Preferential adhesion of surface groups of Bacillus subtilis on gibbsite at different ionic strengths and pHs revealed by ATR-FTIR spectroscopy.

PubMed

Hong, Zhi-Neng; Jiang, Jun; Li, Jiu-Yu; Xu, Ren-Kou

2018-05-01

Adhesion of bacteria onto minerals is a ubiquitous process that plays a central role in many biogeochemical, microbiology and environmental processes in soil and sediment. Although bacterial adhesion onto soil minerals such as phyllosilicates and Fe-oxides have been investigated extensively, little is known about the mechanisms for bacterial attachment onto Al-oxides. Here, we explored the adhesion of Bacillus subtilis onto gibbsite (γ-AlOOH) under various ionic strengths (1, 10, 50, and 100 mM NaCl) and pHs (pH 4, 7, and 9) by in-situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The time evolution of the peak intensities of the attached bacteria suggested that the adhesion underwent an initial rapid reaction followed by a slow pseudo-first-order kinetic stage. Spectral comparison between the attached and free cells, together with the interaction energy calculated with the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory and the micro-morphology of bacteria-gibbsite complexes, indicated that both electrostatic and chemical (bacterial groups such as phosphate and carboxyl covalently bind to gibbsite) interactions participated in the adhesion processes. Both solution ionic strength (IS) and pH impacted the spectra of attached bacteria, but the peak intensity of different bands changed differently with these two factors, showing a preferential adhesion of surface groups (phosphate, carboxyl, and amide groups) on gibbsite at different conditions. The diverse responses to IS and pH alteration of the forces (chemical bonds, electrostatic attractions, and the hydrophobic interactions) that essentially govern the adhesion might be responsible for the preferential adhesion. These results may help to better understand how bacteria adhere onto soil oxides at molecular scales. Copyright © 2018 Elsevier B.V. All rights reserved.

Radiolytic stability of gibbsite and boehmite with adsorbed water

NASA Astrophysics Data System (ADS)

Huestis, Patricia; Pearce, Carolyn I.; Zhang, X.; N'Diaye, Alpha T.; Rosso, Kevin M.; LaVerne, Jay A.

2018-04-01

Aluminum oxyhydroxide (boehmite, AlOOH) and aluminum hydroxide (gibbsite, Al(OH)3) powders with adsorbed water were irradiated with γ-rays and 5 MeV He ions (α-particles) in order to determine overall radiation stability and chemical modification to the surface. No variation in overall phase or crystallinity due to radiolysis was observed with X-ray diffraction (XRD) and Raman spectroscopy for doses up to 2 MGy with γ-rays and 175 MGy with α-particles. Temperature programed desorption (TPD) of the water from the surface to the gas phase indicated that the water was chemisorbed and strongly bound. Water adsorption sites are of similar energy for both gibbsite and boehmite. Observation of the water adsorbed on the surface of gibbsite and boehmite with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed broad peaks at 3100-3600 cm-1 due to OH stretching that slowly decreased on heating to 500 °C, which corresponds well with the water vapor evolution observed with TPD. Both materials were found to be amorphous following heating to 500 °C. X-ray photoelectron spectroscopy (XPS) indicated surface reduction of Al(III) to Al metal on radiolysis with α-particles. Complete loss of chemisorbed water and the formation of bulk O atoms was observed following radiolysis with α-particles.

Radiolytic stability of gibbsite and boehmite with adsorbed water

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

Huestis, Patricia; Pearce, Carolyn I.; Zhang, X.

Aluminum oxyhydroxide (boehmite, AlOOH) and aluminum hydroxide (gibbsite, Al(OH)3) powders with adsorbed water were irradiated with -rays and 5 MeV He ions (α-particles) in order to determine overall radiation stability and chemical modification to the surface. No variation in overall phase or crystallinity due to radiolysis was observed with X-ray diffraction (XRD) and Raman spectroscopy for doses up to 2 MGy with -rays and 175 MGy with α-particles. Temperature programed desorption (TPD) of the water from the surface to the gas phase indicated that the water was chemisorbed and strongly bound. Water adsorption sites are of similar energy for bothmore » gibbsite and boehmite. Observation of the water adsorbed on the surface of gibbsite and boehmite with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed broad peaks at 3100-3600 cm-1 due to OH stretching that slowly decreased on heating to 500oC, which corresponds well with the water vapor evolution observed with TPD. Both materials were found to be amorphous following heating to 500oC. X-ray photoelectron spectroscopy (XPS) indicated surface reduction of Al(III) to Al metal on radiolysis with α-particles. Complete loss of chemisorbed water and the formation of bulk O atoms was observed following radiolysis with α-particles.« less

Free-Energy Landscape of the Dissolution of Gibbsite at High pH.

PubMed

Shen, Zhizhang; Kerisit, Sebastien N; Stack, Andrew G; Rosso, Kevin M

2018-04-05

The individual elementary reactions involved in the dissolution of a solid into solution remain mostly speculative due to a lack of direct experimental probes. In this regard, we have applied atomistic simulations to map the free-energy landscape of the dissolution of gibbsite from a step edge as a model of metal hydroxide dissolution. The overall reaction combines kink formation and kink propagation. Two individual reactions were found to be rate-limiting for kink formation, that is, the displacement of Al from a step site to a ledge adatom site and its detachment from ledge/terrace adatom sites into the solution. As a result, a pool of mobile and labile adsorbed species, or adatoms, exists before the release of Al into solution. Because of the quasi-hexagonal symmetry of gibbsite, kink site propagation can occur in multiple directions. Overall, our results will enable the development of microscopic mechanistic models of metal oxide dissolution.

A Quantitative Geochemical, Mineralogical and Physical Study of Some Selected Rock Weathering Profiles from Brazil

DTIC Science & Technology

1977-08-17

weather to gibbsite (plus or minus iron oxides) in well-drained, and smectite in poorly-drained, environments. Kaolinite found in the vicinity of quartz...rock and completely weathered saprolite. Quartz-rich rock types exhibit wide, gradational weathered zones and usually form kaolinite or halloysite in...free rocks is either formed by re-silication of gibbsite , or is of secondary origin (transported). Texture of the rock (aphanitic vs. phaneric) has

Free-Energy Landscape of the Dissolution of Gibbsite at High pH

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

Shen, Zhizhang; Kerisit, Sebastien N.; Stack, Andrew G.

The individual elementary reactions involved in the dissolution of a solid into solution remain mostly speculative due to a lack of suitable, direct experimental probes. In this regard, we have applied atomistic simulations to map the free energy landscape of the dissolution of gibbsite from a step edge, as a model of metal hydroxide dissolution. The overall reaction combines kink site formation and kink site propagation. Two individual reactions were found to be rate-limiting for kink site formation, that is, the displacement of Al from a step site to a ledge adatom site and its detachment from ledge/terrace adatom sitesmore » into the solution. As a result, a pool of mobile and labile Al adsorbed species, or adatoms, exists before the release of Al into solution. Because of the quasi-hexagonal symmetry of gibbsite, kink site propagation can occur in multiple directions. Overall, the simulation results will enable the development of microscopic mechanistic models of metal oxide dissolution.« less

Structural Characterization of Aluminum (Oxy)hydroxide Films at the Muscovite (001)–Water Interface

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

Lee, Sang Soo; Schmidt, Moritz; Fister, Timothy T.

2016-01-19

The formation of Al (oxy)hydroxide on the basal surface of muscovite mica was investigated to understand how the structure of the substrate controls the nucleation and growth of secondary phases. Atomic force microscopy images showed that solid phases nucleated on the surface initially as two-dimensional islands that were <= 10 angstrom in height and <= 200 angstrom in diameter after 16-50 h of reaction in a 100 mu M AlCl3 solution at pH 4.2 at room temperature. High-resolution X-ray reflectivity data indicated that these islands were gibbsite layers whose basic unit is composed of a plane of Al ions octahedrallymore » coordinated to oxygen or hydroxyl groups. The formation of gibbsite layers is likely favored because of the structural similarity between its basal plane and the underlying mica surface. After 700-2000 h of reaction, a thicker and continuous film had formed on top of the initial gibbsite layers. X-ray diffraction data showed that this film was composed of diaspore that grew predominantly with its [040] and [140] crystallographic directions oriented along the muscovite [001] direction. These results show the structural characteristics of the muscovite (001) and Al (oxy)hydroxide film interface where presumed epitaxy had facilitated nucleation of metastable gibbsite layers which acted as a structural anchor for the subsequent growth of thermodynamically stable diaspore grown from a mildly acidic and Al-rich solution.« less

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy

PubMed Central

2017-01-01

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl2 concentration. Using DLVO theory with charge regulation, we determine from the measured force–distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca2+ ion adsorption, while Cl– adsorption at higher CaCl2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl– ions will co-adsorb, thereby changing the observed ordered surface structure. PMID:29140711

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy.

PubMed

Kumar, N; Andersson, M P; van den Ende, D; Mugele, F; Siretanu, I

2017-12-19

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl 2 concentration. Using DLVO theory with charge regulation, we determine from the measured force-distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl 2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl 2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca 2+ ion adsorption, while Cl - adsorption at higher CaCl 2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca 2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl - ions will co-adsorb, thereby changing the observed ordered surface structure.

Synthesis of Dispersible Mesoporous Nitrogen-Doped Hollow Carbon Nanoplates with Uniform Hexagonal Morphologies for Supercapacitors.

PubMed

Cao, Jie; Jafta, Charl J; Gong, Jiang; Ran, Qidi; Lin, Xianzhong; Félix, Roberto; Wilks, Regan G; Bär, Marcus; Yuan, Jiayin; Ballauff, Matthias; Lu, Yan

2016-11-02

In this study, dispersible mesoporous nitrogen-doped hollow carbon nanoplates have been synthesized as a new anisotropic carbon nanostructure using gibbsite nanoplates as templates. The gibbsite-silica core-shell nanoplates were first prepared before the gibbsite core was etched away. Dopamine as carbon precursor was self-polymerized on the hollow silica nanoplates surface assisted by sonification, which not only favors a homogeneous polymer coating on the nanoplates but also prevents their aggregation during the polymerization. Individual silica-polydopamine core-shell nanoplates were immobilized in a silica gel in an insulated state via a silica nanocasting technique. After pyrolysis in a nanoconfine environment and elimination of silica, discrete and dispersible hollow carbon nanoplates are obtained. The resulted hollow carbon nanoplates bear uniform hexagonal morphology with specific surface area of 460 m 2 ·g -1 and fairly accessible small mesopores (∼3.8 nm). They show excellent colloidal stability in aqueous media and are applied as electrode materials for symmetric supercapacitors. When using polyvinylimidazolium-based nanoparticles as a binder in electrodes, the hollow carbon nanoplates present superior performance in parallel to polyvinylidene fluoride (PVDF) binder.

Subsidence problems related to the development of siliciclastic karst on the Citronelle Formation of southwestern Alabama

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

Isphording, W.C.; Flowers, G.C.

1985-01-01

The irreversible transformation of kaolinite to gibbsite and the concomitant negative volume change associated with the reaction has resulted in residential structural damage in Mobile, Alabama. Failure of the insurance company to honor damage resulting from a sinkhole collapse clause resulted in litigation. The main points of contention in the trial were: (1) were the small depressions in the owner's yard caused by dissolution of material, resulting in the formation of subteranean voids., (2) does the language used in the policy, i.e., We cover for damages caused by sinkhole collapse due to the dissolution of limestone or similar rock formations,more » mean that because the Citronelle Sand is a rock formation that the resident should recover for damage to his house. Evidence introduced for the plaintiff included x-ray diffractograms, SEM photographs and grain size analyses. A summary of literature on the development of karst in non-carbonate terranes was also produced x-ray diffractograms indicated that gibbsite was being formed in the vadose zone; SEM photographs clearly revealed the presence of euhedral gibbsite crystals on both quartz grains and kaolinite. Size analyses were offered to disprove the allegation that the subsidence was a piping effect caused solely by removal of the silt component. Mass-balance equations and chemical analyses of groundwater were used to demonstrate that not only was kaolinite altering to gibbsite, causing loss of volume, but that some quartz was also being taken into solution. After consideration of the evidence, the jury found in favor of the plaintiff and the resident was compensated for damage.« less

Characterization and Beneficiation Studies of a Low Grade Bauxite Ore

NASA Astrophysics Data System (ADS)

Rao, D. S.; Das, B.

2014-10-01

A low grade bauxite sample of central India was thoroughly characterized with the help of stereomicroscope, reflected light microscope and electron microscope using QEMSCAN. A few hand picked samples were collected from different places of the mine and were subjected to geochemical characterization studies. The geochemical studies indicated that most of the samples contain high silica and low alumina, except a few which are high grade. Mineralogically the samples consist of bauxite (gibbsite and boehmite), ferruginous mineral phases (goethite and hematite), clay and silicate (quartz), and titanium bearing minerals like rutile and ilmenite. Majority of the gibbsite, boehmite and gibbsitic oolites contain clay, quartz and iron and titanium mineral phases within the sample as inclusions. The sample on an average contains 39.1 % Al2O3 and 12.3 % SiO2, and 20.08 % of Fe2O3. Beneficiation techniques like size classification, sorting, scrubbing, hydrocyclone and magnetic separation were employed to reduce the silica content suitable for Bayer process. The studies indicated that, 50 % by weight with 41 % Al2O3 containing less than 5 % SiO2 could be achieved. The finer sized sample after physical beneficiation still contains high silica due to complex mineralogical associations.

Mineral saturation states in natural waters and their sensitivity to thermodynamic and analytical errors

USGS Publications Warehouse

Nordstrom, D. Kirk; Ball, James W.

1989-01-01

Saturation indices computed with WATEQ4F chemical analyses from a groundwater in crystalline bedrock and a surface water receiving acid mine drainage are frequently at or above saturation with respect to calcite, fluorite, barite, gibbsite and ferrihydrite. Deep granitic groundwaters from Stripa, Sweden, are supersaturated with respect to calcite and fluorite. Acid mine waters from the Leviathan Mine drainage basin in California are supersaturated with respect to barite by about a factor of three. These mine waters also are 10 times supersaturated with respect to the most soluble form of ferric hydroxide but are near saturation with respect to microcrystalline gibbsite. A sensitivity analysis has been performed by varying the analytic and thermodynamic parameters for which the saturation indices are most sensitive. For calcite, fluorite and barite, the supersaturation effect appears to be real because it is only slightly decreased by sources of uncertainty. Apparent supersaturation for gibbsite is most likely caused by the degree of crystallinity on solubility behavior. Apparent supersaturation for ferric hydroxide is likely caused by small colloidal particles (< 0.1 µm) in the water sample that cannot be removed by standard field filtration, although several other possible explanations cannot be easily excluded.

Revised values for the Gibbs free energy of formation of [Al(OH)4 aq-], diaspore, boehmite and bayerite at 298.15 K and 1 bar, the thermodynamic properties of kaolinite to 800 K and 1 bar, and the heats of solution of several gibbsite samples

USGS Publications Warehouse

Hemingway, B.S.; Robie, R.A.; Kittrick, J.A.

1978-01-01

Solution calorimetric measurements compared with solubility determinations from the literature for the same samples of gibbsite have provided a direct thermochemical cycle through which the Gibbs free energy of formation of [Al(OH)4 aq-] can be determined. The Gibbs free energy of formation of [Al(OH)4 aq-] at 298.15 K is -1305 ?? 1 kJ/mol. These heat-of-solution results show no significant difference in the thermodynamic properties of gibbsite particles in the range from 50 to 0.05 ??m. The Gibbs free energies of formation at 298.15 K and 1 bar pressure of diaspore, boehmite and bayerite are -9210 ?? 5.0, -918.4 ?? 2.1 and -1153 ?? 2 kJ/mol based upon the Gibbs free energy of [A1(OH)4 aq-] calculated in this paper and the acceptance of -1582.2 ?? 1.3 and -1154.9 ?? 1.2 kJ/mol for the Gibbs free energy of formation of corundum and gibbsite, respectively. Values for the Gibbs free energy formation of [Al(OH)2 aq+] and [AlO2 aq-] were also calculated as -914.2 ?? 2.1 and -830.9 ?? 2.1 kJ/mol, respectively. The use of [AlC2 aq-] as a chemical species is discouraged. A revised Gibbs free energy of formation for [H4SiO4aq0] was recalculated from calorimetric data yielding a value of -1307.5 ?? 1.7 kJ/mol which is in good agreement with the results obtained from several solubility studies. Smoothed values for the thermodynamic functions CP0, ( HT0 - H2980) T, ( GT0 - H2980) T, ST0 - S00, ??Hf{hook},2980 kaolinite are listed at integral temperatures between 298.15 and 800 K. The heat capacity of kaolinite at temperatures between 250 and 800 K may be calculated from the following equation: CP0 = 1430.26 - 0.78850 T + 3.0340 ?? 10-4 T2 -1.85158 ?? 10-4 T2 1 2 + 8.3341 ?? 106 T-2. The thermodynamic properties of most of the geologically important Al-bearing phases have been referenced to the same reference state for Al, namely gibbsite. ?? 1978.

Reactions of aqueous aluminum species at mineral surfaces

USGS Publications Warehouse

Brown, David Wayne; Hem, John David

1975-01-01

Aqueous aluminum solutions containing 4.5 ? 10 4 molar aluminum in 0.01 molar NaC104 were partly neutralized with NaOH to give OH:A1 mole ratios from 1.40 to 2.76. Measured amounts of montmorillonite, kaolinite, volcanic ash, or feldspathic sand were added to provide an area of inert surface. Reactions that occurred during 100 days of aging were compared with those in similar solutions without added surfaces, studied in earlier work. Adsorption of monomeric species Al(H20)6+3, AlOH(H2O)5+2, and Al(OH)2(H2O 4? on the added surfaces follows a cation exchange mass law equilibrium model, and adsorption is essentially complete in 1 hour. Only minor changes in monomeric aluminum species occurred after that. Rapid adsorption of polynuclear aluminum hydroxide species also occurs and follows the pattern of the Langmuir adsorption isotherm. In the absence of surfaces, the polynuclear ions slowly increase in size and become microcrystalline gibbsite during aging. Electron micrographs showed microcrystalline gibbsite was present or surfaces after aging only 2 days. However, the analytical data suggest this material must have been adsorbed after it had already attained a near-crystalline state. Adsorbed polynuclear aluminum hydroxide species were not extensively converted to microcrystalline gibbsite during 100 days of aging.

Importance of interlayer H bonding structure to the stability of layered minerals

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

Conroy, Michele; Soltis, Jennifer A.; Wittman, Rick S.

Layered (oxy) hydroxide minerals often possess out-of-plane hydrogen atoms that form hydrogen bonding networks which stabilize the layered structure. However, less is known about how the ordering of these bonds affects the structural stability and solubility of these minerals. Here, we report a new strategy that uses the focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility. In this regard, the dissolution behavior of boehmite (γ-AlOOH) and gibbsite (γ-Al(OH)3) were compared and contrasted in real time via liquid cell electron microscopy. Under identical such conditions, 2D-nanosheets of boehmite (γ-AlOOH) exfoliated from the bulkmore » and then rapidly dissolved, whereas gibbsite was stable. Further, substitution of only 1% Fe(III) for Al(III) in the structure of boehmite inhibited delamination and dissolution. Factors such as pH, radiolytic species, and knock on damage were systematically studied and eliminated as proximal causes for boehmite dissolution. Instead, the creation of electron/hole pairs was considered to be the mechanism that drove dissolution. The widely disparate behaviors of boehmite, gibbsite, and Fe-doped boehmite are discussed in the context of differences in the OH bond strengths, hydrogen bonding networks, and the presence or absence of electron/hole recombination centers.« less

Uranyl interaction with the hydrated (001) basal face of gibbsite: a combined theoretical and spectroscopic study.

PubMed

Veilly, Edouard; Roques, Jérôme; Jodin-Caumon, Marie-Camille; Humbert, Bernard; Drot, Romuald; Simoni, Eric

2008-12-28

The sorption of uranyl cations and water molecules on the basal (001) face of gibbsite was studied by combining vibrational and fluorescence spectroscopies together with density functional theory (DFT) computations. Both the calculated and experimental values of O-H bond lengths for the gibbsite bulk are in good agreement. In the second part, water sorption with this surface was studied to take into account the influence of hydration with respect to the uranyl adsorption. The computed water configurations agreed with previously published molecular dynamics studies. The uranyl adsorption in acidic media was followed by time-resolved laser-induced fluorescence spectroscopy and Raman spectrometry measurements. The existence of only one kind of adsorption site for the uranyl cation was then indicated in good agreement with the DFT calculations. The computation of the uranyl adsorption has been performed by means of a bidentate interaction with two surface oxygen atoms. The optimized structures displayed strong hydrogen bonds between the surface and the -yl oxygen of uranyl. The uranium-surface bond strength depends on the protonation state of the surface oxygen atoms. The calculated U-O(surface) bond lengths range between 2.1-2.2 and 2.6-2.7 A for the nonprotonated and protonated surface O atoms, respectively.

Importance of interlayer H bonding structure to the stability of layered minerals

DOE PAGES

Conroy, Michele; Soltis, Jennifer A.; Wittman, Rick S.; ...

2017-10-16

Layered (oxy) hydroxide minerals often possess out-of-plane hydrogen atoms that form hydrogen bonding networks which stabilize the layered structure. However, less is known about how the ordering of these bonds affects the structural stability and solubility of these minerals. Here, we report a new strategy that uses the focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility. In this regard, the dissolution behavior of boehmite (γ-AlOOH) and gibbsite (γ-Al(OH)3) were compared and contrasted in real time via liquid cell electron microscopy. Under identical such conditions, 2D-nanosheets of boehmite (γ-AlOOH) exfoliated from the bulkmore » and then rapidly dissolved, whereas gibbsite was stable. Further, substitution of only 1% Fe(III) for Al(III) in the structure of boehmite inhibited delamination and dissolution. Factors such as pH, radiolytic species, and knock on damage were systematically studied and eliminated as proximal causes for boehmite dissolution. Instead, the creation of electron/hole pairs was considered to be the mechanism that drove dissolution. The widely disparate behaviors of boehmite, gibbsite, and Fe-doped boehmite are discussed in the context of differences in the OH bond strengths, hydrogen bonding networks, and the presence or absence of electron/hole recombination centers.« less

Effect of aging on aluminum hydroxide complexes in dilute aqueous solutions

USGS Publications Warehouse

Smith, Ross Wilbert; Hem, John David

1972-01-01

Aqueous aluminum solutions containing 4?10 -5 mole/liter aluminum and a constant total ionic strength of 10 -2, but with varying ratios of hydroxide to aluminum (OH:Al), were prepared. Progress of these solutions toward equilibrium conditions over aging periods of as much as 2 years was studied by determining the composition and pH of the solutions at various time intervals. The solutions, after mixing, were supersaturated with respect to both crystalline and amorphous forms of aluminum oxides and aluminum hydroxides. The compositions of the solutions were determined by use of a timed colorimetric analytical procedure which allowed the estimation of three separate forms of aluminum that have been designated Al a, Al b, and Al c. Form Al a appeared to be composed of monomeric species such as Al(H20)6+3, Al(OH)(H20)5+2, Al(OH)2(H20)4 +I and Al(OH)4-. Form Al b was polynuclear material containing perhaps 20-400 aluminum atoms per structure. It appeared to be a metastable material. Form Al c was composed of relatively large, microcrystalline, clearly solid AI(OH)3 particles. For each OH :Al ratio, the concentration of Al a remained constant with aging time, Al b decreased, and Al c increased. It appeared that Al b particles were increasing in size and ultimately were converted to Al c particles. After a few weeks' aging, Al c particles had the structure of gibbsite. In all solutions, equilibrium was only very slowly achieved, and the time required depended on the OH:Al ratio and how rapidly the solution was initially prepared (mixing time). Lower ratios caused a slower approach to equilibrium; sometimes equilibrium was not achieved even after several years' aging. The more slowly base was initially added (to obtain the proper OH:Al ratio), the more slowly was equilibrium approached. Ultimate equilibrium values of dissolved aluminum concentration and pH were consistent with known thermodynamic data on monomeric aluminum species. From data determined during the aging study and by considering Al b material to consist of extremely small solid gibbsite particles, it was possible to estimate the Gibbs free energy of the (001) crystal face (?F, the gibbsite 'face') and the. Gibbs free energy of the (110) and (100) crystal faces (?E, the gibbsite 'edge') of gibbsite in equilibrium with its saturated solution. These values were: ?F=1404 ? 24 ergs/cm 2, and ?E = 483 ?-84 ergs/cm 2.

Solubility of aluminum in the presence of hydroxide, fluoride, and sulfate

USGS Publications Warehouse

Roberson, Charles Elmer; Hem, John David

1969-01-01

The total concentration of aqueous dissolved species of aluminum that will be present in equilibrium with microcrystalline gibbsite at various levels of complexing ligand concentration are shown graphically. The graphs can be used to estimate aluminum solubility, at 25?C and 1 atmosphere total pressure, when the pH of the solution, its ionic strength, and the total sulfate and fluoride concentrations are known. The standard free energy of formation of cryolite calculated from solubility experiments is --745.4 ? 1.0 kcal per mole at 25?C. Diagrams are included showing the solubility of cryolite in terms of aluminum, fluoride, and sodium concentrations. The stability fields of cryolite and microcrystalline gibbsite and their solubilities also are shown on pH-[F] diagrams.

Correlation between Charge Contrast Imaging and the Distribution of Some Trace Level Impurities in Gibbsite

NASA Astrophysics Data System (ADS)

Baroni, Travis C.; Griffin, Brendan J.; Browne, James R.; Lincoln, Frank J.

2000-01-01

Charge contrast images (CCI) of synthetic gibbsite obtained on an environmental scanning electron microscope gives information on the crystallization process. Furthermore, X-ray mapping of the same grains shows that impurities are localized during the initial stages of growth and that the resulting composition images have features similar to these observed in CCI. This suggests a possible correlation between impurity distributions and the emission detected during CCI. X-ray line profiles, simulating the spatial distribution of impurities derived from the Monte Carlo program CASINO, have been compared with experimental line profiles and give an estimate of the localization. The model suggests that a main impurity, Ca, is depleted from the solution within approximately 3 4 [mu]m of growth.

An Improved MUSIC Model for Gibbsite Surfaces

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

Mitchell, Scott C.; Bickmore, Barry R.; Tadanier, Christopher J.

2004-06-01

Here we use gibbsite as a model system with which to test a recently published, bond-valence method for predicting intrinsic pKa values for surface functional groups on oxides. At issue is whether the method is adequate when valence parameters for the functional groups are derived from ab initio structure optimization of surfaces terminated by vacuum. If not, ab initio molecular dynamics (AIMD) simulations of solvated surfaces (which are much more computationally expensive) will have to be used. To do this, we had to evaluate extant gibbsite potentiometric titration data that where some estimate of edge and basal surface area wasmore » available. Applying BET and recently developed atomic force microscopy methods, we found that most of these data sets were flawed, in that their surface area estimates were probably wrong. Similarly, there may have been problems with many of the titration procedures. However, one data set was adequate on both counts, and we applied our method of surface pKa int prediction to fitting a MUSIC model to this data with considerable success—several features of the titration data were predicted well. However, the model fit was certainly not perfect, and we experienced some difficulties optimizing highly charged, vacuum-terminated surfaces. Therefore, we conclude that we probably need to do AIMD simulations of solvated surfaces to adequately predict intrinsic pKa values for surface functional groups.« less

Mineralogical, micromorphological and geochemical transformations in the initial steps of the weathering process of charnockite from the Caparaó Range, southeastern Brazil

NASA Astrophysics Data System (ADS)

Soares, Caroline Cibele Vieira; Varajão, Angélica Fortes Drummond Chicarino; Varajão, César Augusto Chicarino; Boulangé, Bruno

2014-12-01

X-ray diffraction (XRD), X-ray Fluorescence (XRF), optical microscopy, Scanning Electron Microscopy coupled with Energy Dispersive Spectrometry (SEM-EDS) and Electron Probe micro-analyser (EPMA) and Wavelength-Dispersive Spectroscopy (WDS) were conducted on charnockite from the Caparaó Suite and its alteration cortex to determine the mineralogical, micromorphological and geochemical transformations resulting from the weathering process. The hydrolysis of the charnockite occurred in different stages, in accordance with the order of stability of the minerals with respect to weathering: andesine/orthopyroxene, pargasite and alkali feldspar. The rock modifications had begun with the formation of a layer of incipient alteration due to the percolation of weathering solutions first in the pressure relief fractures and then in cleavage and mineral edges. The iron exuded from ferromagnesian minerals precipitated in the intermineral and intramineral discontinuities. The layer of incipient alteration evolves into an inner cortex where the plagioclase changes into gibbsite by direct alitisation, the ferromagnesian minerals initiate the formation of goethitic boxworks with kaolinitic cores, and the alkali feldspar initiates indirect transformation into gibbsite, forming an intermediate phase of illite and kaolinite. In the outer cortex, mostly traces of alkali feldspar remain, and they are surrounded by goethite and gibbsite as alteromorphics, characterising the formation of the isalteritic horizon that occurs along the slope and explains the bauxitization process at the Caparaó Range, SE Brazil.

Sorptive fractionation of organic matter and formation of organo-hydroxy-aluminum complexes during litter biodegradation in the presence of gibbsite

NASA Astrophysics Data System (ADS)

Heckman, K.; Grandy, A. S.; Gao, X.; Keiluweit, M.; Wickings, K.; Carpenter, K.; Chorover, J.; Rasmussen, C.

2013-11-01

Solid and aqueous phase Al species are recognized to affect organic matter (OM) stabilization in forest soils. However, little is known about the dynamics of formation, composition and dissolution of organo-Al hydroxide complexes in microbially-active soil systems, where plant litter is subject to microbial decomposition in close proximity to mineral weathering reactions. We incubated gibbsite-quartz mineral mixtures in the presence of forest floor material inoculated with a native microbial consortium for periods of 5, 60 and 154 days. At each time step, samples were density separated into light (<1.6 g cm-3), intermediate (1.6-2.0 g cm-3), and heavy (>2.0 g cm-3) fractions. The light fraction was mainly comprised of particulate organic matter, while the intermediate and heavy density fractions contained moderate and large amounts of Al-minerals, respectively. Multi-method interrogation of the fractions indicated the intermediate and heavy fractions differed both in mineral structure and organic compound composition. X-ray diffraction analysis and SEM/EDS of the mineral component of the intermediate fractions indicated some alteration of the original gibbsite structure into less crystalline Al hydroxide and possibly proto-imogolite species, whereas alteration of the gibbsite structure was not evident in the heavy fraction. DRIFT, Py-GC/MS and STXM/NEXAFS results all showed that intermediate fractions were composed mostly of lignin-derived compounds, phenolics, and polysaccharides. Heavy fraction organics were dominated by polysaccharides, and were enriched in proteins, N-bearing compounds, and lipids. The source of organics appeared to differ between the intermediate and heavy fractions. Heavy fractions were enriched in 13C with lower C/N ratios relative to intermediate fractions, suggesting a microbial origin. The observed differential fractionation of organics among hydroxy-Al mineral types suggests that microbial activity superimposed with abiotic mineral-surface-mediated fractionation leads to strong density differentiation of organo-mineral complex composition even over the short time scales probed in these incubation experiments. The data highlight the strong interdependency of mineral transformation, microbial community activity, and organic matter stabilization during biodegradation.

Changes in water extractable organic matter during incubation of forest floor material in the presence of quartz, goethite and gibbsite surfaces

NASA Astrophysics Data System (ADS)

Heckman, Katherine; Vazquez-Ortega, Angelica; Gao, Xiaodong; Chorover, Jon; Rasmussen, Craig

2011-08-01

The release of dissolved organic matter (DOM) from forest floor material constitutes a significant flux of C to the mineral soil in temperate forest ecosystems, with estimates on the order of 120-500 kg C ha -1 year -1. Interaction of DOM with minerals and metals results in sorptive fractionation and stabilization of OM within the soil profile. Iron and aluminum oxides, in particular, have a significant effect on the quantity and quality of DOM transported through forest soils due to their high surface area and the toxic effects of dissolved aluminum on microbial communities. We directly examined these interactions by incubating forest floor material, including native microbiota, for 154 days in the presence of (1) goethite (α-FeOOH), (2) gibbsite (γ-Al(OH) 3), and (3) quartz (α-SiO 2) sand (as a control). Changes in molecular and thermal properties of water extractable organic matter (WEOM, as a proxy for DOM) were evaluated. WEOM was harvested on days 5, 10, 20, 30, 60, 90, and 154, and examined by thermogravimetry/differential thermal analysis (TG/DTA) and diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy. Results indicated significant differences in WEOM quality among treatments, though the way in which oxide surfaces influenced WEOM properties did not seem to change significantly with increasing incubation time. Dissolved organic C concentrations were significantly lower in WEOM from the oxide treatments in comparison to the control treatment. Incubation with goethite produced WEOM with mid-to-high-range thermal lability that was depleted in both protein and fatty acids relative to the control. The average enthalpy of WEOM from the goethite treatment was significantly higher than either the gibbsite or control treatment, suggesting that interaction with goethite surfaces increases the energy content of WEOM. Incubation with gibbsite produced WEOM rich in thermally recalcitrant and carboxyl-rich compounds in comparison to the control treatment. These data indicate that interaction of WEOM with oxide surfaces significantly influences the composition of WEOM and that oxides play an important role in determining the biogeochemistry of forest soil DOM.

Structure of bayerite-based lithium-aluminum layered double hydroxides (LDHs): observation of monoclinic symmetry.

PubMed

Britto, Sylvia; Kamath, P Vishnu

2009-12-21

The double hydroxides of Li with Al, obtained by the imbibition of Li salts into bayerite and gibbsite-Al(OH)(3), are not different polytypes of the same symmetry but actually crystallize in two different symmetries. The bayerite-derived double hydroxides crystallize with monoclinic symmetry, while the gibbsite-derived hydroxides crystallize with hexagonal symmetry. Successive metal hydroxide layers in the bayerite-derived LDHs are translated by the vector ( approximately -1/3, 0, 1) with respect to each other. The exigency of hydrogen bonding drives the intercalated Cl(-) ion to a site with 2-fold coordination, whereas the intercalated water occupies a site with 6-fold coordination having a pseudotrigonal prismatic symmetry. The nonideal nature of the interlayer sites has implications for the observed selectivity of Li-Al LDHs toward anions of different symmetries.

New layered double hydroxides by prepared by the intercalation of gibbsite

NASA Astrophysics Data System (ADS)

Rees, Jennifer R.; Burden, Chloe S.; Fogg, Andrew M.

2015-04-01

New layered double hydroxides (LDHs) with the composition [MAl4(OH)12]Cl2·1.5H2O (M=Co, Ni) have been prepared by reacting gibbsite, γ-Al(OH)3, with the appropriate chloride salt in a synthesis in which the water of crystallization is the only solvent present and fully characterized. These LDHs have been shown to undergo facile anion exchange reactions with both organic and inorganic anions at room temperature making them comparable to other LDHs in this respect. Reactions under the same conditions with CuCl2·2H2O and ZnCl2 failed to form the desired LDHs but those with nitrate salts did lead to the formation of the previously reported [MAl4(OH)12](NO3)2·1.5H2O (M=Co, Ni) compounds.

Genesis of Cr(VI) in Sri Lankan soils and its adsorptive removal by calcined gibbsite

NASA Astrophysics Data System (ADS)

Rajapaksha, A. U.; Wijesundara, D. M.; Vithanage, M. S.; Ok, Y. S.

2012-12-01

Hexavalent chromium is highly toxic to biota and considered as a priority pollutant. Industrial sources of Cr(VI) include leather tanning, plating, electroplating, anodizing baths, rinse waters, etc. In addition, weathering of ultramafic rocks rich in chromium, such as serpentine, is known to Cr(VI) sources into natural water. The Cr(III) is the most stable in the environment, however, conversion of Cr(III) into Cr(VI) occurs in soil due to presence of naturally occurring minerals such as manganese dioxides. We investigated the amount of Cr(VI) recorded from the soils from anthropogenically and naturally contaminated soils (serpentine soils) in Sri Lanka and the removal efficacy of Cr(VI) by calcined gibbsite (Al oxides). The effect of pH on Cr(VI) adsorption was determined by adjusting the pH in the range of 4-10. In the experiments, the adsorbent concentration was kept at 1 g/l of solution containing 10 mg/l Cr(VI) at 25 0C. Total chromium recorded were around 11,000 mg kg-1 and 6,000 mg kg-1 for serpentine soil and tannery waste-contaminated soil, respectively. Although total Cr was high in the contaminated soils, Cr(VI) concentration was only about 28 mg kg-1 and 210 mg kg-1 in the serpentine and tannery soils, respectively. The calcined gibbsite has maximum adsorption of 85 % around pH 4 and adsorption generally decreased with increase of pH.

Characterization of acid-base properties of two gibbsite samples in the context of literature results.

PubMed

Adekola, F; Fédoroff, M; Geckeis, H; Kupcik, T; Lefèvre, G; Lützenkirchen, J; Plaschke, M; Preocanin, T; Rabung, T; Schild, D

2011-02-01

Two different gibbsites, one commercial and one synthesized according to a frequently applied recipe, were studied in an interlaboratory attempt to gain insight into the origin of widely differing reports on gibbsite acid-base surface properties. In addition to a thorough characterization of the two solids, several methods relevant to the interfacial charging were applied to the two samples: potentiometric titrations to obtain the "apparent" proton related surface charge density, zeta-potential measurements characterizing the potential at the plane of shear, and Attenuated Total Reflection Infrared Spectroscopy (ATR-IR) to obtain information on the variation of counter-ion adsorption with pH (using nitrate as a probe). Values of the IEP at 9-10 and 11.2-11.3 were found for the commercial and synthesized sample, respectively. The experimental observations revealed huge differences in the charging behavior between the two samples. Such differences also appeared in the titration kinetics. A detailed literature review revealed similar disparity with no apparent systematic trend. While previously the waiting time between additions had been advocated to explain such differences among synthesized samples, our results do not support such a conclusion. Instead, we find that the amount of titrant added in each aliquot appears to have a significant influence on the titration curves. While we can relate a number of observations to others, a number of open questions and contradictions remain. We suggest various processes, which can explain the observed behavior. Copyright © 2010 Elsevier Inc. All rights reserved.

Molecular Dynamics Simulations of the Interfacial Region between Boehmite and Gibbsite Basal Surfaces and High Ionic Strength Aqueous Solutions

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

Shen, Zhizhang; Ilton, Eugene S.; Prange, Micah P.

Classical molecular dynamics (MD) simulations were used to study the interactions of up to 2 M NaCl and NaNO3 aqueous solutions with the presumed inert boehmite (010) and gibbsite (001) surfaces. The force field parameters used in these simulations were validated against density functional theory calculations of Na+ and Cl- hydrated complexes adsorbed at the boehmite (010) surface. In all the classical MD simulations and regardless of the ionic strength or the nature of the anion, Na+ ions were found to preferably form inner-sphere complexes over outer-sphere complexes at the aluminum (oxy)hydroxide surfaces, adsorbing closer to the surface than bothmore » water molecules and anions. In contrast, Cl- ions were distributed almost equally between inner- and outer-sphere positions. The resulting asymmetry in adsorption strengths offers molecular-scale evidence for the observed isoelectric point (IEP) shift to higher pH at high ionic strength for aluminum (oxy)hydroxides. As such, the MD simulations also provided clear evidence against the assumption that the basal surfaces of boehmite and gibbsite are inert to background electrolytes. Finally, the MD simulations indicated that, although the adsorption behavior of Na+ in NaNO3 and NaCl solutions was similar, the different affinities of NO3- and Cl- for the aluminum (oxy)hydroxide surfaces might have macroscopic consequences, such as difference in the sensitivity of the IEP to the electrolyte concentration.« less

Analysis of the Importance of Oxides and Clays in Cd, Cr, Cu, Ni, Pb and Zn Adsorption and Retention with Regression Trees

PubMed Central

González-Costa, Juan José; Reigosa, Manuel Joaquín; Matías, José María; Fernández-Covelo, Emma

2017-01-01

This study determines the influence of the different soil components and of the cation-exchange capacity on the adsorption and retention of different heavy metals: cadmium, chromium, copper, nickel, lead and zinc. In order to do so, regression models were created through decision trees and the importance of soil components was assessed. Used variables were: humified organic matter, specific cation-exchange capacity, percentages of sand and silt, proportions of Mn, Fe and Al oxides and hematite, and the proportion of quartz, plagioclase and mica, and the proportions of the different clays: kaolinite, vermiculite, gibbsite and chlorite. The most important components in the obtained models were vermiculite and gibbsite, especially for the adsorption of cadmium and zinc, while clays were less relevant. Oxides are less important than clays, especially for the adsorption of chromium and lead and the retention of chromium, copper and lead. PMID:28072849

A discovery of extremely-enriched boehmite from coal in the Junger Coalfield, the northeastern Ordos Basin

USGS Publications Warehouse

Dai, S.; Ren, D.; Li, S.; Chou, C.

