coral reefs is complicated by slow biomediated precipitation of calcium carbonate from seawater. Therefore, manufactured artificial coral reefs can be used for the formation of “underwater gardens” in marine parks for the recreational fishing and diving that will protect natural coral reefs from negative anthropogenic effects. Additionally, the coating of the concrete, plastic or wooden surfaces of artificial coral reef with calcium carbonate layer could promote attachment and growth of coral larvae and photosynthetic epibiota on these surfaces. Three methods of biotechnological coating of the artificial coral reefs have been tested: (1 microbially induced calcium carbonate precipitation from concentrated calcium chloride solution using live bacterial culture of Bacillus sp. VS1 or dead but urease-active cells of Yaniella sp. VS8; (2 precipitation from calcium bicarbonate solution; (3 precipitation using aerobic oxidation of calcium acetate by bacteria Bacillus ginsengi strain VSA1. The thickness of biotechnologically produced calcium carbonate coating layer was from 0.3 to 3 mm. Biocoating using calcium salt and urea produced calcite in fresh water and aragonite in seawater. The calcium carbonate-coated surfaces were colonized in aquarium with seawater and hard corals as inoculum or in aquarium with fresh water using cyanobacteria Chlorella sorokiana as inoculum. The biofilm on the light-exposed side of calcium carbonate-coated surfaces was formed after six weeks of incubation and developed up to the average thickness of 250 µm in seawater and about 150 µm in fresh water after six weeks of incubation. The biotechnological manufacturing of calcium carbonate-coated concrete, plastic, or wooden surfaces of the structures imitating natural coral reef is technologically feasible. It could be commercially attractive solution for the introduction of aesthetically pleasant artificial coral reefs in marine parks and

  2. Mg and Sr in Arctic echinoderm calcite: Nature or nurture?

    Iglikowska, A.; Borszcz, T.; Drewnik, A.; Grabowska, M.; Humphreys-Williams, E.; Kędra, M.; Krzemińska, M.; Piwoni-Piórewicz, A.; Kukliński, P.

    2018-04-01

    The Mg/Ca and Sr/Ca ratios in echinoderm skeletal calcite are used as a proxy for Phanerozoic seawater changes, since the skeletal concentrations are, to some extent, controlled by environmental factors. However, it remains unclear how the influence of environmental factors is modified by vital effects, especially in polar waters. Therefore, the goal of this study was to compare the ratios of Mg/Ca and Sr/Ca among the skeletal parts of 10 common Arctic echinoderm species belonging to three classes Echinoidea, Asteroidea and Ophiuroidea that contribute substantially to the carbon cycle in the Arctic benthic system. Significant differences were recorded in echinoid skeletal element concentrations among specific skeletal parts. The lowest Mg/Ca and Sr/Ca ratios were detected in the spines (mean Mg/Ca 37.5 ± 8.8 SD; Sr/Ca 1.8 ± 0.1). The components of the Aristotle's lantern (epiphyses, pyramids and rotulas) were characterised by the highest Mg levels (Mg/Ca 79.9 ± 6.0; 75.2 ± 9.1; 60.1 ± 3.8, respectively). It is likely that mouth parts experience greater mechanical pressure compared to other body parts, and the higher content of Mg in the Aristotle's lantern contributes to its robustness. We did not find any distinctive trends in the distribution of skeletal elements in the asteroid and ophiuroid skeletal parts. The heterogeneous concentrations of Mg and Sr in different skeleton parts of the echinoids suggest possible physiological regulation of the chemical composition rather than the composition only being influenced by the environment. We cannot recommend echinoderm skeletons as reliable indicators in palaeoenvironmental reconstructions due to the possible biological control of skeletal chemistry, which may interfere with the effect of environmental variables.

  3. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    Bevilaqua, Rochele C. A.; Miranda, Caetano R. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Rigo, Vagner A. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Universidade Tecnológica Federal do Paraná, UTFPR, Cornélio Procópio, PR (Brazil); Veríssimo-Alves, Marcos [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Departamento de Física, ICEx, Universidade Federal Fluminense, UFF, Volta Redonda, RJ (Brazil)

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  4. Sea urchin tooth mineralization: Calcite present early in the aboral plumula

    Stock, Stuart R.; Veis, Arthur; Xiao, Xianghui; Almer, Jonathan D.; Dorvee, Jason R.

    2012-01-01

    In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: When and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron x-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth. PMID:22940703

  5. Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization

    Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.

    2017-12-01

    We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

  6. Sealing of rock joints by induced calcite precipitation. A case study from Bergeforsen hydro power plant

    Hakami, E.; Qvarfort, U.; Ekstav, A.

    1991-01-01

    The possibilities of sealing rock fractures by injecting water saturated with calcite solution, and hereby inducing a calcite precipitation inside the fracture, is investigated. The way of reaction and the amount of calcite precipitation will depend on the saturation of calcium carbonate in the water, the temperature, the pH and the CO 2 -pressure. There is experience of lime-saturated water injection in the rock foundation below the dam at Bergeforsens power plant (1955-1968). It was observed that the consumption of injected lime water decreased with time. A possible reason to the decrease in lime water consumption is that calcite has precipitated such that the permeability of the rock in general is lowered. Another explanation to this could be that calcite precipitation is concentrated to the fractures surrounding the injection holes, thus preventing the lime water from penetrating further into the rock. It is recommended that further studies of the fracture fillings in drill cores from Bergeforsen is performed. The aim of such study should be to determine the extent of induced calcite precipitation and to investigate its chemical and physical properties. (authors)

  7. Sea urchin tooth mineralization: calcite present early in the aboral plumula.

    Stock, Stuart R; Veis, Arthur; Xiao, Xianghui; Almer, Jonathan D; Dorvee, Jason R

    2012-11-01

    In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: when and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron X-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth. Copyright © 2012 Elsevier Inc. All rights reserved.

  8. Mechanical properties of simulated Mars materials: gypsum-rich sandstones and lapilli tuff

    Morrow, Carolyn; Lockner, David; Okubo, Chris

    2013-01-01

    Observations by the Mars Exploration Rover (MER) Opportunity, and other recent studies on diagenesis in the extensive equatorial layered deposits on Mars, suggest that the likely lithologies of these deposits are gypsum-rich sandstones and tuffaceous sediments (for example, Murchie and others, 2009; Squyres and others, 2012; Zimbelman and Scheidt, 2012). Of particular interest is how the diagenesis history of these sediments (degree of cementation and composition) influences the strength and brittle behavior of the material. For instance, fractures are more common in lower porosity materials under strain, whereas deformation bands, characterized by distributed strain throughout a broader discontinuity in a material, are common in higher porosity sedimentary materials. Such discontinuities can either enhance or restrict fluid flow; hence, failure mode plays an important role in determining the mechanics of fluid migration through sediments (Antonellini and Aydin, 1994; 1995; Taylor and Pollard, 2000; Ogilvie and Glover, 2001). As part of a larger study to characterize processes of fault-controlled fluid flow in volcaniclastic and gypsum-rich sediments on Mars, we have completed a series of laboratory experiments to focus on how gypsum clast content and degree of authigenic cementation affects the strength behavior of simulated Mars rocks. Both axial deformation and hydrostatic pressure tests were done at room temperature under dry conditions.

  9. Clay stabilization by using gypsum and paddy husk ash with reference to UCT and CBR value

    Roesyanto; Iskandar, R.; Hastuty, I. P.; Dianty, W. O.

    2018-02-01

    Clays that have low shear strength need to be stabilized in order to meet the technical requirements to serve as a subgrade material. One of the usual soil stabilization methods is by adding chemicals such as Portland cement, lime, and bitumen. The clay stabilization research was done by adding gypsum and paddy husk ash. The research goals were to find out the value of engineering properties of clay due to the addition of 2% gypsum and 2% - 15% paddy husk ash. The soil was classified as Clay - Low Plasticity (CL) based on USCS and was classified as A-7-6 (10) based on AASHTO classification system. The UCT value of original soil was 1.41 kg/cm2. While the CBR soaked and unsoaked values of original soil were 4.41% and 6.23% respectively. The research results showed the addition of paddy husk ash decreased the value of unconfined compressive strength as well as CBR. The stabilized soil by 2% gypsum and 0% paddy husk ash gave maximum UCT value of 1.67 kg/cm2, while the maximum value of CBR were found 6.71% for CBR soaked and 8.00% for CBR unsoaked. The addition of paddy husk ash did not alter the soil classification according to AASHTO or USCS, even degrade the engineering properties of original soil.

  10. Developing biodiversity indicators on a stakeholders' opinions basis: the gypsum industry Key Performance Indicators framework.

    Pitz, Carline; Mahy, Grégory; Vermeulen, Cédric; Marlet, Christine; Séleck, Maxime

    2016-07-01

    This study aims to establish a common Key Performance Indicators (KPIs) framework for reporting about the gypsum industry biodiversity at the European level. In order to integrate different opinions and to reach a consensus framework, an original participatory process approach has been developed among different stakeholder groups: Eurogypsum, European and regional authorities, university scientists, consulting offices, European and regional associations for the conservation of nature, and the extractive industry. The strategy is developed around four main steps: (1) building of a maximum set of indicators to be submitted to stakeholders based on the literature (Focus Group method); (2) evaluating the consensus about indicators through a policy Delphi survey aiming at the prioritization of indicator classes using the Analytic Hierarchy Process method (AHP) and of individual indicators; (3) testing acceptability and feasibility through analysis of Environmental Impact Assessments (EIAs) and visits to three European quarries; (4) Eurogypsum final decision and communication. The resulting framework contains a set of 11 indicators considered the most suitable for all the stakeholders. Our KPIs respond to European legislation and strategies for biodiversity. The framework aims at improving sustainability in quarries and at helping to manage biodiversity as well as to allow the creation of coherent reporting systems. The final goal is to allow for the definition of the actual biodiversity status of gypsum quarries and allow for enhancing it. The framework is adaptable to the local context of each gypsum quarry.

  11. Risk minimisation of FGD gypsum leachates by incorporation of aluminium sulphate

    Alvarez-Ayuso, E. [Department of Environmental Geology, Institute of Earth Sciences ' Jaume Almera' (CSIC), C/ Lluis Sole i Sabaris, s/n, 08028 Barcelona (Spain); Department of Environmental Geochemistry, IRNASA, CSIC, Apto. 257, 37071 Salamanca (Spain)], E-mail: ealvarez@ija.csic.es; Querol, X. [Department of Environmental Geology, Institute of Earth Sciences ' Jaume Almera' (CSIC), C/ Lluis Sole i Sabaris, s/n, 08028 Barcelona (Spain); Ballesteros, J.C.; Gimenez, A. [Endesa Generacion, S.A., C/ Ribera de Loira, 60, 28042 Madrid (Spain)

    2008-11-15

    The incorporation of aluminium sulphate to (flue gas desulphurisation) FGD gypsum before its disposal was investigated as a way to minimise the risk supposed by the high fluoride content of its leachates. Using a bath method the kinetic and equilibrium processes of fluoride removal by aluminium sulphate were studied at fluoride/aluminium molar concentration (F/Al) ratios in the range 1.75 10{sup -2}-1.75 under the pH conditions (about 6.5) of FGD gypsum leachates. It was found that fluoride removal was a very fast process at any of the (F/Al) ratios subject of study, with equilibrium attained within the first 15 min of interaction. High decreases in solution fluoride concentrations (50-80%) were found at the equilibrium state. The use of aluminium sulphate in the stabilization of FGD gypsum proved to greatly decrease its fluoride leachable content (in the range 20-90% for aluminium sulphate doses of 0.1-5%, as determined by the European standard EN 12457-4). Such fluoride leaching minimisation assures the characterization of this by-product as a waste acceptable at landfills for non-hazardous wastes according to the Council Decision 2003/33/EC on waste disposal. Furthermore, as derived from column leaching studies, the proposed stabilization system showed to be highly effective in simulated conditions of disposal, displaying fluoride leaching reduction values about 55 and 80% for aluminium sulphate added amounts of 1 and 2%, respectively.

  12. Mineral potential of clays that cover the gypsum deposits in Araripina-PE region

    Lira, B.B.; Anjos, I.F. dos; Rego, S.A.B.C.

    2011-01-01

    In the present work the applicability of the clays that cover the deposits of Gypsum Plaster in the region of Araripina - PE for use as the ceramic pigments and for bricks production in the red ceramic industry was analyzed. The clay minerals contained the illite, kaolinite and smectite, with high proportion of the last one. The possibility of industrial application of this mineral clay is considerable; however, the mining industries that mine and process the gypsum in the region do not take the clays into account as the potential mineral. In general, industries use the clay minerals in manufacturing processes or as key raw materials, or as the alternatives for some kinds of the chemical processing industries. This paper aims to highlight the potential of materials that cover the deposits of gypsum in reference. The material sampled from different deposit layers was characterized and the physical treatment of ore was applied. The results showed that the material analyzed can be used in various kinds of industry, such as the production of natural ceramic pigments. (author)

  13. In Situ Observation of Gypsum-Anhydrite Transition at High Pressure and High Temperature

    Liu Chuan-Jiang; Zheng Hai-Fei

    2012-01-01

    An in-situ Raman spectroscopic study of gypsum-anhydrite transition under a saturated water condition at high pressure and high temperature is performed using a hydrothermal diamond anvil cell (HDAC). The experimental results show that gypsum dissolvs in water at ambient temperature and above 496 MPa. With increasing temperature, the anhydrite (CaSO 4 ) phase precipitates at 250–320°C in the pressure range of 1.0–1.5GPa, indicating that under a saturated water condition, both stable conditions of pressure and temperature and high levels of Ca and SO 4 ion concentrations in aqueous solution are essential for the formation of anhydrite. A linear relationship between the pressure and temperature for the precipitation of anhydrite is established as P(GPa) = 0.0068T−0.7126 (250°C≤T≤320°C). Anhydrite remained stable during rapid cooling of the sample chamber, showing that the gypsum-anhydrite transition involving both dissolution and precipitation processes is irreversible at high pressure and high temperature. (geophysics, astronomy, and astrophysics)

  14. Implications of moisture content determination in the environmental characterisation of FGD gypsum for its disposal in landfills

    Alvarez-Ayuso, E. [Department of Environmental Geology, Institute of Earth Sciences ' Jaume Almera' (CSIC), C/ Lluis Sole i Sabaris s/n, 08028 Barcelona (Spain)], E-mail: ealvarez@ija.csic.es; Querol, X. [Department of Environmental Geology, Institute of Earth Sciences ' Jaume Almera' (CSIC), C/ Lluis Sole i Sabaris s/n, 08028 Barcelona (Spain); Tomas, A. [Endesa Generacion, S.A., C/ Ribera de Loira 60, 28042 Madrid (Spain)

    2008-05-01

    The leachable contents of elements of environmental concern considered in the Council Decision 2003/33/EC on waste disposal were determined in flue gas desulphurisation (FGD) gypsum. To this end, leaching tests were performed following the standard EN-12457-4 which specifies the determination of the dry mass of the material at 105 deg. C and the use of a liquid to solid (L/S) ratio of 10 l kg{sup -1} dry matter. Additionally, leaching tests were also carried out taking into account the dry mass of the material at 60 deg. C and using different L/S ratios (2, 5, 8, 10, 15 and 20 l kg{sup -1} dry matter). It was found that the dry mass determination at 105 deg. C turns out to be inappropriate for FGD gypsum since at this temperature gypsum transforms into bassanite, and so, in addition to moisture content, crystalline water is removed. As a consequence the moisture content is overvalued (about 16%), what makes consider a lower L/S ratio than that specified by the standard EN-12457-4. As a result the leachable contents in FGD gypsum are, in general, overestimated, what could lead to more strict environmental requirements for FGD gypsum when considering its disposal in landfills, specially concerning those elements (e.g., F) risking the characterisation of FGD gypsum as a waste acceptable at landfills for non-hazardous wastes.

  15. Pressure response of vacancy ordered maghemite (γ-Fe2O3) and high pressure transformed hematite (α-Fe2O3)

    Hearne, Giovanni; Pischedda, Vittoria

    2012-01-01

    Combined XRD and Mössbauer effect spectroscopy studies to high pressures of ∼30 GPa of vacancy ordered maghemite are presented. The vacancy ordered superstructure is robust and remains intact up to the pressure-induced onset transition to hematite at 13–16 GPa. The pressure transformed hematite is shown to be crystallographically textured, unlike the randomised low pressure maghemite phase. This arises out of a pressure or stress instigated topotactic transformation of the cubic-spinel to hexagonal-corundum structure. The textured sample permits us to obtain information on the spin reorientation behavior of the pressure transformed hematite in compression and decompression sequences. Spin reorientation is restricted to ∼15° over wide pressure ranges, attributable to the effect of entrapped vacancies in the high pressure structure. Thus there are structural and magnetic peculiarities specific to pressure transformed hematite not evident in pressurized hematite starting material. These are triggered by the maghemite→hematite transformation. - Graphical abstract: Pressure instigated topotactic transformation of vacancy ordered γ-Fe 2 O 3 →α-Fe 2 O 3 . There is restricted spin (B hf ) reorientation in the new pressure transformed hematite due to entrapped vacancies. The change in direction of V zz signifies a distortion of the FeO 6 octahedral local environment. Highlights: ► Robust vacancy ordered superstructure in maghemite to high pressures. ► Pressure instigated topotactic transformation to hematite and subsequent texture. ► Defect trapping in the pressure transformed hematite. ► Entrapped defects restricts spin reorientation in pressure transformed hematite. ► Contrasting behavior with pressurized hematite starting material.

  16. Synthesis of high-purity precipitated calcium carbonate during the process of recovery of elemental sulphur from gypsum waste

    De Beer, Morris

    2015-08-01

    Full Text Available (PCC). The process used an acid gas (H2S) to improve the aqueous dissolution of CaS, which is otherwise poorly soluble. The carbonate product was primarily calcite (99.5%) with traces of quartz (0.5%). Calcite was the only CaCO3 polymorph obtained...

  17. Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites

    Nedim Ay Ahmet

    2011-01-01

    Full Text Available Abstract A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules.

  18. Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites.

    Nedim Ay, Ahmet; Konuk, Deniz; Zümreoglu-Karan, Birgul

    2011-02-03

    A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules.