2006-01-01

The authors found an extremely-enriched boehmite and its associated minerals for the first time in the super-thick No. 6 coal seam from the Junger Coalfield in the northeastern Ordos Basin by using technologies including the X-ray diffraction analysis (XRD), scanning electron microscope equipped with an energy dispersive X-ray spectrometer, and optical microscope. The content of boehmite is as high as 13.1%, and the associated minerals are goyazite, zircon, rutile, goethite, galena, clausthalite, and selenio-galena. The heavy minerals assemblage is similar to that in the bauxite of the Benxi Formation from North China. The high boehmite in coal is mainly from weathering crust bauxite of the Benxi Formation from the northeastern coal-accumulation basin. The gibbsite colloidstone solution was removed from bauxite to the peat mire, and boehmite was formed via compaction and dehydration of gibbsite colloidstone solution in the period of peat accumulation and early period of diagenesis.

Bioinspired assembly of surface-roughened nanoplatelets.

PubMed

Lin, Tzung-Hua; Huang, Wei-Han; Jun, In-Kook; Jiang, Peng

2010-04-15

Here we report a novel electrophoretic deposition technology for assembling surface-roughened inorganic nanoplatelets into ordered multilayers that mimic the brick-and-mortar nanostructure found in the nacreous layer of mollusk shells. A thin layer of sol-gel silica is coated on smooth gibbsite nanoplatelets in order to increase the surface roughness to mimic the asperity of aragonite platelets found in nacres. To avoid the severe cracking caused by the shrinkage of sol-gel silica during drying, polyelectrolyte polyethyleneimine is used to reverse the surface charge of silica-coated-gibbsite nanoplatelets and increase the adherence and strength of the electrodeposited films. Polymer nanocomposites can then be made by infiltrating the interstitials of the aligned nanoplatelet multilayers with photocurable monomer followed by photopolymerization. The resulting self-standing films are highly transparent and exhibit nearly three times higher tensile strength and one-order-of-magnitude higher toughness than those of pure polymer. The measured tensile strength agrees with that predicted by a simple shear lag model. Published by Elsevier Inc.

Encapsulation of aluminium in geopolymers produced from metakaolin

NASA Astrophysics Data System (ADS)

Kuenzel, C.; Neville, T. P.; Omakowski, T.; Vandeperre, L.; Boccaccini, A. R.; Bensted, J.; Simons, S. J. R.; Cheeseman, C. R.

2014-04-01

Magnox swarf contaminated with trace levels of Al metal is an important UK legacy waste originated from the fuel rod cladding system used in Magnox nuclear power stations. Composite cements made from Portland cement and blast furnace slag form a potential encapsulation matrix. However the high pH of this system causes the Al metal to corrode causing durability issues. Geopolymers derived from metakaolin are being investigated as an alternative encapsulation matrix for Magnox swarf waste and the corrosion kinetics and surface interactions of Al with metakaolin geopolymer are reported in this paper. It is shown that the pH of the geopolymer paste can be controlled by the selection of metakaolin and the sodium silicate solution used to form the geopolymer. A decrease in pH of the activation solution reduces corrosion of the Al metal and increases the stability of bayerite and gibbsite layers formed on the Al surface. The bayerite and gibbsite act as a passivation layer which inhibits further corrosion and mitigates H2 generation. The research shows that optimised metakaolin geopolymers have potential to be used to encapsulate legacy Magnox swarf wastes.

Chemical mimicking of bio-assisted aluminium extraction by Aspergillus niger's exometabolites.

PubMed

Boriová, Katarína; Urík, Martin; Bujdoš, Marek; Pifková, Ivana; Matúš, Peter

2016-11-01

Presence of microorganisms in soils strongly affects mobility of metals. This fact is often excluded when mobile metal fraction in soil is studied using extraction procedures. Thus, the first objective of this paper was to evaluate strain Aspergillus niger's exometabolites contribution on aluminium mobilization. Fungal exudates collected in various time intervals during cultivation were analyzed and used for two-step bio-assisted extraction of alumina and gibbsite. Oxalic, citric and gluconic acids were identified in collected culture media with concentrations up to 68.4, 2.0 and 16.5 mmol L -1 , respectively. These exometabolites proved to be the most efficient agents in mobile aluminium fraction extraction with aluminium extraction efficiency reaching almost 2.2%. However, fungal cultivation is time demanding process. Therefore, the second objective was to simplify acquisition of equally efficient extracting agent by chemically mimicking composition of main organic acid components of fungal exudates. This was successfully achieved with organic acids mixture prepared according to medium composition collected on the 12th day of Aspergillus niger cultivation. This mixture extracted similar amounts of aluminium from alumina compared to culture medium. The aluminium extraction efficiency from gibbsite by organic acids mixture was lesser than 0.09% which is most likely because of more rigid mineral structure of gibbsite compared to alumina. The prepared organic acid mixture was then successfully applied for aluminium extraction from soil samples and compared to standard single step extraction techniques. This showed there is at least 2.9 times higher content of mobile aluminium fraction in soils than it was previously considered, if contribution of microbial metabolites is considered in extraction procedures. Thus, our contribution highlights the significance of fungal metabolites in aluminium extraction from environmental samples, but it also simplifies the extraction procedure inspired by bio-assisted extraction of aluminium by common soil fungus A. niger. Copyright © 2016 Elsevier Ltd. All rights reserved.

The apparent solubility of aluminum (III) in Hanford high-level waste.

PubMed

Reynolds, Jacob G

2012-01-01

The solubility of aluminum in Hanford nuclear waste impacts on the processability of the waste by a number of proposed treatment options. For many years, Hanford staff has anecdotally noted that aluminum appears to be considerably more soluble in Hanford waste than the simpler electrolyte solutions used as analogues. There has been minimal scientific study to confirm these anecdotal observations, however. The present study determines the apparent solubility product for gibbsite in 50 tank samples. The ratio of hydroxide to aluminum in the liquid phase for the samples is calculated and plotted as a function of total sodium molarity. Total sodium molarity is used as a surrogate for ionic strength, because the relative ratios of mono-, di- and trivalent anions are not available for all of the samples. These results were compared to the simple NaOH-NaAl(OH)(4)-H(2)O system, and the NaOH-NaAl(OH)(4)-NaCl-H(2)O system data retrieved from the literature. The results show that gibbsite is apparently more soluble in the samples than in the simple systems whenever the sodium molarity is greater than 2M. This apparent enhanced solubility cannot be explained solely by differences in ionic strength. The change in solubility with ionic strength in simple systems is small compared to the difference between aluminum solubility in Hanford waste and the simple systems. The reason for the apparent enhanced solubility is unknown, but could include kinetic or thermodynamic factors that are not present in the simple electrolyte systems. Any kinetic explanation would have to explain why the samples are always supersaturated whenever the sodium molarity is above 2M. Real waste characterization data should not be used to validate thermodynamic solubility models until it can be confirmed that the apparent enhanced gibbsite solubility is a thermodynamic effect and not a kinetic effect.

The apparent solubility of aluminum (III) in Hanford high-level waste

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

Reynolds, Jacob G.

2012-12-01

The solubility of aluminum in Hanford nuclear waste impacts on the process ability of the waste by a number of proposed treatment options. For many years, Hanford staff has anecdotally noted that aluminum appears to be considerably more soluble in Hanford waste than the simpler electrolyte solutions used as analogues. There has been minimal scientific study to confirm these anecdotal observations, however. The present study determines the apparent solubility product for gibbsite in 50 tank samples. The ratio of hydroxide to aluminum in the liquid phase for the samples is calculated and plotted as a function of total sodium molarity.more » Total sodium molarity is used as a surrogate for ionic strength, because the relative ratios of mono, di and trivalent anions are not available for all of the samples. These results were compared to the simple NaOH-NaAl(OH{sub 4})H{sub 2}O system, and the NaOH-NaAl(OH{sub 4})NaCl-H{sub 2}O system data retrieved from the literature. The results show that gibbsite is apparently more soluble in the samples than in the simple systems whenever the sodium molarity is greater than two. This apparent enhanced solubility cannot be explained solely by differences in ionic strength. The change in solubility with ionic strength in simple systems is small compared to the difference between aluminum solubility in Hanford waste and the simple systems. The reason for the apparent enhanced solubility is unknown, but could include. kinetic or thermodynamic factors that are not present in the simple electrolyte systems. Any kinetic explanation would have to explain why the samples are always supersaturated whenever the sodium molarity is above two. Real waste characterization data should not be used to validate thermodynamic solubility models until it can be confirmed that the apparent enhanced gibbsite solubility is a thermodynamic effect and not a kinetic effect.« less

The effect of sulfate on aluminum concentrations in natural waters: some stability relations in the system Al2O3-SO3-H2O at 298 K

USGS Publications Warehouse

Nordstrom, D. Kirk

1982-01-01

While gibbsite and kaolinite solubilities usually regulate aluminum concentrations in natural waters, the presence of sulfate can dramatically alter these solubilities under acidic conditions, where other, less soluble minerals can control the aqueous geochemistry of aluminum. The likely candidates include alunogen, Al2(SO4)3 ?? 17H2O, alunite, KAl3(SO4)2(OH)6, jurbanite, Al(SO4)(OH) ?? 5H2O, and basaluminite, Al4(SO4)(OH)10 ?? 5H2O. An examination of literature values shows that the log Ksp = -85.4 for alunite and log Ksp = -117.7 for basaluminite. In this report the log Ksp = -7.0 is estimated for alunogen and log Ksp = -17.8 is estimated for jurbanite. The solubility and stability relations among these four minerals and gibbsite are plotted as a function of pH and sulfate activity at 298 K. Alunogen is stable only at pH values too low for any natural waters (<0) and probably only forms as efflorescences from capillary films. Jurbanite is stable from pH < 0 up to the range of 3-5 depending on sulfate activity. Alunite is stable at higher pH values than jurbanite, up to 4-7 depending on sulfate activity. Above these pH limits gibbsite is the most stable phase. Basaluminite, although kinetically favored to precipitate, is metastable for all values of pH and sulfate activity. These equilibrium calculations predict that both sulfate and aluminum can be immobilized in acid waters by the precipitation of aluminum hydroxysulfate minerals. Considerable evidence supports the conclusion that the formation of insoluble aluminum hydroxy-sulfate minerals may be the cause of sulfate retention in soils and sediments, as suggested by Adams and Rawajfih (1977), instead of adsorption. ?? 1982.

Sorptive fractionation of organic matter and formation of organo-hydroxy-aluminum complexes during litter biodegradation in the presence of gibbsite

Treesearch

K. Heckman; A.S. Grandy; X. Gao; M. Keiluweit; K. Wickings; K. Carpenter; J. Chorover; C. Rasmussen

2013-01-01

Solid and aqueous phase Al species are recognized to affect organic matter (OM) stabilization in forest soils. However, little is known about the dynamics of formation, composition and dissolution of organo-Al hydroxide complexes in microbially-active soil systems, where plant litter is subject to microbial decomposition in close proximity to mineral weathering...

Mineralogy and arsenic mobility in arsenic-rich Brazilian soils and sediments

USGS Publications Warehouse

de Mello, J.W.V.; Roy, W.R.; Talbott, J.L.; Stucki, J.W.

2006-01-01

Background. Soils and sediments in certain mining regions of Brazil contain an unusually large amount of arsenic (As), which raises concerns that mining could promote increased As mobility, and thereby increase the risks of contaminating water supplies. Objectives. The purpose of t his study was to identify the most important factors governing As mobility in sediments and soils near three gold-mining sites in the State of Minas Gerais, Brazil. Methods. Surface and sub-surface soil samples were collected at those sites and characterized by chemical and mineralogical analyses. Oxalate (Feo) and citrate-bicarbonate-dithionite (Fed) iron contents were determined by atomic absorption spectroscopy (AAS). Arsenic mobilization was measured after incubating the samples in a 2.5 mM CaCl2 solution under anaerobic conditions for 1, 28, 56, 84, or 112 days. The solution concentrations of As, Fe, and Mn were then measured by inductively coupled plasma-mass spectrometry (ICP-MS) and AAS, respectively. Results and Discussion. Results indicated that As mobilization is largely independent of both the total As and the Feo/Fed ratio of the solid phase. Soluble As is roughly controlled by the Fe (hydr)oxide content of the soil, but a closer examination of the data revealed the importance of other highly weathered clay minerals and organic matter. Large amounts of organic matter and a low iron oxide content should favor As leaching from soils and sediments. Under reducing conditions, As is mobilized by the reductive dissolution of Fe and/or Mn oxides. However, released As may be readsorbed depending on the sorptive properties of the soil. Gibbsite is particularly effective in adsorbing or readsorbing As, as is the remaining unreduced fraction of the iron (hydr)oxides. Conclusion and Outlook. In general, low soluble As is rel ated to the presence of gibbsite, a large amount of iron oxides, and a lack of organic matter in the solid phase. This has environmental significance because gibbsite is thermodynamically more stable than Fe oxides under anaerobic conditions, such as those found in waterlogged soils and lake sediments. ?? 2006 ecomed publishers (Verlagsgruppe Hu??thig Jehle Rehm GmbH), D-86899 Landsberg and Tokyo.

Characterization of dissolved organic matter during reactive transport: A column experiment with spectroscopic detection

NASA Astrophysics Data System (ADS)

Vazquez, A.; Hernández, S.; Rasmussen, C.; Chorover, J.

2010-12-01

Al and Fe oxy-hydroxide minerals have been implicated in dissolved organic matter (DOM) stabilization. DOM solutions from a Pinus ponderosa forest floor (PPDOM) were used to irrigate polypropylene columns, 3.2 cm long by 0.9 cm diameter (total volume 2.0 cm3), that were packed with quartz sand (QS), gibbsite-quartz sand (Al-QS), and goethite-quartz sand (Fe-QS) mixtures. To investigate the mobilization and fractionation of DOM during reactive transport, effluent solutions were characterized by UV-Vis absorbance and excitation-emission matrix (EEM) fluorescence spectroscopies. Magnitude of PPDOM sorption followed the trend Al-QS > Fe-QS > QS during the initial transport. Effluent pH values suggest that ligand exchange is a primary mechanism for PPDOM sorption onto oxy-hydroxide minerals. Low molar absorptivity values were observed in effluent solutions of early pore volumes, indicating preferential mobilization of compounds with low aromatic character. Compounds traditionally characterized by EEM spectroscopy as being more highly humified were favorably absorbed onto the gibbsite and goethite surfaces. Humification index values (HIX) were also correlated with DOM aromaticity. HIX results suggest that the presence of low mass fractions of oxy-hydroxide minerals affect the preferential uptake of high molar mass constituents of PPDOM during reactive transport.

Balancing Sodium Impurities in Alumina for Improved Properties

NASA Astrophysics Data System (ADS)

Wijayaratne, Hasini; Hyland, Margaret; McIntosh, Grant; Perander, Linus; Metson, James

2018-06-01

As there are direct and indirect impacts of feed material purity on the aluminum production process and metal grade, there is a high demand on the so-called pure smelter grade alumina (SGA)—the main feedstock for aluminum production. In this work, impurities within the precursor gibbsite used for SGA production and SGA are studied using NanoSIMS and XPS with a focus on sodium—the most abundant impurity. Although the industry trend is towards minimizing sodium due to the well-known negative impacts on the process, high sodium is also correlated with relatively attrition-resistant calcined products. Here, we show that this relationship is indirect and arises from sodium's role in inhibiting α-alumina formation. Alpha alumina formation in SGA has previously been demonstrated to induce a macro-porous and therefore attrition-prone microstructure. Sodium distribution within the precursor gibbsite and its migration during the calcination process are proposed to be most likely responsible for the spatial distribution of α-alumina within the calcined product grain. This in turn determines the behavior of the product during its transportation and handling (i.e., attrition). Therefore, tolerance of a certain amount of sodium within the precursor material does demonstrate a net benefit while balancing its negative impacts on the process.

Investigation of Cyclodextrin-Enhanced Electrokinetic Soil Remediation. Fate and Transport of Nitroaromatic Contaminants and Cyclodextrin Amendments in Expansive Clays

DTIC Science & Technology

2004-09-01

report increasing adsorption capacity depending on the specific clay type, in the order kaolinite < illite < montmorillonite (11). This finding suggests... kaolinite , illite, and montmorillonite . Finally, there is a wide varia- tion in adsorption constants among the different nitroaromatic compounds...common to micas, chlorites, pyrophyllite, talc, kaolinite , and gibbsite . As is now known, clays typically consist of layered crystalline structures

Microbial Composition in Decomposing Pine Litter Shifts in Response to Common Soil Secondary Minerals

NASA Astrophysics Data System (ADS)

Welty-Bernard, A. T.; Heckman, K.; Vazquez, A.; Rasmussen, C.; Chorover, J.; Schwartz, E.

2011-12-01

A range of environmental and biotic factors have been identified that drive microbial community structure in soils - carbon substrates, redox conditions, mineral nutrients, salinity, pH, and species interactions. However, soil mineralogy has been largely ignored as a candidate in spite of recent studies that indicate that minerals have a substantial impact on soil organic matter stores and subsequent fluxes from soils. Given that secondary minerals and organic colloids govern a soil's biogeochemical activity due to surface area and electromagnetic charge, we propose that secondary minerals are a strong determinant of the communities that are responsible for process rates. To test this, we created three microcosms to study communities during decomposition using pine forest litter mixed with two common secondary minerals in soils (goethite and gibbsite) and with quartz as a control. Changes in bacterial and fungal communities were tracked over the 154-day incubation by pyrosequencing fragments of the bacterial 16S and fungal 18S rRNA genes. Ordination using nonmetric multidimensional scaling showed that bacterial communities separated on the basis of minerals. Overall, a single generalist - identified as an Acidobacteriaceae isolate - dominated all treatments over the course of the experiment, representing roughly 25% of all communities. Fungal communities discriminated between the quartz control alone and mineral treatments as a whole. Again, several generalists dominated the community. Coniochaeta ligniaria dominated communities with abundances ranging from 29 to 40%. The general stability of generalist populations may explain the similarities between treatment respiration rates. Variation between molecular fingerprints, then, were largely a function of unique minor members with abundances ranging from 0.01 to 8%. Carbon availability did not surface as a possible mechanism responsible for shifts in fingerprints due to the relatively large mass of needles in the incubation. Other possible mechanisms include the presence of soluble Fe as an alternative energy source in the goethite treatment, the presence of toxic soluble Al in the gibbsite treatment, the loss of available phosphorus in the secondary mineral treatments due to sorption by secondary mineral surfaces, and variations in mineral surfaces as microhabitats. These findings suggest that Al and Fe oxides, such as goethite or gibbsite, are a factor in determining microbial community structure.

Equilibrium studies of oxalate and aluminum containing solutions

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

Hay, M. S.; King, W. D.; Peters, T. B.

2015-11-01

The Savannah River National Laboratory (SRNL) was tasked to develop data on the solubility and conditions leading to precipitation of sodium oxalate, sodium nitrate, Bayerite (a polymorph of gibbsite, Al(OH) 3), and sodium aluminosilicate solids recently found in the Modular Caustic Side Solvent Extraction Unit (MCU). The data generated will be used to improve the OLI Systems thermodynamic database for these compounds allowing better prediction of solids formation by the modeling software in the future.

Characterization of the surface charge distribution on kaolinite particles using high resolution atomic force microscopy

NASA Astrophysics Data System (ADS)

Kumar, Naveen; Zhao, Cunlu; Klaassen, Aram; van den Ende, Dirk; Mugele, Frieder; Siretanu, Igor

2016-02-01

Most solid surfaces, in particular clay minerals and rock surfaces, acquire a surface charge upon exposure to an aqueous environment due to adsorption and/or desorption of ionic species. Macroscopic techniques such as titration and electrokinetic measurements are commonly used to determine the surface charge and ζ -potential of these surfaces. However, because of the macroscopic averaging character these techniques cannot do justice to the role of local heterogeneities on the surfaces. In this work, we use dynamic atomic force microscopy (AFM) to determine the distribution of surface charge on the two (gibbsite-like and silica-like) basal planes of kaolinite nanoparticles immersed in aqueous electrolyte with a lateral resolution of approximately 30 nm. The surface charge density is extracted from force-distance curves using DLVO theory in combination with surface complexation modeling. While the gibbsite-like and the silica-like facet display on average positive and negative surface charge values as expected, our measurements reveal lateral variations of more than a factor of two on seemingly atomically smooth terraces, even if high resolution AFM images clearly reveal the atomic lattice on the surface. These results suggest that simple surface complexation models of clays that attribute a unique surface chemistry and hence homogeneous surface charge densities to basal planes may miss important aspects of real clay surfaces.

Calcium aluminates hydration in presence of amorphous SiO{sub 2} at temperatures below 90 deg. C

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

Rivas Mercury, J.M.; Turrillas, X.; Aza, A.H. de

2006-10-15

The hydration behaviour of Ca{sub 3}Al{sub 2}O{sub 6}, Ca{sub 12}Al{sub 14}O{sub 33} and CaAl{sub 2}O{sub 4} with added amorphous silica at 40, 65 and 90 deg. C has been studied for periods ranging from 1 to 31 days. In hydrated samples crystalline phases like katoite (Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-} {sub x} (OH){sub 4} {sub x} ) and gibbsite, Al(OH){sub 3}, were identified, likewise amorphous phases like Al(OH) {sub x} , calcium silicate hydrates, C-S-H, and calcium aluminosilicate hydrates, C-S-A-H, were identified. The stoichiometry of Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-} {sub x} (OH){sub 4} {sub x} (0{<=}3-x{<=}0.334), which was themore » main crystalline product, was established by Rietveld refinement of X-ray and neutron diffraction data and by transmission electron microscopy. - Graphical abstract: Katoite, Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-} {sub x} (OH){sub 4} {sub x} (0{<=}3-x{<=}0.334), was identified besides gibbsite, Al(OH){sub 3}, as a crystalline stable hydration products in Ca{sub 3}Al{sub 2}O{sub 6}, Ca{sub 12}Al{sub 14}O{sub 33} and CaAl{sub 2}O{sub 4} hydrated with added amorphous silica between 40 and 90 deg. C.« less

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

Poirier, M.; Burket, P.

The Savannah River Site (SRS) is currently treating radioactive liquid waste with the Actinide Removal Process (ARP) and the Modular Caustic Side Solvent Extraction Unit (MCU). Recently, the low filter flux through the ARP of approximately 5 gallons per minute has limited the rate at which radioactive liquid waste can be treated. Salt Batch 6 had a lower processing rate and required frequent filter cleaning. Savannah River Remediation (SRR) has a desire to understand the causes of the low filter flux and to increase ARP/MCU throughput. SRR requested SRNL to conduct bench-scale filter tests to evaluate whether sodium oxalate, sodiummore » aluminosilicate, or aluminum solids (i.e., gibbsite and boehmite) could be the cause of excessive fouling of the crossflow or secondary filter at ARP. The authors conducted the tests by preparing slurries containing 6.6 M sodium Salt Batch 6 supernate, 2.5 g MST/L slurry, and varying concentrations of sodium oxalate, sodium aluminosilicate, and aluminum solids, processing the slurry through a bench-scale filter unit that contains a crossflow primary filter and a dead-end secondary filter, and measuring filter flux and transmembrane pressure as a function of time. Among the conclusions drwn from this work are the following: (1) All of the tests showed some evidence of fouling the secondary filter. This fouling could be from fine particles passing through the crossflow filter. (2) The sodium oxalate-containing feeds behaved differently from the sodium aluminosilicate- and gibbsite/boehmite-containing feeds.« less

Adsorption of aliphatic polyhydroxy carboxylic acids on gibbsite: pH dependency and importance of adsorbate structure.

PubMed

Schneckenburger, Tatjana; Riefstahl, Jens; Fischer, Klaus

2018-01-01

Aliphatic (poly)hydroxy carboxylic acids [(P)HCA] occur in natural, e.g. soils, and in technical (waste disposal sites, nuclear waste repositories) compartments . Their distribution, mobility and chemical reactivity, e.g. complex formation with metal ions and radionuclides, depend, among others, on their adsorption onto mineral surfaces. Aluminium hydroxides, e.g. gibbsite [α-Al(OH) 3 ], are common constituents of related solid materials and mimic the molecular surface properties of clay minerals. Thus, the study was pursued to characterize the adsorption of glycolic, threonic, tartaric, gluconic, and glucaric acids onto gibbsite over a wide pH and (P)HCA concentration range. To consider specific conditions occurring in radioactive wastes, adsorption applying an artificial cement pore water (pH 13.3) as solution phase was investigated additionally. The sorption of gluconic acid at pH 4, 7, 9, and 12 was best described by the "two-site" Langmuir isotherm, combining "high affinity" sorption sites (adsorption affinity constants [Formula: see text] > 1 L mmol -1 , adsorption capacities < 6.5 mmol kg -1 ) with "low affinity" sites ([Formula: see text] < 0.1 L mmol -1 , adsorption capacities ≥ 19 mmol kg -1 ). The total adsorption capacities at pH 9 and 12 were roughly tenfold of that at pH 4 and 7. The S-shaped pH sorption edge of gluconic acid was modelled applying a constant capacitance model, considering electrostatic interactions, hydrogen bonding, surface complex formation, and formation of solved polynuclear complexes between Al 3+ ions and gluconic acid. A Pearson and Spearman rank correlation between (P)HCA molecular properties and adsorption parameters revealed the high importance of the size and the charge of the adsorbates. The adsorption behaviour of (P)HCAs is best described by a combination of adsorption properties of carboxylic acids at acidic pH and of polyols at alkaline pH. Depending on the molecular properties of the adsorbates and on pH, electrostatic interactions, hydrogen bonding, and ternary surface complexation contribute in varying degrees to the adsorption process. Linear distribution coefficients K d between 8.7 and 60.5 L kg -1 (1 mmol L -1 initial PHCA concentration) indicate a considerable mineral surface affinity at very high pH, thus lowering the PHCA fraction available for the complexation of metal ions including radionuclides in solution and their subsequent mobilization.

Mineralogical variation in the size fractions of a Ranong kaolin, southern Thailand

NASA Astrophysics Data System (ADS)

Pisutha-Arnond, Visut; Phuvichit, Suraphol; Leepowpanth, Quanchai

A representative crude Ranong kaolin from the Thungkla-Ranong mine was separated into > 2 mm (granule), 2-1 mm (very coarse sand), 1-0.5 mm (coarse sand), 0.5-0.25 mm (medium sand), 0.25-0.125 mm (fine sand), 0.125-0.062 mm (very fine sand) and 62-28, 28-14, 17-7, 7-4, 4-2, 2-1 and < 1 μ m size fractions. Those size fractions were analyzed by X-ray powder diffractometry (XRD), differential thermal analysis (DTA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) with attached energy dispersive X-ray spectrometer (EDX). Kaolin group minerals were differentiated by using XRD in combination with various chemical and heat treatments together with TEM, SEM and DTA. The Ranong kaolin consists predominantly of tubular halloysite, poorly crystallized kaolinite and quartz with minor amounts of mica and K-feldspars. Other trace constituents include gibbsite, tourmaline, zircon and colored impurities (i.e. extractable iron hydroxide coating on clay mineral surface). The kaolin minerals are found in all size fractions by which their contents and halloysite/kaolinite ratios increase as the particle sizes become finer. Quartz and mica are also detected in almost all size fractions. They are, however, more abundant with coarsening particle size. Gibbsite, K-feldspar and tourmaline are mainly concentrated in the fine sand to silt size fractions. Crystallinity of kaolin minerals as measured by XRD varied moderately with size. Relatively pure kaolin minerals, predominantly halloysite and kaolinite, can be obtained in the particle size below 1 or 2 μm.

A THEORETICAL INVESTIGATION OF RADIOLYTIC H2 GENERATION FROM SOLIDS

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

Westbrook, M.; Sindelar, R.; Fisher, D.

2012-02-01

Hydrogen generation from materials in nuclear materials storage is of critical interest due to the potential for pressurization and/or flammability issues. Studies have focused on aqueous systems or those with minor amounts of physisorbed water, since conventional knowledge identifies the radiolytic decomposition of water as the source of H{sub 2} gas. Furthermore, the approach to characterize gas generation is typically strictly empirical, relying on determination of G-values from which production in systems is estimated. Interestingly, exploratory work at SRNL1 on gamma exposure to fully-dried solids with chemically-bound water that are typical of those produced on aluminium-clad nuclear fuel in reactormore » and post-discharge storage has shown a profound production of hydrogen (as the sole gaseous species) from fully dried boehmite ({gamma}-AlOOH or Al{sub 2}O{sub 3} {center_dot} H{sub 2}O) powders and no observable hydrogen from gibbsite ({gamma}-Al(OH){sub 3} or Al{sub 2}O{sub 3} {center_dot} 3H{sub 2}O) under gamma irradiation from cobalt-60. This observation is significant in that gibbsite is known to thermally decompose at 80 C whereas boehmite is stable to 400 C. Radiation damage can have various effects on solids, including heating, bond breaking, and rearrangements in the bonding structure. For example, a molecule can be ionized resulting in the generation of free electrons which can, in turn, ionize another molecule. Alternately, reactive radical species such as {lg_bullet}OH or cation species may be formed, which can go on to change bonding structures.« less

Sand dunes on the central Delmarva Peninsula, Maryland and Delaware

USGS Publications Warehouse

Denny, Charles Storrow; Owens, James Patrick

1979-01-01

Inconspicuous ancient sand dunes are present in parts of the central Delmarva Peninsula, Maryland and Delaware. Many dunes are roughly V-shaped, built by northwest winds, especially on the east sides of some of the large rivers. On the uplands, the form and spacing of the dunes are variable. A surficial blanket composed mainly of medium and fine-grained sand-the Parsonsburg Sand-forms both the ancient dunes and the broad plains between the dunes. The sand that forms the dunes is massive and intensely burrowed in the upper part; traces of horizontal or slightly inclined bedding appear near the base. Quartz is the dominant mineral constituent of the sand. Microline is abundant in the very fine to fine sand fraction. The heavy-mineral assemblages (high zircon, tourmaline, rutile) are more mature than in most of the possible source rocks. The most abundant minerals in the clay-sized fraction are dioctahedral vermiculite, kaolinite, illite, montmorillonite, and gibbsite. The first four minerals are common in deposits of late Wisconsin and Holocene age. The gibbsite may be detrital, coming from weathered rocks of Tertiary age. The soil profile in the dune sand is weakly to moderately developed. At or near the base of the Parsonsburg Sand are peaty beds that range in age from about 30,000 to about 13,000 radiocarbon years B.P. Microfloral assemblages in the peaty beds suggest that the dunes on the uplands formed in a spruce parkland during the late Wisconsin glacial maximum. The river dunes may also be of late Wisconsin age, but could be Holocene.

Characterization of tank 51 sludge samples (HTF-51-17-44/ HTF-51-17-48) in support of sludge batch 10 processing

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

Oji, L. N.

The Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (SRR) Engineering (SRR-E) to provide sample characterization and analyses of Tank 51 sludge samples in support of Sludge Batch (SB) 10. The two Tank 51 sludge samples were sampled and delivered to SRNL in May of 2017. These two tank 51 sludge samples were combined into one composite sample and analyzed for corrosion controls analytes, select radionuclides, chemical elements, density and weight percent total solids and aluminum hydroxides (gibbsite and boehmite) by x-ray diffraction.

Fabrication of bioinspired nanostructured materials via colloidal self-assembly

NASA Astrophysics Data System (ADS)

Huang, Wei-Han

Through millions of years of evolution, nature creates unique structures and materials that exhibit remarkable performance on mechanicals, opticals, and physical properties. For instance, nacre (mother of pearl), bone and tooth show excellent combination of strong minerals and elastic proteins as reinforced materials. Structured butterfly's wing and moth's eye can selectively reflect light or absorb light without dyes. Lotus leaf and cicada's wing are superhydrophobic to prevent water accumulation. The principles of particular biological capabilities, attributed to the highly sophisticated structures with complex hierarchical designs, have been extensively studied. Recently, a large variety of novel materials have been enabled by natural-inspired designs and nanotechnologies. These advanced materials will have huge impact on practical applications. We have utilized bottom-up approaches to fabricate nacre-like nanocomposites with "brick and mortar" structures. First, we used self-assembly processes, including convective self-assembly, dip-coating, and electrophoretic deposition to form well oriented layer structure of synthesized gibbsite (aluminum hydroxide) nanoplatelets. Low viscous monomer was permeated into layered nanoplatelets and followed by photo-curing. Gibbsite-polymer composite displays 2 times higher tensile strength and 3 times higher modulus when compared with pure polymer. More improvement occurred when surface-modified gibbsite platelets were cross-linked with the polymer matrix. We observed ˜4 times higher strength and nearly 1 order of magnitude higher modulus than pure polymer. To further improve the mechanical strength and toughness of inorganicorganic nanocomposites, we exploited ultrastrong graphene oxide (GO), a single atom thick hexagonal carbon sheet with pendant oxidation groups. GO nanocomposite is made by co-filtrating GO/polyvinyl alcohol suspension on 0.2 im pore-sized membrane. It shows ˜2 times higher strength and ˜15 times higher ultimate strains than nacre and pure GO paper (also synthesized by filtration). Specifically, it exhibits ˜30 times higher fracture energy than filtrated graphene paper and nacre, ˜100 times tougher than filtrated GO paper. Besides reinforced nanocomposites, we further explored the self-assembly of spherical colloids and the templating nanofabrication of moth-eye-inspired broadband antireflection coatings. Binary crystalline structures can be easily accomplished by spin-coating double-layer nonclose-packed colloidal crystals as templates, followed by colloidal templating. The polymer matrix between self-assembled colloidal crystal has been used as a sacrificial template to define the resulting periodic binary nanostructures, including intercalated arrays of silica spheres and polymer posts, gold nanohole arrays with binary sizes, and dimple-nipple antireflection coatings. The binary-structured antireflection coatings exhibit better antireflective properties than unitary coatings. Natural optical structures and nanocomposites teach us a great deal on how to create high performance artificial materials. The bottom-up technologies developed in this thesis are scalable and compatible with standard industrial processes, promising for manufacturing high-performance materials for the benefits of human beings.

Nickel and cobalt distribution in the laterites of the Lomié region, south-east Cameroon

NASA Astrophysics Data System (ADS)

Yongue-Fouateu, R.; Ghogomu, R. T.; Penaye, J.; Ekodeck, G. E.; Stendal, H.; Colin, F.

2006-05-01

In the Lomié region (south-east Cameroon), strong weathering of serpentinized ultramafic rocks has produced a thick laterite cover with significant nickel and cobalt contents. The highest concentrations of these elements are located in the middle section of the laterite profiles, in the lower clay horizon, and preferentially along the slopes of the interfluves. The investigation of the composition of the laterite ores (by whole-rock analysis) and of the main components, using SEM/microprobe and XRD, reveals the presence of four main enriched facies: a non-differentiated facies, a layered smectitic facies, a quartz-rich facies and a gibbsitic nodular facies. Nickel, with generally low concentrations (less than 2% NiO), is hosted by several secondary mineral phases (goethite, Mn-oxyhydroxides and smectite locally). Cobalt is generally of higher grade (up to 0.9% CoO), and is associated with cryptocrystalline and crystallized Mn-oxyhydroxides. SEM/microprobe observations suggest that nickel and cobalt concentration in secondary minerals is due to repeated remobilization. This has also favored the formation of mineral phases, of which the best crystallized and most richly mineralized are mainly those of the asbolan-lithiophorite group. The SEM studies indicate that these mineral phases show various morphologies related to their chemical composition: poorly crystallized nipple shaped (Fe, Mn, Ni), fine cross-bedded needles (Mn, Ni) and elongated crystals (Mn, Al, Ni, Co) occur in the layered smectitic facies, while platy and needle-like forms (Mn, Al, Ni, Co) characterize the gibbsitic nodular facies. The predominantly cobaltiferous nature of the Lomié laterite ore deposit is the result of remobilizations and transformations of elements that led to the impoverishment of both the Ni-Co contents of the laterite but most importantly of Ni rather than Co.

Landscape types and pH control organic matter mediated mobilization of Al, Fe, U and La in boreal catchments

NASA Astrophysics Data System (ADS)

Köhler, Stephan J.; Lidman, Fredrik; Laudon, Hjalmar

2014-06-01

In this study we present data from a seven-year time series from 15 nested streams within a 68 km2 catchment, covering a pH gradient of almost three units. We demonstrate that the two landscape types, forest and wetlands, control the relative mobilization of Al and Fe in this boreal landscape. The La/U ratio is almost constant across the whole catchment despite large variations in pH, Al/Fe and TOC, whereas U and La mobilization increases with increasing contribution of deeper soils and groundwater further downstream. High Al/TOC ratios in the forested catchments suggest that Al originates from the underlying mineral soils, and low Al/TOC ratios derive from wetlands where Al is retained. We observe a competition effect on the binding to TOC between Al and La and also that the relationship between TOC, Al and La changes from the smaller (0.05-2 km2) catchments to larger (3-68 km2) downstream locations. As pH increase downstream, Al and Fe are gradually removed from the aqueous phase by precipitation of particulate gibbsite-like phases and ferrihydrite. This selective removal of Al and Fe from TOC binding sites results in higher La, and U concentrations downstream. Observed element patterns (U, La) and the range of upper continental crust normalized (La/Nd)UCC and (La/Yb)UCC in the near stream, riparian zone were very similar to the observed ratios across the whole catchment. The rising (La/Nd)UCC over (La/Yb)UCC may be due to a selective removal of REE binding to ferrihydrate in the riparian soil, the result of two distinctly different end-members but most probably not due to the in-stream precipitation of ferrihydrate or gibbsite-like phases.

Speciation and equilibrium relations of soluble aluminum in a headwater stream at base flow and during rain events

USGS Publications Warehouse

Burns, Douglas A.

1989-01-01

In a small watershed in the Shenandoah National Park, Virginia, the short-term dynamics of soluble aluminum in stream water sampled during rain events differed significantly from stream water sampled during base flow conditions. Three fractions of dissolved aluminum were measured. The inorganic monomeric fraction made up approximately two thirds of the total reactive aluminum at base flow, followed by the acid-soluble and organic monomeric fractions, respectively. Equilibrium modeling showed that hydroxide complexes were the most abundant form of inorganic monomeric aluminum followed by fluoride, free aluminum ion, and sulfate. The activity of inorganic monomeric aluminum at base flow appears to be in equilibrium with an Al(OH)3 phase with solubility intermediate between microcrystalline gibbsite and natural gibbsite. During two rain events, the concentration of all three aluminum fractions increased significantly. Available chemical evidence indicates that acidic soil water was the primary source of dissolved aluminum. As flow increased, the Al(OH)3 saturation index in the stream water increased significantly. The primary cause of the transient increase in the Al(OH)3 saturation index appears to have been the neutralization of excess H+ added by soil water through reaction with stream water HCO3− at a more rapid rate than excess inorganic monomeric aluminum could be removed from solution by hydroxide mineral precipitation. A soil water/stream water mixing model was developed based on measured changes of stream water alkalinity, silica concentration, and charge imbalance during the rain events. Model results indicate that a small amount of soil water (3–11%) was present in the stream at peak stage.

Conversion of nuclear waste to molten glass: Formation of porous amorphous alumina in a high-Al melter feed

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

Xu, Kai; Hrma, Pavel; Washton, Nancy

The transition of Al phases in a simulated high-Al high-level nuclear waste melter feed heated at 5 K min-1 to 700°C was investigated with transmission electron microscopy, 27Al nuclear magnetic resonance spectroscopy, the Brunauer-Emmett-Teller method, and X-ray diffraction. At temperatures between 300 and 500°C, porous amorphous alumina formed from the dehydration of gibbsite, resulting in increased specific surface area of the feed (~8 m2 g-1). The high-surface-area amorphous alumina formed in this manner could potentially stop salt migration in the cold cap during nuclear waste vitrification.

In-Tank Elutriation Test Report And Independent Assessment

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

Burns, H. H.; Adamson, D. J.; Qureshi, Z. H.

2011-04-13

The Department of Energy (DOE) Office of Environmental Management (EM) funded Technology Development and Deployment (TDD) to solve technical problems associated with waste tank closure for sites such as Hanford Site and Savannah River Site (SRS). One of the tasks supported by this funding at Savannah River National Laboratory (SRNL) and Pacific Northwest Laboratory (PNNL) was In-Tank Elutriation. Elutriation is the process whereby physical separation occurs based on particle size and density. This report satisfies the first phase of Task WP_1.3.1.1 In-Tank Elutriation, which is to assess the feasibility of this method of separation in waste tanks at Hanford Sitemore » and SRS. This report includes an analysis of scoping tests performed in the Engineering Development Laboratory of SRNL, analysis of Hanford's inadvertent elutriation, the viability of separation methods such as elutriation and hydrocyclones and recommendations for a path forward. This report will demonstrate that the retrieval of Hanford salt waste tank S-112 very successfully decreased the tank's inventories of radionuclides. Analyses of samples collected from the tank showed that concentrations of the major radionuclides Cs-136 and Sr-90 were decreased by factors of 250 and 6 and their total curie tank inventories decreased by factors of 60,000 and 2000. The total tank curie loading decreased from 300,000 Ci to 55 Ci. The remaining heel was nearly all innocuous gibbsite, Al(OH){sub 3}. However, in the process of tank retrieval approximately 85% of the tank gibbsite was also removed. Significant amounts of money and processing time could be saved if more gibbsite could be left in tanks while still removing nearly all of the radionuclides. There were factors which helped to make the elutriation of Tank S-112 successful which would not necessarily be present in all salt tanks. 1. The gibbsite particles in the tank were surprisingly large, as much as 200 {micro}m. The gibbsite crystals had probably grown in size over a period of decades. 2. The radionuclides were apparently either in the form of soluble compounds, like cesium, or micrometer sized particles of actinide oxides or hydroxides. 3. After the initial tank retrieval the tank contained cobble which is not conducive to elutriation. Only after the tank contents were treated with thousands of gallons of 50 wt% caustic, were the solids converted to sand which is compatible with elutriation. Discussions between SRNL and PNNL resulted in plans to test elutriation in two phases; in Phase 1 particles would be separated by differences in settling velocity in an existing scaled tank with its associated hardware and in Phase 2 additional hardware, such as a hydrocyclone, would be added downstream to separate slow settling partciels from liquid. Phase 1 of in-tank elutriation was tested for Proof of Principle in theEngineering Development Laboratory of SRNL in a 41" diameter, 87 gallon tank. The tank had been previously used as a 1/22 scale model of Hanford Waste Tank AY-102. The objective of the testing was to determine which tank operating parameters achieved the best separation between fast- and slow-settling particles. For Phase 1 testing a simulated waste tank supernatant, slow-settling particles and fast-settling particles were loaded to the scaled tank. Because this was a Proof of Principle test, readily available solids particles were used that represented fast-settling and slow-settling particles. The tank contents were agitated using rotating mixer jet pumps (MJP) which suspended solids while liquids and solids were drawn out of the tank with a suction tube. The goal was to determine the optimum hydraulic operating conditions to achieve clean separation in which the residual solids in the tank were nearly all fast-settling particles and the solids transferred out of the tank were nearly all slow-settling particles. Tests were conducted at different pump jet velocities, suction tube diameters and suction tube elevations. Testing revealed that the most important variable was jet velocity which translates to a downstream fluid velocity in the vicinity of the suction tube which can suspend particles and potentially allow their removal from the tank. The optimum jet velocity in the vicinity of the sucti9on tube was between 1.5 and 2 ft/s (4-5 gpm). During testing at lower velocities a significant amount of slow-settling particles remained in the tank. At higher velocities a significant amount of fast-settling particles were elutriated from the tank. It should be noted that this range of velocities is appropriate for this particular geometry and particles. However, the principle of In-Tank Elutriation was proved. In-tank elutriation has the potential to save much money in tank closure. However, more work, both analytical and experimental, must be done before an improved version of the process could be applied to actual waste tanks. It is recommended that testing with more prototypic simulants be conducted. Also, scale-up criteria for elutriation and the resulting size of pilot scale test equipment require investigation during future research. In addition, it is recommended that the use of hydrocyclones be pursued in Phase 2 testing. Hydrocyclones are a precise and efficient separation tool that are frequently used in industry.« less

Aluminium X-ray absorption Near Edge Structure in model compounds and Earth's surface minerals

NASA Astrophysics Data System (ADS)

Ildefonse, P.; Cabaret, D.; Sainctavit, P.; Calas, G.; Flank, A.-M.; Lagarde, P.

Aluminium K-edge X-ray absorption near edge spectra (XANES) of a suite of silicate and oxides minerals consist of electronic excitations occurring in the edge region, and multiple scattering resonances at higher energies. The main XANES feature for four-fold Al is at around 2 eV lower energy than the main XANES feature for six-fold Al. This provides a useful probe for coordination numbers in clay minerals, gels, glasses or material with unknown Al-coordination number. Six-fold aluminium yields a large variety of XANES features which can be correlated with octahedral point symmetry, number of aluminium sites and distribution of Al-O distances. These three parameters may act together, and the quantitative interpretation of XANES spectra is difficult. For a low point symmetry (1), variations are mainly related to the number of Al sites and distribution of Al-O distances: pyrophyllite, one Al site, is clearly distinguished from kaolinite and gibbsite presenting two Al sites. For a given number of Al-site (1), variations are controlled by changes in point symmetry, the number of XANES features being increased as point symmetry decreases. For a given point symmetry (1) and a given number of Al site (1), variations are related to second nearest neighbours (gibbsite versus kaolinite). The amplitude of the XANES feature at about 1566 eV is a useful probe for the assessment of AlIV/Altotal ratios in 2/1 phyllosilicates. Al-K XANES has been performed on synthetic Al-bearing goethites which cannot be studied by 27Al NMR. At low Al content, Al-K XANES is very different from that of α-AlOOH but at the highest level, XANES spectrum tends to that of diaspore. Al-K XAS is thus a promising tool for the structural study of poorly ordered materials such as clay minerals and natural alumino-silicate gels together with Al-subsituted Fe-oxyhydroxides.

Geology and resources of the Andersonville, Georgia, kaolin and bauxite district

USGS Publications Warehouse

Cofer, Harland E.; Manker, John Phillip

1983-01-01

The kaolin and kaolin-rich sediments of the Andersonville district were deposited in an estuary environment with restricted circulation and little tidal or longshore current influence. Micaceous kaolinitic clays were deposited during late Paleocene time on broad, shallow water flats between deeper water distributary channels in the estuarine system. During the cycle of deposition, kaolinitic sediments were temporarily exposed to weathering leading to bauxitization and further kaolinization. Subsequently, subaerial and/or subaqueous erosion planed off and redeposited some of the weathering products as organic-rich clays and silts, berthierine-bearing clays, and rarely as colluvial bauxite and sedimentary bauxitic clays. Upon resubmergence, gibbsite-rich, porous bauxite, and bauxitic clays were exposed to silica-saturated water of the estuary. Gibbsite reacted with silica to form kaolinite and resulted in the formation of the transitional (bauxitic) clays overlying the bauxite. Kaolinitic sediments transported by streams again spread over the altered and redeposited material. At the close of the kaolin depositional period movement along the Andersonville Fault Zone and related faults changed the basinal configuration, and the area of the uplifted (southern) block of the fault was exposed to weathering and bauxitization for a limited period of time. General submergence again occurred and much of the district was covered by marine and brackish water, ending the period of commercial kaolin deposition. The kaolin and bauxite deposits in the Andersonville district form a broad belt 15 kilometers wide and 22 kilometers long trending in a northwest-southeastward direction. Most of the kaolin and bauxite of commercial value occur within a narrow 10-kilometer-wide zone in the belt. The reserves of kaolin suitable for refractory and chemical use are approximately 290 million tonnes. Paramarginal resources of sandy kaolin suitable for refractory, chemical, or aluminum manufacture after beneficiation are approximately 240 million tonnes. Indicated and inferred reserves of bauxite and bauxitic clay are 1.8 million tonnes and 7.3 million tonnes respectively.

Raman spectroscopic analysis of real samples: Brazilian bauxite mineralogy

NASA Astrophysics Data System (ADS)

Faulstich, Fabiano Richard Leite; Castro, Harlem V.; de Oliveira, Luiz Fernando Cappa; Neumann, Reiner

2011-10-01

In this investigation, Raman spectroscopy with 1064 and 632.8 nm excitation was used to investigate real mineral samples of bauxite ore from mines of Northern Brazil, together with Raman mapping and X-rays diffraction. The obtained results show clearly that the use of microRaman spectroscopy is a powerful tool for the identification of all the minerals usually found in bauxites: gibbsite, kaolinite, goethite, hematite, anatase and quartz. Bulk samples can also be analysed, and FT-Raman is more adequate due to better signal-to-noise ratio and representativity, although not efficient for kaolinite. The identification of fingerprinting vibrations for all the minerals allows the acquisition of Raman-based chemical maps, potentially powerful tools for process mineralogy applied to bauxite ores.

Partial compilation and revision of basic data in the WATEQ programs

USGS Publications Warehouse

Nordstrom, D. Kirk; Valentine, S.D.; Ball, J.W.; Plummer, Niel; Jones, B.F.

1984-01-01

Several portions of the basic data in the WATEQ series of computer programs (WATEQ, WATEQF, WATEQ2, WATEQ3, and PHREEQE) are compiled. The density and dielectric constant of water and their temperature dependence are evaluated for the purpose of updating the Debye-Huckel solvent parameters in the activity coefficient equations. The standard state thermodynamic properties of the Fe2+ and Fe3+ aqueous ions are refined. The main portion of this report is a comprehensive listing of aluminum hydrolysis constants, aluminum fluoride, aluminum sulfate, calcium chloride, magnesium chloride, potassium sulfate and sodium sulfate stability constants, solubility product constants for gibbsite and amorphous aluminum hydroxide, and the standard electrode potentials for Fe (s)/Fe2+(aq) and Fe2 +(aq)/Fe3+(aq). (USGS)

Magnetic properties of chemical remanent magnetization in synthetic and natural goethite - Prospects for a natural remanent magnetization/thermoremanent magnetization ratio paleomagnetic stability test?

NASA Astrophysics Data System (ADS)

Dekkers, Mark J.; Rochette, Pierre

1992-11-01

Results are presented of measurements of chemical remanent magnetization properties in natural goethite and in goethite samples synthesized under controlled field conditions (horizontally directed field of 0.30 mT) at 30 C and 55 C, with and without the presence of microfiber glass filters. Results indicate that both the temperature and the presence of a substrate (microfiber glass filters) affect the goethite aging process and the magnetic properties of the resulting goethite. The goethite aging from ferrihydrite was much faster at 55 C than at 30 C, likely because of increased ion diffusion velocity in solution. Results of goethite aging in the presence of other mineral substrate (gibbsite) indicate that the type of mineral substrate is important.

Alcoa Pressure Calcination Process for Alumina

NASA Astrophysics Data System (ADS)

Sucech, S. W.; Misra, C.

A new alumina calcination process developed at Alcoa Laboratories is described. Alumina is calcined in two stages. In the first stage, alumina hydrate is heated indirectly to 500°C in a decomposer vessel. Released water is recovered as process steam at 110 psig pressure. Partial transformation of gibbsite to boehmite occurs under hydrothermal conditions of the decomposer. The product from the decomposer containing about 5% LOI is then calcined by direct heating to 850°C to obtain smelting grade alumina. The final product is highly attrition resistant, has a surface area of 50-80 m2/g and a LOI of less than 1%. Accounting for the recovered steam, the effective fuel consumption for the new calcination process is only 1.6 GJ/t A12O3.

Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

NASA Technical Reports Server (NTRS)

Coyne, L.; Mariner, R.; Rice, A.

1991-01-01

Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

Structure of hydrated gibbsite and brucite edge surfaces: DFT results and further development of the ClayFF classical force field with metal–O–H angle bending terms

DOE PAGES

Pouvreau, Maxime; Greathouse, Jeffery A.; Cygan, Randall T.; ...

2017-06-28

Molecular scale understanding of the structure and properties of aqueous interfaces with clays, metal (oxy-) hydroxides, layered double hydroxides, and other inorganic phases is strongly affected by significant degrees of structural and compositional disorder of the interfaces. ClayFF was originally developed as a robust and flexible force field for classical molecular simulations of such systems. However, despite its success, multiple limitations have also become evident with its use. One of the most important limitations is the difficulty to accurately model the edges of finite size nanoparticles or pores rather than infinitely layered periodic structures. Here we propose a systematic approachmore » to solve this problem by developing specific metal–O–H (M–O–H) bending terms for ClayFF, E bend = k (θ – θ 0) 2 to better describe the structure and dynamics of singly protonated hydroxyl groups at mineral surfaces, particularly edge surfaces. On the basis of a series of DFT calculations, the optimal values of the Al–O–H and Mg–O–H parameters for Al and Mg in octahedral coordination are determined to be θ 0,AlOH = θ 0,MgOH = 110°, k AlOH = 15 kcal mol –1 rad –2 and k MgOH = 6 kcal mol –1 rad –2. Molecular dynamics simulations were performed for fully hydrated models of the basal and edge surfaces of gibbsite, Al(OH) 3, and brucite, Mg(OH) 2, at the DFT level of theory and at the classical level, using ClayFF with and without the M–O–H term. The addition of the new bending term leads to a much more accurate representation of the orientation of O–H groups at the basal and edge surfaces. Finally, the previously observed unrealistic desorption of OH 2 groups from the particle edges within the original ClayFF model is also strongly constrained by the new modification.« less

Geochemical behavior and dissolved species control in acid sand pit lakes, Sepetiba sedimentary basin, Rio de Janeiro, SE - Brazil

NASA Astrophysics Data System (ADS)

Marques, Eduardo D.; Sella, Sílvia M.; Bidone, Edison D.; Silva-Filho, Emmanoel V.

2010-12-01

This work shows the influence of pluvial waters on dissolved components and mineral equilibrium of four sand pit lakes, located in the Sepetiba sedimentary basin, SE Brazil. The sand mining activities promote sediment oxidation, lowering pH and increasing SO 4 contents. The relatively high acidity of these waters, similar to ore pit lakes environment and associated acid mine drainage, increases weathering rate, especially of silicate minerals, which produces high Al concentrations, the limiting factor for fish aquaculture. During the dry season, basic cations (Ca, Mg, K and Na), SiO 2 and Al show their higher values due to evapoconcentration and pH are buffered. In the beginning of the wet season, the dilution factor by rainwater increases SO 4 and decreases pH values. The aluminum monomeric forms (Al(OH) 2+ and Al(OH) 2+), the most toxic species for aquatic organisms, occur during the dry season, while AlSO 4+ species predominate during the wet season. Gibbsite, allophane, alunite and jurbanite are the reactive mineral phases indicated by PHREEQC modeling. During the dry season, hydroxialuminosilicate allophane is the main phase in equilibrium with the solution, while the sulphate salts alunite and jurbanite predominate in the rainy season due to the increasing of SO 4 values. Gibbsite is also in equilibrium with sand pit lakes waters, pointing out that hydrolysis reaction is a constant process in the system. Comparing to SiO 2, sulphate is the main Al retriever in the pit waters because the most samples (alunite and jurbanite) are in equilibrium with the solution in both seasons. This Al hydrochemical control allied to some precaution, like pH correction and fertilization of these waters, allows the conditions for fishpond culture. Equilibrium of the majority samples with kaolinite (Ca, Mg, Na diagrams) and primary minerals (K diagram) points to moderate weathering rate in sand pit sediments, which cannot be considered for the whole basin due to the anomalous acidification of the studied waters.

Calcium aluminate coated and uncoated free form fabricated CoCr implants: a comparative study in rabbit.

PubMed

Palmquist, A; Jarmar, T; Hermansson, L; Emanuelsson, L; Taylor, A; Taylor, M; Engqvist, H; Thomsen, P

2009-10-01

The purpose of this study was to compare the integration in bone of uncoated free form fabricated cobalt chromium (CoCr) implants to the same implant with a calcium aluminate coating. The implants of cylindrical design with a pyramidal surface structure were press-fit into the limbs of New Zealand white rabbits. After 6 weeks, the rabbits were sacrificed, and samples were retrieved and embedded. Ground sections were subjected to histological analysis and histomorphometry. The section counter part was used for preparing an electron transparent transmission electron microscopy sample by focused ion beam milling. Calcium aluminate dip coating provided a significantly greater degree of bone contact than that of the native CoCr. The gibbsite hydrate formed in the hardening reaction of the calcium aluminate was found to be the exclusive crystalline phase material in direct contact with bone. (c) 2009 Wiley Periodicals, Inc.

Aluminum in Precipitation, Streams, and Shallow Groundwater in the New Jersey Pine Barrens

NASA Astrophysics Data System (ADS)

Budd, W. W.; Johnson, A. H.; Huss, J. B.; Turner, R. S.

1981-08-01

Total (acid reactive) aluminum deposited in bulk precipitation in the McDonalds Branch (New Jersey) basin was 140 mg m-2 yr-1 for the period May 1978-May 1980. Stream and groundwater outputs for the same period were 149 and 110 mg m-2 yr-1, respectively. Aluminum inputs and outputs were highest during summer months because of elevated concentrations coupled with increased precipitation and streamflow. Median acid reactive Al concentrations in precipitation, stream water, and groundwater were 100, 350, and 230 μg 1-1, respectively. In streams, acid reactive Al concentration is correlated with dissolved organic matter concentration, suggesting that Al is transported as an organometallic complex. Shallow groundwater Al concentration is apparently controlled by gibbsite solubility in mineral soils and thus is pH dependent. The relatively high Al concentrations are attributable to acid conditions and mobile organic matter.

Importance of interlayer H bonding structure to the stability of layered minerals

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

Conroy, Michele; Soltis, Jennifer A.; Wittman, Rick S.

2017-10-16

The exact atomic structures of layered minerals have been difficult to characterize because the layers often possess out-of-plane hydrogen atoms that cannot be detected by many analytical techniques. However, the ordering of these bonds are thought to play a fundamental role in the structural stability and solubility of layered minerals. We report a new strategy of using the intense radiation field of a focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility while simultaneously imaging the dissolution behavior in real time via liquid cell electron microscopy. We show the loss in hydrogens frommore » interlayers of boehmite (γ-AlOOH) resulted in 2D nanosheets exfoliating from the bulk that subsequently and rapidly dissolved. However gibbsite (γ-Al(OH)3), with its higher concentration of OH terminating groups, was more accommodating to the deprotonation and stable under the beam.« less

Investigation of Tank 241-AW-104 Composite Floating Layer

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

Meznarich, H. K.; Bolling, S. D.; Lachut, J. S.

Seven grab samples and one field blank were taken from Tank 241-AW-104 (AW-104) on June 2, 2017, and received at 222-S Laboratory on June 5, 2017. A visible layer with brown solids was observed floating on the top of two surface tank waste samples (4AW-17-02 and 4AW 17 02DUP). The floating layer from both samples was collected, composited, and submitted for chemical analyses and solid phase characterization in order to understand the composition of the floating layer. Tributyl phosphate and tridecane were higher in the floating layer than in the aqueous phase. Density in the floating layer was slightly lowermore » than the mean density of all grab samples. Sodium nitrate and sodium carbonate were major components with a trace of gibbsite and very small size agglomerates were present in the solids of the floating layer. The supernate consisted of organics, soluble salt, and particulates.« less

Relationships Between Smelter Grade Alumina Characteristics and Strength Determined by Nanoindentation and Ultrasound-Mediated Particle Breakage

NASA Astrophysics Data System (ADS)

Wijayaratne, Hasini; McIntosh, Grant; Hyland, Margaret; Perander, Linus; Metson, James

2017-06-01

The mechanical strength of smelter grade alumina (SGA) is of considerable practical significance for the aluminum reduction process. Attrition of alumina during transportation and handling generates an increased level of fines. This results in generation of dust, poor flow properties, and silo segregation that interfere with alumina feeding systems. These lead to process instabilities which in turn result in current efficiency losses that are costly. Here we are concerned with developing a fundamental understanding of SGA strength in terms of its microstructure. Nanoindentation and ultrasound-mediated particle breakage tests have been conducted to study the strength. Strength of SGA samples both industry calcined and laboratory prepared, decrease with increasing α-alumina (corundum) content contrary to expectation. The reducing strength of alumina with increasing degree of calcination is attributed to the development of a macroporous and abrasion-prone microstructure resulting from the `pseudomorphic' transformation of precursor gibbsite during the calcination process.

Element mobilization and redistribution under extreme tropical weathering of basalts from the Hainan Island, South China

NASA Astrophysics Data System (ADS)

Jiang, Ke; Qi, Hua-Wen; Hu, Rui-Zhong

2018-06-01

Chemical weathering of rocks has substantial influence on the global geochemical cycle. In this paper, the geochemical profile of a well-developed basalt weathering profile (>15 m thick, including soil, saprolite, semi-weathered rock and fresh basalt) on the Island of Hainan (South China) was presented. The soil and saprolite samples from this profile are characterized by high Al2O3 and Fe2O3 concentrations (up to 32.3% and 28.5%, respectively). The mineral assemblage is dominated by kaolinite, Fe-oxides/-hydroxides and gibbsite (or boehmite), indicating extensive desilicate and ferrallitic weathering. The acidic and organic-rich environment in the soil horizon may have promoted elemental remobilization and leaching. The strongest SiO2 depletion and Al2O3 enrichment at about 2.4 m deep indicate that the main kaolinite hydrolysis and gibbsite formation occurred near the soil-saprolite interface. The mild Sr reconcentration at about 3.9 m and 7.1 m deep may be attributed to secondary carbonate precipitation. Mn-oxides/-hydroxides precipitated at 6.1 m deep, accompanied by the strongest enrichment of Ba and Co. Uranium is mildly enriched in the middle part (about 7.1 m and 9.1 m deep) of the weathering profile, and the enrichment may have been caused by the decomposition of uranyl carbonates or the accumulation of zircon. Immobile element (i.e., Zr, Hf, Nb, Ta, Th and Ti) distributions at different depths are mainly controlled by secondary Fe-oxides/-hydroxides, and follow the stability sequence of Nb ≈ Ta ≈ Th > Zr ≈ Hf > Ti. The limited thickness (∼15 cm) of the semi-weathered basalt horizon at the rock-regolith interface (15.28 m deep) suggests that plagioclase and pyroxene are readily altered to kaolinite, smectite and Fe-oxides under tropical climate. The marked enrichment of transitional metals (such as Cu, Zn, Ni, and Sc) along the rock-regolith interface may have associated mainly with increasing pH values, as well as the dissolution of primary apatite and formation of secondary phosphates. Our findings highlight the importance of secondary phosphates in the redistribution of transition metals, and in the possible Mg, Cu, and Ni isotopic fractionation under extreme weathering of basalt in tropic climate.

Mineralogical and geochemical characterization of weathering profiles developed on mylonites in the Fodjomekwet-Fotouni section of the Cameroon Shear Zone (CSZ), West Cameroon

NASA Astrophysics Data System (ADS)

Tematio, P.; Tchaptchet, W. T.; Nguetnkam, J. P.; Mbog, M. B.; Yongue Fouateu, R.

2017-07-01

The mineralogical and geochemical investigation of mylonitic weathering profiles in Fodjomekwet-Fotouni was done to better trace the occurrence of minerals and chemical elements in this area. Four representative soil profiles were identified in two geomorphological units (upland and lowland) differentiating three weathering products (organo-mineral, mineral and weathered materials). Weathering of these mylonites led to some minerals association such as vermiculite, kaolinite, goethite, smectite, halloysite, phlogopite and gibbsite. The minerals in a decreasing order of abundance are: quartz (24.2%-54.8%); kaolinite (8.4%-36.0%); phlogopite (5.5%-21.9%); goethite (7.8%-16.1%); vermiculite (6.7%-15.7%); smectite (10.2%-11.9%); gibbsite (9.0%-11.8%) and halloysite (5.6%-11.5%) respectively. Patterns of chemical elements allow highlighting three behaviors (enriched elements, depleted elements and elements with complex behavior), depending on the landscape position of the profiles. In the upland weathering products, K, Cr and REEs are enriched; Ca, Mg, Na, Mn, Rb, S and Sr are depleted while Si, Al, Fe, Ti, Ba, Co, Cu, Ga, Mo, Nb, Ni, Pb, Sc, V, Y, Zn and Zr portray a complex behavior. Contrarily, the lowland weathering profiles enriched elements are Fe, Ti, Co, Cr, Cu, V, Zr, Pr, Sm, Tb, Dy, Er and Yb; while depleted elements are Ca, Mg, K, Na, Mn, Ba, Ga, S, Sr, Y, Zn, La, Ce and Nd; and Si, Al, Mo, Nb, Ni, Pb, Rb, Sc evidenced complex behaviors. In all the studied weathering products, the REEs fractionation was also noticeable with a landscape-position dependency, showing light REEs (LREEs) enrichment in the upland areas and heavy REEs (HREEs) in lowland areas. SiO2, Al2O3 and Fe2O3 are positively correlated with most of the traces and REEs (Co, Cu, Nb, Ni, Mo, Pb, Sc, V, Zn, Zr, La, Ce, Sm, Tb, Dy, Er, Yb), pointing to the fact that they may be incorporated into newly formed clay minerals and oxides. Ba, Cr, Ga, Rb, S, Sr, Y, Pr and Nd behave like alkalis and alkaline earths, and are thus highly mobile during weathering.

Impacts on seafloor geology of drilling disturbance in shallow waters.

PubMed

Corrêa, Iran C S; Toldo, Elírio E; Toledo, Felipe A L

2010-08-01

This paper describes the effects of drilling disturbance on the seafloor of the upper continental slope of the Campos Basin, Brazil, as a result of the project Environmental Monitoring of Offshore Drilling for Petroleum Exploration--MAPEM. Field sampling was carried out surrounding wells, operated by the company PETROBRAS, to compare sediment properties of the seafloor, including grain-size distribution, total organic carbon, and clay mineral composition, prior to drilling with samples obtained 3 and 22 months after drilling. The sampling grid used had 74 stations, 68 of which were located along 7 radials from the well up to a distance of 500 m. The other 6 stations were used as reference, and were located 2,500 m from the well. The results show no significant sedimentological variation in the area affected by drilling activity. The observed sedimentological changes include a fining of grain size, increase in total organic carbon, an increase in gibbsite, illite, and smectite, and a decrease in kaolinite after drilling took place.

Melter Feed Reactions at T ≤ 700°C for Nuclear Waste Vitrification

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

Xu, Kai; Hrma, Pavel R.; Rice, Jarrett A.

2015-07-23

Batch reactions and phase transitions in a nuclear waste feed heated at 5 K min-1 up to 600°C were investigated by optical microscopy, scanning electron microscopy with energy dispersive X-ray spectrometer, and X-ray diffraction. Quenched samples were leached in deionized water at room temperature and 80°C to extract soluble salts and early glass-forming melt, respectively. To determine the content and composition of leachable phases, the leachates were analyzed by the inductively-coupled plasma spectroscopy. By ~400°C, gibbsite and borax lost water and converted to amorphous and intermediate crystalline phases. Between 400°C and 600°C, the sodium borate early glass-forming melt reacted withmore » amorphous aluminum oxide and calcium oxide to form intermediate products containing Al and Ca. At ~600°C, half Na and B converted to the early glass-forming melt, and quartz began to dissolve in the melt.« less

X-ray Diffraction and Rietveld Refinement in Deferrified Clays for Forensic Science.

PubMed

Prandel, Luis V; Melo, Vander de F; Brinatti, André M; Saab, Sérgio da C; Salvador, Fábio A S

2018-01-01

Soil vestiges might provide information about a crime scene. The Rietveld method with X-ray diffraction data (RM-XRD) is a nondestructive technique that makes it possible to characterize minerals present in the soils. Soil clays from the metropolitan region of Curitiba (Brazil) were submitted to DCB treatment and analyzed using XRD with CuK α radiation in the step-scan mode (0.02° 2θ/5 s). The GSAS+EXPGUI software was used for RM refinement. The RM-XRD results, together with the principal component analysis (PCA) (52.6% total variance), showed the kaolinite predominance in most analyzed samples and the highest quartz contents in "site 1." Higher anatase, and gibbsite and muscovite contents influenced discrimination, mainly in "site 3" and "site 1," respectively. These results were enough to discriminate clays of four sites and two horizons using a reduced amount of sample showing that the technique can be applied to the investigation into soil vestiges. © 2017 American Academy of Forensic Sciences.

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

USGS Publications Warehouse

Broshears, R.E.; Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

1996-01-01

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Thermodynamic tabulations for selected phases in the system CaO-Al2O3-SiO2-H2 at 101.325 kPa (1 atm) between 273.15 and 1800 K

USGS Publications Warehouse

Haas, John L.; Robinson, Glipin R.; Hemingway, Bruch S.

1981-01-01

The standard thermodynamic properties of phases in the lime‐alumina‐silica‐ water system between 273.15 and 1800 K at 101.325 kPa (1 atm) were evalated from published experimental data. Phases included in the compilation are boehmite, diaspore, gibbsite, kaolinite, dickite, halloysite, andalusite, kyanite, sillimanite, Ca‐Al cliniopyroxene, anorthite, gehlenite, grossular, prehnite, zoisite, margarite, wollastonite, cyclowollastonite ( = pseudowollastonite), larnite, Ca olivine, hatrurite, and rankinite. The properties include heat capacity, entropy, relative enthalpy, and the Gibbs energy function of the phases and the enthalpies, Gibbs energies, and equilibrium constants for formation both from the elements and the oxides. Tabulated values are given at 50 K intervals with the 2‐sigma confidence limit at 250 K intervals. Summaries for each phase give the temperature‐ dependent functions for heat capacity, entropy, and relative enthalpy and the experimental data used in the final evaluation.

Questa baseline and pre-mining ground-water quality investigation. 3. Historical ground-water quality for the Red River Valley, New Mexico

USGS Publications Warehouse

LoVetere, Sara H.; Nordstrom, D. Kirk; Maest, Ann S.; Naus, Cheryl A.

2003-01-01

Historical ground-water quality data for 100 wells in the Red River Valley between the U.S. Geological Survey streamflow-gaging station (08265000), near Questa, and Placer Creek east of the town of Red River, New Mexico, were compiled and reviewed. The tabulation included 608 water-quality records from 23 sources entered into an electronic database. Groundwater quality data were first collected at the Red River wastewater-treatment facility in 1982. Most analyses, however, were obtained between 1994 and 2002, even though the first wells were developed in 1962. The data were evaluated by considering (a) temporal consistency, (b) quality of sampling methods, (c) charge imbalance, and (d) replicate analyses. Analyses that qualified on the basis of these criteria were modeled to obtain saturation indices for gypsum, calcite, fluorite, gibbsite, manganite, and rhodocrosite. Plots created from the data illustrate that water chemistry in the Red River Valley is predominantly controlled by calcite dissolution, congruent gypsum dissolution, and pyrite oxidation.

Effect of melter feed foaming on heat flux to the cold cap

NASA Astrophysics Data System (ADS)

Lee, SeungMin; Hrma, Pavel; Pokorny, Richard; Klouzek, Jaroslav; VanderVeer, Bradley J.; Dixon, Derek R.; Luksic, Steven A.; Rodriguez, Carmen P.; Chun, Jaehun; Schweiger, Michael J.; Kruger, Albert A.

2017-12-01

The glass production rate, which is crucial for the nuclear waste cleanup lifecycle, is influenced by the chemical and mineralogical nature of melter feed constituents. The choice of feed materials affects both the conversion heat and the thickness of the foam layer that forms at the bottom of the cold cap and controls the heat flow from molten glass. We demonstrate this by varying the alumina source, namely, substituting boehmite or corundum for gibbsite, in a high-alumina high-level-waste melter feed. The extent of foaming was determined using the volume expansion test and the conversion heat with differential scanning calorimetry. Evolved gas analysis was used to identify gases responsible for the formation of primary and secondary foam. The foam thickness, a critical factor in the rate of melting, was estimated using known values of heat conductivities and melting rates. The result was in reasonable agreement with the foam thickness experimentally observed in quenched cold caps from the laboratory-scale melter.

Synthesis of three commercial products from Bayer electrofilter powders.

PubMed

Ayala, Julia; Fernández, Begoña; Sancho, José Pedro; García, Purificación

2010-06-15

Electrofilter powders, a by-product of the Bayer process for the production of alumina from bauxite, were leached with sulphuric acid to dissolve gibbsite and transition aluminas, thus obtaining a commercial aluminium sulphate solution and a solid residue. This residue is treated again under more drastic conditions with sulphuric acidic in a furnace at a higher temperature, is then leached with water and filtered, a small amount of solid remaining (alpha-alumina). The liquid is a highly acidic aluminium sulphate solution which does not fulfil commercial grade specifications; the liquor is accordingly treated with potassium hydroxide or ammonium hydroxide to obtain potassium or ammonium alum. Experimental tests were conducted to investigate the synthesis of alum by crystallization. The effects on alum formation of various operating conditions, including the amount of potassium or ammonium hydroxide, temperature and seed alum dosage, were examined. The crystallization process was found to be quite effective in obtaining alum. Copyright 2010 Elsevier B.V. All rights reserved.

Effect of melter feed foaming on heat flux to the cold cap

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

Lee, SeungMin; Hrma, Pavel; Pokorny, Richard

The glass production rate, which is crucial for the nuclear waste cleanup lifecycle, is influenced by the chemical and mineralogical nature of melter feed constituents. The choice of feed materials affects both the conversion heat and the thickness of the foam layer that forms at the bottom of the cold cap and controls the heat flow from molten glass. We demonstrate this by varying the alumina source, namely, substituting boehmite or corundum for gibbsite, in a high-alumina high-level-waste melter feed. The extent of foaming was determined using the volume expansion test and the conversion heat with differential scanning calorimetry. Evolvedmore » gas analysis was used to identify gases responsible for the formation of primary and secondary foam. The foam thickness, a critical factor in the rate of melting, was estimated using known values of heat conductivities and melting rates. The result was in reasonable agreement with the foam thickness experimentally observed in the laboratory-scale melter.« less

Physico-chemistry and geochemistry of Balengou clay deposit (West Cameroon) with inference to an argillic hydrothermal alteration

NASA Astrophysics Data System (ADS)

Tassongwa, Bernard; Eba, François; Njoya, Dayirou; Tchakounté, Jacqueline Numbem; Jeudong, Narcisse; Nkoumbou, Charles; Njopwouo, Daniel

2017-09-01

Field description and sampling along two pits, granulometry, Atterberg limits, mineralogical (XRD, FTIR, DSC & TGA) and geochemical analyses of the Balengou clays help to determine their characteristics and the genesis of the deposit. The mineralogical composition is comprised of halloysite-kaolinite, quartz, montmorillonite, hematite, anatase, feldspar, zircon, chromite, and apatite. Gibbsite and illite occur at the shallow and deep depth, respectively. Dikes of sand-poor clays contain also cristobalite and tridymite. Pairs of elements Rb-Ba, Rb-Sr, Nb-Ta, Ta-Zr, TiO2-Zr display good positive correlations (R2 > 0.85). REE patterns are highly fractionated (LaN up to 3312, LaN/YbN: 19-10) and are marked by deep Ce and Eu negative anomalies. Immobile element canonical ratios indicate that the protoliths were commendite/pantelerite, rhyolite and dacite, or their plutonic equivalents. Mineralogical and geochemical features lead to the suggestion that the clays derived from an advanced argillic hydrothermal alteration.

Results of Characterization and Retrieval Testing on Tank 241-C-110 Heel Solids

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

Callaway, William S.

2013-09-30

Nine samples of heel solids from tank 241-C-110 were delivered to the 222-S Laboratory for characterization and dissolution testing. After being drained thoroughly, the sample solids were primarily white to light-brown with minor dark-colored inclusions. The maximum dimension of the majority of the solids was <2 mm; however, numerous pieces of aggregate, microcrystalline, and crystalline solids with maximum dimensions ranging from 5-70 mm were observed. In general, the larger pieces of aggregate solids were strongly cemented. Natrophosphate [Na{sub 7}F(PO{sub 4}){sub 2}°19H{sub 2}O] was the dominant solid phase identified in the heel solids. Results of chemical analyses suggested that 85-87 wt%more » of the heel solids were the fluoridephosphate double salt. The average bulk density measured for the heel solids was 1.689 g/mL; the reference density of natrophosphate is 1.71 g/mL. Dissolution tests on composite samples indicate that 94 to 97 wt% of the tank 241-C-110 heel solids can be retrieved by dissolution in water. Dissolution and recovery of the soluble components in 1 kg (0.59 L) of the heel solids required the addition of ≈9.5 kg (9.5 L) of water at 15 °C and ≈4.4 kg (4.45 L) of water at 45 °C. Calculations performed using the Environmental Simulation Program indicate that dissolution of the ≈0.86 kg of natrophosphate in each kilogram of the tank 241-C-110 heel solids would require ≈9.45 kg of water at 15 °C and ≈4.25 kg of water at 45 °C. The slightly larger quantities of water determined to be required to retrieve the soluble components in 1 kg of the heel solids are consistent with that required for the dissolution of solids composed mainly of natrophosphate with a major portion of the balance consisting of highly soluble sodium salts. At least 98% of the structural water, soluble phosphate, sodium, fluoride, nitrate, carbonate, nitrite, sulfate, oxalate, and chloride in the test composites was dissolved and recovered in the dissolution tests. Most of the {sup 99}Tc and {sup 137}Cs present in the initial heel solids composites was removed in the water dissolution tests. The estimated activities/weights of {sup 129}I, {sup 234}U, {sup 235}U, {sup 236}U, and {sup 238}U in the dry residual solids were <25% of the weights/activities in the initial composite solids. Gibbsite and nordstrandite [both Al(OH){sub 3}] were the major solid phases identified in the solids remaining after completion of the dissolution tests. Chemical analysis indicated that the residual solids may have contained up to 62 wt% Al(OH){sub 3}. Significant quantities of unidentified phosphate-, iron-, bismuth-, silicon-, and strontium- bearing species were also present in the residual solids. The reference density of gibbsite (and nordstrandite) is 2.42 g/mL. The measured density of the residual solids, 2.65 g/mL, would be a reasonable value for solids containing gibbsite as the major component with minor quantities of other, higher density solids. Sieve analysis indicated that 22.2 wt% of the residual solids were discrete particles >710 μm in size, and 77.8 wt% were particulates <710 μm in size. Light-scattering measurements suggested that nearly all of the <710-μm particulates with diameters >12 μm were weakly bound aggregates of particles with diameters <2 μm. The <710-μm residual solids settled very slowly when dispersed in reagent water. The physical appearance of a suspension containing ≈0.4 vol% of the solids in pure water changed very little over a period of 46.5 hours. It should be noted that the distribution of particle sizes in the residual solids and the observed settling behavior were both strongly influenced by the procedures followed in the dissolution tests.« less

Global distribution of clay-size minerals on land surface for biogeochemical and climatological studies

PubMed Central

Ito, Akihiko; Wagai, Rota

2017-01-01

Clay-size minerals play important roles in terrestrial biogeochemistry and atmospheric physics, but their data have been only partially compiled at global scale. We present a global dataset of clay-size minerals in the topsoil and subsoil at different spatial resolutions. The data of soil clay and its mineralogical composition were gathered through a literature survey and aggregated by soil orders of the Soil Taxonomy for each of the ten groups: gibbsite, kaolinite, illite/mica, smectite, vermiculite, chlorite, iron oxide, quartz, non-crystalline, and others. Using a global soil map, a global dataset of soil clay-size mineral distribution was developed at resolutions of 2' to 2° grid cells. The data uncertainty associated with data variability and assumption was evaluated using a Monte Carlo method, and validity of the clay-size mineral distribution obtained in this study was examined by comparing with other datasets. The global soil clay data offer spatially explicit studies on terrestrial biogeochemical cycles, dust emission to the atmosphere, and other interdisciplinary earth sciences. PMID:28829435

Ab initio 27Al NMR chemical shifts and quadrupolar parameters for Al2O3 phases and their precursors

NASA Astrophysics Data System (ADS)

Ferreira, Ary R.; Küçükbenli, Emine; Leitão, Alexandre A.; de Gironcoli, Stefano

2011-12-01

The gauge-including projector augmented wave (GIPAW) method, within the density functional theory (DFT) generalized gradient approximation (GGA) framework, is applied to compute solid state NMR parameters for 27Al in the α, θ, and κ aluminium oxide phases and their gibbsite and boehmite precursors. The results for well established crystalline phases compare very well with available experimental data and provide confidence in the accuracy of the method. For γ-alumina, four structural models proposed in the literature are discussed in terms of their ability to reproduce the experimental spectra also reported in the literature. Among the considered models, the Fd3¯m structure proposed by Paglia [Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.71.224115 71, 224115 (2005)] shows the best agreement. We attempt to link the theoretical NMR parameters to the local geometry. Chemical shifts depend on coordination number but no further correlation is found with geometrical parameters. Instead, our calculations reveal that, within a given coordination number, a linear correlation exists between chemical shifts and Born effective charges.