  19. Fabrication and properties of microencapsulated-paraffin/gypsum-matrix building materials for thermal energy storage

    Su Junfeng; Wang Xinyu; Wang Shengbao; Zhao Yunhui; Huang Zhen

    2012-01-01

    Graphical abstract: DSC curves of microPCMs/gypsum composite samples before and after a thermal cycling treatment. Highlights: ► Microcapsules containing paraffin was fabricated by in-situ polymerization. ► Methanol-modified melamine–formaldehyde (MMF) was used as shell material. ► MicroPCMs/gypsum-matrix building materials were applied for solar energy storage. ► The structure and thermal conductivity of composites had been investigated. - Abstract: Microencapsulated phase change materials (microPCMs) have been widely applied in solid matrix as thermal-storage or temperature-controlling functional composites. The aim of this work was to prepare and investigate the properties of microPCMs/gypsum-matrix building materials for thermal energy storage. MicroPCMs contain paraffin was fabricated by in situ polymerization using methanol-modified melamine–formaldehyde (MMF) as shell material. A series of microPCMs samples were prepared under emulsion stirring rates in range of 1000–3000 r min −1 with core/shell weight ratios of 3/1, 2/1, 1/1, 1/2 and 1/3, respectively. The shell of microPCMs was smooth and compact with global shape, its thickness was not greatly affected by the core/shell ratio and emulsion stirring rate. DSC tests showed that the shell of microPCMs did not influence the phase change behavior of pure paraffin. It was found from TGA analysis that microPCMs samples containing paraffin lost their weight at the temperature of nearly 250 °C, which indicated that the PCM had been protected by shell. More shell material in microPCMs could enhance the thermal stability and provide higher compact condition for core material. After a 100-times thermal cycling treatment, the microPCMs contain paraffin also nearly did not change the phase change behaviors of PCM. With the increasing of weight contents of microPCMs in gypsum board, the thermal conductivity (λ) values of composites had decreased. The simulation of temperature tests proved that the

  20. Calcite Fluid Inclusion, Paragenetic, and Oxygen Isotopic Records of Thermal Event(s) at Yucca Mountain, Nevada

    Peterman, B.; Moscati, R.

    2000-01-01

    Yucca Mountain, Nevada, is under consideration as a potential high-level radioactive waste repository situated above the water table in 12.7 Ma tuffs. A wealth of textural and geochemical evidence from low-temperature deposits of calcite and silica, indicates that their genesis is related to unsaturated zone (UZ) percolation and that the level of the potential repository has never been saturated. Nonetheless, some scientists contend that thermal waters have periodically risen to the surface depositing calcite and opal in the tuffs and at the surface. This hypothesis received some support in 1996 when two-phase fluid inclusions (FIs) with homogenization temperatures (Th) between 35 and 75 C were reported from UZ calcite. Calcite deposition likely followed closely on the cooling of the tuffs and continues into the present. The paragenetic sequence of calcite and silica in the UZ is early stage calcite followed by chalcedony and quartz, then calcite with local opal during middle and late stages. Four types of FIs are found in calcite assemblages: (1) all-liquid (L); (2) all-vapor (V); (3) 2-phase with large and variable V:L ratios; and (4) a few 2-phase with small and consistent V:L ratios. Late calcite contains no FI assemblages indicating elevated depositional temperatures. In early calcite, the Th of type 4 FIs ranges from ∼ 40 to ∼ 85 C. Such temperatures (sub-boiling) and the assemblage of FIs are consistent with deposition in the UZ. Some delta 18O values < 10 permil in early calcite support such temperatures. Type 4 FIs, however, seem to be restricted to the early calcite stage, during which either cooling of the tuffs or regional volcanism were possible heat sources. Nonetheless, at present there is no compelling evidence of upwelling water as a source for the calcite/opal deposits

  1. Hematite Nanoparticles-Modified Electrode Based Electrochemical Sensing Platform for Dopamine

    Zangeneh Kamali, Khosro; Alagarsamy, Pandikumar; Huang, Nay Ming; Ong, Boon Hoong; Lim, Hong Ngee

    2014-01-01

    Hematite (α-Fe2O3) nanoparticles were synthesized by the solid transformation of ferrous hydroxide and ferrihydrite in hydrothermal condition. The as-prepared α-Fe2O3 nanoparticles were characterized by UV-vis, PL, XRD, Raman, TEM, AFM, FESEM, and EDX analysis. The experimental results indicated the formation of uniform hematite nanoparticles with an average size of 45 nm and perfect crystallinity. The electrochemical behavior of a GC/α-Fe2O3 electrode was studied using CV and EIS techniques with an electrochemical probe, [Fe(CN)6]3−/4− redox couple. The electrocatalytic activity was investigated toward DA oxidation in a phosphate buffer solution (pH 6.8) by varying different experimental parameters. The chronoamperometric study showed a linear response in the range of 0–2 μM with LoD of 1.6 μM for DA. Square wave voltammetry showed a linear response in the range of 0–35 μM with LoD of 236 nM for DA. PMID:25136664

  2. Low-cost superior solid-state symmetric supercapacitors based on hematite nanocrystals

    Peng, Shaomin; Yu, Lin; Lan, Bang; Sun, Ming; Cheng, Gao; Liao, Shuhuan; Cao, Han; Deng, Yulin

    2016-12-01

    We present a facile method for the fabrication of hematite nanocrystal-carbon cloth (Fe2O3-CC) composite. Hierarchical manganite is chosen as the sacrificial precursor, that does not contribute to the component of final iron oxide but can be in situ dissolved by the acid produced from the Fe3+ hydrolysis. This method effectively enhances the specific surface area and conductivity of hematite (Fe2O3) by attaching Fe2O3 nanocrystals (around 5 nm) firmly on the surface of carbon fibers. The obtained Fe2O3-CC can be directly used as a binder-free electrode for a supercapacitor. Interestingly, the composite electrode exhibits synergistic electrochemical capacitance (electrochemical double-layer capacitance and pseudo-capacitance). It manifests a very high areal capacitance of 1.66 F cm-2 (1660 F g-1) at 2 mA cm-2 and excellent cycling performance at large current densities (88.6% retention at 30 mA cm-2 after 5000 cycles) in a three-electrode testing system, which is among the best performances reported in the literature. Importantly, when fabricated as a solid-state flexible symmetric supercapacitor it still shows a maximum energy density of 8.74 mW h cm-3 and power density of 253.9 mW cm-3. Additionally, its good flexibility makes it suitable for portable devices.

  3. Hematite Nanoparticles-Modified Electrode Based Electrochemical Sensing Platform for Dopamine

    Khosro Zangeneh Kamali

    2014-01-01

    Full Text Available Hematite (α-Fe2O3 nanoparticles were synthesized by the solid transformation of ferrous hydroxide and ferrihydrite in hydrothermal condition. The as-prepared α-Fe2O3 nanoparticles were characterized by UV-vis, PL, XRD, Raman, TEM, AFM, FESEM, and EDX analysis. The experimental results indicated the formation of uniform hematite nanoparticles with an average size of 45 nm and perfect crystallinity. The electrochemical behavior of a GC/α-Fe2O3 electrode was studied using CV and EIS techniques with an electrochemical probe, [Fe(CN6]3−/4− redox couple. The electrocatalytic activity was investigated toward DA oxidation in a phosphate buffer solution (pH 6.8 by varying different experimental parameters. The chronoamperometric study showed a linear response in the range of 0–2 μM with LoD of 1.6 μM for DA. Square wave voltammetry showed a linear response in the range of 0–35 μM with LoD of 236 nM for DA.

  4. Reversibility of sorption of plutonium-239 onto hematite and goethite colloids

    Lu, N.; Cotter, C.R.; Kitten, H.D.; Bentley, J.; Triay, I.R.

    1998-01-01

    Laboratory batch sorption experiments were conducted to evaluate: (1) sorption of plutonium-239 ( 239 Pu) on different iron oxide colloids (hematite and geothite), (2) sorption kinetics of colloidal Pu(IV) and soluble Pu(V) onto these two colloids, and (3) desorption of colloidal Pu(IV) and soluble Pu(V) from 239 Pu-loaded colloids as a function of time. Natural groundwater and carbonate-rich synthetic groundwater were used in this study. To examine the possible influence of bicarbonate on 239 Pu sorption, an additional set of experiments was conducted in sodium nitrate (NaNO 3 ) solutions under carbon dioxide free environments. Our results show that colloidal Pu(IV) as well as soluble Pu(V) was rapidly adsorbed by hematite and goethite colloids in both natural and synthetic groundwater. The amount of 239 Pu adsorbed by both iron oxide colloids in synthetic groundwater was higher than in natural groundwater. The presence of carbonate did not influence the sorption of 239 Pu. While sorption of soluble Pu(V) is a slow process, sorption of colloidal Pu(IV) occurs rapidly. Desorption of Pu from iron oxide colloids is much slower than the sorption processes. Our findings suggest that different sorption and desorption behaviors of 239 Pu by iron oxide colloids in groundwater may facilitate the transport of 239 Pu along potential flowpaths from the areas contaminated by radionuclide and release to the accessible environment. (orig.)