Intensity and duration of chemical weathering: An example from soil clays of the southeastern Koolau Mountains, Oahu, Hawaii

USGS Publications Warehouse

Johnsson, Mark J.; Ellen, Stephen D.; McKittrick, Mary Anne

1993-01-01

Orographic precipitation on the southern flank of the southeastern Koolau Mountains produces a pronounced precipitation gradient. The corresponding gradient in the intensity of the chemical weathering environment provides an opportunity to address the effects of varying chemical weathering intensity on the composition of clay-size weathering products in soils developed on basalt. In addition, little-modified remnants of the constructional surface of the Koolau Volcano, isolated by stream dissection, remain as facets on the southern ends of the parallel ridges of the study area. By comparing clay mineralogy of soils developed on these older geomorphic surfaces with those developed on the younger sharp-crested ridges and steep side slopes, the effects of weathering duration on clay mineralogy can also be addressed.Soil clays in this part of the Koolau Mountains are mineralogically complex; principal phases include smectite, kaolinite, and halloysite, but pure end member phases are uncommon. Rather, most phases contain some amount of mixed layering. Smectite may contain small (<5%) amounts of randomly interstratified halloysite. Similarly, kaolinite commonly contains a small proportion of halloysite interlayers. A complex halloysitic phase shows evidence of interstratification with both smectite and kaolinite. Nonphyllosilicates found in the clay fraction include gibbsite, goethite, rare quartz, and perhaps cristobalite.The gradient in precipitation is reflected in soil clay mineralogy by varying proportions of dominantly smectitic, kaolinitic, and halloysitic phases. In regions of relatively low precipitation (<2,000 mm/yr), soils are dominated by the smectitic and halloysitic phases. With increased precipitation (as much as ∼4,000 mm/yr), kaolinitic and halloysitic phases become the dominant clay minerals, and goethite and gibbsite become increasingly abundant.Older soils developed on geomorphic surfaces representing the original constructional surface of Koolau Volcano are markedly more leached than those from younger landscapes in the same precipitation regime. Although smectite may be present, kaolinite is the dominant phase, and accumulations of Fe and Ti occur in the uppermost soil levels. Enrichment of Zr and Ti in these soils, as compared to concentrations in the original basaltic parent material, indicates that as much as 75% of the parent material has been lost. Thus weathering duration may affect soil clay composition in the same way as weathering intensity.Because smectite and halloysite are expandable clay minerals, their presence in soils may decrease slope stability and influence the nature of slope processes. Soil avalanches occur on steep slopes throughout the study area, whereas slow-moving landslides appear to be restricted to gentler slopes in drier parts of the study area where smectite is abundant. The clay mineralogy of soils thus appears to influence the nature of slope processes in the southeastern Koolau Mountains.

Aging of coprecipitated Cu in alumina: changes in structural location, chemical form, and solubility

NASA Astrophysics Data System (ADS)

Martínez, Carmen Enid; McBride, Murray B.

2000-05-01

The longterm fate of metals in mineral solid phases is not well established, as aging effects can alter metal forms and solubility. We use a model system (Cu coprecipitation with alumina) to examine copper solubility, chemical form, and structural location during longterm aging (up to 2 y), and as a function of Cu concentration, suspension pH, and rate of coprecipitate formation. Electron spin resonance (ESR) spectroscopy and extractability with EDTA were used to determine the chemical form and structural location of Cu in coprecipitates with alumina. Soluble Cu was measured by differential pulse anodic stripping voltammetry (dpasv) and alumina transformation monitored by XRD. Decreased Cu solubility resulted after prolonged aging of the coprecipitates formed at pH 6 and pH 7.5. Longterm aging (up to 2 y at 23°C) induced the transformation of an initially noncrystalline alumina to more ordered products including gibbsite. Results obtained by ESR and EDTA extraction indicate Cu movement towards the surface of the coprecipitate at increased aging time. Copper was initially evenly distributed within the alumina, but segregated at or near the alumina surface forming CuO and/or clusters after longterm reaction (2 y) with alumina.

Molecular Simulations of Carbon Dioxide and Water: Cation Solvation and Wettability

NASA Astrophysics Data System (ADS)

Criscenti, L. J.; Bracco, J.; Cygan, R. T.

2010-12-01

Proposed carbon dioxide sequestration scenarios in sedimentary basins require investigation into the interaction between supercritical carbon dioxide, brines, and the mineral phases found in the basin and overlying caprock. Classical molecular dynamics (MD) simulations can be used to investigate some of these interactions such as the partitioning of metal cations between aqueous solutions and supercritical carbon dioxide, and the relative wettability of basin and caprock minerals with different fluid phases including water, carbon dioxide, and oil. Initial research has lead to the development of a new flexible carbon dioxide force field that successfully reproduces the vibrational properties of carbon dioxide, and a methodology for extracting contact angle information from large-scale MD simulations. Molecular simulations were performed to compare the solvation of alkali and alkaline metal cations in water and liquid carbon dioxide at 300K, using a flexible simple point charge (SPC) model for water and the new carbon dioxide force field. Solvation energies for Na+, Cs+, Mg2+, and Ba2+ are larger in water than in carbon dioxide, suggesting that these cations will partition preferentially into water. In both solutions, the solvation energy for the cations decreases with ion size and increases with ion charge. However, changes in solvation energy with increasing ionic radii are smaller in carbon dioxide than in water. Therefore, the overall partitioning of cations into carbon dioxide is predicted to increase with ion size. Molecular dynamics simulations are also useful to examine the relative wettability of minerals with different fluid phases. Large-scale MD simulations involving between 100,000 and 200,000 atoms have been conducted to establish a dynamic equilibrium between a drop of liquid water, water vapor, and kaolinite surfaces. The water drops consisted of at least 1700 molecules. Simulations were performed for five nanoseconds. The contact angle calculated for the siloxane surface of kaolinite is approximately 110°, and compares well with calculated contact angles for silica reported in the literature. The contact angle determined for the gibbsite surface of kaolinite is approximately 13° and compares favorably to reported experimental results. As expected, the siloxane surface is calculated to be hydrophobic and the gibbsite surface hydrophilic. This technique should prove useful to investigate the relative wettability of different minerals with subsurface fluids including supercritical CO2. This material is based upon work partially supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.

Form and stability of aluminum hydroxide complexes in dilute solution

USGS Publications Warehouse

Hem, John David; Roberson, Charles Elmer

1967-01-01

Laboratory studies of solutions 4.53 x 10 -4 to 4.5 x 10 -5 molal (12.2-1.2 ppm) in aluminum, in 0.01 molal sodium perchlorate, were conducted to obtain information as to the probable behavior of aluminum in natural water. When the solutions were brought to pH 7.5-9.5 and allowed to stand for 24 hours, a precipitate was obtained which was virtually amorphous as shown by X-rays, and which had a solubility equivalent to that of boehmite. This precipitate had a hydrolysis constant (*Ks4) of 1.93 x 10 -13a. When solutions were allowed to stead at this pH range for 10 days, their precipitates gave the X-ray pattern of bayerite (*Ks4 = 1.11 > (10- 4). These hydrolysis constants were obtained at 25?C. and corrected to zero ionic strength and are in close agreement with other published values. The predominant dissolved form in this pH range is Al(OH) -4. Below neutral pH (7.0) the dissolved aluminum species consist of octahedral units in which each aluminum ion is surrounded by six water molecules or hydroxide ions. Single units such as Al(OH2)6 + 3 and AlOH(OH2)5+2 are most abundant below pH 5.0, and where the molar ratio (r) of combined hydroxide to total dissolved aluminum is low. When r is greater than 1.0, polymerization of the octahedral units occurs. When r is between 2.0 and 3.0, solutions aged for 10 days or more contained colloidal particles between 0.10 and 0.45 ? in diameter. Particles whose diameters were greater than 0.10 ? were identified by X-ray diffraction as gibbsite. Particles smaller than 0.10 ? were also present and were shown by means of the electron microscope to have a hexagonal crystal pattern. Structured material consisting of sheets of coalesced six-membered rings of aluminum ions held together by double OH bridges has a distinctive kinetic behavior. This property was used to determine amounts of polymerized material in solutions having r between 1.0 and 3.0 after aging times ranging from a few hours to more than 4 months. Aging increased the size and orderliness of the polymeric aggregates and was accompanied by a decrease in the pH of the solution. The kinetic experiments and stoichiometric data for solutions aged for long periods provided a means of determining activities of polymerized aluminum. From these values the solubility product for microcrystalline gibbsite was determined to be 2.24 x 10 -3, and its free energy of formation, -? 272.3 0.4 kcal per mole. Where polymerization was observed, the process did not stop with small polynuclear complexes containing a few aluminum ions, but proceeded with aging until macromolecules or colloidal-sized particles were formed.

The use of red mud as an immobiliser for metal/metalloid-contaminated soil: A review.

PubMed

Hua, Yumei; Heal, Kate V; Friesl-Hanl, Wolfgang

2017-03-05

This review focuses on the applicability of red mud as an amendment for metal/metalloid-contaminated soil. The varying properties of red muds from different sources are presented as they influence the potentially toxic element (PTE) concentration in amended soil. Experiments conducted worldwide from the laboratory to the field scale are screened and the influencing parameters and processes in soils are highlighted. Overall red mud amendment is likely to contribute to lowering the PTE availability in contaminated soil. This is attributed to the high pH, Fe and Al oxide/oxyhydroxide content of red mud, especially hematite, boehmite, gibbsite and cancrinite phases involved in immobilising metals/metalloids. In most cases red mud amendment resulted in a lowering of metal concentrations in plants. Bacterial activity was intensified in red mud-amended contaminated soil, suggesting the toxicity from PTEs was reduced by red mud, as well as indirect effects due to changes in soil properties. Besides positive effects of red mud amendment, negative effects may also appear (e.g. increased mobility of As, Cu) which require site-specific risk assessments. Red mud remediation of metal/metalloid contaminated sites has the potential benefit of reducing red mud storage and associated problems. Copyright © 2016 Elsevier B.V. All rights reserved.

Arsenic solid-phase speciation and reversible binding in long-term contaminated soils.

PubMed

Rahman, M S; Clark, M W; Yee, L H; Comarmond, M J; Payne, T E; Kappen, P; Mokhber-Shahin, L

2017-02-01

Historic arsenic contamination of soils occurs throughout the world from mining, industrial and agricultural activities. In Australia, the control of cattle ticks using arsenicals from the late 19th to mid 20th century has led to some 1600 contaminated sites in northern New South Wales. The effect of aging in As-mobility in two dip-site soil types, ferralitic and sandy soils, are investigated utilizing isotopic exchange techniques, and synchrotron X-ray adsorption spectroscopy (XAS). Findings show that historic soil arsenic is highly bound to the soils with >90% irreversibly bound. However, freshly added As (either added to historically loaded soils or pristine soils) has a significantly higher degree of As-accessibility. XAS data indicates that historic soil arsenic is dominated as Ca- (svenekite, & weilite), Al-(mansfieldite), and Fe- (scorodite) like mineral precipitates, whereas freshly added As is dominated by mineral adsorption surfaces, particularly the iron oxy-hydroxides (goethite and hematite), but also gibbsite and kaolin surfaces. SEM data further confirmed the presence of scorodite and mansfieldite formation in the historic contaminated soils. These data suggest that aging of historic soil-As has allowed neoformational mineral recrystallisation from surface sorption processes, which greatly reduces As-mobility and accessibility. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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

2018-01-15

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

Chemical equilibrium modeling of organic acids, pH, aluminum, and iron in Swedish surface waters.

PubMed

Sjöstedt, Carin S; Gustafsson, Jon Petter; Köhler, Stephan J

2010-11-15

A consistent chemical equilibrium model that calculates pH from charge balance constraints and aluminum and iron speciation in the presence of natural organic matter is presented. The model requires input data for total aluminum, iron, organic carbon, fluoride, sulfate, and charge balance ANC. The model is calibrated to pH measurements (n = 322) by adjusting the fraction of active organic matter only, which results in an error of pH prediction on average below 0.2 pH units. The small systematic discrepancy between the analytical results for the monomeric aluminum fractionation and the model results is corrected for separately for two different fractionation techniques (n = 499) and validated on a large number (n = 3419) of geographically widely spread samples all over Sweden. The resulting average error for inorganic monomeric aluminum is around 1 µM. In its present form the model is the first internally consistent modeling approach for Sweden and may now be used as a tool for environmental quality management. Soil gibbsite with a log *Ks of 8.29 at 25°C together with a pH dependent loading function that uses molar Al/C ratios describes the amount of aluminum in solution in the presence of organic matter if the pH is roughly above 6.0.

Molecular dynamics simulation study of the early stages of nucleation of iron oxyhydroxide nanoparticles in aqueous solutions

DOE PAGES

Zhang, Hengzhong; Waychunas, Glenn A.; Banfield, Jillian F.

2015-07-29

Nucleation is a fundamental step in crystal growth. Of environmental and materials relevance are reactions that lead to nucleation of iron oxyhydroxides in aqueous solutions. These reactions are difficult to study experimentally due to their rapid kinetics. Here, we used classical molecular dynamics simulations to investigate nucleation of iron hydroxide/oxyhydroxide nanoparticles in aqueous solutions. Results show that in a solution containing ferric ions and hydroxyl groups, iron–hydroxyl molecular clusters form by merging ferric monomers, dimers, and other oligomers, driven by strong affinity of ferric ions to hydroxyls. When deprotonation reactions are not considered in the simulations, these clusters aggregate tomore » form small iron hydroxide nanocrystals with a six-membered ring-like layered structure allomeric to gibbsite. By comparison, in a solution containing iron chloride and sodium hydroxide, the presence of chlorine drives cluster assembly along a different direction to form long molecular chains (rather than rings) composed of Fe–O octahedra linked by edge sharing. Further, in chlorine-free solutions, when deprotonation reactions are considered, the simulations predict ultimate formation of amorphous iron oxyhydroxide nanoparticles with local atomic structure similar to that of ferrihydrite nanoparticles. Overall, our simulation results reveal that nucleation of iron oxyhydroxide nanoparticles proceeds via a cluster aggregation-based nonclassical pathway.« less

Geotechnical properties of ash deposits near Hilo, Hawaii

USGS Publications Warehouse

Wieczorek, G.F.; Jibson, R.W.; Wilson, R.C.; Buchanan-Banks, J. M.

1982-01-01

Two holes were hand augered and sampled in ash deposits near Hilo, Hawaii. Color, water content and sensitivity of the ash were measured in the field. The ash alternated between reddish brown and dark reddish brown in color and had water contents as high as 392%. A downhole vane shear device measured sensitivities as high as 6.9. A series of laboratory tests including grain size distribution, Atterberg limits, X-ray diffraction analysis, total carbon determination, vane shear, direct shear and triaxial tests were performed to determine the composition and geotechnical properties of the ash. The ash is very fine grained, highly plastic and composed mostly of gibbsite and amorphous material presumably allophane. The ash has a high angle of internal friction ranging from 40-43? and is classified as medium to very sensitive. A series of different ash layers was distinguished on the basis of plasticity and other geotechnical properties. Sensitivity may be due to a metastable fabric, cementation, leaching, high organic content, and thixotropy. The sensitivity of the volcanic ash deposits near Hilo is consistent with documented slope instability during earthquakes in Hawaii. The high angles of internal friction and cementation permit very steep slopes under static conditions. However, because of high sensitivity of the ash, these slopes are particularly susceptible to seismically-induced landsliding.

Size and Morphology Controlled Synthesis of Boehmite Nanoplates and Crystal Growth Mechanisms

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

Zhang, Xin; Cui, Wenwen; Page, Katharine L.

The aluminum oxyhydroxide boehmite is an important crystalline phase in nature and industry. We report development of a flexible additive-free hydrothermal synthesis method to prepare high quality boehmite nanoplates with sizes ranging from under 20 nm to 5 um via using hydrated alumina gels and amorphous powders as precursors. The size and morphology of the boehmite nanoplates was systematically varied between hexagonal and rhombic by adjusting precursor concentrations, pH, and the synthesis temperature, due to face-specific effects. The transformation mechanism is consistent with dissolution and reprecipitation, and involves transitory initial appearance of metastable gibbsite that is later consumed upon nucleationmore » of boehmite. Detailed X-ray pair distribution characterization of the solids over time showed similarities in short-range order that suggest linkages in local chemistry and bonding topology between the precursors and product boehmite, yet also that precursor-specific differences in long-range order appear to manifest subtle changes in resulting boehmite characteristics, suggesting that the rate and extent of water release or differences in the resulting solubilized aluminate speciation leads to slightly different polymerization and condensation pathways. The findings suggest that during dissolution of the precursor that precursor-specific dehydration or solution speciation could be important aspects of the transformation impacting the molecular level details of boehmite nucleation and growth.« less

Rates of weathering rind formation on Costa Rican basalt

NASA Astrophysics Data System (ADS)

Sak, Peter B.; Fisher, Donald M.; Gardner, Thomas W.; Murphy, Katherine; Brantley, Susan L.

2004-04-01

Weathering rind thicknesses were measured on ∼ 200 basaltic clasts collected from three regionally extensive alluvial fill terraces (Qt 1, Qt 2, and Qt 3) preserved along the Pacific coast of Costa Rica. Mass balance calculations suggest that conversion of unweathered basaltic core minerals (plagioclase and augite) to authigenic minerals in the porous rind (kaolinite, allophane, gibbsite, Fe oxyhydroxides) is iso-volumetric and Ti and Zr are relatively immobile. The hierarchy of cation mobility (Ca ≈ Na > K ≈ Mg > Si > Al > Fe ≈ P) is similar to other tropical weathering profiles and is indicative of differential rates of mineral weathering (anorthite > albite ≈ hypersthene > orthoclase ≫ apatite). Alteration profiles across the cm-thick rinds document dissolution of plagioclase and augite and the growth of kaolinite, with subsequent dissolution of kaolinite and precipitation of gibbsite as weathering rinds age. The rate of weathering rind advance is evaluated using a diffusion-limited model which predicts a parabolic rate law for weathering rind thickness, rr, as a function of time, t(rr =κt), and an interface-limited model which predicts a linear rate law for weathering rind thickness as a function of time (rr = kappt). In these rate laws, κ is a diffusion parameter and kapp is an apparent rate constant. The rate of advance is best fit by the interface model. Terrace exposures are confined to the lower reaches of streams draining the Pacific slope near the coast where the stream gradient is less than ∼3 m/km, and terrace deposition is influenced by eustatic sea level fluctuations. Geomorphological evidence is consistent with terrace deposition coincident with sea level maxima when the stream gradient would be lowest. Assigning the most weathered regionally extensive terrace Qt 1 (mean rind thickness 6.9 ± 0. 6cm) to oxygen isotope stage (OIS) 7 (ca. 240 ka), and assuming that at time = 0 rind thickness = 0, it is inferred that terrace Qt 2 (rr = 2.9 ± 0.1 cm) is coincident with stage 5e (ca. 125 ka) and that Qt 3 (rr = 0.9 ± 0.1 cm) is consistent with OIS 3 (ca. 37 ka). These assignments yield a value of kapp of 8.6 × 10-13 cm s-1 (R2 = 0.99). Only this value satisfies both the existing age controls and yields ages coincident with sea level maxima. Using this value, elemental weathering release fluxes across a weathering rind from Qt 2 range from 6.0 × 10-9 mol Si m-2 s-1 to 2.5 × 10-11 mol K m-2 s-1. The rate of rind advance for the Costa Rican terraces is 2.8 × 10-7 m yr-1. Basalt rind formation rates in lower temperature settings described in the literature are also consistent with interface-controlled weathering with an apparent activation energy of about 50 kJ mol-1. Rates of rind formation in Costa Rica are an order of magnitude slower than reported for global averages of soil formation rates.

Clay mineralogy in different geomorphic surfaces in sugarcane areas

NASA Astrophysics Data System (ADS)

Camargo, L.; Marques, J., Jr.

2012-04-01

The crystallization of the oxides and hydroxides of iron and aluminum and kaolinite of clay fraction is the result of pedogenetic processes controlled by the relief. These minerals have influence on the physical and chemical attributes of soil and exhibit spatial dependence. The pattern of spatial distribution is influenced by forms of relief as the geomorphic surfaces. In this sense, the studies aimed at understanding the relationship between relief and the distribution pattern of the clay fraction attributes contribute to the delineation of specific areas of management in the field. The objective of this study was to evaluate the spatial distribution of oxides and hydroxides of iron and aluminum and kaolinite of clay fraction and its relationship with the physical and chemical attributes in different geomorphic surfaces. Soil samples were collected in a transect each 25 m (100 samples) and in the sides of the same (200 samples) as well as an area of 500 ha (1 sample each six hectare). Geomorphic surfaces (GS) in the transect were mapped in detail to support mapping the entire area. The soil samples were taken to the laboratory for chemical, physical, and mineralogical analysis, and the pattern of spatial distribution of soil attributes was obtained by statistics and geostatistics. The GS I is considered the oldest surface of the study area, with depositional character, and a slope ranging from 0 to 4%. GS II and III are considered to be eroded, and the surface II plan a gentle slope that extends from the edge of the surface until the beginning of I and III. The crystallographic characteristics of the oxides and hydroxides of iron and aluminum and kaolinite showed spatial dependence and the distribution pattern corresponding to the limits present of the GS in the field. Surfaces I and II showed the best environments to the degree of crystallinity of hematite and the surface III to the greatest degree of crystallinity of goethite agreeing to the pedoenvironment conditions of each surface. The rate goethite/(goethite+hematite) decreases the surface I to III this result is the variation of the source material that has an increase of clay which is characteristic of sandstone rock (Adamantine Formation) in the surface III. The rate kaolinite/(kaolinite+gibbsite) also shows a decrease of the surface I to the surface III. The spatial distribution pattern of mineralogy influenced the pattern of physical and chemical properties. On the surface III (with higher iron and gibbsite) had the best physical condition (lower density, higher porosity and aggregates) and greater phosphorus sorption. In this sense, the identification and mapping of the GSs, allowed a better understanding of cause and effect of the distribution of soils in the area, and the recognition of areas of controlled variability of soil attributes. These areas can be considered specific areas of management, useful for planning and management practices in the culture of sugarcane. Besides, suggesting criteria for the recognition of map units that would be equivalent to the future series of soils of the Brazilian System of Soil Classification.

The role of biochar, natural iron oxides, and nanomaterials as soil amendments for immobilizing metals in shooting range soil.

PubMed

Rajapaksha, Anushka Upamali; Ahmad, Mahtab; Vithanage, Meththika; Kim, Kwon-Rae; Chang, Jun Young; Lee, Sang Soo; Ok, Yong Sik

2015-12-01

High concentration of toxic metals in military shooting range soils poses a significant environmental concern due to the potential release of metals, such as Pb, Cu, and Sb, and hence requires remediation. The current study examined the effectiveness of buffalo weed (Ambrosia trifida L.) biomass and its derived biochars at pyrolytic temperatures of 300 and 700 °C, natural iron oxides (NRE), gibbsite, and silver nanoparticles on metal immobilization together with soil quality after 1-year soil incubation. Destructive (e.g., chemical extractions) and non-destructive (e.g., molecular spectroscopy) methods were used to investigate the immobilization efficacy of each amendment on Pb, Cu, and Sb, and to explore the possible immobilization mechanisms. The highest immobilization efficacy was observed with biochar produced at 300 °C, showing the maximum decreases of bioavailability by 94 and 70% for Pb and Cu, respectively, which were attributed to the abundance of functional groups in the biochar. Biochar significantly increased the soil pH, cation exchange capacity, and P contents. Indeed, the scanning electron microscopic elemental dot mapping and X-ray absorption fine structure spectroscopic (EXAFS) studies revealed associations of Pb with P (i.e., the formation of stable chloropyromorphite [Pb5(PO4)3Cl]) in the biomass- or biochar-amended soils. However, no amendment was effective on Sb immobilization.

Leaching Characteristics of Hanford Ferrocyanide Wastes

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

Edwards, Matthew K.; Fiskum, Sandra K.; Peterson, Reid A.

2009-12-21

A series of leach tests were performed on actual Hanford Site tank wastes in support of the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The samples were targeted composite slurries of high-level tank waste materials representing major complex, radioactive, tank waste mixtures at the Hanford Site. Using a filtration/leaching apparatus, sample solids were concentrated, caustic leached, and washed under conditions representative of those planned for the Pretreatment Facility in the WTP. Caustic leaching was performed to assess the mobilization of aluminum (as gibbsite, Al[OH]3, and boehmite AlO[OH]), phosphates [PO43-], chromium [Cr3+] and, to a lesser extent, oxalates [C2O42-]). Ferrocyanidemore » waste released the solid phase 137Cs during caustic leaching; this was antithetical to the other Hanford waste types studied. Previous testing on ferrocyanide tank waste focused on the aging of the ferrocyanide salt complex and its thermal compatibilities with nitrites and nitrates. Few studies, however, examined cesium mobilization in the waste. Careful consideration should be given to the pretreatment of ferrocyanide wastes in light of this new observed behavior, given the fact that previous testing on simulants indicates a vastly different cesium mobility in this waste form. The discourse of this work will address the overall ferrocyanide leaching characteristics as well as the behavior of the 137Cs during leaching.« less

Arsenic sorption by red mud-modified biochar produced from rice straw.

PubMed

Wu, Chuan; Huang, Liu; Xue, Sheng-Guo; Huang, Yu-Ying; Hartley, William; Cui, Meng-Qian; Wong, Ming-Hung

2017-08-01

Red mud-modified biochar (RM-BC) has been produced to be utilized as a novel adsorbent to remove As because it can effectively combine the beneficial features of red mud (rich metal oxide composition and porous structure) and biochar (large surface area and porous structure properties). SEM-EDS and XRD analyses demonstrated that red mud had loaded successfully on the surface of biochar. With the increasing of pH in solution, arsenate (As(V)) adsorption on RM-BC decreased while arsenite (As(III)) increased. Arsenate adsorption kinetics process on RM-BC fitted the pseudo-second-order model, while that of As(III) favored the Elovich model. All sorption isotherms produced superior fits with the Langmuir model. RM-BC exhibited improved As removal capabilities, with a maximum adsorption capacity (Q max ) for As(V) of 5923 μg g -1 , approximately ten times greater than that of the untreated BC (552.0 μg g -1 ). Furthermore, it has been indicated that the adsorption of As(V) on RM-BC may be strongly associated with iron oxides (hematite and magnetite) and aluminum oxides (gibbsite) by X-ray absorption near-edge spectroscopy (XANES), which was possibly because of surface complexation and electrostatic interactions. RM-BC may be used as a valuable adsorbent for removing As in the environment due to the waste materials being relatively abundant.

The mobilization of aluminum in a natural soil system: Effects of hydrologic pathways

USGS Publications Warehouse

Cozzarelli, Isabelle M.; Herman, Janet S.; Parnell, Roderic A.

1987-01-01

A two-component soil water flow model was used in conjunction with an equilibrium speciation model WATEQF to study aluminum mobility in soils of a forested watershed, White Oak Run, in the Shenandoah National Park, Virginia. Soil solution samples, taken from the O, E, B, C1, and C2horizons, were collected from zero-tension lysimeters designed to collect faster gravitational macropore flow and tension lysimeters designed to collect slower capillary micropore flow. Dissolved aluminum was fractionated into acid-soluble, inorganic monomeric, and organic monomeric aluminum. Soil water aluminum concentrations decreased with depth indicating that the deep soil is a sink for aluminum. All waters contained significant concentrations of acid-soluble aluminum and exhibited a negative correlation between pH and the inorganic monomeric aluminum concentrations. Water in the shallow soil showed distinctly different chemical compositions for the two flow types, while C horizon micropore and macropore waters were more similar. Because of its shorter residence time, water flowing in deep soil macropores underwent less extensive neutralization and immobilization of aqueous aluminum than micropore water. The O horizon macropore waters were undersaturated for all hydroxide, silicate, and sulfate mineral phases considered. The C horizon samples from both flow types were near equilibrium with respect to kaolinite and synthetic gibbsite, indicating that mineral solubility controls water chemistry in the deep soil, while organic substances are the key control in the shallow macropore waters.

Groundwater geochemistry in the Seminole Well Field, Cedar Rapids, Iowa

USGS Publications Warehouse

Boyd, Robert A.

1999-01-01

The City of Cedar Rapids obtains its municipal water supply from four well fields in an alluvial aquifer along the Cedar River in east-central Iowa. Since 1992, the City and the U.S. Geological Survey have cooperatively studied the groundwater-flow system and water chemistry near the well fields. The geochemistry in the alluvial aquifer near the Seminole Well Field was assessed to identify potentially reactive minerals and possible chemical reactions that produce observed changes in water chemistry. Calcite, dolomite, ferrihydrite, quartz, rhodochrosite, and siderite were identified as potentially reactive minerals by calculating saturation indexes. Aluminosiicate minerals including albite, Ca-montmorillonite, gibbsite, illite, K-feldspar, and kaolinite were identified as potentially reactive minerals using hypothetical saturation indexes calculated with an assumed dissolved aluminum concentration of 1 microgram per liter. Balanced chemical equations derived from inverse-modeling techniques were used to assess chemical reactions as precipitation percolates to the water table. Calcite dissolution was predominate, but aluminosilicate weathering, cation exchange, and redox reactions also likely occurred. Microbial-catalyzed redox reactions altered the chemical composition of water infiltrating from the Cedar River into the alluvial aquifer by consuming dissolved oxygen, reducing nitrate, and increasing dissolved iron and manganese concentrations. Nitrate reduction only occurred in relatively shallow (3 to 7 meters below land surface) groundwater near the Cedar River and did not occur in water infiltrating to deeper zones of the alluvial aquifer.

Hydrology and Alkalinity Regulation of Soft Florida Waters: An Integrated Assessment

NASA Astrophysics Data System (ADS)

Stauffer, Robert E.; Canfield, Daniel E., Jr.

1992-06-01

Natural waters in ridge provinces of Florida and southeast Georgia were classified geographically, by degrees of cultural disturbance, and according to the dominant hydrologic and biogeochemical processes controlling chemistry. The ionic composition of lakes, upland streams, and surficial aquifer (water table) springs in relatively undeveloped catchments reflects the geographic variations in bulk deposition corrected for evapotranspiration (Na, Cl), plus a slight gain (net watershed mobilization) of Mg, and partial to nearly complete losses (net retention) of nitrate, sulfate, Ca, and K. Recharge to the Floridan aquifer in infertile, forested, sandy ridge provinces of northern Florida contains 360-580 μmol CO2. On the basis of indirect geochemical evidence, sulfate retention appears less important in lake sediments than in the region's highly weathered, ferruginous, kaolinitic, sand soils. Silica concentrations in upland streams and water table springs closely reflect the predicted equilibrium between kaolinite and gibbsite. Along with other evidence, the Si concentrations in ridge lakes indicate that seepage inflow is much more important than assumed in Baker et al.'s (1988) regional model. Lakes and streams are acidified either by humic acids or nonmarine sulfate but rarely by both, as reflected by the significant inverse correlation between these two components. Contrary to previous reports, there is no significant difference in alkalinity for culturally undisturbed lakes in the northern Trail versus southern Highlands Ridge areas.

Effective Remediation of Groundwater Fluoride with Inexpensively Processed Indian Bauxite.

PubMed

Cherukumilli, Katya; Maurer, Tessa; Hohman, J Nathan; Mehta, Yash; Gadgil, Ashok J

2018-04-17

India represents one-third of the world's fluorosis burden and is the fifth global producer of bauxite ore, which has previously been identified as a potential resource for remediating fluoride-contaminated groundwater in impoverished communities. Here, we use thermal activation and/or groundwater acidification to enhance fluoride adsorption by Indian bauxite obtained from Visakhapatnam, an area proximate to endemic fluorosis regions. We compare combinatorial water treatment and bauxite-processing scenarios through batch adsorption experiments, material characterization, and detailed cost analyses. Heating Indian bauxite above 300 °C increases available surface area by > 15× (to ∼170 m 2 /g) through gibbsite dehydroxylation and reduces the bauxite dose for remediating 10 ppm F - to 1.5 ppm F - by ∼93% (to 21 g/L). Additionally, lowering groundwater pH to 6.0 with HCl or CO 2 further reduces the average required bauxite doses by 43-73% for ores heated at 300 °C (∼12 g/L) and 100 °C (∼77 g/L). Product water in most examined treatment scenarios complies with EPA standards for drinking water (e.g., As, Cd, Pb, etc.) but potential leaching of Al, Mn, and Cr is of concern in some scenarios. Among the defluoridation options explored here, bauxite heated at 300 °C in acidified groundwater has the lowest direct costs ($6.86 per person per year) and material-intensity.

Chemical Processes and Thresholds in Hawaiin Soils

NASA Astrophysics Data System (ADS)

Chadwick, O.

2007-12-01

The Hawaiian Islands are a useful natural laboratory for studying soil development particularly those that can be understood using a matrix of chonosequences and climosequences. The islands are formed over a stationary mantle plume and then are carried to the northwest on the Pacific Plate. Thus the islands get older with distance from the hotspot; Kauai has remnant shield surfaces whose lavas date to about 4,000 ky. It is possible to sample soils that are developing on different age flows ranging from a few hundred years to a few million years. Additionally, individual volcanoes are impacted by differing amounts of rainfall depending on location with respect to the northeasterly trade winds. Whereas rainfall over the open ocean near Hawaii is about 700 mm, rainfall over the Islands ranges from 150 to 11,000 mm. Hawaii is minimally impacted by mineral aerosol additions compared to continental areas and this has a significant impact on soil development. More than 100 soil profiles have been sampled along the Hawaii time-climate matrix with some surprising results. For example, in arid soils might be expected to develop smectite clays, but they are rich in halloysite and allophane. Importantly, these same soils show a trend from high-Mg calcite to dolomite as carbonates accumulate within the profiles - this is one of the first documented occurrences of pedogenic dolomite that is not associated with high levels of salts. It appears that lack of smectite formation lowers the incorporation of Mg into silicate clays and increases its incorporation into carbonates. This is an unusual pedogenic process that seems to be enhanced by the lack of substantial amounts of mica in the basalt derived soils. The only mica is in surface horizons that receive dust derived from distant continents. Without mica there is no template to allow smectite clay formation under the rapid wetting and drying regimes encountered in the arid soils. At the same time that halloysite is forming, iron and aluminum oxides tend to move rapidly from poorly crystalline to crystalline forms, which in turn leads to formation of Oxisols under an arid climate regimes - Torrox formation without substantial climate change. By contrast, soils forming in humid environments along the same time trajectory take much longer to go through the same transformations (allophane to halloysite; poorly crystalline goethite to well crystallized goethite; poorly crystalline gibbsite to well crystallized gibbsite). The longer time required for transformation is related to wet rather than wet- dry cycles and interference by organic carbon in the transformation process. Thus whereas it takes about 400,000 years to form a Torrox, it takes more than three times that long to form a humid-zone Oxisol. In Hawaii we have identified several important thresholds in soil properties that have universal applicability: 1. the shift from udic to perudic soil moisture regime is accompanied by reduction related changes in soil properties particularly accumulation of organic matter and loss of iron-bound phosphorus; 2. shift from ustic to udic moisture leads to rapid loss of nutrients with far reaching implications for soil exchange properties and prehistoric land use, 3. the shift from from ustic to aridic soil conditions leads to greater losses of plant nutrients (bases, P, Si) due to greater wind erosion. Based on archeological evidence, it is clear that Polynesians made land-use decisions that incorporated observations of the soil properties associated with these thresholds.

Final Report For The Erosion And Corrosion Analysis Of Waste Transfer Primary Pipeline Sections From 241-SY Tank Farm

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

Page, J. S.; Wyrwas, R. B.; Cooke, G. A.

Three sections of primary transfer pipeline removed from the 241-SY Tank Farm in Hanford's 200 West area, labeled as SN-285, SN-286, and SN-278, were analyzed for the presence and amount of corrosion and erosion on the inside surface of the transfer pipe. All three sections of pipe, ranging in length between 6 and 8 in., were received at the 222-S Laboratory still in the pipe-in-pipe assembly. The annular spaces were filled with urethane foam injected into the pipes for as low as reasonably achievable (ALARA) purposes. The 3-in. primary transfer pipes were first separated from the outer encasement, 6-in. pipes.more » The pipes were cut into small sections, or coupons, based upon the results of a non-destructive pipe wall thickness measurement which used an ultrasonic transducer. Following removal of the foam, the coupons were subjected to a series of analytical methods utilizing both optical microscopy and scanning electron microscopy to obtain erosion and corrosion information. The ultrasonic transducer analysis of the SN-285 primary pipe did not show any thinned locations in the pipe wall which were outside the expected range for the 3-in. schedule 40 pipe of 216 mils. A coupon was cut from the thinnest area on the pipe, and analysis of the inside surface, which was in contact with the tank waste, revealed a continuous layer of corrosion ~ 100 11m (4 mils) thick under a semi-continuous layer of tank waste residue ~ 20 11m (1 mil) thick. This residue layer was composed of an amorphous phase rich in chromium, magnesium, calcium, and chlorine. Small pits were detected throughout the inside pipe surface with depths up to ~ 50 11m (2 mils). Similarly, the SN-286 primary pipe did not show, by the ultrasonic transducer measurements, any thinned locations in the pipe wall which were outside the expected range for this pipe. Analysis of the coupon cut from the pipe section showed the presence of a tank waste layer containing sodium aluminate and phases rich in iron, calcium, and chromium. This layer was removed by a cleaning process that left a pipe surface continuous in iron oxide/hydroxide (corrosion) with pockets of aluminum oxide, possibly gibbsite. The corrosion layer was ~ 50 11m (2 mil) thick over non-continuous pits less than ~ 50 11m deep (2 mils). Small particles of aluminum oxide were also detected under the corrosion layer. The ultrasonic transducer analysis of SN-278, like the previous primary pipes, did not reveal any noticeable thinning of the pipe wall. Analysis of the coupon cut from the pipe showed that the inside surface had a layer of tank waste residue that was partially detached from the pipe wall. This layer was easily scraped from the surface and was composed of two separate layers. The underlying layer was ~ 350 11m (14 mils) thick and composed of a cementation of small aluminum oxide (probably gibbsite) particles. A thinner layer on top of the aluminum oxide layer was rich in carbon and chlorine. Scattered pitting was observed on the inside pipe surface with one pit as deep as 200 11m (8 mils).« less

Andic soils : mineralogical effect onto organic matter dynamics, organic matter effect onto mineral dynamics, or both?

NASA Astrophysics Data System (ADS)

Basile-Doelsch, Isabelle; Amundson, Ronald; Balesdent, Jérome; Borschneck, Daniel; Bottero, Jean-Yves; Colin, Fabrice; de Junet, Alexis; Doelsch, Emmanuel; Legros, Samuel; Levard, Clément; Masion, Armand; Meunier, Jean-Dominique; Rose, Jérôme

2014-05-01

From a strictly mineralogical point of view, weathering of volcanic glass produces secondary phases that are short range ordered alumino-silicates (SRO-AlSi). These are imogolite tubes (2 to 3 nm of diameter) and allophane supposedly spheres (3.5 to 5 nm). Their local structure is composed of a curved gibbsite Al layer and Si tetrahedra in the vacancies (Q0). Proto-imogolites have the same local structure but are roof-shape nanoparticles likely representing the precursors of imogolite and allophanes (Levard et al. 2010). These structures and sizes give to the SRO-AlSi large specific surfaces and high reactivities. In some natural sites, imogolites and allophanes are formed in large quantities. Aging of these phases may lead to the formation of more stable minerals (halloysite, kaolinite and gibbsite) (Torn et al 1997). In natural environments, when the weathering of volcanic glass is associated with the establishment of vegetation, the soils formed are generally andosols. These soils are particularly rich in organic matter (OM), which is explained by the high ability of SRO-AlSi mineral phases to form bonds with organic compounds. In a first order "bulk" approach, it is considered that these bonds strongly stabilize the organic compounds as their mean age can reach more than 10 kyrs in some studied sites (Basile-Doelsch et al. 2005; Torn et al. 1997). However, the structure of the mineral phases present in andosols deserves more attention. Traditionally, the presence in the SRO-AlSi andosols was shown by selective dissolution approaches by oxalate and pyrophosphate. Using spectroscopic methods, mineralogical analysis of SRO-AlSi in andosols samples showed that these mineral phases were neither imogolites nor allophanes as originally supposed, but only less organized structures remained in a state of proto-imogolites (Basile-Doelsch al. 2005 ; Levard et al., 2012). The presence of OM would have an inhibitory effect on the formation of secondary mineral phases, by blocking the crystal growth of SRO-AlSi. Conversely, the effect of minerals on the dynamics of organic compounds also deserves to be studied in greater detail. If the "bulk" approaches showed that proto-imogolites involve long-term stabilized OM, other approaches such as densimetric fractionation and C3/C4 chronosequences (Basile-Doelsch et al. 2007; De Junet et al. 2013) led us to consider a new model involving two types of organo-mineral interactions: (1) OM stabilized by strong bonds to proto-imogolite, leading to a slow OM turnover and (2) OM retained within the porosity of the 3D structure formed by the proto-imogolite (similar to a gel structure), leading to a faster OM turnover. Understanding the mechanisms of organo-mineral interactions in andosols will open new research directions for understanding the mechanisms of stabilization of OM in any type of soil (Bonnard et al. 2012). Basile-Doelsch et al., Geoderma, 137, 477-489, 2007. Basile-Doelsch et al., European Journal of Soil Science, 56, 689-703, 2005. Bonnard et al., European Journal of Soil Science, 63, 5, 625-636, 2012. de Junet, et al., Journal of Analytical and Applied Pyrolysis, 99, 92-10, 2013, Levard et al, Geoderma, 183-184, 100-108, 2012. Levard et al. Chemistry Of Materials, 22, 2466-2473, 2010 Torn et al. Nature, London, 389, 170-173, 1997.

Effect of blast furnace slag on self-healing of microcracks in cementitious materials

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

Huang, Haoliang, E-mail: haoliang.huang@tudelft.nl; Ye, Guang; Magnel Laboratory for Concrete Research, Department of Structural Engineering, Ghent University

The physico-chemical process of self-healing in blast furnace slag cement paste was investigated in this paper. With a high slag content i.e., 66% in cement paste and saturated Ca(OH)₂ solution as activator, it was found that the reaction products formed in cracks are composed of C-S-H, ettringite, hydrogarnet and OH–hydrotalcite. The fraction of C-S-H in the reaction products is much larger than the other minerals. Large amount of ettringite formed in cracks indicates the leaching of SO₄⁻² ions from the bulk paste and consequently the recrystallization. Self-healing proceeds fast within 50 h and then slows down. According to thermodynamic modeling,more » when the newly formed reaction products are carbonated, the filling fraction of crack increases first and then decreases. Low soluble minerals such as silica gel, gibbsite and calcite are formed. Compared to Portland cement paste, the potential of self-healing in slag cement paste is higher when the percentage of slag is high. Highlights: • Self-healing reaction products in slag cement paste were characterized. • Self-healing reaction products formed in time were quantified with image analysis. • Self-healing in slag cement paste was simulated with a reactive transport model. • Effect of carbonation on self-healing was investigated by thermodynamic modeling. • Effect of slag on self-healing was discussed based on experiments and simulation.« less

Adsorption coefficients for TNT on soil and clay minerals

NASA Astrophysics Data System (ADS)

Rivera, Rosángela; Pabón, Julissa; Pérez, Omarie; Muñoz, Miguel A.; Mina, Nairmen

2007-04-01

To understand the fate and transport mechanisms of TNT from buried landmines is it essential to determine the adsorption process of TNT on soil and clay minerals. In this research, soil samples from horizons Ap and A from Jobos Series at Isabela, Puerto Rico were studied. The clay fractions were separated from the other soil components by centrifugation. Using the hydrometer method the particle size distribution for the soil horizons was obtained. Physical and chemical characterization studies such as cation exchange capacity (CEC), surface area, percent of organic matter and pH were performed for the soil and clay samples. A complete mineralogical characterization of clay fractions using X-ray diffraction analysis reveals the presence of kaolinite, goethite, hematite, gibbsite and quartz. In order to obtain adsorption coefficients (K d values) for the TNT-soil and TNT-clay interactions high performance liquid chromatography (HPLC) was used. The adsorption process for TNT-soil was described by the Langmuir model. A higher adsorption was observed in the Ap horizon. The Freundlich model described the adsorption process for TNT-clay interactions. The affinity and relative adsorption capacity of the clay for TNT were higher in the A horizon. These results suggest that adsorption by soil organic matter predominates over adsorption on clay minerals when significant soil organic matter content is present. It was found that, properties like cation exchange capacity and surface area are important factors in the adsorption of clayey soils.

Function of minerals in the natural radioactivity level of Vaigai River sediments, Tamilnadu, India--spectroscopical approach.

PubMed

Ramasamy, V; Paramasivam, K; Suresh, G; Jose, M T

2014-01-03

Using Gamma ray and Fourier Transform Infrared (FTIR) spectroscopic techniques, level of natural radioactivity ((238)U, (232)Th and (40)K) and mineralogical characterization of Vaigai River sediments have been analyzed with the view of evaluating the radiation risk and its relation to available minerals. Different radiological parameters are calculated to know the entire radiological characterization. The average of activity concentrations and all radiological parameters are lower than the recommended safety limit. However, some sites are having higher radioactivity values than the safety limit. From the FTIR spectroscopic technique, the minerals such as quartz, microcline feldspar, orthoclase feldspar, kaolinite, gibbsite, calcite, montmorillonite and organic carbon are identified and they are characterized. The extinction co-efficient values are calculated to know the relative distribution of major minerals such as quartz, microcline feldspar, orthoclase feldspar and kaolinite. The calculated values indicate that the amount of quartz is higher than orthoclase feldspar, microcline feldspar and much higher than kaolinite. Crystallinity index is calculated to know the crystalline nature of quartz and the result indicates that the presence of ordered crystalline quartz in the present sediment. The role of minerals in the level of radioactivity is assessed by multivariate statistical analysis (Pearson's correlation and Cluster analysis). The statistical analysis confirms that the clay mineral kaolinite is the major factor than other major minerals to induce the important radioactivity variables such as absorbed dose rate and concentrations of (232)Th and (238)U. Copyright © 2013 Elsevier B.V. All rights reserved.

Lipid peroxidation and cytotoxicity induced by respirable volcanic ash.

PubMed

Cervini-Silva, Javiera; Antonio-Nieto-Camacho; Gomez-Vidales, Virginia; Ramirez-Apan, María Teresa; Palacios, Eduardo; Montoya, Ascención; Kaufhold, Stephan; Abidin, Zeanal; Theng, Benny K G

2014-06-15

This paper reports that the main component of respirable volcanic ash, allophane, induces lipid peroxidation (LP), the oxidative degradation of lipids in cell membranes, and cytotoxicity in murin monocyle/macrophage cells. Naturally-occurring allophane collected from New Zealand, Japan, and Ecuador was studied. The quantification of LP was conducted using the Thiobarbituric Acid Reactive Substances (TBARS) assay. The cytotoxic effect was determined by the 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide colorimetric assay. Electron-Paramagnetic Resonance (EPR) determinations of naturally-occurring allophane confirmed the incorporation in the structure and clustering of structural Fe(3+), and nucleation and growth of small-sized Fe (oxyhydr)oxide or gibbsite. LP induced by allophane varied with time, and solid concentration and composition, reaching 6.7 ± 0.2 nmol TBARS mg prot(-1). LP was surface controlled but not restricted by structural or surface-bound Fe(3+), because redox processes induced by soluble components other than perferryl iron. The reactivity of Fe(3+) soluble species stemming from surface-bound Fe(3+) or small-sized Fe(3+) refractory minerals in allophane surpassed that of structural Fe(3+) located in tetrahedral or octahedral sites of phyllosilicates or bulk iron oxides. Desferrioxamine B mesylate salt (DFOB) or ethylenediaminetetraacetic acid (EDTA) inhibited LP. EDTA acted as a more effective inhibitor, explained by multiple electron transfer pathways. Registered cell-viability values were as low as 68.5 ± 6.7%. Copyright © 2014 Elsevier B.V. All rights reserved.

Anomalous columnar order of charged colloidal platelets

NASA Astrophysics Data System (ADS)

Morales-Anda, L.; Wensink, H. H.; Galindo, A.; Gil-Villegas, A.

2012-01-01

Monte Carlo computer simulations are carried out for a model system of like-charged colloidal platelets in the isothermal-isobaric ensemble (NpT). The aim is to elucidate the role of electrostatic interactions on the structure of synthetic clay systems at high particle densities. Short-range repulsions between particles are described by a suitable hard-core model representing a discotic particle. This potential is supplemented with an electrostatic potential based on a Yukawa model for the screened Coulombic potential between infinitely thin disklike macro-ions. The particle aspect-ratio and electrostatic parameters were chosen to mimic an aqueous dispersion of thin, like-charged, rigid colloidal platelets at finite salt concentration. An examination of the fluid phase diagram reveals a marked shift in the isotropic-nematic transition compared to the hard cut-sphere reference system. Several statistical functions, such as the pair correlation function for the center-of-mass coordinates and structure factor, are obtained to characterize the structural organization of the platelets phases. At low salinity and high osmotic pressure we observe anomalous hexagonal columnar structures characterized by interpenetrating columns with a typical intercolumnar distance corresponding to about half of that of a regular columnar phase. Increasing the ionic strength leads to the formation of glassy, disordered structures consisting of compact clusters of platelets stacked into finite-sized columns. These so-called "nematic columnar" structures have been recently observed in systems of charge-stabilized gibbsite platelets. Our findings are corroborated by an analysis of the static structure factor from a simple density functional theory.

Mineralogy of a perudic Andosol in central Java, Indonesia

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

Van Ranst, Eric; Utami, S. R.; Verdoodt, A.

2008-02-15

We studied the mineralogy of a perudic Andosol developed on the Dieng Tephra Sequence in central Java, Indonesia. The objective was to confirm the presence and determine the origin and stability of 2:1 and interlayered 2:1 phyllosilicates in well-drained Andosols. This was and still is a debated topic in the literature. Total elemental and selective dissolution, as well as microscopic and X-ray diffraction analyses, were performed on the soil samples collected from this site. These analyses confirmed that andic properties were present in the soil samples. The allophane content determined by selective dissolution was 3-4% in the A horizons, andmore » increased to 12-18% in the deeper subsoil horizons. In addition, the clay fraction contained dioctahedral smectite, hydroxy-Al-interlayered 2:1 minerals (HIS), Al-chlorite, kaolinite, pyrophyllite, mica, cristobalite and some gibbsite. The silt and sand fractions were rich in plagioclase and pyroxene. The 2:1 minerals (smectite and pyrophyllite), as well as chlorite and kaolinite were of hydrothermal origin and were incorporated in the tephra during volcanic eruption. Besides desilication during dissolution of unstable minerals, Al interlayering of 2:1 layer silicates was most likely the most prominent pedogenic process. Although hydroxy-Al polymeric interlayers would normally stabilize the 2:1 clay phases, the strong weakening, and even disappearance of the characteristic XRD peaks, indicated instability of these minerals in the upper A horizons due to the perudic and intensive leaching conditions.« less

Chemical interactions of aluminum with aqueous silica at 25 degrees Celsius

USGS Publications Warehouse

Hem, John David; Roberson, C.E.; Lind, Carol J.; Polxer, W.L.

1973-01-01

Solutions containing from 10 -5 to 10 -2 moles per liter of aluminum and dissolved silica in various ratios were aged at pH levels between 4 and 10 at 25?C. A colloidal amorphous product having the composition of halloysite was produced in most solutions. It had a consistent and reversible equilibrium solubility equivalent to a standard free energy of formation of -8974 ? 1.0 kcal per mole for the formula A12Si2O5(OH)4. Some aging times were longer than 4 years, but most solutions gave consistent solubilities after only a few months of aging. Where silica concentrations were below about 10 -4 molar, microcrystalline gibbsite was formed below pH 6.0 and crystalline bayerite above pH 7.0, but only after much longer aging than was required for crystallization in silica-free solutions. Electron micrographs and diffraction patterns of the synthesized material indicate some crystallinity in the aluminosilicate, but no X-ray diffraction patterns could be obtained even in the material aged 4 years. Solubility relationships for solutions containing fluoride as well as silica and aluminum are explainable by using cryolite stabilities determined in previous work. Aluminum contents of 51 samples of water analyzed for other purposes are in reasonable agreement with the assumption of equilibrium with amorphous clay mineral species similar to the material synthesized in this work. Solubility calculations are summarized graphically for solutions of ionic strength of 0.01 and 0.10.

Characterization and evaluation of sorption potential of the iron mine waste after Samarco dam disaster in Doce River basin - Brazil.

PubMed

Almeida, Cristiane Aparecida; Oliveira, André Fernando de; Pacheco, Anderson Almeida; Lopes, Renata Pereira; Neves, Antônio Augusto; Lopes Ribeiro de Queiroz, Maria Eliana

2018-06-14

The Fundão dam collapsed releasing 60 million tons of mining waste into the environment. The mining wastes should be better studied, since some of them are deposited on the alluvial plains soil and at the bottom of the rivers, like sediments, of the region affected. Thus, this work aims to perform the chemical, physical and adsorptive characterization of the samples colleted in region de Paracatu de Baixo. The mining waste has uneven surface, with sizes ranging from 2 to 200 μm, pHPCZ in 6.0. Are composed predominantly by kaolinite, goethite, hematite, gibbsite and quartz. It has been classified as non-hazardous residues. The adsorption studies showed the mining waste have a low Cationic Exchange Capacity. The sorption process was occurs by ion exchange and the kinetics follows the pseudo second order model (R 2  > 0.78). The process is endothermic (ΔH in 29.33 kJ mol -1 ) and spontaneous (ΔG in -24.7 kJ mol -1 at 25 °C). The Langmuir model presented a better fit (R 2  > 0.995) to the experimental data. Therefore, the methylene blue can be used as a cation model to predict the behavior of cationic species on the mining waste, with maximum adsorption capacity of 4.42 mg g -1 at 25 °C. Copyright © 2018. Published by Elsevier Ltd.

Geochemistry of Selected Kaolins from Cameroon and Nigeria

NASA Astrophysics Data System (ADS)

Bukalo, Nenita N.; Ekosse, Georges-Ivo E.; Odiyo, John O.; Ogola, Jason S.

2017-12-01

The geochemical characteristics of selected kaolins from Cameroon and Nigeria are presented, with an attempt to elucidate on their possible industrial applications by comparing them to world-known kaolin deposits. Major oxides concentrations were subjected to factor analyses in interpreting their relationships. Geochemical indices, including chemical index of alteration (CIA), chemical index of weathering (CIW) and the index of compositional variability (ICV) were computed and plotted on binary and ternary diagrams to determine the intensity of weathering of the kaolins and discriminate their different source rock types. Kaolinite was the major phase, followed by quartz, illite and goethite as minor phases. Minerals in trace phases included smectite, anatase, muscovite, gibbsite, microcline, palygorskite and calcite. Mean abundances of major oxides in wt% were: SiO2 (56.96)>Al2O3 (24.09)>Fe2O3 (3.78)>TiO2 (1.53)> K2O (1.26)> MgO (0.27)>CaO (0.20)>Na2O (0.17)>P2O5 (0.05)>MnO (0.04). The CIW versus CIA and ICV versus CIA plots showed that most of the kaolins clearly depicted extreme silicate weathering. The current applications of kaolins from Cameroon and Nigeria include ceramics and manufacturing of bricks and tiles. Low MgO, CaO, Na2O, K2O and TiO2 further position the kaolins for pharmaceutics, cosmetics, rubber and plastic applications. Thus, the studied kaolins have the potential to contribute to improved economic development of these countries.

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

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

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

2016-10-01

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

Crystallographic controls on the frictional behavior of dry and water-saturated sheet structure minerals

USGS Publications Warehouse

Moore, Diane E.; Lockner, D.A.

2004-01-01

We compare the frictional strengths of 17 sheet structure mineral powders, measured under dry and water-saturated conditions, to identify the factors that cause many of them to be relatively weak. The dry coefficient of friction ?? ranges upward from 0.2 for graphite, leveling off at 0.8 for margarite, clintonite, gibbsite, kaolinite, and lizardite. The values of ?? (dry) correlate directly with calculated (001) interlayer bond strengths of the minerals. This correlation occurs because shear becomes localized along boundary and Riedel shears and the platy minerals in them rotate into alignment with the shear planes. For those gouges with ?? (dry) < 0.8, shear occurs by breaking the interlayer bonds to form new cleavage surfaces. Where ?? (dry) = 0.8, consistent with Byerlee's law, the interlayer bonds are sufficiently strong that other frictional processes dominate. The transition in dry friction mechanisms corresponds to calculated surface energies of 2-3 J/m2. Adding water causes ?? to decrease for every mineral tested except graphite. If the minerals are separated into groups with similar crystal structures, ?? (wet) increases with increasing interlayer bond strength within each group. This relationship also holds for the swelling clay montmorillonite, whose water-saturated strength is consistent with the strengths of nonswelling clays of similar crystal structure. Water in the saturated gouges forms thin, structured films between the plate surfaces. The polar water molecules are bonded to the plate surfaces in proportion to the mineral's surface energy, and ?? (wet) reflects the stresses required to shear through the water films. Copyright 2004 by the American Geophysical Union.

Formation of crystalline Zn-Al layered double hydroxide precipitates on γ-alumina: the role of mineral dissolution.

PubMed

Li, Wei; Livi, Kenneth J T; Xu, Wenqian; Siebecker, Matthew G; Wang, Yujun; Phillips, Brian L; Sparks, Donald L

2012-11-06

To better understand the sequestration of toxic metals such as nickel (Ni), zinc (Zn), and cobalt (Co) as layered double hydroxide (LDH) phases in soils, we systematically examined the presence of Al and the role of mineral dissolution during Zn sorption/precipitation on γ-Al(2)O(3) (γ-alumina) at pH 7.5 using extended X-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HR-TEM), synchrotron-radiation powder X-ray diffraction (SR-XRD), and (27)Al solid-state NMR. The EXAFS analysis indicates the formation of Zn-Al LDH precipitates at Zn concentration ≥0.4 mM, and both HR-TEM and SR-XRD reveal that these precipitates are crystalline. These precipitates yield a small shoulder at δ(Al-27) = +12.5 ppm in the (27)Al solid-state NMR spectra, consistent with the mixed octahedral Al/Zn chemical environment in typical Zn-Al LDHs. The NMR analysis provides direct evidence for the existence of Al in the precipitates and the migration from the dissolution of γ-alumina substrate. To further address this issue, we compared the Zn sorption mechanism on a series of Al (hydr)oxides with similar chemical composition but differing dissolubility using EXAFS and TEM. These results suggest that, under the same experimental conditions, Zn-Al LDH precipitates formed on γ-alumina and corundum but not on less soluble minerals such as bayerite, boehmite, and gibbsite, which point outs that substrate mineral surface dissolution plays an important role in the formation of Zn-Al LDH precipitates.

Implementation of reverse flotation method to reduce reactive and non-reactive silica in bauxite ore from West Kalimantan

NASA Astrophysics Data System (ADS)

Wulandari, Winny; Purwasasmita, Mubiar; Sanwani, Edy; Pixelina, Adinda Asri; Maulidan, Agus

2017-01-01

This paper reports a study that implements reverse flotation method to separate silica from West Kalimantan bauxite ores. The study is aimed to find the good process condition to obtain low-silica bauxite as the feed for the Bayer process. The experiments were carried out in a 1 L of flotation cell tank. Dodecylamine was used as the collector, starch as the depressant, and MIBC as the frother. The varied parameters were solid content to solution (15-30% w/w), and pH (6 - 10). The results of XRF of products show that in all reverse flotation experiments, the ratio of alumina to silica (Al/Si) are increased from 7 up to 14. The increase of solid percentage in the flotation gives a good result for Al/Si ratio as well as alumina and silica recovery in concentrate, with 30% w/w solid percentage to solution increases Al/Si ratio to 14.38, with silica recovery of 20%. The good separation with variation of depressants is obtained with depressant concentration of 400 g/ton bauxite, with Al/Si ratio in concentrate 15 and ratio in tailing 7. For the pH variation, the good condition is obtained at pH 8, while for collector concentration, the good condition is obtained at 200 g/ton bauxite. XRD analysis of the feed indicates that bauxite ore consists of gibbsite, diaspore, kaolinite, halloysite, quartz, boehmite, hematite and rutile. It is found that the concentrate has similar minerals, but halloysite became very minor or classified as a trace.

Applied geochemistry, geology and mineralogy of the northernmost Carlin trend, Nevada

USGS Publications Warehouse

Theodore, T.G.; Kotlyar, B.B.; Singer, D.A.; Berger, V.I.; Abbott, E.W.; Foster, A.L.

2003-01-01

Investigations in the northernmost Carlin trend were undertaken to advance understanding of the geochemical signatures and genesis of precious metal deposits in the trend. Two fundamental geologic relationships near the trend significantly affect regional geochemical distributions: a remarkably intact lower Paleozoic stratigraphic sequence of siliceous rocks in the upper plate of the middle Paleozoic Roberts Mountains thrust, and the widespread repetition of rocks high in the upper plate during late Paleozoic thrusting that thickens the cover above mineralized rock in the lower plate. A compilation of previously published chemical analyses of 440 stream sediment samples and 115 rocks from two 7 1/2-minute quadrangles, as well as new chemical analyses of approximately 1,000 drill core samples in a 1,514 m (4,970 ft) hole through the Rodeo Creek deposit were used to construct three-dimensional element distribution models that highlight metal zonation in the mineralized systems. The Rodeo Creek deposit comprises deep Ag base-metal ?? Au-mineralized rock below the Roberts Mountains thrust and contains an unusually high Ag/Au ratio greater than 30. Stacked geochemical halos related to the deposit are confined to the lower plate of the Roberts Mountains thrust and include two horizons of Hg, Cu, and Zn anomalies-as much as 180 m above the deposit-that mostly result from mercurian sphalerite. Extremely subtle indications of mineralization in the upper plate of the Roberts Mountains thrust above the deposit include arsenopyrite overgrowths on small pyrite crystals in 50- to 75-??m-wide clay-carbonate veinlets that lack alteration halos, arsenical rims on small disseminated crystal of recrystallized diagenetic pyrite, and partial replacement of diagenetic pyrite by tennantite. Some of these minerals contain anomalously high Au. However, these As-(Au)-bearing rocks most likely represent another locus of largely untested mineralized rock rather than distal halos related to either the Rodeo Creek or the nearby Dee and Storm gold deposits. Application of micromineralogic techniques helped to identify mineral assemblages that are specific to mineralization and provided an empirical foundation for interpretations of geochemical halos in the Carlin trend. District-scale geochemical patterns of several elements in stream sediments and surface rocks coincide with the northernmost Carlin trend and can be used to explore for Carlin-type deposits. Concentrations of elevated As and Sb in stream sediments (as much as 54 ppm As) have northwest-elongate lobate patterns that clearly outline the trend across a width of approximately 4 km. Arsenic contents of exposed rocks (as much as 90 ppm As) strongly correlate with As contents of derivative stream sediments, and rock contents of Sb show a somewhat lesser but nonetheless strong and similar correspondence. Factor analysis of stream-sediment data shows that those factor scores that are correlated with As, Sb, Au, and Pb also are high along the trend and suggest that mineralized rocks may be present. Although As was not detected by scanning electron microscope-energy dispersive spectrometer (SEM-EDS) studies in heavy mineral concentrates of high-As stream sediments in the Carlin trend, X-ray absorption near-edge spectra (XANES) of selected light fractions of stream sediment samples indicate that Al-bearing phases, such as gibbsite, amorphous Al oxyhydroxides, or aluminosilicate clay minerals host most of the As(V). The best fit, visually and in terms of the lowest residual, was obtained by a model compound of As(V) sorbed to gibbsite. Thus, most As in stream sediments derived from altered rock within the Carlin trend apparently is contained in light fractions. The geochemical character of young, unconsolidated, postmineral deposits that cover mineralized rocks on the Carlin trend partly results from mineralized sources along the trend. Concentration of As in the Miocene Carlin Formation shows an exceptio

Geochemical characteristics of the San Miguel aquifer, Baja California, Mexico.

NASA Astrophysics Data System (ADS)

Tostado-Plascencia, Miriam; Rosas-Elguera, Jose; Kretzschmar, Thomas

2010-05-01

The valley of San Miguel, located in the state of Baja California, Mexico, is an important region because of the wine industry. It is therefore important to know groundwater characteristics. Two aquifers can be recognized in the San Miguel basin, first one is in fractured granitic rocks (in the upper part of the basin, called UB) and other is free-type in detritc sediments (in the lower part of the basin, close to the sea, called LB). The water temperature ranges between 25°C y 11°C without significant variations along the year. The conductivity increases with the water temperature and decreases in February when the temperature is lower. The pH of the waters in UB is between 8.5 and 6.5 but in the LB is in the range of 6.8 to 7.3. Our data show that Na, Mg, and HCO3- concentrations decrease during the rainy season due to ion exchange. According to the Stiff diagrams the waters of the LB are classified as sodium chloride. In the UB the water classification includes calcium and magnesium bicarbonate, magnesium chloride, and few calcium chloride and sodium chloride. The saturation indexes of the waters suggest that the mineral phases which can be present are: K-feldspar, gibbsite, albite, quartz, calcite, aragonite, gypsum, and magnesite. Because of SI>0 then the first four phases can precipitate but the SI of magnesite and gypsum is negative thus the can be dissolved. Finally, calcite and aragonite are in equilibrium due to they are close to zero. Our results suggest that the aquifers of the San Miguel basin do not show evidence of saline intrusion.

Reaction modeling of drainage quality in the Duluth Complex, northern Minnesota, USA

USGS Publications Warehouse

Seal, Robert; Lapakko, Kim; Piatak, Nadine; Woodruff, Laurel G.

2015-01-01

Reaction modeling can be a valuable tool in predicting the long-term behavior of waste material if representative rate constants can be derived from long-term leaching tests or other approaches. Reaction modeling using the REACT program of the Geochemist’s Workbench was conducted to evaluate long-term drainage quality affected by disseminated Cu-Ni-(Co-)-PGM sulfide mineralization in the basal zone of the Duluth Complex where significant resources have been identified. Disseminated sulfide minerals, mostly pyrrhotite and Cu-Fe sulfides, are hosted by clinopyroxene-bearing troctolites. Carbonate minerals are scarce to non-existent. Long-term simulations of up to 20 years of weathering of tailings used two different sets of rate constants: one based on published laboratory single-mineral dissolution experiments, and one based on leaching experiments using bulk material from the Duluth Complex conducted by the Minnesota Department of Natural Resources (MNDNR). The simulations included only plagioclase, olivine, clinopyroxene, pyrrhotite, and water as starting phases. Dissolved oxygen concentrations were assumed to be in equilibrium with atmospheric oxygen. The simulations based on the published single-mineral rate constants predicted that pyrrhotite would be effectively exhausted in less than two years and pH would rise accordingly. In contrast, only 20 percent of the pyrrhotite was depleted after two years using the MNDNR rate constants. Predicted pyrrhotite depletion by the simulation based on the MNDNR rate constant matched well with published results of laboratory tests on tailings. Modeling long-term weathering of mine wastes also can provide important insights into secondary reactions that may influence the permeability of tailings and thereby affect weathering behavior. Both models predicted the precipitation of a variety of secondary phases including goethite, gibbsite, and clay (nontronite).

Hydrogeochemical and mineralogical effects of sustained CO2 contamination in a shallow sandy aquifer: A field-scale controlled release experiment

NASA Astrophysics Data System (ADS)

Cahill, Aaron G.; Marker, Pernille; Jakobsen, Rasmus

2014-02-01

A shallow aquifer CO2 contamination experiment was performed to investigate evolution of water chemistry and sediment alteration following leakage from geological storage by physically simulating a leak from a hypothetical storage site. In a carbonate-free aquifer, in western Denmark, a total of 1600 kg of gas phase CO2 was injected at 5 and 10 m depth over 72 days through four inclined injection wells into aeolian and glacial sands. Water chemistry was monitored for pH, EC, and dissolved element evolution through an extensive network of multilevel sampling points over 305 days. Sediment cores were taken pre and postinjection and analyzed to search for effects on mineralogy and sediment properties. Results showed the simulated leak to evolve in two distinct phases; an advective elevated ion pulse followed by increasing persistent acidification. Spatial and temporal differences in evolution of phases suggest separate chemical mechanisms and geochemical signatures. Dissolved element concentrations developed exhibiting four behaviors: (1) advective pulse (Ca, Mg, Na, Si, Ba, and Sr), (2) pH sensitive abundance dependent (Al and Zn), (3) decreasing (Mn and Fe), and (4) unaffected (K). Concentration behaviors were characterized by: (1) a maximal front moving with advective flow, (2) continual increase in close proximity to the injection plane, (3) removal from solution, and (4) no significant change. Only Al was observed to exceed WHO guidelines, however significantly so (10-fold excess). The data indicate that pH is controlled by equilibrium with gibbsite which is again coupled to cation exchange processes. Pre and postinjection sediment analysis indicated alteration of sediment composition and properties including depletion of reactive mineral species.

Analysis of ASTER data for mapping bauxite rich pockets within high altitude lateritic bauxite, Jharkhand, India

NASA Astrophysics Data System (ADS)

Guha, Arindam; Singh, Vivek Kr.; Parveen, Reshma; Kumar, K. Vinod; Jeyaseelan, A. T.; Dhanamjaya Rao, E. N.

2013-04-01

Bauxite deposits of Jharkhand in India are resulted from the lateritization process and therefore are often associated with the laterites. In the present study, ASTER (Advanced Space borne Thermal Emission and Reflection Radiometer) image is processed to delineate bauxite rich pockets within the laterites. In this regard, spectral signatures of lateritic bauxite samples are analyzed in the laboratory with reference to the spectral features of gibbsite (main mineral constituent of bauxite) and goethite (main mineral constituent of laterite) in VNIR-SWIR (visible-near infrared and short wave infrared) electromagnetic domain. The analysis of spectral signatures of lateritic bauxite samples helps in understanding the differences in the spectral features of bauxites and laterites. Based on these differences; ASTER data based relative band depth and simple ratio images are derived for spatial mapping of the bauxites developed within the lateritic province. In order to integrate the complementary information of different index image, an index based principal component (IPC) image is derived to incorporate the correlative information of these indices to delineate bauxite rich pockets. The occurrences of bauxite rich pockets derived from density sliced IPC image are further delimited by the topographic controls as it has been observed that the major bauxite occurrences of the area are controlled by slope and altitude. In addition to above, IPC image is draped over the digital elevation model (DEM) to illustrate how bauxite rich pockets are distributed with reference to the topographic variability of the terrain. Bauxite rich pockets delineated in the IPC image are also validated based on the known mine occurrences and existing geological map of the bauxite. It is also conceptually validated based on the spectral similarity of the bauxite pixels delineated in the IPC image with the ASTER convolved laboratory spectra of bauxite samples.

Quantitative X-ray Diffraction (QXRD) analysis for revealing thermal transformations of red mud.

PubMed

Liao, Chang-Zhong; Zeng, Lingmin; Shih, Kaimin

2015-07-01

Red mud is a worldwide environmental problem, and many authorities are trying to find an economic solution for its beneficial application or/and safe disposal. Ceramic production is one of the potential waste-to-resource strategies for using red mud as a raw material. Before implementing such a strategy, an unambiguous understanding of the reaction behavior of red mud under thermal conditions is essential. In this study, the phase compositions and transformation processes were revealed for the Pingguo red mud (PRM) heat-treated at different sintering temperatures. Hematite, perovskite, andradite, cancrinite, kaolinite, diaspore, gibbsite and calcite phases were observed in the samples. However, unlike those red mud samples from the other regions, no TiO2 (rutile or anatase) or quartz were observed. Titanium was found to exist mainly in perovskite and andradite while the iron mainly existed in hematite and andradite. A new silico-ferrite of calcium and aluminum (SFCA) phase was found in samples treated at temperatures above 1100°C, and two possible formation pathways for SFCA were suggested. This is the first SFCA phase to be reported in thermally treated red mud, and this finding may turn PRM waste into a material resource for the iron-making industry. Titanium was found to be enriched in the perovskite phase after 1200°C thermal treatment, and this observation indicated a potential strategy for the recovery of titanium from PRM. In addition to noting these various resource recovery opportunities, this is also the first study to quantitatively summarize the reaction details of PRM phase transformations at various temperatures. Copyright © 2015 Elsevier Ltd. All rights reserved.

Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance

USGS Publications Warehouse

Blum, A.E.; Eberl, D.D.

2004-01-01

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ~0.99 mg/m2, which corresponds to ~0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (~725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

Soil forensics: How far can soil clay analysis distinguish between soil vestiges?

PubMed

Corrêa, R S; Melo, V F; Abreu, G G F; Sousa, M H; Chaker, J A; Gomes, J A

2018-03-01

Soil traces are useful as forensic evidences because they frequently adhere to individuals and objects associated with crimes and can place or discard a suspect at/from a crime scene. Soil is a mixture of organic and inorganic components and among them soil clay contains signatures that make it reliable as forensic evidence. In this study, we hypothesized that soils can be forensically distinguished through the analysis of their clay fraction alone, and that samples of the same soil type can be consistently distinguished according to the distance they were collected from each other. To test these hypotheses 16 Oxisol samples were collected at distances of between 2m and 1.000m, and 16 Inceptisol samples were collected at distances of between 2m and 300m from each other. Clay fractions were extracted from soil samples and analyzed for hyperspectral color reflectance (HSI), X-ray diffraction crystallographic (XRD), and for contents of iron oxides, kaolinite and gibbsite. The dataset was submitted to multivariate analysis and results were from 65% to 100% effective to distinguish between samples from the two soil types. Both soil types could be consistently distinguished for forensic purposes according to the distance that samples were collected from each other: 1000m for Oxisol and 10m for Inceptisol. Clay color and XRD analysis were the most effective techniques to distinguish clay samples, and Inceptisol samples were more easily distinguished than Oxisol samples. Soil forensics seems a promising field for soil scientists as soil clay can be useful as forensic evidence by using routine analytical techniques from soil science. Copyright © 2017 The Chartered Society of Forensic Sciences. Published by Elsevier B.V. All rights reserved.

Seasonal provenance changes in present-day Saharan dust collected in and off Mauritania

NASA Astrophysics Data System (ADS)

Friese, Carmen A.; van Hateren, Johannes A.; Vogt, Christoph; Fischer, Gerhard; Stuut, Jan-Berend W.

2017-08-01

Saharan dust has a crucial influence on the earth climate system and its emission, transport and deposition are intimately related to, e.g., wind speed, precipitation, temperature and vegetation cover. The alteration in the physical and chemical properties of Saharan dust due to environmental changes is often used to reconstruct the climate of the past. However, to better interpret possible climate changes the dust source regions need to be known. By analysing the mineralogical composition of transported or deposited dust, potential dust source areas can be inferred. Summer dust transport off northwest Africa occurs in the Saharan air layer (SAL). In continental dust source areas, dust is also transported in the SAL; however, the predominant dust input occurs from nearby dust sources with the low-level trade winds. Hence, the source regions and related mineralogical tracers differ with season and sampling location. To test this, dust collected in traps onshore and in oceanic sediment traps off Mauritania during 2013 to 2015 was analysed. Meteorological data, particle-size distributions, back-trajectory and mineralogical analyses were compared to derive the dust provenance and dispersal. For the onshore dust samples, the source regions varied according to the seasonal changes in trade-wind direction. Gibbsite and dolomite indicated a Western Saharan and local source during summer, while chlorite, serpentine and rutile indicated a source in Mauritania and Mali during winter. In contrast, for the samples that were collected offshore, dust sources varied according to the seasonal change in the dust transporting air layer. In summer, dust was transported in the SAL from Mauritania, Mali and Libya as indicated by ferroglaucophane and zeolite. In winter, dust was transported with the trades from Western Sahara as indicated by, e.g., fluellite.

Bioavailability of cadmium adsorbed on various oxides minerals to wetland plant species Phragmites australis.

PubMed

Wang, He; Jia, Yongfeng; Wang, Shaofeng; Zhu, Huijie; Wu, Xing

2009-08-15

The bioavailability of heavy metals strongly depends on their speciation in the environment. The effect of different chemical speciations of cadmium ions (i.e. adsorbed on different oxide minerals) on its bioavailability to wetland plant Phragmites australis was studied. Goethite, magnetite, gibbsite, alumina, and manganese oxide were chosen as representatives of metal (hydr)oxides commonly present in sediment. The cultivar system with Hoagland solution as nutrition supply, and single metal oxide with adsorbed Cd as contaminant was applied to study Cd accumulation by P. australis. The bioaccumulation degree in root after the 45-day treatment followed the order: Al(OH)(3)>Al(2)O(3)>Fe(3)O(4)>MnO(2)>FeOOH. The concentration of Cd in stem and leaf followed a similar order although it was considerably lower than that in root. Low-molecular-weight organic acids (LMWOAs), acetic acid, malic acid and citric acid were used to evaluate the desorbability of Cd from different oxides, which can be indicative of Cd-oxide bonding strength and Cd bioavailability. Desorption of Cd by acetic acid and malic acid followed the order: Al(OH)(3)>Fe(3)O(4)>Al(2)O(3)>FeOOH>MnO(2), while by citric acid: Al(OH)(3)> or =Al(2)O(3)>Fe(3)O(4)>FeOOH>MnO(2). This was consistent with the Cd accumulation degree in the plant. Cd adsorbed on Al(OH)(3) was the most easily desorbable species and most bioavailable to P. australis among the oxide minerals, whereas MnO(2) adsorbed Cd was least desorbable by LMWOAs hence constituted the least bioavailable Cd species adsorbed on the oxide minerals.

Kinetics of thermal decomposition of hydrated minerals associated with hematite ore in a fluidized bed reactor

NASA Astrophysics Data System (ADS)

Beuria, P. C.; Biswal, S. K.; Mishra, B. K.; Roy, G. G.

2017-03-01

The kinetics of removal of loss on ignition (LOI) by thermal decomposition of hydrated minerals present in natural iron ores (i.e., kaolinite, gibbsite, and goethite) was investigated in a laboratory-scale vertical fluidized bed reactor (FBR) using isothermal methods of kinetic analysis. Experiments in the FBR in batch processes were carried out at different temperatures (300 to 1200°C) and residence time (1 to 30 min) for four different iron ore samples with various LOIs (2.34wt% to 9.83wt%). The operating velocity was maintained in the range from 1.2 to 1.4 times the minimum fluidization velocity ( U mf). We observed that, below a certain critical temperature, the FBR did not effectively reduce the LOI to a desired level even with increased residence time. The results of this study indicate that the LOI level could be reduced by 90% within 1 min of residence time at 1100°C. The kinetics for low-LOI samples (<6wt%) indicates two different reaction mechanisms in two temperature regimes. At lower temperatures (300 to 700°C), the kinetics is characterized by a lower activation energy (diffusion-controlled physical moisture removal), followed by a higher activation energy (chemically controlled removal of LOI). In the case of high-LOI samples, three different kinetics mechanisms prevail at different temperature regimes. At temperature up to 450°C, diffusion kinetics prevails (removal of physical moisture); at temperature from 450 to 650°C, chemical kinetics dominates during removal of matrix moisture. At temperatures greater than 650°C, nucleation and growth begins to influence the rate of removal of LOI.