  5. Synthesis and characterization of hematite pigment obtained from a steel waste industry.

    Prim, S R; Folgueras, M V; de Lima, M A; Hotza, D

    2011-09-15

    Pigments that meet environmental and technology requirements are the focus of the research in the ceramic sector. This study focuses on the synthesis of ceramic pigment by encapsulation of hematite in crystalline and amorphous silica matrix. Iron oxide from a metal sheet rolling process was used as chromophore. A different content of hematite and silica was homogenized by conventional and high energy milling. The powders obtained after calcinations between 1050 and 1200 °C for 2h were characterized by X-ray diffraction and SEM analysis. The pigments were applied to ceramic enamel and porcelain body. The effect of pigment was measured by comparing L*a*b* values of the heated samples. Results showed that the color developed is influenced by variables such as oxide content employed, conditions of milling and processing temperature. The results showed that the use of pigment developed does not interfere in microstructural characteristics of pigmented material. The best hue was obtained from samples with 15 wt% of chromophore, heated at 1200 °C in amorphous silica matrix. Copyright © 2011 Elsevier B.V. All rights reserved.

  6. Interaction of Zn(II) with hematite nanoparticles and microparticles: Part 2. ATR-FTIR and EXAFS study of the aqueous Zn(II)/oxalate/hematite ternary system.

    Ha, Juyoung; Trainor, Thomas P; Farges, François; Brown, Gordon E

    2009-05-19

    Sorption of Zn(II) to hematite nanoparticles (HN) (av diam=10.5 nm) and microparticles (HM) (av diam=550 nm) was studied in the presence of oxalate anions (Ox2-(aq)) in aqueous solutions as a function of total Zn(II)(aq) to total Ox2-(aq) concentration ratio (R=[Zn(II)(aq)]tot/[Ox2-(aq)]tot) at pH 5.5. Zn(II) uptake is similar in extent for both the Zn(II)/Ox/HN and Zn(II)/Ox/HM ternary systems and the Zn(II)/HN binary system at [Zn(II)(aq)](tot)system than for the Zn(II)/Ox/HM ternary and the Zn(II)/HN and Zn(II)/HM binary systems at [Zn(II)(aq)]tot>4 mM. In contrast, Zn(II) uptake for the Zn(II)/HM binary system is a factor of 2 greater than that for the Zn(II)/Ox/HM and Zn(II)/Ox/HN ternary systems and the Zn(II)/HN binary system at [Zn(II)(aq)]totternary system at both R values examined (0.16 and 0.68), attenuated total reflectance Fourier transform infrared (ATR-FTIR) results are consistent with the presence of inner-sphere oxalate complexes and outer-sphere ZnOx(aq) complexes, and/or type A ternary complexes. In addition, extended X-ray absorption fine structure (EXAFS) spectroscopic results suggest that type A ternary surface complexes (i.e., >O2-Zn-Ox) are present. In the Zn(II)/Ox/HN ternary system at R=0.15, ATR-FTIR results indicate the presence of inner-sphere oxalate and outer-sphere ZnOx(aq) complexes; the EXAFS results provide no evidence for inner-sphere Zn(II) complexes or type A ternary complexes. In contrast, ATR-FTIR results for the Zn/Ox/HN sample with R = 0.68 are consistent with a ZnOx(s)-like surface precipitate and possibly type B ternary surface complexes (i.e., >O2-Ox-Zn). EXAFS results are also consistent with the presence of ZnOx(s)-like precipitates. We ascribe the observed increase of Zn(II)(aq) uptake in the Zn(II)/Ox/HN ternary system at [Zn(II)(aq)]tot>or=4 mM relative to the Zn(II)/Ox/HM ternary system to formation of a ZnOx(s)-like precipitate at the hematite nanoparticle/water interface.

  7. Reforestation and landscape reconstruction in gypsum mine area from the semiarid region of NE Brazil

    Bittar, S. M. B.; Straaten, P. V.; de Araujo Vieura Santos, M. de Fatima; Agra Bezerra da Silva, Y. J.; da Silva, M.; Saraiva de Melo Pinheiro, T.; Gusmao Didier de Moraes, F.; de Aguiar Accioly, A. M.; Alves de Santana, S. R.; dos Santos, H. A.; de Carvalho, D. M.; de Lima Ferreira, G.; de Carvalho Santos, C.

    2012-04-01

    In the Araripe region, Northeast Brazil, exist the world's second largest reserve of gypsum, estimated at over than one billion tons, which accounts for 95% of the Brazilian production and constitutes an important segment of the regional economy. The gypsum deposit occurs in the Lower Cretaceous Santana Formation of the Araripe basin, which is constituted by siltstones, marls, limestones, shales and gypsum layers. The ore extraction is from an open pit, on simple benches with a height of about 15 meters. Activities in mining operations involve stripping, drilling, loading explosives, blast, fragmentation and block loading / transport. Currently, gypsum mining and processing results in major changes in the landscape (pits and wastes heaps sedimentary rocks and soil mixture), deforestation of the "caatinga" ecosystem for use as firewood in small calcinations, dust pollution and changes in hydrology. To promote environmental remediation of this area, a multidisciplinary research has being done with the aim to support reforestation at the wastes heaps. The study involved the following activities: collection and physical, chemical and mineralogical characterization of mine waste materials; a floristic survey around the mines (botanical identification and measuring physical parameters in 16 plots, in order to identify which species are best suited to the conditions of the substrate at the mine site); an experiment (randomized block design) developed in a greenhouse, where seedlings of various native tree species were grown in a "constructed soil" made up of gypsum waste combined with chicken, goat and cattle manure, aimed to select tree species and soil treatment to be used in a waste heap; and an assessment of water quality for irrigation of the reforestation areas. The waste materials consist of large clayey aggregates, which may present physical/chemical properties unfavorable for plant development. The mineralogy of the sand fraction (> 85% quartz, gypsum and

  8. Polymeric-SiO2-PCMs for improving the thermal properties of gypsum applied in energy efficient buildings

    Borreguero, Ana M.; Serrano, Angel; Garrido, Ignacio; Rodríguez, Juan F.; Carmona, Manuel

    2014-01-01

    Highlights: • Inorganic–organic PCM microcapsules were incorporated into gypsum. • The physical and thermal properties of the gypsum composites were studied. • The gypsum composites presented better properties than some previously investigated. • 10.20 kW h/operating cycle could be saved in a room with 1 m 3 of this material. • 1.26 kg of CO 2 emissions could be reduced per one operating cycle. - Abstract: A new thermoregulating material containing the commercial paraffin Rubitherm®RT27 stabilized by SiO 2 with a polymeric shell from polystyrene–divinylbenzene (Polymeric-SiO 2 -PCMs) was incorporated into gypsum up to a 15 mass ratio respect to the initial hemihydrate in order to develop building materials with a high thermal energy store (TES) capacity. The effect of this material on the gypsum crystals and the main physical, thermal and mechanical properties were studied and compared to those caused by another three kinds of thermoregulating materials. Polymeric-SiO 2 -PCMs presented the lowest agglomeration and therefore, the best distribution into the gypsum pores. As expected, the thermoregulating effect of the PCM improved the thermal properties of the gypsum since, the higher the microcapsules content, the higher the equivalent heat capacity (c p ) and the accumulated heat power (q acc ). Considering a conversion of 100% of the accumulated heat into electricity savings, the addition of a 15% of microcapsules respect to the hemihydrate allowed to save 10.20 kW h/m 3 and, consequently, reduced the CO 2 emissions in a 1.26 kg of CO 2 per operating cycle. Besides, the addition of the Polymeric-SiO 2 -PCMs reduces the gypsum density, but it is always higher than 600 kg/m 3 , as required by the European regulation EN 13279-2. The thermal conductivity (k) is also reduced by the microcapsules addition but for the case of a content of 15%. On the other hand, the porosity is barely affected just varying always less than a 3.5%. Finally, despite of the

  9. Evaluation of potential for mercury volatilization from natural and FGD gypsum products using flux-chamber tests.

    Shock, Scott S; Noggle, Jessica J; Bloom, Nicholas; Yost, Lisa J

    2009-04-01

    Synthetic gypsum produced by flue-gas desulfurization (FGD) in coal-fired power plants (FGD gypsum) is put to productive use in manufacturing wallboard. FGD gypsum wallboard is widely used, accounting for nearly 30% of wallboard sold in the United States. Mercury is captured in flue gas and thus is one of the trace metals present in FGD gypsum; raising questions about the potential for mercury exposure from wallboard. Mercury is also one of the trace metals present in "natural" mined gypsum used to make wall board. Data available in the literature were not adequate to assess whether mercury in wallboard from either FGD or natural gypsum could volatilize into indoor air. In this study, mercury volatilization was evaluated using small-scale (5 L) glass and Teflon flux chambers, with samples collected using both iodated carbon and gold-coated sand traps. Mercury flux measurements made using iodated carbon traps (n=6) were below the detection limit of 11.5 ng/m2-day for all natural and synthetic gypsum wallboard samples. Mercury flux measurements made using gold-coated sand traps (n=6) were 0.92 +/- 0.11 ng/m2-day for natural gypsum wallboard and 5.9 +/- 2.4 ng/m2-day for synthetic gypsum wallboard. Room air mercury concentrations between 0.028 and 0.28 ng/m3 and between 0.13 and 2.2 ng/m3 were estimated based on the flux-rate data for natural and synthetic gypsum wallboard samples, respectively, and were calculated assuming a 3 m x 4 m x 5 m room, and 10th and 90th percentile air exchange rates of 0.18/hour and 1.26/hour. The resulting concentration estimates are well below the U.S. Environmental Protection Agency (EPA) reference concentration for indoor air elemental mercury of 300 ng/m3 and the Agency for Toxic Substances and Disease Registry minimal risk level (MRL) of 200 ng/m3. Further, these estimates are below background mercury concentrations in indoor air and within or below the range of typical background mercury concentrations in outdoor air.

  10. The application of Lorentz transmission electron microscopy to the study of lamellar magnetism in hematite-ilmenite

    Kasama, Takeshi; Dunin-Borkowski, Rafal E.; Asaka, T

    2009-01-01

    . However, the magnitude of the experimental contrast is higher than that in the simulations, suggesting that an alternative origin for the observed asymmetry cannot be ruled out. Electron tomography was used to show that the lamellae have lens-like shapes and that (001) planes make up a significant...... in hematite. The likelihood that lamellar magnetism may be responsible for this contrast is assessed using simulations that incorporate interfacial magnetic moments on the (001) basal planes of hematite and ilmenite. The simulations suggest qualitatively that the asymmetric contrast is magnetic in origin...

  11. Biogenic processes in crystalline bedrock fractures indicated by carbon isotope signatures of secondary calcite

    Sahlstedt, Elina; Karhu, Juha A.; Pitkänen, Petteri; Whitehouse, Martin

    2016-01-01

    Variation in 13 C/ 12 C-isotope ratios of fracture filling calcite was analyzed in situ to investigate carbon sources and cycling in fractured bedrock. The study was conducted by separating sections of fracture fillings, and analyzing the 13 C/ 12 C-ratios with secondary ion mass spectrometry (SIMS). Specifically, the study was aimed at fillings where previously published sulfur isotope data indicated the occurrence of bacterial sulfate reduction. The results showed that the δ 13 C values of calcite were highly variable, ranging from −53.8‰ to +31.6‰ (VPDB). The analysis also showed high variations within single fillings of up to 39‰. The analyzed calcite fillings were mostly associated with two calcite groups, of which Group 3 represents possible Paleozoic fluid circulation, based on comparison with similar dated coatings within the Baltic Shield and the succeeding Group 1–2 fillings represent late-stage, low temperature mineralization and are possibly late Paleozoic to Quaternary in age. Both generations were associated with pyrite with δ 34 S values indicative of bacterial sulfate reduction. The δ 13 C values of calcite, however, were indicative of geochemical environments which were distinct for these generations. The δ 13 C values of Group 3 calcite varied from −22.1‰ to +11‰, with a distinct peak at −16‰ to −12‰. Furthermore, there were no observable depth dependent trends in the δ 13 C values of Group 3 calcite. The δ 13 C values of Group 3 calcite were indicative of organic matter degradation and methanogenesis. In contrast to the Group 3 fillings, the δ 13 C values of Group 1–2 calcite were highly variable, ranging from −53.8‰ to +31.6‰ and they showed systematic variation with depth. The near surface environment of <30 m (bsl) was characterized by δ 13 C values indicative of degradation of surface derived organic matter, with δ 13 C values ranging from −30.3‰ to −5.5‰. The intermediate depth of

  12. Thermal and Evolved Gas Behavior of Calcite Under Mars Phoenix TEGA Operating Conditions

    Ming, D.W.; Niles, P.B.; Morris, R.V.; Boynton, W.V.; Golden, D.C.; Lauer, H.V.; Sutter, B.

    2009-01-01

    The Mars Phoenix Scout Mission with its diverse instrument suite successfully examined several soils on the Northern plains of Mars. The Thermal and Evolved Gas Analyzer (TEGA) was employed to detect organic and inorganic materials by coupling a differential scanning calorimeter (DSC) with a magnetic-sector mass spectrometer (MS). Martian soil was heated up to 1000 C in the DSC ovens and evolved gases from mineral decomposition products were examined with the MS. TEGA s DSC has the capability to detect endothermic and exothermic reactions during heating that are characteristic of minerals present in the Martian soil. Initial TEGA results indicated the presence of endothermic peaks with onset temperatures that ranged from 675 C to 750 C with corresponding CO2 release. This result suggests the presence of calcite (CaCO3. CaO + CO2). Organic combustion to CO2 is not likely since this mostly occurs at temperatures below 550 C. Fe-carbonate and Mg-carbonate are not likely because their decomposition temperatures are less than 600 C. TEGA enthalpy determinations suggest that calcite, may occur in the Martian soil in concentrations of approx.1 to 5 wt. %. The detection of calcite could be questioned based on previous results that suggest Mars soils are mostly acidic. However, the Phoenix landing site soil pH was measured at pH 8.3 0.5, which is typical of terrestrial soils where pH is controlled by calcite solubility. The range of onset temperatures and calcite concentration as calculated by TEGA is poorly con-strained in part because of limited thermal data of cal-cite at reduced pressures. TEGA operates at calcite literature thermal data was obtained at 1000 mbar or higher pressures.

  13. FORMATION OF CALCITE AND SILICA FROM PERCOLATION IN A HYDROLOGICALLY UNSATURATED SETTING, YUCCA MOUNTAIN, NEVADA

    Paces, J.B.; Whelan, J.F.; Peterman, Z.E.; Marshall, B.D.

    2000-01-01

    Geological, mineralogical, chemical, and isotopic evidence from coatings of calcite and silica on open fractures and lithophysal cavities within welded tuffs at Yucca Mountain indicate an origin from meteoric water percolating through a thick (500 to 700 m) unsaturated zone (UZ) rather than from pulses of ascending ground water. Geologic evidence for a UZ setting includes the presence of coatings in only a small percentage of cavities, the restriction of coatings to fracture footwalls and cavity floors, and an absence of mineral high-water marks indicative of water ponding. Systematic mineral sequences (early calcite, followed by chalcedony with minor quartz and fluorite, and finally calcite with intercalated opal forming the bulk of the coatings) indicate progressive changes in UZ conditions through time, rather than repeated saturation by flooding. Percolation under the influence of gravity also results in mineral textures that vary between steeply dipping sites (thinner coatings of blocky calcite) and shallowly dipping sites (thicker coatings of coarse, commonly bladed calcite, with globules and sheets of opal). Micrometer-scale growth banding in both calcite and opal reflects slow average growth rates (scale of mm/m.y.) over millions of years rather than only a few rapidly deposited growth episodes. Isotopic compositions of C, O, Sr, and U from calcite and opal indicate a percolation-modified meteoric water source, and collectively refute a deeper ground-water source. Chemical and isotopic variations in coatings also indicate long-term evolution of water compositions. Although some compositional changes are related to shifts in climate, growth rates in the deeper UZ are buffered from large changes in meteoric input. Coatings most likely formed from films of water flowing down connected fracture pathways. Mineral precipitation is consistent with water vapor and carbon dioxide loss from films at very slow rates. Data collectively indicate that mineral coatings

  14. Why does carbon increase in highly weathered soil under no-till upon lime and gypsum use?

    Inagaki, Thiago Massao; de Moraes Sá, João Carlos; Caires, Eduardo Fávero; Gonçalves, Daniel Ruiz Potma

    2017-12-01

    Field experiments have been used to explain how soil organic carbon (SOC) dynamics is affected by lime and gypsum applications, however, how SOC storage occurs is still debatable. We hypothesized that although many studies conclude that Ca-based soil amendments such as lime and gypsum may lead to SOC depletion due to the enhancement of microbial activity, the same does not occur under conservation agriculture conditions. Thus, the objective of this study was to elucidate the effects of lime and gypsum applications on soil microbial activity and SOC stocks in a no-till field and in a laboratory incubation study simulating no-till conditions. The field experiment was established in 1998 in a clayey Oxisol in southern Brazil following a completely randomized blocks design with a split-plot arrangement and three replications. Lime and gypsum were surface applied in 1998 and reapplied in 2013. Undisturbed soil samples were collected before the treatments reapplications, and one year after. The incubation experiment was carried out during 16months using these samples adding crop residues on the soil surface to simulate no-till field conditions. Lime and gypsum applications significantly increased the labile SOC stocks, microbial activity and soil fertility attributes in both field and laboratory experiments. Although the microbial activity was increased, no depletion of SOC stocks was observed in both experiments. Positive correlations were observed between microbial activity increase and SOC gains. Labile SOC and Ca 2+ content increase leads to forming complex with mineral soil fractions. Gypsum applications performed a higher influence on labile SOC pools in the field than in the laboratory experiment, which may be related to the presence of active root system in the soil profile. We conclude that incubation experiments using lime and gypsum in undisturbed samples confirm that soil microbial activity increase does not deplete SOC stocks under conservation agriculture

  15. Mechanism of Calcite Co-Orientation in the Sea Urchin Tooth

    Killian, Christopher; Metzler, Rebecca; Gong, Y. U. T.; Olson, Ian; Aizenberg, Joanna; Politi, Yael; Wilt, Fred; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan; Gilbert, P. U. P. A.

    2009-12-01

    Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO{sub 3}) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin (Strongylocentrotus purpuratus), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction ({mu}XRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO{sub 3} is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

  16. Selective adsorption of benzhydroxamic acid on fluorite rendering selective separation of fluorite/calcite

    Jiang, Wei; Gao, Zhiyong; Khoso, Sultan Ahmed; Gao, Jiande; Sun, Wei; Pu, Wei; Hu, Yuehua

    2018-03-01

    Fluorite, a chief source of fluorine in the nature, usually coexists with calcite mineral in ore deposits. Worldwide, flotation techniques with a selective collector and/or a selective depressant are commonly preferred for the separation of fluorite from calcite. In the present study, an attempt was made to use benzhydroxamic acid (BHA) as a collector for the selective separation of fluorite from calcite without using any depressant. Results obtained from the flotation experiments for single mineral and mixed binary minerals revealed that the BHA has a good selective collecting ability for the fluorite when 50 mg/L of BHA was used at pH of 9. The results from the zeta potential and X-ray photoelectron spectroscopy (XPS) indicated that the BHA easily chemisorbs onto the fluorite as compared to calcite. Crystal chemistry calculations showed the larger Ca density and the higher Ca activity on fluorite surface mainly account for the selective adsorption of BHA on fluorite, leading to the selective separation of fluorite from calcite. Moreover, a stronger hydrogen bonding with BHA and the weaker electrostatic repulsion with BHA- also contribute to the stronger interaction of BHA species with fluorite surface.