Effect of grain-coating mineralogy on nitrate and sulfate storage in the unsaturated zone

USGS Publications Warehouse

Reilly, T.J.; Fishman, N.S.; Baehr, A.L.

2009-01-01

Unsaturated-zone sediments and the chemistry of shallow groundwater underlying a small (???8-km2) watershed were studied to identify the mechanisms responsible for anion storage within the Miocene Bridgeton Formation and weathered Coastal Plain deposits in southern New Jersey. Lower unsaturated-zone sediments and shallow groundwater samples were collected and concentrations of selected ions (including NO3- and SO42-) from 11 locations were determined. Grain size, sorting, and color of the lower unsaturated-zone sediments were determined and the mineralogy of these grains and the composition of coatings were analyzed by petrographic examination, scanning electron microscopy and energy dispersive analysis of x-rays, and quantitative whole-rock x-ray diffraction. The sediment grains, largely quartz and chert (80-94% w/w), are coated with a very fine-grained (<20 ??m), complex mixture of kaolinite, halloysite, goethite, and possibly gibbsite and lepidocrocite. The mineral coatings are present as an open fabric, resulting in a large surface area in contact with pore water. Significant correlations between the amount of goethite in the grain coatings and the concentration of sediment-bound SO42- were observed, indicative of anion sorption. Other mineral-chemical relations indicate that negatively charged surfaces and competition with SO 42- results in exclusion of NO3- from inner sphere exchange sites. The observed NO3- storage may be a result of matrix forces within the grain coatings and outer sphere complexation. The results of this study indicate that the mineralogy of grain coatings can have demonstrable effects on the storage of NO 3- and SO42- in the unsaturated zone. ?? Soil Science Society of America. All rights reserved.

Long-term leaching from recycled concrete aggregates applied as sub-base material in road construction.

PubMed

Engelsen, Christian J; van der Sloot, Hans A; Petkovic, Gordana

2017-06-01

In the present study, the metal leaching from recycled concrete aggregates (RCA) used in road sub-base is presented after >10years of exposure. The released levels of inorganic constituents, the effect of small variation of pH and the use of de-icing salt during winter season were studied. In addition, speciation modelling for the major elements has been provided. The pH varied from 7.5 to 8.5 for the sub-base constructed with RCA whereas the pH of around 8 was obtained for the test section not affected by the traffic and de-icing salts. Despite a small variation in pH, the leachability of Al, Ca and Mg was found to be strongly dependent on pH and fair agreement between the measured and predicted concentrations was obtained. The speciation modelling indicated that gibbsite, calcite and magnesite controlled the solubility of Al, Ca and Mg, respectively, which was in agreement with the expected carbonation products. Due to the larger pH fluctuations in the test sections exposed to the road traffic, increased concentrations were observed for the oxyanions. The same effect was not seen for the trace metal cations Cd, Cu, Ni, Pb and Zn. The distinct pH dependent leaching profile (solubility maximum in the mildly basic pH region) for vanadium could be seen after 10years of exposure. The simplified risk assessment showed that the released quantities did not exceed the chosen acceptance criteria for groundwater and fresh water. The results obtained for the test section not influenced by road dust and de-icing salts, complied with these criteria even without considering any dilution effects caused by the mixing of pore water with groundwater. Copyright © 2017 Elsevier B.V. All rights reserved.

Kinetic behavior of Fe(o,o-EDDHA)-humic substance mixtures in several soil components and in calcareous soils.

PubMed

Cerdán, Mar; Alcañiz, Sara; Juárez, Margarita; Jordá, Juana D; Bermúdez, Dolores

2007-10-31

Ferric ethylenediamine- N, N'-bis-(o-hydroxyphenylacetic)acid chelate (Fe(o, o-EDDHA)) is one of the most effective Fe fertilizers in calcareous soils. However, humic substances are occasionally combined with iron chelates in drip irrigation systems in order to lower costs. The reactivity of iron chelate-humic substance mixtures in several soil components and in calcareous soils was investigated through interaction tests, and their behavior was compared to the application of iron chelates and humic substances separately. Two commercial humic substances and two Fe(o, o-EDDHA) chelates (one synthesized in the laboratory and one commercial) were used to prepare iron chelate-humic substance mixtures at 50% (w/w). Various soil components (calcium carbonate, gibbsite, amorphous iron oxide, hematite, tenorite, zincite, amorphous Mn oxide, and peat) and three calcareous soils were shaken for 15 days with the mixtures and with iron chelate and humic substance solutions. The kinetic behavior of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) (Fe bonded to (o,p-EDDHA) and other polycondensated ligands) and of the different nutrients solubilized after the interaction assay was determined. The results showed that the mixtures did not significantly reduce the retention of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) in the soil components and the calcareous soils compared to the iron chelate solutions, but they did produce changes in the retention rate. Moreover, the competition between humic substances and synthetic chelating agents for complexing metal cations limited the effectiveness of the mixtures to mobilize nutrients from the substrates. The presence of Fe(o, p-EDDHA) and other byproducts in the commercial iron chelate had an important effect on the evolution of Fe(o, o-EDDHA) and the nutrient solubilization process.

The influence of particles recycling on the geochemistry of sediments in a large tropical dam lake in the Amazonian region, Brazil

NASA Astrophysics Data System (ADS)

Fonseca, Rita; Pinho, Catarina; Oliveira, Manuela

2016-12-01

As a result of over-erosion of soils, the fine particles, which contain the majority of nutrients, are easily washed away from soils, which become deficient in a host of components, accumulating in lakes. On one hand, the accumulation of nutrients-rich sediments are a problem, as they affect the quality of the overlying water and decrease the water storage capacity of the system; on the other hand, sediments may constitute an important resource, as they are often extremely rich in organic and inorganic nutrients in readily available forms. In the framework of an extensive work on the use of rock related materials to enhance the fertility of impoverish soils, this study aimed to evaluate the role on the nutrients cycle, of particles recycling processes from the watershed to the bottom of a large dam reservoir, at a wet tropical region under high weathering conditions. The study focus on the mineralogical transformations that clay particles undergo from the soils of the drainage basin to their final deposition within the reservoir and their influence in terms of the geochemical characteristics of sediments. We studied the bottom sediments that accumulate in two distinct seasonal periods in Tucuruí reservoir, located in the Amazonian Basin, Brazil, and soils from its drainage basin. The surface layers of sediments in twenty sampling points with variable depths, are representative of the different morphological sections of the reservoir. Nineteen soil samples, representing the main soil classes, were collected near the margins of the reservoir. Sediments and soils were subjected to the same array of physical, mineralogical and geochemical analyses: (1) texture, (2) characterization and semi-quantification of the clay fraction mineralogy and (3) geochemical analysis of the total concentration of major elements, organic compounds (organic C and nitrogen), soluble fractions of nutrients (P and K), exchangeable fractions (cation exchange capacity, exchangeable bases and acidity) and pH(H2O). There is a remarkable homogeneity in the sedimentary distribution along the reservoir in terms of the texture and mineralogy of the clay fraction and of the chemistry of the total, soluble and exchangeable phases. These observations contrast with the physical, morphological and chemical heterogeneity of the soils and the setting lithology. Most of the sediments has a higher contribution of fine-grained material and the mineralogy of the clay fraction is dominated by kaolinite in soils and kaolinite and illite in sediments, followed by lesser amounts of gibbsite, goethite, and metahaloisite and by small/vestigial contents of chlorite and smectite. The sediments are mainly inherited from the watershed but there exist marked differences between the accumulated sediments and their parent materials. These differences mainly come from the selective erosion of fine-grained particles and the extreme climatic conditions which enhance complex transformations of mineralogical and chemical nature. Compared with the parental soils, the reservoir sediments show the following differences: (1) enrichment in fine-grained and less dense inorganic particles, (2) aggradative mineralogical transformations, including enrichment in clay minerals with higher cationic adsorption and exchange capacity, (3) degradation of the crystalline structure of Fe- and Al-oxides (goethite, gibbsite), (4) increase in easily leached elements (Mg, Ca, P, K, Na) and decrease in chemically less mobile elements (Si, Fe) and (5) higher contents of organic carbon, nitrogen, and soluble forms of P and K, mainly concentrated in the clay fraction. These transformations are extremely important in the nutrients cycle, denoting that sediments represent an efficient sink for nutrients from the over-erosion of soils. Mineral and organic compounds can permanently or temporarily sequester these nutrients, recycling them and enhancing their availability through the slow release of components from relatively loose crystal structures. These processes can easily explain the enrichment in soluble and exchangeable forms of elements such as P, K, Ca or Mg. This study conclude that the particles recycling in a large tropical dam reservoir which receives high fluxes of allochthonous nutrients, has an important role in the good quality of sediments for agricultural use and in the profitable use of this technology to recover depleted soils in remediation projects in regions near large hydroelectric plants.

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Viers, J.; Emnova, E. E.; Kompantseva, E. I.; Freydier, R.

2008-04-01

This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric ( Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic ( Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine ( Skeletonema costatum) and freshwater ( Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ 65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria ( Rhodobacter sp.), cyanobacteria ( Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria ( P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ 65Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ 65Cu (solid-solution) = -1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ 65Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively. Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu 2+ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution. Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.

Hydrochemical evaluation and identification of geochemical processes in the shallow and deep wells in the Ramganga Sub-Basin, India.

PubMed

Rajmohan, Natarajan; Patel, Neelam; Singh, Gaurav; Amarasinghe, Upali A

2017-09-01

Groundwater samples were collected from 44 wells in the Ramganga Sub-Basin (RSB), India, and analysed for major ions, nutrients and trace metals. The primary goal of this study is to evaluate the hydrochemistry and to identify the geochemical processes that govern the water chemistry in the shallow and deep tube wells in the study area using geochemical methods. The knowledge of changes in hydrochemistry of the aquifers is important for both groundwater recharge and use in the region. This study found that there are substantial differences of water chemistry between shallow and deep wells. In the shallow wells, the average concentrations of total dissolved solid (TDS), Na, K, Ca, Mg, HCO 3 , Cl, SO 4 , NO 3 , PO 4 , F, Cu, Mn, Fe and Cr are twofold higher than the deep wells. The concentrations of dissolved silica in the groundwater do not vary with the depth, which implies that the variation in the water chemistry is not due to mineral dissolution alone. Major ion ratios and saturation indices suggest that the water chemistry is predominantly controlled by dissolution of carbonate minerals, silicate weathering and ion exchange reactions. Thermodynamic evaluation (ion activity ratios and stability filed diagrams) indicates that the kaolinite and gibbsite controlled the water chemistry in the both shallow and deep wells. In addition, the groundwater chemistry in the shallow wells is affected by the vertical infiltration of contaminated water from surface contamination sources and nitrification process. In the deep wells, absence of NO 3 and low concentrations of Cl, SO 4 , PO 4 and F imply the role of regional flow and denitrification in the groundwater. Results concluded that proper management plan is necessary to protect the shallow aquifer in the RSB since shallow aquifer pumping is less expensive than the deeper one.

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

Pouvreau, Maxime; Greathouse, Jeffery A.; Cygan, Randall T.

Molecular scale understanding of the structure and properties of aqueous interfaces with clays, metal (oxy-) hydroxides, layered double hydroxides, and other inorganic phases is strongly affected by significant degrees of structural and compositional disorder of the interfaces. ClayFF was originally developed as a robust and flexible force field for classical molecular simulations of such systems. However, despite its success, multiple limitations have also become evident with its use. One of the most important limitations is the difficulty to accurately model the edges of finite size nanoparticles or pores rather than infinitely layered periodic structures. Here we propose a systematic approachmore » to solve this problem by developing specific metal–O–H (M–O–H) bending terms for ClayFF, E bend = k (θ – θ 0) 2 to better describe the structure and dynamics of singly protonated hydroxyl groups at mineral surfaces, particularly edge surfaces. On the basis of a series of DFT calculations, the optimal values of the Al–O–H and Mg–O–H parameters for Al and Mg in octahedral coordination are determined to be θ 0,AlOH = θ 0,MgOH = 110°, k AlOH = 15 kcal mol –1 rad –2 and k MgOH = 6 kcal mol –1 rad –2. Molecular dynamics simulations were performed for fully hydrated models of the basal and edge surfaces of gibbsite, Al(OH) 3, and brucite, Mg(OH) 2, at the DFT level of theory and at the classical level, using ClayFF with and without the M–O–H term. The addition of the new bending term leads to a much more accurate representation of the orientation of O–H groups at the basal and edge surfaces. Finally, the previously observed unrealistic desorption of OH 2 groups from the particle edges within the original ClayFF model is also strongly constrained by the new modification.« less

Differentiating pedogenesis from diagenesis in early terrestrial paleoweathering surfaces formed on granitic composition parent materials

USGS Publications Warehouse

Driese, S.G.; Medaris, L.G.; Ren, M.; Runkel, Anthony C.; Langford, R.P.

2007-01-01

Unconformable surfaces separating Precambrian crystalline basement and overlying Proterozoic to Cambrian sedimentary rocks provide an exceptional opportunity to examine the role of primitive soil ecosystems in weathering and resultant formation of saprolite (weathered rock retaining rock structure) and regolith (weathered rock without rock structure), but many appear to have been affected by burial diagenesis and hydrothermal fluid flow, leading some researchers to discount their suitability for such studies. We examine one modern weathering profile (Cecil series), four Cambrian paleoweathering profiles from the North American craton (Squaw Creek, Franklin Mountains, Core SQ-8, and Core 4), one Neoproterozoic profile (Sheigra), and one late Paleoproterozoic profile (Baraboo), to test the hypothesis that these paleoweathering profiles do provide evidence of primitive terrestrial weathering despite their diagenetic and hydrothermal overprinting, especially additions of potassium. We employ an integrated approach using (1) detailed thin-section investigations to identify characteristic pedogenic features associated with saprolitization and formation of well-drained regoliths, (2) electron microprobe analysis to identify specific weathered and new mineral phases, and (3) geochemical mass balance techniques to characterize volume changes during weathering and elemental gains and losses of major and minor elements relative to the inferred parent materials. There is strong pedogenic evidence of paleoweathering, such as clay illuviation, sepic-plasmic fabrics, redoximorphic features, and dissolution and alteration of feldspars and mafic minerals to kaolinite, gibbsite, and Fe oxides, as well as geochemical evidence, such as whole-rock losses of Na, Ca, Mg, Si, Sr, Fe, and Mn greater than in modern profiles. Evidence of diagenesis includes net additions of K, Ba, and Rb determined through geochemical mass balance, K-feldspar overgrowths in overlying sandstone sections, and K-feldspars with reaction rims in weathered basement. The sub-Cambrian paleoweathering profiles formed on granite are remarkably similar to modern weathering profiles formed on granite, in spite of overprinting by potassium diagenesis. ?? 2007 by The University of Chicago. All rights reserved.

Electron spin resonance as a high sensitivity technique for environmental magnetism: determination of contamination in carbonate sediments

NASA Astrophysics Data System (ADS)

Crook, Nigel P.; Hoon, Stephen R.; Taylor, Kevin G.; Perry, Chris T.

2002-05-01

This study investigates the application of high sensitivity electron spin resonance (ESR) to environmental magnetism in conjunction with the more conventional techniques of magnetic susceptibility, vibrating sample magnetometry (VSM) and chemical compositional analysis. Using these techniques we have studied carbonate sediment samples from Discovery Bay, Jamaica, which has been impacted to varying degrees by a bauxite loading facility. The carbonate sediment samples contain magnetic minerals ranging from moderate to low concentrations. The ESR spectra for all sites essentially contain three components. First, a six-line spectra centred around g = 2 resulting from Mn2+ ions within a carbonate matrix; second a g = 4.3 signal from isolated Fe3+ ions incorporated as impurities within minerals such as gibbsite, kaolinite or quartz; third a ferrimagnetic resonance with a maxima at 230 mT resulting from the ferrimagnetic minerals present within the bauxite contamination. Depending upon the location of the sites within the embayment these signals vary in their relative amplitude in a systematic manner related to the degree of bauxite input. Analysis of the ESR spectral components reveals linear relationships between the amplitude of the Mn2+ and ferrimagnetic signals and total Mn and Fe concentrations. To assist in determining the origin of the ESR signals coral and bauxite reference samples were employed. Coral representative of the matrix of the sediment was taken remote from the bauxite loading facility whilst pure bauxite was collected from nearby mining facilities. We find ESR to be a very sensitive technique particularly appropriate to magnetic analysis of ferri- and para-magnetic components within environmental samples otherwise dominated by diamagnetic (carbonate) minerals. When employing typical sample masses of 200 mg the practical detection limit of ESR to ferri- and para-magnetic minerals within a diamagnetic carbonate matrix is of the order of 1 ppm and 1 ppb respectively, approximately 102 and 105 times the sensitivity achievable employing the VSM in our laboratory.

First principles study of the atomic layer deposition of alumina by TMA-H2O-process.

PubMed

Weckman, Timo; Laasonen, Kari

2015-07-14

Atomic layer deposition (ALD) is a coating technology used to produce highly uniform thin films. Aluminiumoxide, Al2O3, is mainly deposited using trimethylaluminium (TMA) and water as precursors and is the most studied ALD-process to date. However, only few theoretical studies have been reported in the literature. The surface reaction mechanisms and energetics previously reported focus on a gibbsite-like surface model but a more realistic description of the surface can be achieved when the hydroxylation of the surface is taken into account using dissociatively adsorbed water molecules. The adsorbed water changes the structure of the surface and reaction energetics change considerably when compared to previously studied surface model. Here we have studied the TMA-H2O process using density functional theory on a hydroxylated alumina surface and reproduced the previous results for comparison. Mechanisms and energetics during both the TMA and the subsequent water pulse are presented. TMA is found to adsorb exothermically onto the surface. The reaction barriers for the ligand-exchange reactions between the TMA and the surface hydroxyl groups were found to be much lower compared to previously presented results. TMA dissociation on the surface is predicted to saturate at monomethylaluminium. Barriers for proton diffusion between surface sites are observed to be low. TMA adsorption was also found to be cooperative with the formation of methyl bridges between the adsorbants. The water pulse was studied using single water molecules reacting with the DMA and MMA surface species. Barriers for these reactions were found to reasonable in the process conditions. However, stabilizing interactions amongst water molecules were found to lower the reaction barriers and the dynamical nature of water is predicted to be of importance. It is expected that these calculations can only set an upper limit for the barriers during the water pulse.

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

PubMed

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

2012-03-30

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

Multi-technique characterisation of commercial alizarin-based lakes

NASA Astrophysics Data System (ADS)

Pronti, Lucilla; Mazzitelli, Jean-Baptiste; Bracciale, Maria Paola; Massini Rosati, Lorenzo; Vieillescazes, Cathy; Santarelli, Maria Laura; Felici, Anna Candida

2018-07-01

The characterization of ancient and modern alizarin-based lakes is a largely studied topic in the literature. Analytical data on contemporary alizarin-based lakes, however, are still poor, though of primary importance, since these lakes might be indeed present in contemporary and fake paintings as well as in retouchings. In this work we systematically investigate the chemical composition and the optical features of fifteen alizarin-based lakes, by a multi-analytical technique approach combining spectroscopic methods (i.e. Energy Dispersive X-ray Fluorescence Spectroscopy, EDXRF; Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy, ATR-FTIR; X-ray Powder Diffraction, XRD; UV induced fluorescence and reflectance spectroscopies) and chromatography (i.e. High-performance Liquid Chromatography coupled with a Photodiode Array Detector, HPLC-PDA). Most of the samples contain typical compounds from the natural roots of madder, as occurring in ancient and modern lakes, but in two samples (23600-Kremer-Pigmente and alizarin crimson-Zecchi) any anthraquinonic structures were identified, thus leading to hypothesize the presence of synthetic dyes. The detection of lucidin primeveroside and ruberythrique acid in some lakes suggest the use of Rubia tinctorum. One sample (23610-Kremer-Pigmente) presents alizarin as the sole compound, thereby revealing to be a synthetic dye. Moreover, gibbsite, alunite and kaolinite were found to be used as substrates and/or mordants. Visible absorption spectra of the anthraquinonic lakes show two main absorption bands at about 494-511 nm and 537-564 nm, along with a shoulder at about 473-479 nm in presence of high amounts of purpurin. Finally, from the results obtained by UV induced fluorescence spectroscopy it is possible to figure out that, although it is commonly assumed that the madder lake presents an orange-pink fluorescence, the inorganic compounds, added to the recipe, could induce a quenching phenomenon or an inhibition of the fluorescence, as occurring in some commercial alizarin-based lakes.

Sorption kinetics of Hg and HgCl[sub 2] on Kirkwood-Cohansey aquifer sediments from the New Jersey Coastal Plain

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

MacLeod, C.; Peterson, J.

1992-01-01

Anomalously high Hg concentrations have been detected from domestic wells in the Kirkwood-Cohansey Aquifer System, New Jersey Coastal Plain. Mercury concentrations ranging from 0.2--83.0 [mu]g/l in relatively shallow wells ([lt] 100 feet) have been detected. Concentrations in excess of 2.0 [mu]g/l, (the USEPA Drinking Water Standard) have been detected in wells where the Cohansey Sand is overlain by the Bridgeton Formation; a fluvial iron-rich sand with some gravelly channel deposits containing goethite and gibbsite nodules. In this study, Bridgeton Fm. sediments were used to determine the sorption kinetics for solutions containing HgCl[sub 2] and for solutions containing dissolved elemental Hgmore » in order to assess the potential for the Bridgeton sediments to act as a conduit for Hg mobilized from the surface. Results of batch equilibrium experiments suggest that dissolved elemental Hg sorbs to Bridgeton sediments by a risk-order kinetic process. Sorption of the Hg proceeded exponentially and equilibrium was reached within 14 hours. The sorption kinetics for the HgCl[sub 2] solutions, however, appear to be of a second or higher order. For this compound sorption to the sediments begins exponentially, but after 6 hours desorption into the water begins to predominate followed by a slower exponential sorption step that requires nearly 36 hours to reach equilibrium. These experiments illustrate the necessity of determining the distribution coefficients of possible source compounds when attempting to evaluate mobilization potential of a contaminant in the unsaturated zone. Moreover, these data also suggest that HgCl[sub 2], a seed dressing for corn, medial bacteriacide, and embalming fluid ingredient, is more mobile in the environment than dissolved elemental Hg. Consequently, the ground water contamination potential appears to be greater for HgCl[sub 2] than for elemental Hg.« less

Effects of organic solutes on chemical reactions of aluminum

USGS Publications Warehouse

Lind, Carol J.; Hem, John David

1975-01-01

Concentrations of organic matter in the general range of 1-10 milligrams per litre organic carbon are common in natural water, and many naturally occurrin7 organic compounds form aluminum complexes. The aluminum concentrations in near-neutral pH solutions may be 10-100 times higher than the values predicted from solubility data if formation of such organic complexes is ignored. The processes of polymerization of aluminum hydroxide and precipitation of gibbsite are inhibited by the presence of the organic flavone compound quercetin in concentrations as low as 10 x -5.3 mole per litre. Quercetin forms a complex, with a probable molar ratio of 1:2 aluminum to quercetin, that has a formation constant (f12) of about 10 12. A complex with a higher aluminum-quercetin ratio also was observed, but this material tends to evolve into a compound of low solubility that removes aluminum from solution. In the presence of both dissolved aluminum and aqueous silica, low concentrations of quercetin improved the yield of crystallized kaolinite and halloysite. Small amounts of well-shaped kaolinite and halloysite crystals were identified by electron microscopy in solutions with pH's in the range 6.5-8.5 after 155 days aging in one experimer t and 481 days aging in a repeated experiment. The bulk of the precipitated material was amorphous to X-rays, and crystalline material was too small a proportion of the total to give identifiable X-ray diffraction peaks. The precipitates had aluminum-silicon ratios near 1, and their solubility corresponded to that found by Hem, Roberson, Lind, and Polzer (1973) for similar aluminosilicate precipitated in the absence of organic solutes. The improved yield of crystalline material obtained in the presence of quercetin probably is the result of the influence of the organic compound on the aluminum hydroxide polymerization process. Natural water containing color imparted by organic material tends to be higher in aluminum than would be predicted by pH, silica concentrations, and solubility data for inorganic aluminum species.

Geochemical evolution of groundwater salinity at basin scale: a case study from Datong basin, Northern China.

PubMed

Wu, Ya; Wang, Yanxin

2014-05-01

A hydrogeochemical investigation using integrated methods of stable isotopes ((18)O, (2)H), (87)Sr/(86)Sr ratios, Cl/Br ratios, chloride-mass balance, mass balance and hydrogeochemical modeling was conducted to interpret the geochemical evolution of groundwater salinity in Datong basin, northern China. The δ(2)H, δ(18)O ratios in precipitation exhibited a local meteoric water line of δ(2)H = 6.4 δ(18)O -5 (R(2) = 0.94), while those in groundwater suggested their meteoric origin in a historically colder climatic regime with a speculated recharge rate of less than 20.5 mm overall per year, in addition to recharge from a component of deep residual ancient lake water enriched with Br. According to the Sr isotope binary mixing model, the mixing of recharges from the Shentou karst springs (24%), the western margins (11%) and the eastern margins (65%) accounts for the groundwater from the deep aquifers of the down-gradient parts in the central basin is a possible mixing mechanism. In Datong, hydrolysis of silicate minerals is the most important hydrogeochemical process responsible for groundwater chemistry, in addition to dissolution of carbonate and evaporites. In the recharge areas, silicate chemical weathering is typically at the bisiallitization stage, while that in the central basin is mostly at the monosiallitization stage with limited evidence of being in equilibrium with gibbsite. Na exchange with bound Ca, Mg prevails at basin scale, and intensifies with groundwater salinity, while Ca, Mg exchange with bound Na locally occurs in the east pluvial and alluvial plains. Although groundwater salinity increases with the progress of water-rock/sediment interactions along the flow path, as a result of carbonate solubility control and continuous evapotranspiration, Na-HCO3 and Na-Cl-SO4 types of water are usually characterized respectively in the deep and the shallow aquifers of an inland basin with a silicate terrain in an arid climatic regime.

Stabilization of carbon in composts and biochars in relation to carbon sequestration and soil fertility.

PubMed

Bolan, N S; Kunhikrishnan, A; Choppala, G K; Thangarajan, R; Chung, J W

2012-05-01

There have been increasing interests in the conversion of organic residues into biochars in order to reduce the rate of decomposition, thereby enhancing carbon (C) sequestration in soils. However energy is required to initiate the pyrolysis process during biochar production which can also lead to the release of greenhouse gasses. Alternative methods can be used to stabilize C in composts and other organic residues without impacting their quality. The objectives of this study include: (i) to compare the rate of decomposition among various organic amendments and (ii) to examine the effect of clay materials on the stabilization of C in organic amendments. The decomposition of a number of organic amendments (composts and biochars) was examined by monitoring the release of carbon-dioxide using respiration experiments. The results indicated that the rate of decomposition as measured by half life (t(1/2)) varied between the organic amendments and was higher in sandy soil than in clay soil. The half life value ranged from 139 days in the sandy soil and 187 days in the clay soil for poultry manure compost to 9989 days for green waste biochar. Addition of clay materials to compost decreased the rate of decomposition, thereby increasing the stabilization of C. The half life value for poultry manure compost increased from 139 days to 620, 806 and 474 days with the addition of goethite, gibbsite and allophane, respectively. The increase in the stabilization of C with the addition of clay materials may be attributed to the immobilization of C, thereby preventing it from microbial decomposition. Stabilization of C in compost using clay materials did not impact negatively the value of composts in improving soil quality as measured by potentially mineralizable nitrogen and microbial biomass carbon in soil. Copyright © 2012 Elsevier B.V. All rights reserved.

Modification of Lime Mortars with Synthesized Aluminosilicates

NASA Astrophysics Data System (ADS)

Loganina, Valentina I.; Sadovnikova, Marija E.; Jezierski, Walery; Małaszkiewicz, Dorota

2017-10-01

The increasing attention for restoration of buildings of historical and architectural importance has increased the interest for lime-based binders, which could be applied for manufacturing repair mortars and plasters compatible with historical heritage. Different additives, admixtures or fibers may be incorporated to improve mechanical and thermal features of such materials. In this study synthesized aluminosilicates (SA) were applied as an additive for lime mortar. The technology of synthesis consisted in the deposition of aluminosilicates from a sodium liquid glass by the aluminum sulphate Al2(SO4)3. The goal of this investigation was developing a new method of aluminosilicates synthesis from a sodium liquid glass and using this new material as a component for a lime mortar. Aluminosilicates were precipitated from the solution of aluminum sulphate Al2(SO)3 and sodium silicate. SA were then used as an additive to calcareous compositions and their influence was tested. Mortars were prepared with commercial air lime and siliceous river sand. Air lime binder was replaced by 5 and 10 wt.% of SA. Calcareous composition specimens were formed at water/lime ratio 1.0. The following analyses were made: grain size distribution of SA, X-ray diffraction analysis (XRD), sorption properties, plastic strength and compressive strength of lime mortars. XRD pattern of the SA shows the presence of thenardite, gibbsite and amorphous phase represented by aggregate of nano-size cristobalite-like crystallites. Application of SA leads to increase of compressive strength after 90 days of hardening by 28% and 53% at SA content 5 and 10% respectively comparing to specimens without this additive. Contents of chemically bound lime in the reference specimens after 28 days of hardening in air-dry conditions was 46.5%, while in specimens modified with SA contained 50.0-55.3% of bound lime depending on filtrate pH. This testifies to high activity of calcareous composition. The new blended lime mortar was developed based on SA. SA in lime composites turned out to be effective as structure-forming additive, both plastic and compressive strength increased after addition of SA.

Texture, mineralogy and geochemistry of the continental slope sediments in front of Los Tuxtlas, Gulf of Mexico, Mexico: implications on weathering, origin and depositional environments

NASA Astrophysics Data System (ADS)

Marca-Castillo, M. E.; Armstrong-Altrin, J.

2017-12-01

The textural analysis, mineralogy and geochemistry of two sediment cores recovered from the deep water zone of the southwestern part of the Gulf of Mexico ( 1666 and 1672 m water depth) were studied to infer the provenance and depositional behavior. The textural analysis revealed that both cores are dominated by silt, which occupy more than 50% in both samples and the clay occupy 40%. The petrographic analysis revealed remains of biogenic origin sediments and lithic fragments with an angular shape and low sphericity, indicating a low energy environment and therefore a low level of weathering in the sediment, which suggests that the sediments were not affected by transport and derived from a nearby source rock. In both cores quartz fragments were identified; also volcanic lithic and pyroxenes fragments, which are rocks of intermediate composition and are generally associated with the volcanic activity of the continental margins. SEM-EDS studies showed that the analysed samples have concentrations of minerals such as barite, gibbsite, kaolinite, grossular, magnetite, plagioclase and chlorite, which are probably derived from the mainland to the deep sea zone. In the trace element analysis it was observed a low Sc content, while Co, Ni, V and Cu are slightly enriched with respect to the upper continental crust; this enrichment is related to sediments from intermediate sources. The sediments are classified as shale in the log (SiO2 / Al2O3) - log (Fe2O / K2O) diagram. The fine particles of the shale indicate that a deposit occurred as a result of the gradual sedimentation due to relatively non-turbulent currents, which is consistent with the petrographic analysis. The geochemical features of major and trace elements suggest sediments were derived largely from the natural andesite erosion of coastal regions along the Gulf of Mexico. High values of Fe2O3 and MnO are observed in the upper intervals, reflecting the influence of volcanic sediments. The major element discriminant function diagrams indicate the provenance of sediments from a passive margin, which is consistent with the geology of the Gulf of Mexico.

PEP Support Laboratory Leaching and Permeate Stability Tests

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

Russell, Renee L.; Peterson, Reid A.; Rinehart, Donald E.

2009-09-25

Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed, constructed, and operated as part of a plan to respond to issue M12, "Undemonstrated Leaching Processes," of the External Flowsheet Review Team (EFRT) issue response plan.( ) The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes.more » The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. A simplified flow diagram of the PEP system is shown in Figure 1.1. Two operating scenarios are currently being evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario has caustic leaching performed in the UFP-2 ultrafiltration feed vessels (i.e., vessel UFP-VSL-T02A in the PEP and vessels UFP-VSL-00002A and B in the WTP PTF). The second scenario has caustic leaching conducted in the UFP-1 ultrafiltration feed preparation vessels (i.e., vessels UFP-VSL-T01A and B in the PEP and vessels UFP-VSL-00001A and B in the WTP PTF). In both scenarios, 19-M sodium hydroxide solution (NaOH, caustic) is added to the waste slurry in the vessels to leach solid aluminum compounds (e.g., gibbsite, boehmite). Caustic addition is followed by a heating step that uses direct injection of steam to accelerate the leach process. Following the caustic leach, the vessel contents are cooled using vessel cooling jackets and/or external heat exchangers. The main difference between the two scenarios is that for leaching in UFP-VSL-T01A and B, the 19-M NaOH is added to un-concentrated waste slurry (3 to 8 wt% solids), while for leaching in UFP-VSL-T02A, the slurry is concentrated to nominally 20 wt% solids using cross-flow ultrafiltration before adding caustic.« less

Geochemical Controls on the Partitioning and Hydrological Transport of Metals in a Human Impacted, Non-Acidic, River System

NASA Astrophysics Data System (ADS)

Thorslund, J.; Jarsjo, J.; Wällstedt, T.; Morth, C. M.; Lychagin, M.; Chalov, S.

2014-12-01

The knowledge of coupled processes controlling the spreading and fate of metals in non-acidic river systems is currently much more limited than the knowledge of metal behavior under acidic conditions (e.g., in acid mine drainage systems). Critical geochemical controls governing metal speciation may thus differ substantially between acidic and non-acidic hydrological systems. We here aim at expanding the knowledge of metals in non-acidic river systems, by considering a high pH river, influenced by mining by the largest gold mining area in the Mongolian part of the transboundary Lake Baikal drainage basin. The combined impact of geochemical and hydrological processes is investigated, to be able to understand the solubility of various heavy metals, their partitioning between particulate and dissolved phase and its impact on overall transport. We show, through site specific measurements and a geochemical modelling approach, that the combined effects of precipitation of ferrihydrite and gibbsite and associated sorption complexes of several metals can explain the high impact of suspended transport relative to total transport often seen under non-acidic conditions. Our results also identifies the phosphate mineral Hydroxyapatite as a potential key sorption site for many metals, which has both site specific and general relevance for metal partitioning under non-acidic conditions. However, an adsorption database, which is currently unavailable for hydroxyapatite, needs to be developed for appropriate sorption quantification. Furthermore, Cd, Fe, Pb and Zn were particularly sensitive to increasing DOC concentrations, which increased the solubility of these metals due to metal-organic complexation. Modeling the sensitivity to changes in geochemical parameters showed that decreasing pH and increasing DOC concentrations in downstream regions would increase the dissolution and hence the toxicity and bioavailability of many pollutants of concern in the downstream ecosystem. In general, this study suggests that in non-acidic hydrological systems, both seasonality of DOC concentrations (which could vary by several 100%), changing DOC concentrations (resulting from climate and land use changes) and potential phosphate solids can majorly influence on the spreading and toxicity of several metals.

Hematite (α-Fe2O3) - A potential Ce4+ carrier in red mud.

PubMed

Bolanz, Ralph M; Kiefer, Stefan; Göttlicher, Jörg; Steininger, Ralph

2018-05-01

Cerium is the most abundant rare earth element (REE) within the waste product of alumina production (red mud), but its speciation in this complex material is still barely understood. Previous studies showed evidence for a correlation between Ce and the main constituent of red mud, iron oxides, which led us to investigate the most abundant iron oxide in red mud, hematite, as possible carrier phase for Ce. Synthetic hematite can incorporate up to 1.70±0.01wt% Ce, which leads to a systematical increase of all unit cell parameters. Investigations by extended X-ray absorption fine structure spectroscopy suggest an incorporation of Ce 4+ O 6 into the hematite structure by a novel atomic arrangement, fundamentally different from the close-range order around Fe 3+ in hematite. Samples of red mud were taken in Lauta (Saxony), Germany and analyzed by powder X-ray diffraction, inductively coupled plasma mass and optical emission spectrometry, electron microprobe analysis and X-ray absorption near-edge structure spectroscopy. Red mud samples consist of hematite (Fe 2 O 3 ) (34-58wt%), sodalite (Na 8 Al 6 Si 6 O 24 Cl 2 ) (4-30wt%), gibbsite (Al(OH) 3 ) (0-25wt%), goethite (FeOOH) (10-23wt%), böhmite (AlOOH) (0-11wt%), rutile (TiO 2 ) (4-8wt%), cancrinite (Na 6 Ca 2 Al 6 Si 6 O 24 (CO 3 ) 2 ) (0-5wt%), nordstrandite (Al(OH) 3 ) (0-5wt%) and quartz (SiO 2 ) (0-4wt%). While the main elemental composition is Fe>Al>Na>Ti>Ca (Si not included), the average concentration of REE is 1109±6mg/kg with an average Ce concentration of 464±3mg/kg. The main carrier of Ce was located in the Fe-rich fine-grained fraction of red mud (0.10wt% Ce 2 O 3 ), while other potential Ce carriers like monazite, lead oxides, secondary Ce-minerals and particles of potentially anthropogenic origin are of subordinated relevance. Cerium in red mud occurs predominantly as Ce 4+ , which further excludes Ce 3+ minerals as relevant sources. Copyright © 2017. Published by Elsevier B.V.

Coprecipitation of arsenate with metal oxides. 3. Nature, mineralogy, and reactivity of iron(III)-aluminum precipitates.

PubMed

Violante, Antonio; Pigna, Massimo; Del Gaudio, Stefania; Cozzolino, Vincenza; Banerjee, Dipanjan

2009-03-01

Coprecipitation involving arsenic with aluminum or iron has been studied because this technique is considered particularly efficient for removal of this toxic element from polluted waters. Coprecipitation of arsenic with mixed iron-aluminum solutions has received scant attention. In this work we studied (i)the mineralogy, surface properties, and chemical composition of mixed iron-aluminum oxides formed at initial Fe/Al molar ratio of 1.0 in the absence or presence of arsenate [As/ Fe+Al molar ratio (R) of 0, 0.01, or 0.1] and at pH 4.0, 7.0, and 10.0 and aged for 30 and 210 days at 50 degrees C and (ii) the removal of arsenate from the coprecipitates after addition of phosphate. The amounts of short-range ordered precipitates (ferrihydrite, aluminous ferrihydrite and/or poorly crystalline boehmite) were greater than those found in iron and aluminum systems (studied in previous works), due to the capacity of both aluminum and arsenate to retard or inhibitthe transformation of the initially formed precipitates into well-crystallized oxides (gibbsite, bayerite, and hematite). As a consequence, the surface areas of the iron-aluminum oxides formed in the absence or presence of arsenate were usually much larger than those of aluminum or iron oxides formed under the same conditions. Arsenate was found to be associated mainly into short-range ordered materials. Chemical composition of all samples was affected by pH, initial R, and aging. Phosphate sorption was facilitated by the presence of short-range ordered materials, mainly those richer in aluminum, but was inhibited by arsenate present in the samples. The quantities of arsenate replaced by phosphate, expressed as percentages of its total amount present in the samples, were particularly low, ranging from 10% to 26%. A comparison of the desorption of arsenate by phosphate from aluminum-arsenate and iron-arsenate (studied in previous works) and iron-aluminum-arsenate coprecipitates evidenced that phosphate has a greater capacity to desorb arsenate from aluminum than iron sites.

Mineralogical, chemical, and physical properties of the regolith overlying crystalline rocks, Fairfax County, Virginia: a preliminary report

USGS Publications Warehouse

Leo, Gerhard W.; Pavich, M.J.; Obermeier, Stephen F.