  17. Selective Separation of Fluorite, Barite and Calcite with Valonea Extract and Sodium Fluosilicate as Depressants

    Zijie Ren

    2017-02-01

    Full Text Available Fluorite, barite and calcite are important industry minerals. However, they often co-exist, presenting difficulty in selectively separating them due to their similar surface properties. In this study, valonea extract and sodium fluosilicate were used as depressants to selectively separate them by flotation, with sodium oleate as the collector. The single mineral flotation results showed that valonea extract displayed the strongest depression on calcite, while sodium fluosilicate displayed the strongest depression on barite. These two depressants allowed selective separation of the three minerals through sequential flotation. The flotation of mixed minerals showed that 94% of the calcite was successfully depressed by the valonea extract, and 95% recovery of the fluorite was achieved in the subsequent flotation with sodium fluosilicate depressing barite. The different depressant–mineral interactions were investigated via electro-kinetic studies and molecular dynamics (MD simulations using the Materials Studio 6.0 program. The valonea extract exhibited the strongest adsorption on the calcite surface, and sodium fluosilicate exhibited the strongest adsorption on the barite surface, which prevented oleate species from reacting with Ca2+ or Ba2+ surface sites. This study provides useful guidance for how to process fluorite, barite and calcite resources.

  18. Sequestration of Antimony on Calcite Observed by Time-Resolved Nanoscale Imaging.

    Renard, François; Putnis, Christine V; Montes-Hernandez, German; King, Helen E; Breedveld, Gijs D; Okkenhaug, Gudny

    2018-01-02

    Antimony, which has damaging effects on the human body and the ecosystem, can be released into soils, ground-, and surface waters either from ore minerals that weather in near surface environments, or due to anthropogenic releases from waste rich in antimony, a component used in batteries, electronics, ammunitions, plastics, and many other industrial applications. Here, we show that dissolved Sb can interact with calcite, a widespread carbonate mineral, through a coupled dissolution-precipitation mechanism. The process is imaged in situ, at room temperature, at the nanometer scale by using an atomic force microscope equipped with a flow-through cell. Time-resolved imaging allowed following the coupled process of calcite dissolution, nucleation of precipitates at the calcite surface and growth of these precipitates. Sb(V) forms a precipitate, whereas Sb(III) needs to be oxidized to Sb(V) before being incorporated in the new phase. Scanning-electron microscopy and Raman spectroscopy allowed identification of the precipitates as two different calcium-antimony phases (Ca 2 Sb 2 O 7 ). This coupled dissolution-precipitation process that occurs in a boundary layer at the calcite surface can sequester Sb as a solid phase on calcite, which has environmental implications as it may reduce the mobility of this hazardous compound in soils and groundwaters.

  19. The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite.

    Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Benning, Liane G

    2011-01-01

    The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

  20. Sorption of phosphate onto calcite; results from batch experiments and surface complexation modeling

    Sø, Helle Ugilt; Postma, Dieke; Jakobsen, Rasmus

    2011-01-01

    The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3h) and low concentrations of phosphate (⩽50μM). Sorption of phosphate on calcite was stud......The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3h) and low concentrations of phosphate (⩽50μM). Sorption of phosphate on calcite...... of a high degree of super-saturation with respect to hydroxyapatite (SIHAP⩽7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the CO32- activity decreases (at constant pH) and as pH increases (at constant CO32- activity). The primary effect...... of ionic strength on phosphate sorption onto calcite is its influence on the activity of the different aqueous phosphate species. The experimental results were modeled satisfactorily using the constant capacitance model with >CaPO4Ca0 and either >CaHPO4Ca+ or >CaHPO4- as the adsorbed surface species...

  1. Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations.

    Wetzel, Maria; Kempka, Thomas; Kühn, Michael

    2018-04-01

    The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution.

  2. Mechanism of Methane Chemical Looping Combustion with Hematite Promoted with CeO 2

    Miller, Duane D.; Siriwardane, Ranjani

    2013-08-15

    Chemical looping combustion (CLC) is a promising technology for fossil fuel combustion that produces sequestration-ready CO{sub 2} stream, reducing the energy penalty of CO{sub 2} separation from flue gases. An effective oxygen carrier for CLC will readily react with the fuel gas and will be reoxidized upon contact with oxygen. This study investigated the development of a CeO{sub 2}-promoted Fe{sub 2}O{sub 3}-hematite oxygen carrier suitable for the methane CLC process. Composition of CeO{sub 2} is between 5 and 25 wt % and is lower than what is generally used for supports in Fe{sub 2}O{sub 3} carrier preparations. The incorporation of CeO{sub 2} to the natural ore hematite strongly modifies the reduction behavior in comparison to that of CeO{sub 2} and hematite alone. Temperature-programmed reaction studies revealed that the addition of even 5 wt % CeO{sub 2} enhances the reaction capacity of the Fe{sub 2}O{sub 3} oxygen carrier by promoting the decomposition and partial oxidation of methane. Fixed-bed reactor data showed that the 5 wt % cerium oxides with 95 wt % iron oxide produce 2 times as much carbon dioxide in comparison to the sum of carbon dioxide produced when the oxides were tested separately. This effect is likely due to the reaction of CeO{sub 2} with methane forming intermediates, which are reactive for extracting oxygen from Fe{sub 2}O{sub 3} at a considerably faster rate than the rate of the direct reaction of Fe{sub 2}O{sub 3} with methane. These studies reveal that 5 wt % CeO{sub 2}/Fe{sub 2}O{sub 3} gives stable conversions over 15 reduction/oxidation cycles. Lab-scale reactor studies (pulsed mode) suggest the methane reacts initially with CeO{sub 2} lattice oxygen to form partial oxidation products (CO + H{sub 2}), which continue to react with oxygen from neighboring Fe{sub 2}O{sub 3}, leading to its complete oxidation to form CO{sub 2}. The reduced cerium oxide promotes the methane decomposition reaction to form C + H{sub 2}, which continue to

  3. Competitive adsorption of arsenate and phosphate onto calcite; experimental results and modeling with CCM and CD-MUSIC

    Sø, Helle Ugilt; Postma, Dieke; Jakobsen, Rasmus

    2012-01-01

    The competitive adsorption of arsenate and phosphate onto calcite was studied in batch experiments using calcite-equilibrated solutions. The solutions had circum-neutral pH (7–8.3) and covered a wide span in the activity of Ca2+ and View the MathML source. The results show that the adsorption...... that adsorption of arsenate onto calcite is of minor importance in most groundwater aquifers, as phosphate is often present at concentration levels sufficient to significantly reduce arsenate adsorption. The CD-MUSIC model for calcite was used successfully to model adsorption of arsenate and phosphate separately...

  4. Hematite Spherules in Basaltic Tephra Altered Under Aqueous, Acid-Sulfate Conditions on Mauna Kea Volcano, Hawaii: Possible Clues for the Occurrence of Hematite-Rich Spherules in the Burns Formation at Meridiani Planum, Mars

    Morris, R. V.; Ming, D. W.; Graff, T. G.; Arvidson, R. E.; Bell, J. F., III; Squyres, S. W.; Mertzman, S. A.; Gruener, J. E.; Golden, D. C.; Robinson, G. A.

    2005-01-01

    Iron-rich spherules (>90% Fe2O3 from electron microprobe analyses) approx.10-100 microns in diameter are found within sulfate-rich rocks formed by aqueous, acid-sulfate alteration of basaltic tephra on Mauna Kea volcano, Hawaii. Although some spherules are nearly pure Fe, most have two concentric compositional zones, with the core having a higher Fe/Al ratio than the rim. Oxide totals less than 100% (93-99%) suggest structural H2O and/or /OH. The transmission Moessbauer spectrum of a spherule-rich separate is dominated by a hematite (alpha-Fe2O3) sextet whose peaks are skewed toward zero velocity. Skewing is consistent with Al(3+) for Fe(3+) substitution and structural H2O and/or /OH. The grey color of the spherules implies specular hematite. Whole-rock powder X-ray diffraction spectra are dominated by peaks from smectite and the hydroxy sulfate mineral natroalunite as alteration products and plagioclase feldspar that was present in the precursor basaltic tephra. Whether spherule formation proceeded directly from basaltic material in one event (dissolution of basaltic material and precipitation of hematite spherules) or whether spherule formation required more than one event (formation of Fe-bearing sulfate rock and subsequent hydrolysis to hematite) is not currently constrained. By analogy, a formation pathway for the hematite spherules in sulfate-rich outcrops at Meridiani Planum on Mars (the Burns formation) is aqueous alteration of basaltic precursor material under acid-sulfate conditions. Although hydrothermal conditions are present on Mauna Kea, such conditions may not be required for spherule formation on Mars if the time interval for hydrolysis at lower temperatures is sufficiently long.