1977-01-01

Undisturbed cores of saprolite developed on crystalline rocks of the Piedmont Province in Fairfax County, Virginia have been obtained using a combination of Shelby tubes, Denison sampler, and modified diamond core-drilling. The principal purpose of the core study is to correlate variations in chemistry, mineralogy and texture with engineering properties throughout the weathering profile. Coring sites were chosen to obtain a maximum depth of weathering on diverse lithologies. The rocks investigated include pelitic schist, metagraywacke, granite, diabase and serpentinite. Four to twelve samples per core were selected, depending on thickness of 1) the weathering profile (from about 1 m in serpentinite to more than 30 m in pelitic schist) and on 2) megascopic changes in saprolite character for analysis of petrography, texture, clay mineralogy andd major element chemistry. Shear strength and compressibility were determined on corresponding segments of core. Standard penetration tests were performed adjacent to coring sites to evaluate engineering properties in situ. Geochemical changes of saprolite developed from each rock type follow predictable trends from fresh rock to soil profile, with relative Increases in Si, Ti, Al, Fe3+ and H20; variable K; and relative loss of Fe 2+, Mg, Ca, and Na. These variations are more pronounced in the weathering profiles over mafic and ultramafic rocks than metagraywacke. Clay minerals in granite, schist and metagraywacke saprolite are kaolinite, dioctahedral vermiculite, interlayered micavermiculite, and minor illite. Gibbsite is locally developed in near-surface samples of schist. Standard penetration test data for the upper 7 m of saprolite over schist and metagraywacke suggest alternations between stronger and weaker horizons than probably reflect variations in lithology including the presence of quartz lenses. Results for granite saprolite are most consistent but indicate lower strength. Shear strength increases fairly regularly downward in the weathering profile. The engineering behavior of diabase saprolite is controlled by a dense, plastic, near-surface clay layer (montmorillonite and kaolinite)overlying rock which is weathered to a granular state (grus), while engineering properties of serpentinite are determined by a very thin weathering profile.

Effective use of iron-aluminum rich laterite based soil mixture for treatment of landfill leachate.

PubMed

Nayanthika, I V K; Jayawardana, D T; Bandara, N J G J; Manage, P M; Madushanka, R M T D

2018-04-01

Landfill leachate poses environmental threats worldwide and causes severe issues on adjacent water bodies and soil by direct discharge. The primary objective of this study is to analyze the efficient use of compost and laterite mixtures (0, 10, 20, 30 and 40 wt% compost/laterite) on leachate treatment and to investigate the associated removal efficiencies under different sorption processes. Therefore, in the experimental design, laterite is used for providing adsorption characteristics, and compost for activating biological properties of the filter. The filtering process is continued until major physical changes occur in the filter at approximately 100 days. The raw leachate used for the experiment shows higher average values for many analyzed parameters. Parameters for the experiment are selected based on their availability in raw leachate in the Sri Lanka. During filtering, removal efficiencies of BOD (>90%), COD (>85%), phosphate (>90%) and nitrate (75-95%) show higher values for all filters. These removals are mainly associated with biodegradation, which is activated by the added compost. Perhaps the removal of nitrate steadily increases with time, which indicates in denitrification by the added excess carbon from the leachate. The removal of total suspended solids (TSS) is moderate to high, but conversely, the electric conductivity (EC) is unsteady, indicating an association between iron exchange and carbonate degradation. A very high removal efficiency is reported in Fe (90-100%), and wide ranges of efficiencies in Mn (30-90%), Cu (45-85%), Ni (30-93%), Cd (37-98%), Zn (15-98%), and Pb (35-98%) involve heterogeneous sorption processes. Furthermore, the normalization of raw leachate by the liquid filtrate has apparent improvements. The differences (p > .05) in removal efficiencies between the filters are significant. It can be concluded that the filter with laterite mixed with 20% of compost has the optimum conditions. Further, the Fourier-transforminfrared (FT-IR) models for filter media conclude multiple sorptions and reveal evidence on vacant sites. X-ray diffraction (XRD) analyses indicate secondary minerals gibbsite, hematite, goethite and kaolinite as the major minerals that involved on the sorption process. Copyright © 2018 Elsevier Ltd. All rights reserved.

Simulation of the mobility of metal - EDTA complexes in groundwater: The influence of contaminant metals

USGS Publications Warehouse

Friedly, J.C.; Kent, D.B.; Davis, J.A.

2002-01-01

Reactive transport simulations were conducted to model chemical reactions between metal - EDTA (ethylenediaminetetraacetic acid) complexes during transport in a mildly acidic quartz - sand aquifer. Simulations were compared with the results of small-scale tracer tests wherein nickel-, zinc-, and calcium - EDTA complexes and free EDTA were injected into three distinct chemical zones of a plume of sewage-contaminated groundwater. One zone had a large mass of adsorbed, sewage-derived zinc; one zone had a large mass of adsorbed manganese resulting from mildly reducing conditions created bythe sewage plume; and one zone had significantly less adsorbed manganese and negligible zinc background. The chemical model assumed that the dissolution of iron(III) from metal - hydroxypolymer coatings on the aquifer sediments by the metal - EDTA complexes was kinetically restricted. All other reactions, including metal - EDTA complexation, zinc and manganese adsorption, and aluminum hydroxide dissolution were assumed to reach equilibrium on the time scale of transport; equilibrium constants were either taken from the literature or determined independently in the laboratory. A single iron(III) dissolution rate constant was used to fit the breakthrough curves observed in the zone with negligible zinc background. Simulation results agreed well with the experimental data in all three zones, which included temporal moments derived from breakthrough curves at different distances downgradient from the injections and spatial moments calculated from synoptic samplings conducted at different times. Results show that the tracer cloud was near equilibrium with respect to Fe in the sediment after 11 m of transport in the Zn-contaminated region but remained far from equilibrium in the other two zones. Sensitivity studies showed that the relative rate of iron(III) dissolution by the different metal - EDTA complexes was less important than the fact that these reactions are rate controlled. Results suggest that the published solubility for ferrihydrite reasonably approximates the Fe solubility of the hydroxypolymer coatings on the sediments. Aluminum may be somewhat more soluble than represented by the equilibrium constant for gibbsite, and its dissolution may be rate controlled when reacting with Ca - EDTA complexes.

Facile Preparation of Ultrafine Aluminum Hydroxide Particles with or without Mesoporous MCM-41 in Ambient Environments.

PubMed

Dubovoy, Viktor; Subramanyam, Ravi; Stranick, Michael; Du-Thumm, Laurence; Pan, Long

2017-05-11

An aqueous suspension of nanogibbsite was synthesized via the titration of aluminum aqua acid [Al(H2O)6] 3+ with L-arginine to pH 4.6. Since the hydrolysis of aqueous aluminum salts is known to produce a wide array of products with a wide range of size distributions, a variety of state-of-the-art instruments (i.e., 27 Al/ 1 H NMR, FTIR, ICP-OES, TEM-EDX, XPS, XRD, and BET) were used to characterize the synthesis products and identification of byproducts. The product, which was comprised of nanoparticles (10-30 nm), was isolated using gel permeation chromatography (GPC) column technique. Fourier transform infrared (FTIR) spectroscopy and powder X-ray diffraction (PXRD) identified the purified material as the gibbsite polymorph of aluminum hydroxide. The addition of inorganic salts (e.g., NaCl) induced electrostatic destabilization of the suspension, thereby agglomerating the nanoparticles to yield Al(OH)3 precipitate with large particle sizes. By utilizing the novel synthetic method described here, Al(OH)3 was partially loaded inside the highly ordered mesoporous framework of MCM-41, with average pore dimensions of 2.7 nm, producing an aluminosilicate material with both octahedral and tetrahedral Al (Oh/Td = 1.4). The total Al content, measured using energy-dispersive X-ray spectrometry (EDX), was 11% w/w with a Si/Al molar ratio of 2.9. A comparison of bulk EDX with surface X-ray photoelectron spectroscopy (XPS) elemental analysis provided insight into the distribution of Al within the aluminosilicate material. Furthermore, a higher ratio of Si/Al was observed on the external surface (3.6) as compared to the bulk (2.9). Approximations of O/Al ratios suggest a higher concentration of Al(O)3 and Al(O)4 groups near the core and external surface, respectively. The newly developed synthesis of Al-MCM-41 yields a relatively high Al content while maintaining the integrity of the ordered silica framework and can be used for applications where hydrated or anhydrous Al2O3 nanoparticles are advantageous.

Effects of alteration product precipitation on glass dissolution

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

Strachan, Denis M.; Neeway, James J.

2014-06-01

Understanding the mechanisms that control the durability of nuclear waste glass is paramount if reliable models are to be constructed so that the glass dissolution rate in a given geological repository can be calculated. Presently, it is agreed that (boro)silicate glasses dissolve in water at a rate dependent on the solution concentration of orthosilicic acid (H 4SiO 4) with higher [H 4SiO 4] leading to lower dissolution rates. Once the reaction has slowed as a result of the buildup of H 4SiO 4, another increase in the rate has been observed that corresponds to the precipitation of certain silica-bearing alterationmore » products. However, it has also been observed that the concentration of silica-bearing solution species does not significantly decrease, indicating saturation, while other glass tracer elements concentrations continue to increase, indicating that the glass is still dissolving. In this study, we have used the Geochemist’s Workbench code to investigate the relationship between glass dissolution rates and the precipitation rate of a representative zeolitic silica-bearing alteration product, analcime [Na(AlSi 2O 6)∙H 2O]. To simplify the calculations, we suppressed all alteration products except analcime, gibbsite (Al(OH) 3), and amorphous silica. The pseudo-equilibrium-constant matrix for amorphous silica was substituted for the glass pseudo-equilibrium-constant matrix because it has been shown that silicate glasses act as a silica-only solid with respect to kinetic considerations. In this article, we present the results of our calculations of the glass dissolution rate at different values for the analcime precipitation rate constant and the effects of varying the glass dissolution rate constant at a constant analcime precipitation rate constant. From the simulations we conclude, firstly, that the rate of glass dissolution is dependent on the kinetics of formation of the zeolitic phase. Therefore, the kinetics of secondary phase formation is an important parameter that should be taken into account in future glass dissolution modeling efforts. Secondly, the results indicate that, in the absence of a gel layer, the glass dissolution rate controls the rate of analcime precipitation in the long term. Finally, the meaning of these results pertinent to long-term glass durability is discussed.« less

Processes of mineralization in the Hauran Basin (Syria and Jordan) and in adjoining areas

NASA Astrophysics Data System (ADS)

Raggad, Marwan Al; Elias, Salameh; Inbar, Nimrod; Rosenthal, Eliahu; Möller, Peter; Siebert, Christian; Magri, Fabien

2017-04-01

Volcanic rocks covering vast areas in central north Jordan and in central and southern Syria erupted during 6 different phases starting in Miocene and continuing - with major interruptions - into the Holocene. The petrological composition of the different flows of the Harrat ash Shaam Basalt complex is quite homogeneous with the major minerals: Plagioclase, K-feldspar, clinopyroxene, amphibole, biotite, olivine, magnetite, limonite, goethite, pyrite and chalcopyrite. The oldest basalts cover Cretaceous and Paleogene sediments, which at that time formed the land surface of drainage basins. The basaltic aquifer contains groundwater with a wide range of salinities. They represent a continuous sequence of increasingly mineralized groundwater originating from precipitation over Jebel Druz flowing radially into all directions, in coincidence with the topographic slopes. Along the flow-paths halite and gypsum are dissolved. Ca2+ not only depends on gypsum dissolution but also increases proportionally to Mg. This may suggest that the combination of Ca2+, Mg2+ and sulfate is a saline endmember fluid originating from the underlying carbonate formations of the basalt. Mixing with recharge water could explain the chemical composition of the various types of water. The signature of dissolved gypsum and halite indicates dissolution of evaporites that might have formed by evaporation either before the basalt covered the area or due to the hot basalts heating up the underlying carbonates and their enclosed fluids. Evaporation of water precipitated evaporites. Ca and Mg halides are hygroscopic, thus they are only present in solution. Such saline water, however, has not affected the low saline groundwater because their increase in Ca depends neither on the increase of Mg2+ nor of SO42-. This leaves the formation of clay minerals as the probably sink for Na. Inverse modelling applying PHREEQC with phreeq.dat database reveals that the mineralization of groundwater increases due to dissolution of increasing amounts of halite and gypsum which are mass-wise, the most important reactants. Concurrently, albite increasingly precipitates. Montmorillonite, gibbsite and calcite form, whereas kaolinite is consumed. Sulfides are oxidized. δD and δ18O of well and springs fit an evaporation line rooted on the Ajloun MWL. Hydrochemically, there are two sources of salts: Mixing with a saline endmember brine and/or dissolution of evaporites. Near Jebel Druz, dissolution of evaporites dominates, whereas mixing with a saline endmember and formation of clay minerals occur at greater distances.

Experiment and simulation study on the effects of cement minerals on the water-rock-CO2 interaction during CO2 geological storage

NASA Astrophysics Data System (ADS)

Liu, N.; Cheng, J.

2016-12-01

The CO2 geological storage is one of the most promising technology to mitigate CO2 emission. The fate of CO2 underground is dramatically affected by the CO2-water-rock interaction, which are mainly dependent on the initial aquifer mineralogy and brine components. The cement minerals are common materials in sandstone reservoir but few attention has been paid for its effects on CO2-water-rock interaction. Five batch reactions, in which 5% cement minerals were assigned to be quartz, calcite, dolomite, chlorite and Ca-montmorillonite, respectively, were conducted to understanding the cement minerals behaviors and its corresponding effects on the matrix minerals alterations during CO2 geological storage. Pure mineral powders were selected to mix and assemble the 'sandstone rock' with different cement components meanwhile keeping the matrix minerals same for each group as 70% quartz, 20% K-feldspar and 5% albite. These `rock' reacted with 750ml deionized water and CO2 under 180° and 18MPa for 15 days, during which the water chemistry evolution and minerals surface micromorphology changes has been monitored. The minerals saturation indexes calculation and phase diagram as well as the kinetic models were made by PHREEQC to uncover the minerals reaction paths. The experiment results indicated that the quartz got less eroded, on the contrary, K-feldspar and albite continuously dissolved to favor the gibbsite and kaolinite precipitations. The carbonates cement minerals quickly dissolved to reach equilibrium with the pH buffered and in turn suppressed the alkali feldspar dissolutions. No carbonates minerals precipitations occurred until the end of reactions for all groups. The simulation results were basically consistent with the experiment record but failed to simulate the non-stoichiometric reactions and the minerals kinetic rates seemed underestimated at the early stage of reactions. The cement minerals significantly dominated the reaction paths during CO2 geological storage and its effects on the CO2-water-rock interaction should be focused no matter for the benefit of injection sustainability or carbon sequestration capability. And more cement minerals such as ankerite should be included and the reservoir quality changes should also be taken consideration in the further study.

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

Josephson, Gary B.; Geeting, John GH; Bredt, Ofelia P.

Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Waste Treatment Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed, constructed, and operated as part of a plan to respond to issue M12, "Undemonstrated Leaching Processes." The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEPmore » also includes non-prototypic ancillary equipment to support the core processing. Two operating scenarios are currently being evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario has caustic leaching performed in the UFP-2 ultrafiltration feed vessels (i.e., vessel UFP-VSL-T02A in the PEP; and vessels UFP-VSL-00002A and B in the WTP PTF). The second scenario has caustic leaching conducted in the UFP-1 ultrafiltration feed preparation vessels (i.e., vessels UFP-VSL-T01A and B in the PEP; vessels UFP-VSL-00001A and B in the WTP PTF). In both scenarios, 19-M sodium hydroxide solution (NaOH, caustic) is added to the waste slurry in the vessels to leach solid aluminum compounds (e.g., gibbsite, boehmite). Caustic addition is followed by a heating step that uses direct injection of steam to accelerate the leach process. Following the caustic leach, the vessel contents are cooled using vessel cooling jackets and/or external heat exchangers. The main difference between the two scenarios is that for leaching in UFP-1, the 19-M NaOH is added to un-concentrated waste slurry (3-8 wt% solids), while for leaching in UFP-2, the slurry is concentrated to nominally 20 wt% solids using cross-flow ultrafiltration before the addition of caustic. In both scenarios, following the caustic leach, the slurry was then concentrated to 17 wt% and washed with inhibited water to remove NaOH and other soluble salts. Next, the slurry was oxidatively leached using sodium permanganate to solubilize chrome. The slurry was then washed to remove the dissolved chrome and concentrated.« less

Gallium

USGS Publications Warehouse

Foley, Nora K.; Jaskula, Brian W.; Kimball, Bryn E.; Schulte, Ruth F.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Gallium is a soft, silvery metallic element with an atomic number of 31 and the chemical symbol Ga. Gallium is used in a wide variety of products that have microelectronic components containing either gallium arsenide (GaAs) or gallium nitride (GaN). GaAs is able to change electricity directly into laser light and is used in the manufacture of optoelectronic devices (laser diodes, light-emitting diodes [LEDs], photo detectors, and solar cells), which are important for aerospace and telecommunications applications and industrial and medical equipment. GaAs is also used in the production of highly specialized integrated circuits, semiconductors, and transistors; these are necessary for defense applications and high-performance computers. For example, cell phones with advanced personal computer-like functionality (smartphones) use GaAs-rich semiconductor components. GaN is used principally in the manufacture of LEDs and laser diodes, power electronics, and radio-frequency electronics. Because GaN power transistors operate at higher voltages and with a higher power density than GaAs devices, the uses for advanced GaN-based products are expected to increase in the future. Gallium technologies also have large power-handling capabilities and are used for cable television transmission, commercial wireless infrastructure, power electronics, and satellites. Gallium is also used for such familiar applications as screen backlighting for computer notebooks, flat-screen televisions, and desktop computer monitors.Gallium is dispersed in small amounts in many minerals and rocks where it substitutes for elements of similar size and charge, such as aluminum and zinc. For example, gallium is found in small amounts (about 50 parts per million) in such aluminum-bearing minerals as diaspore-boehmite and gibbsite, which form bauxite deposits, and in the zinc-sulfide mineral sphalerite, which is found in many mineral deposits. At the present time, gallium metal is derived mainly as a byproduct of the processing of bauxite ore for aluminum; lesser amounts of gallium metal are produced from the processing of sphalerite ore from three types of deposits (sediment-hosted, Mississippi Valley-type, and volcanogenic massive sulfide) for zinc. The United States is expected to meet its current and expected future needs for gallium through imports of primary, recycled, and refined gallium, as well as through domestic production of recycled and refined gallium. The U.S. Geological Survey estimates that world resources of gallium in bauxite exceed 1 billion kilograms, and a considerable quantity of gallium could be present in world zinc reserves.

Rare Earth Element Behavior During Incongruent Weathering and Varying Discharge Conditions in Silicate Dominated River Systems: The Australian Victorian Alps

NASA Astrophysics Data System (ADS)

Hagedorn, K. B.; Cartwright, I.

2008-12-01

The distribution of rare earth elements (REE) and trace elements was measured by ICP-MS on fresh, slightly weathered and weathered granite and surface water samples from a network of 11 pristine rivers draining the Australian Victorian Alps during (i) high and (ii) low discharge conditions. River water REE concentrations are largely derived from atmospheric precipitation (rain, snow), as indicated by similar Chondrite normalized REE patterns (higher LREE over HREE; negative Ce anomalies, positive Eu anomalies) and similar total REE concentrations during both dry and wet seasons. Calculations based on the covariance between REE and Cl concentrations and oxygen and hydrogen isotopes indicate precipitation input coupled with subsequent evaporation may account for 30% o 100% of dissolved REE in stream waters. The dissolved contribution to the granitic substratum to stream water comes mainly from the transformation of plagioclase to smectite, kaolinite and gibbsite and minor apatite dissolution. However, since most REE of the regional granite are present in accessory minerals (titanite, zircon, etc.) they do not significantly contribute to the river REE pool. REE concentrations drop sharply downstream as a result of dilution and chemical attenuation. A trend of downstream enrichment of the heavier REE is due to selective partitioning of the lighter REE (as both free REE or REECO3 complexes) to hydrous oxides of suspended Al which, in turn, is controlled by a downstream increase of pH to values > 6.1 (for free REE) and > 7.3 (for REECO3 complexes). Although most circumneutral waters were supersaturated with REE phosphate compounds, precipitation of LnPO4 is not believed to have been a dominant process because the predicted phosphate fractionation pattern is inconsistent with the observed trends. Negative saturation indices of hydrous ferric oxides also militate against surface complexation onto goethite. Instead, REE attenuation most likely resulted from adsorption onto hydrous aluminium oxide. Seasonally, higher total REE concentrations during the dry season are due to longer residence time of water within rock fractures as well as high rainfall REE concentrations which, for the summer of 2007, might be related to organic carbon rich dust released after bushfires in the region. Lower pH values and low oxidation potentials at that time also contribute to raise REE concentrations through desorption.

Weathering processes in the Rio Icacos and Rio Mameyes watersheds in Eastern Puerto Rico: Chapter I in Water quality and landscape processes of four watersheds in eastern Puerto Rico

USGS Publications Warehouse

Buss, Heather L.; White, Arthur F.; Murphy, Sheila F.; Stallard, Robert F.

2012-01-01

Streams draining watersheds of the two dominant lithologies (quartz diorite and volcaniclastic rock) in the Luquillo Experimental Forest of eastern Puerto Rico have very high fluxes of bedrock weathering products. The Río Blanco quartz diorite in the Icacos watershed and the Fajardo volcaniclastic rocks in the Mameyes watershed have some of the fastest documented rates of chemical weathering of siliceous rocks in the world. Rapid weathering produces thick, highly leached saprolites in both watersheds that lie just below the soil and largely isolate subsurface biogeochemical and hydrologic processes from those in the soil. The quartz diorite bedrock in the Icacos watershed weathers spheroidally, leaving large, relatively unweathered corestones that are enveloped by slightly weathered rock layers called rindlets. The rindlets wrap around the corestones like an onionskin. Within the corestones, biotite oxidation is thought to induce the spheroidal fracturing that leads to development of rindlets; plagioclase in the rindlets dissolves, creating additional pore spaces. Near the rindlet-saprolite interface, the remaining plagioclase dissolves, hornblende dissolves to completion, and precipitation of kaolinite, gibbsite, and goethite becomes pervasive. In the saprolite, biotite weathers to kaolinite and quartz begins to dissolve. In the soil layer, both quartz and kaolinite dissolve. The volcaniclastic bedrock of the Mameyes watershed weathers even faster than the quartz diorite bedrock of the Icacos watershed, leaving thicker saprolites that are devoid of all primary minerals except quartz. The quartz content of volcaniclastic bedrock may help to control watershed geomorphology; high-quartz rocks form thick saprolites that blanket ridges. Hydrologic flow paths within the weathering profiles vary with total fluid flux, and they influence the chemistry of streams. Under low-flow conditions, the Río Icacos and its tributaries are fed by rainfall and by groundwater from the fracture zones; during storm events, intense rainfall rapidly raises stream levels and water is flushed through the soil as shallow flow. As a result, weathering constituents that shed into streamwaters are dominated by rindlet-zone weathering processes during base flow and by soil weathering processes during stormflow. The upper reaches of the Mameyes watershed are characterized by regolith more than 35 meters thick in places that contains highly fractured rock embedded in its matrix. Weathering contributions to stream chemistry at base flow are predicted to be more spatially variable in the Mameyes watershed than in the Icacos watershed owing to the more complex subsurface weathering profile of the volcaniclastic bedrocks of the Mameyes watershed.

Equilibrium aluminium hydroxo-oxalate phases during initial clay formation; H +-Al 3+-oxalic acid-Na + system

NASA Astrophysics Data System (ADS)

Bilinski, Halka; Horvath, Laszlo; Ingri, Nils; Sjöberg, Staffan

1986-09-01

The conditions necessary for initial clay formation have been studied in different model systems comprising different organic acids besides Si and Al. In the present paper the solid phases and the precipitation boundary characterizing the subsystem H +-Al 3+-oxalic acid (H 2L) are discussed. pH and tyndallometric measurements were performed in an ionic medium of 0.6 M Na(Cl) at 25 °C. The two phases Al 3(OH) 7(C 2O 4) · 3H 2O (phase I) and NaAl(OH) 2(C 2O 4) · 3H 2O (phase II) determine the precipitation boundary. The following formation constants for the two phases were deduced: lgβ1 = lg([ Al3+] -3[ H2C2O4] -1[ H+] 9 = -21.87 ± 0.08 and lgβ11 = lg([ Al3+] -1[ H2C2O4] -1[ H+] 4 = -5.61 ± 0.06. Phase I exists in the range [ Al] tot≥ 10 -4.4moldm-3,[ H2C2O4] tot ≥ 10 -4.9moldm-3 and at pH < 6.8, thus being a possible precipitate in oxalic-rich natural waters. The more soluble sodium phase is unlikely to exist in natural waters. The two phases are metastable relative to crystalline gibbsite and may be considered as the first precipitation step in the transition from aqueous Al oxalates down to stable Al hydroxide. Model calculations illustrating these competing hydrolysis-complexation reactions are discussed in terms of predominance and speciation diagrams. The solid phases have been characterized by X-ray analysis of powders, TGA and IR spectra, and tentative structures are proposed. Phase I seems to be an octahedral layer structure, in which 3/5 of the octahedral sites between two close packed oxygen sheets are occupied by Al 3+ and the oxalate ion acts as a bridge ligand between two aluminium atoms. Phase II forms a more open sheet structure and has ion exchange properties. Powder data for a phase crystallized from the studied solution after a year are also presented. This phase, Na 4Al 2(OH) 2(C 2O 4) 4 · 10H 2O, supports the results from the equilibrium analysis of recent solution data by SJöBERG and ÖHMAN (1985), who have found the dinuclear complex Al 2(OH) 2(C 2O 4) 44- to exist in a solution in which the ligand is in excess.

Aluminum Coprecipitates with Fe (hydr)oxides: Does Isomorphous Substitution of Al3plus for Fe3plus in Goethite Occur

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

E Bazilevskaya; D Archibald; M Aryanpour

2011-12-31

Iron (hydr)oxides are common in natural environments and typically contain large amounts of impurities, presumably the result of coprecipitation processes. Coprecipitation of Al with Fe (hydr)oxides occurs, for example, during alternating reduction-oxidation cycles that promote dissolution of Fe from Fe-containing phases and its re-precipitation as Fe-Al (hydr)oxides. We used chemical and spectroscopic analyses to study the formation and transformation of Al coprecipitates with Fe (hydr)oxides. In addition, periodic density functional theory (DFT) computations were performed to assess the structural and energetic effects of isolated or clustered Al atoms at 8 and 25 mol% Al substitution in the goethite structure. Coprecipitatesmore » were synthesized by raising the pH of dilute homogeneous solutions containing a range of Fe and Al concentrations (100% Fe to 100% Al) to 5. The formation of ferrihydrite in initial suspensions with {<=}20 mol% Al, and of ferrihydrite and gibbsite in initial suspensions with {>=}25 mol% Al was confirmed by infrared spectroscopic and synchrotron-based X-ray diffraction analyses. While base titrations showed a buffer region that corresponded to the hydrolysis of Fe in initial solutions with {<=}25 mol% Al, all of the Al present in these solutions was retained by the solid phases at pH 5, thus indicating Al coprecipitation with the primary Fe hydroxide precipitate. In contrast, two buffer regions were observed in solutions with 30 mol% Al (at pH {approx}2.25 for Fe{sup 3+} and at pH {approx}4 for Al{sup 3+}), suggesting the formation of Fe and Al (hydr)oxides as two separate phases. The Al content of initial coprecipitates influenced the extent of ferrihydrite transformation and of its transformation products as indicated by the presence of goethite, hematite and/or ferrihydrite in aged suspensions. DFT experiments showed that: (i) optimized unit cell parameters for Al-substituted goethites (8 and 25 Mol% Al) in clustered arrangement (i.e., the formation of diaspore-like clusters) were in good agreement with available experimental data whereas optimized unit cell parameters for isolated Al atoms were not, and (ii) Al-substituted goethites with Al in diaspore-like clusters resulted in more energetically favored structures. Combined experimental and DFT results are consistent with the coprecipitation of Al with Fe (hydr)oxides and with the formation of diaspore-like clusters, whereas DFT results suggest isomorphous Al for Fe substitution within goethite is unlike at 8 mol% Al substitution.« less

The origins of Late Quaternary debris avalanche and debris flow deposits from Cofre de Perote volcano, México

USGS Publications Warehouse

Diaz-Castellon, Rodolfo; Hubbard, Bernard E.; Carrasco-Nunez, Gerardo; Rodríguez-Vargas, José Luis

2012-01-01

Cofre de Perote volcano is a compound, shield-like volcano located in the northeastern Trans-Mexican volcanic belt. Large debris avalanche and lahar deposits are associated with the evolution of Cofre. The two best preserved of these debris-avalanche and debris-flow deposits are the ∼42 ka “Los Pescados debris flow” deposit and the ∼11–13 ka “Xico avalanche” deposit, both of which display contrasting morphological and textural characteristics, source materials, origins and emplacement environments. Laboratory X-ray diffraction and visible-infrared reflectance spectroscopy were used to identify the most abundant clay, sulfate, ferric-iron, and silica minerals in the deposits, which were either related to hydrothermal alteration or chemical weathering processes. Cloud-free Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) remote sensing imagery, supporting EO-1 Hyperion image spectra, and field ground truth samples were used to map the mineralogy and distribution of hydrothermally altered rocks on the modern summit of Cofre de Perote. The results were then compared to minerals identified in the two debris-avalanche and debris-flow deposits in order to assess possible source materials and origins for the two deposits.The older Los Pescados debris-flow deposit contains mostly halloysite and hydrous silica minerals, which match the dominant mineralogy of soils and weathered volcanic deposit in the surrounding flanks of Cofre de Perote. Its source materials were most likely derived from initially noncohesive or clay-poor flows, which subsequently bulked with clay-rich valley soils and alluvium in a manner similar to lahars from Nevado del Ruiz in 1985, but on a larger scale. The younger Xico avalanche deposit contains abundant smectite, jarosite, kaolinite, gypsum, and mixed-layered illite/smectite, which are either definitely or most likely of hydrothermal alteration origin. Smectite in particular appears to be the most abundant and spectrally dominant mineral in summit ground truth samples, ASTER mapping results, Xico avalanche deposit, and an older (pre-Xico avalanche) deposit derived from collapse(s) of ancestral Cofre de Perote edifice. However, both Xico avalanche and Los Pescados debris flow deposits show some evidence of secondary, postemplacement weathering and induration, which is evident by the presence of gibbsite, and hydroxyl interlayered minerals, in addition to recently formed halloysite and hydrous silica (i.e., indurating) cements. Field-based, visible infrared image spectroscopy (VIS/IR) spectral measurements offer the possibility of distinguishing primary minerals of hydrothermal alteration origin in debris-avalanche and debris-flow deposits from those produced either by in situ chemical weathering or bulked from weathered source materials.

Chemical weathering rates of a soil chronosequence on granitic alluvium: III. Hydrochemical evolution and contemporary solute fluxes and rates

USGS Publications Warehouse

White, A.F.; Schulz, M.S.; Vivit, D.V.; Blum, A.E.; Stonestrom, David A.; Harden, J.W.

2005-01-01

Although long-term changes in solid-state compositions of soil chronosequences have been extensively investigated, this study presents the first detailed description of the concurrent hydrochemical evolution and contemporary weathering rates in such sequences. The most direct linkage between weathering and hydrology over 3 million years of soil development in the Merced chronosequence in Central California relates decreasing permeability and increasing hydrologic heterogeneity to the development of secondary argillic horizons and silica duripans. In a highly permeable, younger soil (40 kyr old), pore water solutes reflect seasonal to decadal-scale variations in rainfall and evapotranspiration (ET). This climate signal is strongly damped in less permeable older soils (250 to 600 kyr old) where solutes increasingly reflect weathering inputs modified by heterogeneous flow. Elemental balances in the soils are described in terms of solid state, exchange and pore water reservoirs and input/output fluxes from precipitation, ET, biomass, solute discharge and weathering. Solute mineral nutrients are strongly dependent on biomass variations as evidenced by an apparent negative K weathering flux reflecting aggradation by grassland plants. The ratios of solute Na to other base cations progressively increase with soil age. Discharge fluxes of Na and Si, when integrated over geologic time, are comparable to solid-state mass losses in the soils, implying similar past weathering conditions. Similarities in solute and sorbed Ca/Mg ratios reflect short-term equilibrium with the exchange reservoir. Long-term consistency in solute ratios, when contrasted against progressive decreases in solid-state Ca/Mg, requires an additional Ca source, probably from dry deposition. Amorphous silica precipitates from thermodynamically-saturated pore waters during periods of high evapotranspiration and result in the formation of duripans in the oldest soils. The degree of feldspar and secondary gibbsite and kaolinite saturation varies both spatially and temporally due to the seasonality of plant-respired CO2 and a decrease in organically complexed Al. In deeper pore waters, K-feldspar is in equilibrium and plagioclase is about an order of magnitude undersaturated. Hydrologic heterogeneity produces a range of weathering gradients that are constrained by solute distributions and matrix and macropore flow regimes. Plagioclase weathering rates, based on precipitation-corrected Na gradients, vary between 3 and 7 ?? 10-16 mol m-2 s-1. These rates are similar to previously determined solid-state rates but are several orders of magnitude slower than for experimental plagioclase dissolution indicating strong inhibitions to natural weathering, partly due to near-equilibrium weathering reactions. Copyright ?? 2005 Elsevier Ltd.

Biological Control on Mineral Transformation in Soils ?

NASA Astrophysics Data System (ADS)

Ziegler, K.; Hsieh, J. C.; Chadwick, O. A.; Kelly, E. F.

2001-12-01

Weathering of primary minerals is commonly linked to biological processes through the production of carbonic and organic acids. Plants can also play a role in weathering by removing soluble constituents and enhancing diffusion gradients within the soil. Here we investigate the synthesis of secondary minerals and the role of plants in removing elements that act as building blocks for these minerals. In order to minimize losses from leaching, we have sampled a chronosequence of soils forming on lava flows on Hawaii Island that receive about 200 mm of rain annually and have never been subjected to high levels of rainfall. The P concentration in the soils drops from almost 3000 mg/kg on a 1.5 ky lava flow to around 1000 mg/kg on a 350 ky lava flow. This loss of P can only be ascribed to P-uptake by plants with subsequent removal through the loss of above ground biomass through fire and/or wind removal. Over the same time frame the amount of plagioclase in the soils drops from around 22% of the <2 mm soil fraction on the youngest lava flow to virtually 0% on the 350 ky flow, suggesting a substantial release of Si. Elevated silicon in arid, basaltic soil environments often leads to formation of smectite, a feature not observed along the chronosequence. In fact, plagioclase is replaced by the kaolin mineral halloysite with allophane as an apparent precursor. Kaolin minerals are associated with moderate to intense leaching environments rather than the mild leaching conditions that influence these soils. We selected an intermediate age soil profile (170 ky lava flow) to conduct an in-depth investigation of the soil mineral composition. We detected a strong dominance of halloysite, the presence of gibbsite, but no smectite. Secondary halloysite formation is preferred over smectite formation when Si activities are relatively low, and the pH is acidic rather than alkaline. Although this mineral assemblage seems to imply formation under a wetter climatic regime, the oxygen isotopic composition of the halloysite suggests formation under soil environmental conditions similar to the present. The Si concentration in grass and tree leaves in the vicinity of the soil contain between 3 and 8% Si. Loss of these leaves to the nearby ocean (either as dried or burned residue) could be responsible for considerable Si removal in a manner similar to the P-removal. The resulting Si-deficient soil-water favors the formation of halloysite over smectite as is demonstrated by construction of mineral stability diagrams using the soil-water data from the soils along the chronosequence.

Preliminary Report on the White Canyon Area, San Juan County, Utah

USGS Publications Warehouse

Benson, William Edward Barnes; Trites, A.F.; Beroni, E.P.; Feeger, J.A.

1952-01-01

The White Canyon area in San Juan County, Utah, contains known deposits of copper-uranium ore and is currently being mapped and studied by the Geological Survey. To date, approximately 75 square miles, or about 20 percent of the area, has been mapped on a scale 1 inch=1 mile. The White Canyon area is underlain by more than 2,000 feet of sedimentary rocks, Carboniferous to Jurassic(?) in age. The area is on the flank of the Elk Ridge anticline, and the strata have a regional dip of 1 deg to 2 deg SW. The Shinarump conglomerate of Late Triassic age is the principal ore-bearing formation. The Shinarump consists of lenticular beds of sandstone, conglomeratic sandstone, clay, and siltstone, and ranges in thickness from a feather edge to as much as 75 feet. Locally the sandstones contain silicified and carbonized wood and fragments of charcoal. These vegetal remains are especially common in channel-fill deposits. Jointing is prominent in the western part of the area, and apparently affects all formations. Adjacent to the joints some of the redbeds in the sequence are bleached. Deposits of copper-uranium minerals have been found in the Moenkopi, Shinarump, and Chinle formations, but the only production of ore has been from the Shinarump conglomerate. The largest concentration of these minerals is in the lower third of the Shinarump, and the deposits seem to be controlled in part by ancient channel fills and in part by fractures. Locally precipitation of the copper and uranium minerals apparently has been aided by charcoal and clays. Visible uranium minerals include both hard and soft pitchblende and secondary hydrosulfates, phosphates, and silicates. In addition, unidentified uranium compounds are present in carbonized wood and charcoal, and in veinlets of hydrocarbons. Base-metal sulfides have been identified in all prospects that extend beyond the oxidized zone. Secondary copper minerals in the oxidized zone include the hydrous sulfates and carbonates, and possibly chrysocolla. The principal gangue minerals are quartz, clay minerals, chlorite, oxides of iron and manganese, alunite, calcite, gypsum, pyrite, allophane, gibbsite, opal, and chalcedony. The origin of the copper-uranium ores has not been determined, but the association of many deposits with fractures, the mineralogic assemblage, and a lead-uranium age determination of 50 to 60 million years for the pitchblende in the Happy Jack mine favor the hypothesis that the ores are of hydrothermal origin and were deposited in early Tertiary time. Criteria believed to be the most useful in prospecting for new deposits are (1) visible uranium minerals; (2) visible copper minerals; (3) alunite; (4) hydrocarbons; and (5) bleaching of the underlying Moenkopi formation.

PEP Integrated Test D Run Report Caustic and Oxidative Leaching in UFP-VSL-T02A

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

Sevigny, Gary J.; Bredt, Ofelia P.; Burns, Carolyn A.

2009-12-11

Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed, constructed and operated as part of a plan to respond to issue M12, "Undemonstrated Leaching Processes" of the External Flowsheet Review Team (EFRT) issue response plan. The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. Themore » PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing. Two operating scenarios are currently being evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario (Test B and D) has caustic leaching performed in the UFP-2 ultrafiltration feed vessels (i.e., vessel UFP-VSL-T02A in the PEP and vessels UFP-VSL-00002A and B in the WTP PTF). The second scenario (Test A) has caustic leaching conducted in the UFP-1 ultrafiltration feed preparation vessels (i.e., vessels UFP-VSL-T01A and B in the PEP and vessels UFP VSL-00001A and B in the WTP PTF). In Test D, 19M sodium hydroxide (NaOH, caustic) was added to the waste slurry in the UFP VSL T02 vessel after the solids were concentrated to ~20% undissolved solids. The NaOH was added to leach solid aluminum compounds (e.g., gibbsite, boehmite). Caustic addition is followed by heating to 85°C using direct injection of steam to accelerate the leach process. The main difference of Test D compared to Test B is that the leach temperature is 85°C for 24 hrs as compared to 100°C for 12 hours. The other difference is the Test D simulant had Cr in the simulant from the start of processing and Test B had Cr added to adjust the simulant composition after aluminum leaching. Following the caustic leach, the UFP-VSL-T02A vessel contents are cooled using the vessel cooling jacket. The slurry was then concentrated to 17 wt% undissolved solids and washed with inhibited water to remove NaOH and other soluble salts. Next, the slurry was oxidatively leached using sodium permanganate to solubilize chrome. The slurry was then washed to remove the dissolved chrome and concentrated.« less

Chemical thermodynamic data. 1. The concept of links to the chemical elements and the historical development of key thermodynamic data [plus Supplementary Electronic Annex 2

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

Wolery, Thomas J.; Jove Colon, Carlos F.