  5. Liquid Adsorption of Organic Compounds on Hematite α-Fe2O3 Using ReaxFF.

    Chia, Chung-Lim; Avendaño, Carlos; Siperstein, Flor R; Filip, Sorin

    2017-10-24

    ReaxFF-based molecular dynamics simulations are used in this work to study the effect of the polarity of adsorbed molecules in the liquid phase on the structure and polarization of hematite (α-Fe 2 O 3 ). We compared the adsorption of organic molecules with different polarities on a rigid hematite surface and on a flexible and polarizable surface. We show that the displacements of surface atoms and surface polarization in a flexible hematite model are proportional to the adsorbed molecule's polarity. The increase in electrostatic interactions resulting from charge transfer in the outermost solid atoms in a flexible hematite model results in better-defined adsorbed layers that are less ordered than those obtained assuming a rigid solid. These results suggest that care must be taken when parametrizing empirical transferable force fields because the calculated charges on a solid slab in vacuum may not be representative of a real system, especially when the solid is in contact with a polar liquid.

  6. Natural Hematite and Siderite as Heterogeneous Catalysts for an Effective Degradation of 4-Chlorophenol via Photo-Fenton Process

    Haithem Bel Hadjltaief

    2018-06-01

    Full Text Available This paper describes a simple and low-cost process for the degradation of 4-Chlorophenol (4-CP from aqueous solution, using natural Tunisian Hematite (M1 and Siderite (M2. Two natural samples were collected in the outcroppings of the Djerissa mining site (Kef district, northwestern Tunisia. Both Hematite and Siderite ferrous samples were characterized using several techniques, including X-Ray Diffraction (XRD, Nitrogen Physisorption (BET, Infrared Spectroscopy (FTIR, H2-Temperature Programmed Reduction (H2-TPR, Scanning Electronic Microscopy (SEM linked with Energy Dispersive X-ray (EDS and High-Resolution Transmission Electron Microscopy (HRTEM. Textural, structural and chemical characterization confirmed the presence of Hematite and Siderite phases with a high amount of iron on the both surface materials. Their activity was evaluated in the oxidation of 4-CP in aqueous medium under heterogeneous photo-Fenton process. Siderite exhibited higher photocatalytic oxidation activity than Hematite at pH 3. The experimental results also showed that 100% conversion of 4-CP and 54% TOC removal can be achieved using Siderite as catalyst. Negligible metal leaching and catalyst reutilization without any loss of activity point towards an excellent catalytic stability for both natural catalysts.

  7. Role of Ion Bombardment, Film Thickness and Temperature of Annealing on PEC Activity of Very-thin Film Hematite .

    Kment, Š.; Čada, M.; Hubička, Z.; Krýsa, J.; Kmentová, Hana; Olejníček, J.; Zlámalová Cílová, Z.; Zbořil, R.

    2016-01-01

    Roč. 41, č. 27 (2016), s. 11547-11557 ISSN 0360-3199. [International Conference on Hydrogen Energy /1./. Aveiro, 20.07.2015-22.07.2015] Institutional support: RVO:67985858 Keywords : ion flux density * hematite photoanode * thin films Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.582, year: 2016

  8. Characteristics of NixFe1−xOy Electrocatalyst on Hematite as Photoanode for Solar Hydrogen Production

    Chih-Ping Yen

    2017-11-01

    Full Text Available The use of hematite as the photoanode for photoelectrochemical hydrogen production by solar energy has been actively studied due to its abundance, stability, and adequate optical properties. Deposition of an electrocatalyst overlayer on the hematite may increase kinetics and lower the onset potential for water splitting. NixFe1−xOy is one of the most effective electrocatalysts reported for this purpose. However, the condition and results of the previous reports vary significantly, and a comprehensive model for NixFe1−xOy/hematite is lacking. Here, we report a simple and novel chemical bath deposition method for depositing low-onset-potential NixFe1−xOy electrocatalyst on hematite. With a Ni percentage of 80% and an immersion time of 2 min, the as-prepared NixFe1−xOy overlayer raised the photovoltage from 0.2 V to 0.7 V, leading to a cathodic shift of the onset potential by 400 mV, while maintaining the same level of current density. The dependence of the electrochemical and photoelectrochemical characteristics of the photoanode on the condition of the electrocatalyst was studied systematically and explained based on energy level diagrams and kinetics.

  9. Photoanodes with fully controllable texture: the enhanced water splitting efficiency of thin hematite films exhibiting solely (110) crystal orientation

    Kment, Š.; Schmuki, P.; Hubička, Zdeněk; Machala, L.; Kirchgeorg, R.; Liu, N.; Wang, L.; Lee, K.; Olejníček, Jiří; Čada, Martin; Gregora, Ivan; Zbořil, R.

    2015-01-01

    Roč. 9, č. 7 (2015), s. 7113-7123 ISSN 1936-0851 R&D Projects: GA MŠk LH12043 Institutional support: RVO:68378271 Keywords : hematite * iron oxide * texture * PEC water splitting * pulsed magnetron sputtering * conversion electron Mössbauer spectroscopy Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 13.334, year: 2015

  10. Fate of gypsum-sulphur applied to soybean on Typic haplustepts

    Saharan, Neelam; Rattan, R.K.

    2004-01-01

    Field experiments were conducted on the sulphur-deficient Typic Haplustepts of the IARI farm for two consecutive, kharif seasons viz. 1996 and 1997 with soybean cultivar Pusa 22 as the crop. Varying rates of S as gypsum were basally applied in the main plots adjacent to the micro plots (1 m x 1 m) to quantify the partitioning of the fertilizer-sulphur taken up by soybean and its distribution in the soil profile. Soybean responded to the application of sulphur, with increase in yield being obtained up to rate of 40 kg S ha -1 . Data computed on distribution of the S derived from labelled gypsum and percent S utilization by the soybean crop increased from 13.23 and 4.15 to 23.41 and 6.39, respectively. During 1996, the per cent utilization of labelled S ranged from 5.6 to 8.8. Monitoring of added sulphur in the soil profile up to a depth of 1 m revealed maximum accumulation of the added S in 30-60 cm soil layer. With the help of 35 S around 11 to 18 per cent of the added S was traced in 60-100 cm soil layer. It can be concluded from the data for two years that during kharif season the application of S through water soluble sources like ammonium sulphate and ammonium phosphate sulphate should be avoided because even S from the sparingly soluble gypsum migrated to a depth of 1 m during the cropping season. (author)

  11. High Levels of Antibiotic Resistance but No Antibiotic Production Detected Along a Gypsum Gradient in Great Onyx Cave, KY, USA

    Kathleen Lavoie

    2017-09-01

    Full Text Available A preliminary study of antibiotic production and antibiotic resistance was conducted in Great Onyx Cave in Mammoth Cave National Park, KY, to determine if gypsum (CaSO4∙2H2O affects these bacterial activities. The cave crosses through the width of Flint Ridge, and passages under the sandstone caprock are dry with different amounts of gypsum. The Great Kentucky Desert hypothesis posits that gypsum limits the distribution of invertebrates in the central areas of Great Onyx Cave. Twenty-four bacterial isolates were cultivated from swabs and soils. Using three methods (soil crumb, soil crumb with indicator bacteria, and the cross-streak method using isolated bacteria we did not detect any production of antibiotics. Antibiotic resistance was widespread, with all 24 isolates resistant to a minimum of two antibiotics of seven tested, with three isolates resistant to all. Antibiotic resistance was high and not correlated with depth into the cave or the amount of gypsum. The Great Kentucky Desert hypothesis of the negative effects of gypsum seems to have no impact on bacterial activity.

  12. The impact of gypsum mine water: A case study on morphology and DNA integrity in the freshwater invertebrate, Gammarus balcanicus

    Ternjej, Ivančica; Mihaljević, Zlatko; Ivković, Marija; Previšić, Ana; Stanković, Igor; Maldini, Krešimir; Želježić, Davor; Kopjar, Nevenka

    2014-01-01

    The aim of our study was to investigate how exposure to heavy metal-rich waters from gypsum mining affects the morphology and levels of primary DNA damage in Gammarus balcanicus. Chemical analysis revealed increased concentrations of metals in water and sediment collected at a site impacted by gypsum mine wastewaters. The specimens also showed elevated total tissue metal levels when compared with the organisms collected at the reference site. The most prominent increase was observed for strontium, followed by iron, nickel, vanadium, aluminium, and manganese. The major pathway of entry for these toxic substances was through the degraded exoskeleton as a consequence of excessive strontium input (unbalanced calcium/strontium ratio) and altered permeability. Disturbed exoskeleton integrity was observed only in individuals collected downstream of the gypsum mine, which was confirmed by electron microscopy. Levels of primary DNA damage were evaluated using the alkaline comet assay in the haemolymph of the specimens. - Highlights: • Our findings suggest toxic potential of gypsum mine wastewaters. • The Gammarus specimens showed elevated total tissue metal levels. • Strontium uptake disturbed exoskeleton integrity. • Corrupted cuticle altered permeability to other toxic substances. • Combined effects of all contaminants caused genotoxicity. - Gypsum mine wastewaters have genotoxic potential and affect the gammarid exoskeleton morphology and biochemistry associated with a high strontium uptake

  13. Estimates of the radiation dose from phospho-gypsum plaster-board if used in domestic buildings

    O'Brien, R.S.; Peggie, J.R.; Leith, I.S.

    1991-02-01

    This report presents the results of a study carried out to estimate the annual effective dose equivalent contribution from phospho-gypsum plaster-board if it were used as an internal lining in buildings. The study considered four sources of radiation exposure that would arise in such use, such as inhalation of 222 Rn and its daughters, inhalation of phospho-gypsum dust and exposure to beta and gamma radiation. Measurements of the 22 6Ra content and 222 Rn exhalation rate were made for a number of samples of phospho-gypsum plaster-board, and the behaviour of 222 Rn and its daughters in a typical building was modelled. The results of the study suggest that, for building ventilation rates greater than approximately 0.5 air changes per hour, the contribution to the total annual effective dose equivalent from inhalation of radon ( 222 Rn) and its daughters ( 218 Po, 214 Pb, 214 Po) exhaled from the phospho-gypsum plaster-board should be well below the recommended limit of 1 milli-Sievert for members of the public. The total annual effective dose equivalent from all these sources should be less than 0.6 milli-Sieverts, provided reasonable work practices are observed during installation of the phospho-gypsum plaster-board and the ventilation rate is kept above approximately 0.5 air changes per hour. 31 refs., 12 tabs., 5 figs

  14. Physical and mechanical characterization of gypsum boards containing phase change materials for latent heat storage

    Oliver-Ramírez, A.

    2011-09-01

    Full Text Available This article describes the design and manufacture of a gypsum board which, despite its 45 % wt content of phase change materials, meets the minimum physical and mechanical requirements laid down in the legislation on gypsum plasters (Spanish and European standard UNE EN 13279 and Spanish specifications for gypsum acceptance, RY 85. Under this design, a one-metre square, 1.5-cm thick board contains 4.75 kg of PCM, much more than in any prior drylining (the maximum attained to date is 3 kg per m2. The mechanical and physical characteristics of this new composite were previously improved with two joint-action additives: polypropylene fibres and melamine formaldehyde as a dispersing agent. In the 20-30 ºC temperature range, a gypsum board 1.5 cm thick containing this percentage of PCMs can store five times more thermal energy than conventional plasterboard of the same thickness, and the same amount of energy as half-foot hollow brick masonry.

    En esta investigación se ha diseñado y fabricado un panel de escayola que incorpora un 45% en peso de material de cambio de fase, manteniendo las propiedades físicas y mecánicas exigidas en la normativa de aplicación para yesos de construcción (UNE EN 13279 y referencias a la RY 85. Así, un panel de 1,0 m2 y 1,5 cm de espesor, contiene 4,75 kg de PCM, cantidad muy superior a la conseguida hasta la fecha (3 kg/m2. Para ello se ha mejorado previamente sus prestaciones mecánicas y físicas mediante adiciones binarias: fibras de polipropileno y dispersión de melanina formaldehído. Este porcentaje es capaz de almacenar en 1,5 cm de espesor cinco veces la energía térmica de un panel de cartón yeso con el mismo espesor y la misma cantidad que una fábrica de 1/2 pie de ladrillo hueco, en el rango de temperaturas próximas a la de confort (20-30 ºC.

  15. Luminescence rigidochromism as a probe for the setting of gypsum plaster

    Kunkely, Horst; Vogler, Arnd

    2008-01-01

    The setting of gypsum plaster can be monitored by luminescence rigidochromism. The progress of the setting process which is accompanied by hardening is indicated by a blue shift of the phosphorescence of a suitable water soluble rhenium complex. This rigidity increase of the plaster/water mixture takes place in two phases. In the beginning the rigidity increase is rather large while in the second much longer phase it is relatively small. The addition of a plasticizer (or retarder) keeps the rigidity smaller in the beginning, but only slightly affects the final rigidity of the set plaster

  16. Climatic control on the growth of gigantic gypsum crystals within hypogenic caves (Naica mine, Mexico)?

    Garofalo, Paolo S.; Fricker, Mattias B.; Günther, Detlef; Forti, Paolo; Mercuri, Anna-Maria; Loreti, Mara; Capaccioni, Bruno

    2010-01-01

    Three hypogenic caves within the Naica mine of Mexico ( Cueva de los Cristales — CLC, Ojo de la Reina — OR, and Cueva de las Velas — CLV) host spectacular gypsum crystals up to 11 m in length. These caves are close to another shallow cave of the area ( Cueva de las Espadas — CLE), with which they cover a 160 m-deep vertical section of the local drainage basin. Similar to other hypogenic caves, all these caves lack a direct connection with the land surface and should be unrelated with climate. A record of multi-technique fluid inclusion data and pollen spectra from cave and mine gypsum indicates surprisingly that climatic changes occurring at Naica could have controlled fluid composition in these caves, and hence crystal growth. Microthermometry and LA-ICP-Mass Spectrometry of fluid inclusions indicate that the shallow, chemically peculiar, saline fluid (up to 7.7 eq. wt.%NaCl) of CLE could have formed from evaporation, during a dry and hot climatic period. The fluid of the deep caves was instead of low salinity (˜ 3.5 eq. wt.% NaCl) and chemically homogeneous, and was poorly affected by evaporation. We propose that mixing of these two fluids, generated at different depths of the Naica drainage basin, determined the stable supersaturation conditions for the gigantic gypsum crystals to grow. Fluid mixing was controlled by the hydraulic communication between CLE and the other deep caves, and must have taken place during cycles of warm-dry and fresh-wet climatic periods, which are known to have occurred in the region. Pollen grains from a 35 ka-old gypsum crystal of CLC corresponds to a fairly homogenous catchment basin made of a mixed broadleaf wet forest, which suggests precipitation during a fresh-wet climatic period and confirms our interpretation of the fluid inclusion data. The unusual combination of geological and geochemical factors of Naica suggests that other hypogenic caves found elsewhere may not host similar crystals. However, this work shows that

  17. Compact hematite buffer layer as a promoter of nanorod photoanode performances

    Milan, R.; Cattarin, S.; Comisso, N.; Baratto, C.; Kaunisto, K.; Tkachenko, N. V.; Concina, I.

    2016-10-01

    The effect of a thin α-Fe2O3 compact buffer layer (BL) on the photoelectrochemical performances of a bare α-Fe2O3 nanorods photoanode is investigated. The BL is prepared through a simple spray deposition onto a fluorine-doped tin oxide (FTO) conducting glass substrate before the growth of a α-Fe2O3 nanorods via a hydrothermal process. Insertion of the hematite BL between the FTO and the nanorods markedly enhances the generated photocurrent, by limiting undesired losses of photogenerated charges at the FTO||electrolyte interface. The proposed approach warrants a marked improvement of material performances, with no additional thermal treatment and no use/dispersion of rare or toxic species, in agreement with the principles of green chemistry.

  18. Nanocrack Formation in Hematite through the Dehydration of Goethite and the Carbon Infiltration from Biotar

    Yoshiaki Kashiwaya

    2010-01-01

    Full Text Available The cracks in nano-order are generated and propagated when the combined water is released during the dehydration. If the nanopore can be utilized for a reaction site, the overall reaction can be extremely accelerated. On the other hand, it is well known that woody biomass is an attractive alternative fuel for the reduction of CO2 emission. However, the process of biomass pyrolysis is disturbed by the tar which causes a clogging in gas tubing system. Hata et al. found that the tar was consumed almost 100% in the iron ore layer having nanocrack or nanopore. The nanocracks formed in hematite crystals after dehydration of goethite were about 4 nm in width, which is in excellent agreement with the result of BET measurement. When the carbon deposited from tar into the nanocracks, reduction reactions were occurred simultaneously. The deposited carbons completely infilled into the nanocracks and the void in the sample.

  19. Index of refraction enhancement of calcite particles coated with zinc carbonate

    Lattaud, Kathleen; Vilminot, Serge; Hirlimann, Charles; Parant, Hubert; Schoelkopf, Joachim; Gane, Patrick

    2006-10-01

    ZnCO 3 coating on calcite particles has been developed in order to enhance the index of refraction of this mineral that is used as a charge in paper, paint and polymer industries. Chemical reaction between calcite particles in an aqueous suspension with zinc chloride promotes the formation of a ZnCO 3 coating consisting of two layers with different interactions with the calcite particle. The refraction index of the resulting composite particles increases with the Zn/Ca ratio. A model allows to evaluate the coating thickness. The value of the scattering S and diffusion K coefficients of sheets coated with the ZnCO 3 coated particles reveal a dependence on the preparation conditions with a 15% increase for the best samples.

  20. Thermoluminescence and cathodoluminescence studies of calcite and MgO: surface defects and heat treatment

    Goeksu, H.Y.; Brown, L.M.

    1988-01-01

    Some of the problems which preclude accurate thermoluminescence (TL) dating of geologically formed calcite stem from different sample pre-treatment procedures, such as grinding, drilling or pre-heating. It has long been known that grinding can introduce spurious TL in calcite, but there have been wide differences of opinion as to the magnitude of the influence and its importance. Therefore, various grinding and acid-washing procedures have been suggested to avoid spurious thermoluminescence. Various models have been developed to explain the mechanism. We have studied the changes in thermoluminescence (TL) and cathodoluminescence (CL) properties as well as in the spectral composition of the glow from calcite and MgO due to surface defects and heat treatment. It is found that both laboratory heat treatment and surface indents give rise to changes in TL efficiency. (author)