Chemical thermodynamic data remain a keystone for geochemical modeling and reactive transport simulation as applied to an increasing number of applications in the earth sciences, as well as applications in other areas including metallurgy, material science, and industrial process design. The last century has seen the development of a large body of thermodynamic data and a number of major compilations. The past several decades have seen the development of thermodynamic databases in digital form designed to support computer calculations. However, problems with thermodynamic data appear to be persistent. One problem pertains to the use of inconsistent primary key reference data.more » Such data pertain to elemental reference forms and key, stoichiometrically simple chemical species including metal oxides, CO 2, water, and aqueous species such as Na + and Cl -. A consistent set of primary key data (standard Gibbs energies, standard enthalpies, and standard entropies for key chemical species) for 298.15K and 1 bar pressure is essential. Thermochemical convention is to define the standard Gibbs energy and the standard enthalpy of an individual chemical species in terms of formation from reference forms of the constituent chemical elements. We propose a formal concept of “links” to the elemental reference forms. This concept involves a documented understanding of all reactions and calculations leading to values for a formation property (standard Gibbs energy or enthalpy). A valid link consists of two parts: (a) the path of reactions and corrections and (b) the associated data, which are key data. Such a link differs from a bare “key” or “reference” datum in that it requires additional information. Some or all of its associated data may also be key data. In evaluating a reported thermodynamic datum, one should identify the links to the chemical elements, a process which can be time-consuming and which may lead to a dead end (an incomplete link). The use of two or more inconsistent links to the same elemental reference form in a thermodynamic database will result in an inconsistency in the database. Thus, in constructing a database, it is important to establish a set of reliable links (generally resulting in a set of primary reference data) and then correct all data adopted subsequently for consistency with that set. Recommended values of key data have not been constant through history. We review some of this history through the lens of major compilations and other influential reports, and note a number of problem areas. Finally, we illustrate the concepts developed in this paper by applying them to some key species of geochemical interest, including liquid water; quartz and aqueous silica; and gibbsite, corundum, and the aqueous aluminum ion.« less

Chemical thermodynamic data. 1. The concept of links to the chemical elements and the historical development of key thermodynamic data

NASA Astrophysics Data System (ADS)

Wolery, Thomas J.; Jové Colón, Carlos F.

2017-09-01

Chemical thermodynamic data remain a keystone for geochemical modeling and reactive transport simulation as applied to an increasing number of applications in the earth sciences, as well as applications in other areas including metallurgy, material science, and industrial process design. The last century has seen the development of a large body of thermodynamic data and a number of major compilations. The past several decades have seen the development of thermodynamic databases in digital form designed to support computer calculations. However, problems with thermodynamic data appear to be persistent. One problem pertains to the use of inconsistent primary key reference data. Such data pertain to elemental reference forms and key, stoichiometrically simple chemical species including metal oxides, CO2, water, and aqueous species such as Na+ and Cl-. A consistent set of primary key data (standard Gibbs energies, standard enthalpies, and standard entropies for key chemical species) for 298.15 K and 1 bar pressure is essential. Thermochemical convention is to define the standard Gibbs energy and the standard enthalpy of an individual chemical species in terms of formation from reference forms of the constituent chemical elements. We propose a formal concept of "links" to the elemental reference forms. This concept involves a documented understanding of all reactions and calculations leading to values for a formation property (standard Gibbs energy or enthalpy). A valid link consists of two parts: (a) the path of reactions and corrections and (b) the associated data, which are key data. Such a link differs from a bare "key" or "reference" datum in that it requires additional information. Some or all of its associated data may also be key data. In evaluating a reported thermodynamic datum, one should identify the links to the chemical elements, a process which can be time-consuming and which may lead to a dead end (an incomplete link). The use of two or more inconsistent links to the same elemental reference form in a thermodynamic database will result in an inconsistency in the database. Thus, in constructing a database, it is important to establish a set of reliable links (generally resulting in a set of primary reference data) and then correct all data adopted subsequently for consistency with that set. Recommended values of key data have not been constant through history. We review some of this history through the lens of major compilations and other influential reports, and note a number of problem areas. Finally, we illustrate the concepts developed in this paper by applying them to some key species of geochemical interest, including liquid water; quartz and aqueous silica; and gibbsite, corundum, and the aqueous aluminum ion.

Chemical thermodynamic data. 1. The concept of links to the chemical elements and the historical development of key thermodynamic data [plus Supplementary Electronic Annex 2

DOE PAGES

Wolery, Thomas J.; Jove Colon, Carlos F.

2016-09-26

Chemical thermodynamic data remain a keystone for geochemical modeling and reactive transport simulation as applied to an increasing number of applications in the earth sciences, as well as applications in other areas including metallurgy, material science, and industrial process design. The last century has seen the development of a large body of thermodynamic data and a number of major compilations. The past several decades have seen the development of thermodynamic databases in digital form designed to support computer calculations. However, problems with thermodynamic data appear to be persistent. One problem pertains to the use of inconsistent primary key reference data.more » Such data pertain to elemental reference forms and key, stoichiometrically simple chemical species including metal oxides, CO 2, water, and aqueous species such as Na + and Cl -. A consistent set of primary key data (standard Gibbs energies, standard enthalpies, and standard entropies for key chemical species) for 298.15K and 1 bar pressure is essential. Thermochemical convention is to define the standard Gibbs energy and the standard enthalpy of an individual chemical species in terms of formation from reference forms of the constituent chemical elements. We propose a formal concept of “links” to the elemental reference forms. This concept involves a documented understanding of all reactions and calculations leading to values for a formation property (standard Gibbs energy or enthalpy). A valid link consists of two parts: (a) the path of reactions and corrections and (b) the associated data, which are key data. Such a link differs from a bare “key” or “reference” datum in that it requires additional information. Some or all of its associated data may also be key data. In evaluating a reported thermodynamic datum, one should identify the links to the chemical elements, a process which can be time-consuming and which may lead to a dead end (an incomplete link). The use of two or more inconsistent links to the same elemental reference form in a thermodynamic database will result in an inconsistency in the database. Thus, in constructing a database, it is important to establish a set of reliable links (generally resulting in a set of primary reference data) and then correct all data adopted subsequently for consistency with that set. Recommended values of key data have not been constant through history. We review some of this history through the lens of major compilations and other influential reports, and note a number of problem areas. Finally, we illustrate the concepts developed in this paper by applying them to some key species of geochemical interest, including liquid water; quartz and aqueous silica; and gibbsite, corundum, and the aqueous aluminum ion.« less

Groundwater Quality Assessment in the Upper East Region of Ghana

NASA Astrophysics Data System (ADS)

Apambire, W. B.

2001-05-01

In Ghana, West Africa, fluoride occurs as a natural pollutant in some groundwaters, while the presence of isolated high levels of nitrate and arsenic in groundwater is due to human activities such as poor sanitation, garbage disposal and mining practices. The challenge for Ghana is to ensure that groundwater quality and environmental adversities such as water level decline are not compromised by attempts to increase water quantity. Concentrations of groundwater fluoride in the study area range from 0.11 to 4.60 mg/L, with the highest concentrations found in the fluorine-enriched Bongo granitoids. Eighty-five out of 400 wells sampled have fluoride concentrations above the World Health Organization maximum guideline value of 1.5 mg/L and thus causes dental fluorosis in children drinking from the wells. The distribution of fluoride in groundwater is highly related to the distribution of dental fluorosis in the UER. Nitrate concentrations ranged from 0.03 to 211.00 mg/L and the mean value was 16.11 mg/L. Twenty-one samples had concentrations in excess of the guideline value of 45 mg/L. Consumption of water in excess of the guideline value, by infants, may cause an infantile disease known as methaemoglobinaemia. It is inferred that groundwaters with exceptionally high NO3 values have been contaminated principally through human activities such as farming and waste disposal. This is because wells with high nitrate concentrations are all located in and around towns and sizable villages. Also, there is good correlation between Cl and NO3 (r = +0.74), suggesting that both elements come from the same sources of pollution. Only two well waters had concentrations of iron in excess of the guideline value of 0.3 mg/L. These samples come from shallow hand-dug wells. The maximum concentration of iron in groundwaters is 3.5 mg/L. The recommended guideline limit for Al in drinking water is 0.2 mg/L; two wells had Al concentrations of 12.0 and 4.0 mg/L, respectively. Other high concentrations of Al are associated with shallow wells and ponds. There is a highly positive correlation (r = +1) between Fe and Al, suggesting that dissolution of weathered lateritic material (e.g., Fe oxides, gibbsite, etc.) is the common source for these elements. Manganese concentrations are generally within acceptable limits, except for 11 wells that have concentrations above the guideline limit of 0.1 mg/L. These anomalous concentrations may be associated with manganiferous deposits in the study area. A majority of the samples contain very low concentrations of the trace elements Zn, Pb, Cd, Cr, As and Se; however, the highest concentrations occur in areas where small-scale mining is practiced.

Reduction of Mn-oxides by ferrous iron in a flow system: column experiment and reactive transport modeling

NASA Astrophysics Data System (ADS)

Postma, D.; Appelo, C. A. J.

2000-04-01

The reduction of Mn-oxide by Fe2+ was studied in column experiments, using a column filled with natural Mn-oxide coated sand. Analysis of the Mn-oxide indicated the presence of both Mn(III) and Mn(IV) in the Mn-oxide. The initial exchange capacity of the column was determined by displacement of adsorbed Ca2+ with Mg2+. Subsequently a FeCl2 solution was injected into the column causing the reduction of the Mn-oxide and the precipitation of Fe(OH)3. Finally the exchange capacity of the column containing newly formed Fe(OH)3 was determined by injection of a KBr solution. During injection of the FeCl2 solution into the column, an ion distribution pattern was observed in the effluent that suggests the formation of separate reaction fronts for Mn(III)-oxide and Mn(IV)-oxide travelling at different velocities through the column. At the proximal reaction front, Fe2+ reacts with MnO2 producing Fe(OH)3, Mn2+ and H+. The protons are transported downstream and cause the disproportionation of MnOOH at a separate reaction front. Between the two Mn reaction fronts, the dissolution and precipitation of Fe(OH)3 and Al(OH)3 act as proton buffers. Reactive transport modeling, using the code PHREEQC 2.0, was done to quantify and analyze the reaction controls and the coupling between transport and chemical processes. A model containing only mineral equilibria constraints for birnessite, manganite, gibbsite, and ferrihydrite, was able to explain the overall reaction pattern with the sequential appearance of Mn2+, Al3+, Fe3+, and Fe2+ in the column outlet solution. However, the initial breakthrough of a peak of Ca2+ and the observed pH buffering indicated that exchange processes were of importance as well. The amount of potential exchangers, such as birnessite and ferrihydrite, did vary in the course of the experiment. A model containing surface complexation coupled to varying concentrations of birnessite and ferrihydrite and a constant charge exchanger in addition to mineral equilibria provided a satisfactory description of the distribution of all solutes in time and space. However, the observed concentration profiles are more gradual than indicated by the equilibrium model. Reaction kinetics for the dissolution of MnO2 and MnOOH and dissolution of Al(OH)3 were incorporated in the model, which explained the shape of the breakthrough curves satisfactorily. The results of this study emphasize the importance of understanding the interplay between chemical reactions and transport in addition to interactions between redox, proton buffering, and adsorption processes when dealing with natural sediments. Reactive transport modeling is a powerful tool to analyze and quantify such interactions.

Modeling pedogenesis at multimillennium timescales: achievements and challenges

NASA Astrophysics Data System (ADS)

Finke, Peter

2013-04-01

The modeling of soil genesis is a particular case of modeling vadose zone processes, because of the variety in processes to be considered and its large (multimillennium) temporal extent. The particular relevancy of pedogenetic modeling for non-pedologists is that it involves the soil compartment carbon cycle. As most of these processes are driven by water flow, modeling hydrological processes is an inevitable component of (non-empirical) modeling of soil genesis. One particular challenge is that both slow and fast pedogenetic processes need to be accounted for. This overview summarizes the state of the art in this new branch of pedology, achievements made so far and current challenges, and is largely based on one particular pedon-scale soil evolution model, SoilGen. SoilGen is essentially a pedon-scale solute transport model that simulates unsaturated water flow, chemical equilibriums of various species with calcite, gypsum and gibbsite as precipitated phases, an exchange phase of Na, K, Ca, Mg, H and Al on clay and organic matter and a solution phase comprising various cations and anions. Additionally, a number of pedogenetic processes are simulated: C-cycling, chemical weathering of primary minerals, physical weathering of soil particles, bioturbation and clay migration. The model was applied onto a climosequence, a chronosequence, a toposequence and as part of a spatio-temporal soilscape reconstruction. Furthermore, the clay migration component has been calibrated and tested and so has the organic matter decomposition component. Quantitative comparisons between simulations and measurements resulted in the identification of possible improvements in the model and associated inputs, identified problems to be solved and identified the current application domain. Major challenges for process-based modeling in the vadose zone at multimillennium timescales can be divided into 4 groups: (i) Reconstruction of initial and boundary conditions; (ii) Accounting for evolution in soil properties such as soil texture and soil structure; (iii) Developing adequate calibration techniques; (iv) Maximizing computational efficiency. Reconstruction of initial and boundary conditions requires multidisciplinary inputs either derived from proxies or from combined vegetation and climate development models. So far, the combination of pedogenetic models and combined vegetation/climate models is rare. At pedogenetic timescales, soil characteristics that are usually considered constant become dynamic: texture, OC, bulk density, precipitated salts, minerals, etc. Interactions and feedbacks between these characteristics and associated hydrological properties need attention, e.g. via pedotransfer functions. The same can be stated for the development of soil structure and associated preferential flow, which is still a challenge. At multimillennium temporal extents, the combination of long model runtime and the fact that most calibration data represent the current stage of soil development requires a special approach. Model performance can be evaluated at various timescales using unconventional proxies. Finally, recognizing the fact that matter redistribution at the landscape scale is of paramount importance at multimillennium extent requires the formulation of computationally efficient 3D models. This will surely involve analysis of the tradeoff between process detail, model accuracy, required boundary inputs and model runtime.

Long-term flow-through column experiments and their relevance to natural granitoid weathering rates

USGS Publications Warehouse

White, Arthur F.; Schulz, Marjorie S.; Lawrence, Corey R.; Vivit, Davison V.; Stonestrom, David A.

2017-01-01

Four pairs of fresh and partly-weathered granitoids, obtained from well-characterized watersheds—Merced River, CA, USA; Panola, GA, USA; Loch Vale, CO, USA, and Rio Icacos, Puerto Rico—were reacted in columns under ambient laboratory conditions for 13.8 yrs, the longest running experimental weathering study to date. Low total column mass losses (<1 wt. %), correlated with the absence of pitting or surface roughening of primary silicate grains. BET surface area (SBET) increased, primarily due to Fe-oxyhydroxide precipitation. Surface areas returned to within factors of 2 to 3 of their original values after dithionite extraction. Miscible displacement experiments indicated homogeneous plug flow with negligible immobile water, commonly cited for column experiments. Fresh granitoid effluent solute concentrations initially declined rapidly, followed by much slower decreases over the next decade. Weathered granitoid effluent concentrations increased modestly over the same time period, indicating losses of natural Fe-oxide and/or clay coatings and the increased exposure of primary mineral surfaces. Corresponding (fresh and weathered) elemental effluent concentrations trended toward convergence during the last decade of reaction. NETPATH/PHREEQC code simulations indicated non-stoichiometric dissolution involving Ca release from disseminated calcite and excess K release from interlayer biotite. Effluent 87Sr/85Sr ratios reflected a progressive weathering sequence beginning and ending with 87Sr/85Sr values of plagioclase with an additional calcite input and a radiogenic biotite excursion proportional to the granitoid ages.Effluents became thermodynamically saturated with goethite and gibbsite, slightly under-saturated with kaolinite and strongly under-saturated with plagioclase, consistent with kinetically-limited weathering in which solutes such as Na varied with column flow rates. Effluent Na concentrations showed no clear trend with time during the last decade of reaction (fresh granitoids) or increased slowly with time (weathered granitoids). Analysis of cumulative Na release indicated that plagioclase dissolution achieved steady state in 3 of the 4 fresh granitoids during the last decade of reaction. Surface-area normalized plagioclase dissolution rates exhibited a narrow range (0.95 to 1.26 10-13 moles m-2 s-1), in spite of significant stoichiometric differences (An0.21 to An0.50). Rates were an order of magnitude slower than previously reported in shorter duration experiments but generally 2 to 3 orders of magnitude faster than corresponding natural analogs. CrunchFlow simulations indicated that more than a hundredfold decrease in column flow rates would be required to produce near-saturation reaction affinities that would start to slow plagioclase weathering to real-world levels. Extending simulations to approximate long term weathering in naturally weathered profiles required additional decreases in the intrinsic plagioclase dissolution and kaolinite precipitation rates and relatively large decreases in the fluid flow rate, implying that exposure to reactive mineral surfaces is significantly limited in the natural environment compared to column experiments.

Controls on rind thickness on basaltic andesite clasts weathering in Guadeloupe

USGS Publications Warehouse

Sak, P.B.; Navarre-Sitchler, A. K.; Miller, C.E.; Daniel, C.C.; Gaillardet, J.; Buss, H.L.; Lebedeva, M.I.; Brantley, S.L.

2010-01-01

A clast of low porosity basaltic andesite collected from the B horizon of a soil developed on a late Quaternary volcaniclastic debris flow in the Bras David watershed on Basse-Terre Island, Guadeloupe, exhibits weathering like that observed in many weathered clasts of similar composition in other tropical locations. Specifically, elemental profiles measured across the core-rind interface document that primary minerals and glass weather to Fe oxyhydroxides, gibbsite and minor kaolinite in the rind. The earliest reaction identified in the core is oxidation of Fe in pyroxene but the earliest reaction that creates significant porosity is plagioclase dissolution. Elemental loss varies in the order Ca???Na>K???Mg>Si>Al>Fe???P??Ti, consistent with the relative reactivity of phases in the clast from plagioclase???pyroxene???glass>apatite>ilmenite. The rind surrounds a core of unaltered material that is more spherical than the original clast. The distance from the core-rind boundary to a visually prominent rind layer, L, was measured as a proxy for the rind thickness at 36 locations on a slab cut vertically through the nominal center of the clast. This distance averaged 24.4??3.1mm. Maximum and minimum values for L, 35.8 and 20.6mm, were observed where curvature of the core-rind boundary is greatest (0.12mm-1) and smallest (0.018mm-1) respectively. Extrapolating from other rinds in other locations, the rate of rind formation is estimated to vary by a factor of about 2 (from ~4 to 7??10-14ms-1) from low to high curvature. The observation of a higher rate of rind formation for a higher curvature interface is consistent with a diffusion-limited model for weathering rind formation. The diffusion-limited model predicts that, like rind thickness, values of the thickness of the reaction front (h) for a given reaction, defined as the zone over which a parent mineral such as plagioclase completely weathers to rind material, should also increase with curvature. Values of h were quantified as a function of interface curvature using bulk chemical analysis (500

Mineralogy and geochemistry of the Lokoundje alluvial clays from the Kribi deposits, Cameroonian Atlantic coast: Implications for their origin and depositional environment

NASA Astrophysics Data System (ADS)

Ndjigui, Paul-Désiré; Onana, Vincent Laurent; Sababa, Elisé; Bayiga, Elie Constantin

2018-07-01

The Lokoundje alluvial clay deposits are located at the left floodplain of the Lokoundje River, towards the estuary in the Kribi region. The mineralogical and geochemical features of the Lokoundje River fine-grained sediments have been reported using XRD, XRF, ICP-MS, and IR instruments in order to understand their provenance and depositional history. The Lokoundje watershed covers a surface area of about 5381 km2. The basement of this watershed is made up of gneisses, amphibolites, migmatites, charnockites, and pyroxenites from the Nyong and Ntem units, in the NW border of the Congo craton. The alluvial materials are about 100 cm thick and cover a total area of 1.4 km2. They are mainly plastic clays with silty-clayey texture and four colors (yellow, red yellow, white, and light grey). The mineral assemblage is composed of kaolinite, quartz, illite, gibbsite, goethite, rutile, and interstratified illite-vermiculite. The infra-red data associated with those of XRD portray the disordering of kaolinite. These materials are mostly constituted by SiO2 (44.33-69.19 wt%, av. = 51.17 wt% with n = 18) and Al2O3 (20.69-30.26 wt%, av. = 26.07 wt%) with very low Fe2O3 contents (1-7.71 wt%, av. = 3.35 wt%). The SiO2/Al2O3 ratio range between 1.46 and 4.1 (av. = 2.06). The alkali contents (Na2O + K2O) are below 5 wt%. ICV, CIA, PIA, and SiO2/Al2O3 portray high degree of chemical weathering in the source area as well as the maturity of sediments. The trace element behavior is quite different probably due to the mixed source rocks; Ba, Sr, Zn have high contents while several elements such as Th and U show low contents. The REE contents are also variable; their concentrations vary between 92 and 1065 ppm (av. = 307 ppm). The mineral assemblage associated with the geochemical data reveal that REE are mainly housed in clay minerals. The behavior of REE is also marked by the abundance of LREE (LREE/HREE = 19.69-34.62). The REE chondrite-normalized spectra confirm the LREE-abundance and exhibit negative Eu anomalies. The PAAS-normalized patterns reveal slight positive Eu anomalies and negative Ce anomalies. The (La/Yb)N values (3.30-8.43, av. = 5.71) display low degree of REE-fractionation in the Lokoundje watershed. The morphological, mineralogical, and geochemical features reveal that the fine-grained sediments derive from the intense weathering of mixed source. The disordering of kaolinite confirms that sediments were sorted during a long transportation before their deposition under oxic conditions (U/Th < 1.25; V/Cr < 2) in the floodplains near the Atlantic coast.

Long-term flow-through column experiments and their relevance to natural granitoid weathering rates

NASA Astrophysics Data System (ADS)

White, Art F.; Schulz, Marjorie S.; Lawrence, Corey R.; Vivit, Davison V.; Stonestrom, David A.

2017-04-01

Four pairs of fresh and partly-weathered granitoids, obtained from well-characterized watersheds-Merced River, CA, USA; Panola, GA, USA; Loch Vale, CO, USA, and Rio Icacos, Puerto Rico-were reacted in columns under ambient laboratory conditions for 13.8 yrs, the longest running experimental weathering study to date. Low total column mass losses (<1 wt.%), correlated with the absence of pitting or surface roughening of primary silicate grains. BET surface area (SBET) increased, primarily due to Fe-oxyhydroxide precipitation. Surface areas returned to within factors of 2-3 of their original values after dithionite extraction. Miscible displacement experiments indicated homogeneous plug flow with negligible immobile water, commonly cited for column experiments. Fresh granitoid effluent solute concentrations initially declined rapidly, followed by much slower decreases over the next decade. Weathered granitoid effluent concentrations increased modestly over the same time period, indicating losses of natural Fe-oxide and/or clay coatings and the increased exposure of primary mineral surfaces. Corresponding (fresh and weathered) elemental effluent concentrations trended toward convergence during the last decade of reaction. NETPATH/PHREEQC code simulations indicated non-stoichiometric dissolution involving Ca release from disseminated calcite and excess K release from interlayer biotite. Effluent 87Sr/85Sr ratios reflected a progressive weathering sequence beginning and ending with 87Sr/85Sr values of plagioclase with an additional calcite input and a radiogenic biotite excursion proportional to the granitoid ages. Effluents became thermodynamically saturated with goethite and gibbsite, slightly under-saturated with kaolinite and strongly under-saturated with plagioclase, consistent with kinetically-limited weathering in which solutes such as Na varied with column flow rates. Effluent Na concentrations showed no clear trend with time during the last decade of reaction (fresh granitoids) or increased slowly with time (weathered granitoids). Analysis of cumulative Na release indicated that plagioclase dissolution achieved steady state in 3 of the 4 fresh granitoids during the last decade of reaction. Surface-area normalized plagioclase dissolution rates exhibited a narrow range (0.95-1.26 10-13 moles m-2 s-1), in spite of significant stoichiometric differences (An0.21 to An0.50). Rates were an order of magnitude slower than previously reported in shorter duration experiments but generally 2-3 orders of magnitude faster than corresponding natural analogs. CrunchFlow simulations indicated that more than a hundredfold decrease in column flow rates would be required to produce near-saturation reaction affinities that would start to slow plagioclase weathering to real-world levels. Extending simulations to approximate long term weathering in naturally weathered profiles required additional decreases in the intrinsic plagioclase dissolution and kaolinite precipitation rates and relatively large decreases in the fluid flow rate, implying that exposure to reactive mineral surfaces is significantly limited in the natural environment compared to column experiments.

Significance of the giant Lower Cretaceous paleoweathering event

NASA Astrophysics Data System (ADS)

Thiry, Médard; Ricordel-Prognon, Caroline; Schmitt, Jean-Michel

2010-05-01

Weathering profiles typically develop at the interface with the atmosphere, and thus, record the fluctuations in the paleoatmosphere's chemistry and climatic conditions. Consequently they are one of the main archives to upgrade our understanding on paleoclimate and the Earth's environmental history. In this presentation, we will focus on the linking between paleoatmosphere compositions, weathering rates, and their impact on the subsequent sedimentary records. Distribution of the Lower Cretaceous lateritic weathering facies. During the Early Cretaceous, sea level drops and wide exondations lead to development of deep "lateritic" weathering profiles. Thick kaolinitic weathering profiles occured on the Hercynian basements and diverse kaolinitic and ferruginous weathering products covered the Jurassic limestone platforms. This major lateritic event is not restricted to Europe but also well know in North-America (up to Canada), South-America (down to Argentina), and in Australia. Moreover, recent paleomagnetic and radiometric datations revealed that numerous kaolinitic and ferruginous formations, which classically were ascribed to Tertiary ages, date back to the Lower Cretaceous period (Thiry et al., 2006). Additionally, the Bonherz iron ore deposits in the paleokarsts of the Jurassic limestone plateform of the Paris Basin also have to be reconsidered as of Cretaceous age, probably as well as the Tertiary age of the Swiss and Bavarian Jura Bonherz. Paleoclimatic interpretation. During a long time, the interpretation of these paleoweathering features has been a major palaeoclimatic argument. The spreading out of deep kaolinitic weathering profiles (from the Scandinavian and Canadian shields to southern Argentina and Australia, which was still situated close to Antarctica at that time) has lead to considerations, that during this period a warm and wet climate prevailed globally, with very little latitudinal differentiation. These paleoclimatic interpretations stand in contradiction to the paleobotanical data and the interpretation of the glacial origin of some sedimentary figures, such as dropstones. Additionally, some isotopic data are contradictory to the hypothesis of a warm climate around the whole world; in fact the data indicate cold water masses or even glaciation at high latitudes (Bornemann, 2008). On the other hand, numerous paleontological as well as some isotopic data support the theory of a greenhouse Earth during Cretaceous times (Sellwood & Valdes, 2006. Cretaceous paleoatmosphere. Taking in account the composition of the paleoatmosphere during the Cretaceous has considerably enriched the paleoclimatic debate. It is know that the CO2 concentrations of the Cretaceous atmosphere may have been 5 to 10 times higher than present day values (Berner & Kothavala, 2001). These high CO2 concentrations have often been used to explain higher rates of silicate mineral alteration. Nevertheless, although it is well understood that the CO2 content of the atmosphere controls the climate and therefore weathering, the specific mechanisms that intervene have rarely been studied. Here we will examine some aspects of the influence of CO2 upon weathering in order to reconsider the nature and the distribution of the Lower Cretaceous paleoweathering features. Simulation of granite weathering in high CO2 atmosphere. Two models, one of rainwater in equilibrium with the present day atmosphere and another with a CO2 atmospheric level 10 times higher than present day values (similar to the Lower Cretaceous atmosphere) have been developed and applied to a granite weathering simulation (Schmitt, 1999). The modelling shows that the successive minerals are the same for both simulations. But, under high atmospheric CO2 content, kaolinite appears with three times less rainwater flushed through the profile. This means that under similar rainfall and temperature conditions profiles would deepen three times faster than under present atmospheric conditions. Increased pCO2 has no direct effect on the appearance of gibbsite and hence on bauxite formation. Simulation of granite weathering at higher temperature (35 instead of 25°C) shows that gibbsite appears earlier, with about 20% less rainwater flushed through the profile, as a result of the increase in silica solubility between 25 and 35°C. The modelling also shows that elevated atmospheric CO2 values strongly accelerate the formation of deep kaolinitic profiles. This explains why deep kaolinized profiles, and kaolinite deposits have been widespread during the Cretaceous, even at extratropical latitudes, and under cool, moderately humide climate conditions. There is no direct effect of the simulated increased CO2 atmosphere on the rapidity of bauxitisation, but we know that the induced greenhouse effect and the particular Cretaceous paleogeography have both resulted in an increase in rainfall and in an important warming at intermediate latitudes. The simulation shows that the conjunction of these two factors is likely responsible for the expansion of the bauxites during the Cretaceous. Imprint in the sedimentary record The massive kaolinite formation during the Lower Cretaceous had a major impact on the clay mineral series of the sedimentary basins. The Upper Cretaceous sea level rise lead to the reworking of the kaolinitic weathering cover. Nevertheless the kaolinitic weathering paleoprofiles remained in place on wide continental areas until the Tertiary. A major reworking of these paleoprofiles occurred in Europe during the early Tertiary, when the climate became seasonally drier and vegetation cover more sparse, combined with the first Alpine tectonic movements. The kaolinite deposits of the Lower Eocene are mostly inherited from the Lower Cretaceous giant paleoweathering event. Berner R.A., Kothavala Z., 2001, GEOCARB III: a revised model of atmospheric CO2 over Phanerozoic time. American Journal of Science, 3001, p. 182-204. Bornemann, R.D. Norris, O. Friedrich, B. Beckmann, S. Schouten, J.S. Sinninghe Damsté, J. Vogel, P. Hofmann, T. Wagner. (2008). Isotopic evidence for glaciation during the cretaceous supergreenhouse. Science. 319 : 189-192. Schmitt J-M., 1999, Weathering, rainwater and atmosphere chemistry: example and modelling of granite weathering in present conditions, in a CO2-rich, and in an anoxic palaeoatmosphere. In : Palaeoweathering, palaeosurfaces and related continental deposits (eds. Thiry M. & Simon-Coinçon R.), Spec. Publ. Intern. Ass. Sediment., 27, p. 21 41. Thiry M., Quesnel F., Yans J., Wyns R., Vergari A., Théveniaut H., Simon-Coinçon R., Ricordel C., Moreau M.-G., Giot D., Dupuis C., Bruxelles L., Barbarand J., Baele J.-M, 2006, Continental France and Belgium during the Early Cretaceous : paleoweatherings and paleolandforms. Bull. Soc. géol Fr., 177/3 , p. 155 175. Sellwood B.W., Valdes P.J., 2006, Mesozoic climates: general circulation models and the rock record. Sedimentary Geology, 100, p. 269-287.

CHARACTERIZATION OF TANK 16H ANNULUS SAMPLES PART II: LEACHING RESULTS

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

Hay, M.; Reboul, S.

2012-06-19

The closure of Tank 16H will require removal of material from the annulus of the tank. Samples from Tank 16H annulus were characterized and tested to provide information to evaluate various alternatives for removing the annulus waste. The analysis found all four annulus samples to be composed mainly of Si, Na, and Al and lesser amounts of other elements. The XRD data indicate quartz (SiO{sub 2}) and sodium aluminum nitrate silicate hydrate (Na{sub 8}(Al{sub 6}Si{sub 6}O{sub 24})(NO{sub 3}){sub 2}.4H{sub 2}O) as the predominant crystalline mineral phases in the samples. The XRD data also indicate the presence of crystalline sodium nitratemore » (NaNO{sub 3}), sodium nitrite (NaNO{sub 2}), gibbsite (Al(OH){sub 3}), hydrated sodium bicarbonate (Na{sub 3}H(CO{sub 3}){sub 2}.2H{sub 2}O), and muscovite (KAl{sub 2}(AlSi{sub 3}O{sub 10})(OH){sub 2}). Based on the weight of solids remaining at the end of the test, the water leaching test results indicate 20-35% of the solids dissolved after three contacts with an approximately 3:1 volume of water at 45 C. The chemical analysis of the leachates and the XRD results of the remaining solids indicate sodium salts of nitrate, nitrite, sulfate, and possibly carbonate/bicarbonate make up the majority of the dissolved material. The majority of these salts were dissolved in the first water contact and simply diluted with each subsequent water contact. The water leaching removed large amounts of the uranium in two of the samples and approximately 1/3 of the {sup 99}Tc from all four samples. Most of the other radionuclides analyzed showed low solubility in the water leaching test. The oxalic acid leaching test result indicate approximately 34-47% of the solids in the four annulus samples will dissolve after three contacts with an approximately 3:1 volume of acid to solids at 45 C. The same sodium salts found in the water leaching test comprise the majority of dissolved material in the oxalic acid leaching test. However, the oxalic acid was somewhat more effective in dissolving radionuclides than the water leach. In contrast to the water leaching results, most constituents continued to dissolve during subsequent cycles of oxalic acid leaching. The somewhat higher dissolution found in the oxalic acid leaching test versus the water leaching test might be offset by the tendency of the oxalic acid solutions to take on a gel-like consistency. The filtered solids left behind after three oxalic acid contacts were sticky and formed large clumps after drying. These two observations could indicate potential processing difficulties with solutions and solids from oxalic acid leaching. The gel formation might be avoided by using larger volumes of the acid. Further testing would be recommended before using oxalic acid to dissolve the Tank 16H annulus waste to ensure no processing difficulties are encountered in the full scale process.« less

Silicon Isotopic Fractionation in a Tropical Soil-Plant System

NASA Astrophysics Data System (ADS)

Opfergelt, S.; Delstanche, S.; Cardinal, D.; Andre, L.; Delvaux, B.

2006-12-01

Silica fluxes to soil solutions and water streams are controlled by both abiotic and biotic processes occurring in a Si soil-plant cycle that can be significant in comparison with Si weathering input and hydrological output. The quantification of Si-isotopic fractionation by these processes is highly promising to study the Si soil-plant cycle. Therein, the fate of aqueous monosilicic acid H4SiO4, as produced by silicate weathering, may take four paths: (1) uptake by plants and recycling through falling litter, (2) formation of clay minerals, (3) specific adsorption onto Al and Fe oxides, (4) leaching in drainage waters and export from watersheds. Here we report on detailed Si-isotopic compositions of various Si pools in a tropical soil-plant system involving old stands of banana (Musa acuminata Colla, cv Grande Naine) cropped on a weathering sequence of soils derived from andesitic volcanic ash and pumice deposits in Cameroon, West Africa. Si-isotopic compositions were measured by MC-ICP-MS in dry plasma mode with external Mg doping with a reproducibility of 0.08 permil (2stdev). Results were expressed as delta29Si vs NBS28. The compositions were determined in plant parts, bulk soils, clay fractions (less than 2um) and stream waters used for crop irrigation. Of the weathering sequence, we selected young (Y) and old (O) volcanic soils (vs). Yvs are rich in weatherable minerals, and contain large amounts of pumice gravels; their clay fraction (10-35 percent) contains allophane, halloysite and ferrihydrite. Oppositely, Ovs are strongly weathered and fine clayey soils (75-96 percent clay) rich in halloysite, kaolinite, gibbsite and goethite. Intra-plant fractionation between roots and shoots and within shoots confirmed our previous data measured on banana plants grown in hydroponics. The bulk plant isotopic composition was heavier at Ovs than at Yvs giving a fractionation factor per atomic mass unit between plants and their irrigation water Si source (+0.61 permil) of -0.33 (Ovs) and -0.56 permil (Yvs), close to the fractionation factor previously measured in hydroponics (-0.40 permil). The average delta29Si of phytoliths in banana plants was +0.17 permil. In the topsoil, the isotopic composition of Yvs ( 0.21 permil) was close to that of unweathered pumice (-0.20 permil). The Ovs were significantly lighter (-0.73 permil), confirming published data pointing to lighter isotopic composition with increased weathering. Heavier bulk plants at Ovs might be related to a heavier residual soil solution due to: (i) the formation of lighter clay minerals at Ovs (clay fraction: -0.94 permil) than at Yvs (-0.60 permil), and (ii) the quantitative adsorption of silica onto iron oxides (see Delstanche et al., 2006, AGU), more abundant in weathered Ovs. Our data support the view that plants can induce a strong imprint on the continental cycle of silicon, just as clay formation and possibly Si adsorption onto iron oxides can do. The quantification of Si-isotopic fractionation in the soil-plant system requires, however, further studies involving all the Si pools to achieve a comprehensive understanding of this cycle.

Investigations of the characteristics, origin, and residence time of the upland residual mantle of the Piedmont of Fairfax County, Virginia

USGS Publications Warehouse

Pavich, M.J.; Leo, G.W.; Obermeier, S.F.; Estabrook, J.R.

1989-01-01

Undisturbed cores of upland regolith developed from a variety of crystalline rocks of the Piedmont province in Fairfax County, Va., have been obtained by using a combination of Shelby tubes, Denison sampler, and modified diamond core drilling. The core study correlated variations in chemistry, mineralogy, and texture with engineering properties throughout individual weathering profiles and contrasted these parameters among weathering profiles developed from various parent rocks. Coring sites were chosen to obtain a maximum depth of weathering on diverse lithologies. The rocks that were investigated included metapelite, metagraywacke, granite, diabase, and serpentinite. Four to twelve samples per core were selected for analysis of petrography, texture, clay mineralogy, and major-element chemistry. The number of samples was determined on the basis of (1) the thickness of the weathering profile (from about 1 m in serpentinite to more than 30 m in pelitic schist) and (2) megascopic changes in the weathering profile. Shear strength and compressibility were determined on corresponding segments of core. Standard penetration tests were performed adjacent to coring sites to evaluate in-place engineering properties. The regolith profiles on all rocks can be subdivided into soil, massive subsoil, saprolite, and weathered rock zones. Major differences in thicknesses of these zones are related to parent rock. Total regolith thickness is related to saprolite thickness. Saprolite is thickest on quartzofeldspathic metapelite, metagraywacke, and granite; thinner on diabase; and thinnest on serpentinite. Thickness of saprolite is related to rock structure and mineralogy. Geochemical changes of saprolite developed from each rock type follow predictable trends from fresh rock to soil profile, with increases in Ti, AI, Fe 3 +, and H 2 0+relative to absolute losses of Si, Fe2+, Mg, Ca, and Na. These variations are more pronounced in the weathering profiles above mafic and ultramafic rocks than in those above metagraywacke. Clay minerals in granite, schist, and metagraywacke saprolites are kaolinite, dioctahedral vermiculite, interlayered mica-vermiculite, and minor illite. Gibbsite is developed in near-surface samples of schist. Standard penetration test data for the upper 7 m of saprolite above schist, metagraywacke, and granite suggest alternations between stronger and weaker horizons that correlate with megascopic ally identified zones: soil, massive subsoil, and saprolite. The data correlate with density. Shear strength increases fairly regularly downward in the weathering profile. The engineering behavior of diabase saprolite is controlled by a dense, plastic, near-surface clay layer (montmorillonite and kaolinite) overlying rock that is weathered to a granular state (grus); the engineering properties of serpentinite are controlled by a very thin weathering profile. Similarities in regolith thickness, zonation, mineralogy, and chemistry of quartzofeldspathic rocks indicate the existence of fundamental geochemical and geomechanical controls on regolith evolution on the Piedmont upland. Data from the profiles of quartzofeldspathic regolith are used to construct a model suggesting the principal rate-control steps in the development and downwasting of the upland regolith. This model is consistent with available information about Piedmont hydrology and tectonic uplift.

Assessing the concentration, speciation, and toxicity of dissolved metals during mixing of acid-mine drainage and ambient river water downstream of the Elizabeth Copper Mine, Vermont, USA

USGS Publications Warehouse

Balistrieri, L.S.; Seal, R.R.; Piatak, N.M.; Paul, B.

2007-01-01

The authors determine the composition of a river that is impacted by acid-mine drainage, evaluate dominant physical and geochemical processes controlling the composition, and assess dissolved metal speciation and toxicity using a combination of laboratory, field and modeling studies. Values of pH increase from 3.3 to 7.6 and the sum of dissolved base metal (Cd + Co + Cu + Ni + Pb + Zn) concentrations decreases from 6270 to 100 ??g/L in the dynamic mixing and reaction zone that is downstream of the river's confluence with acid-mine drainage. Mixing diagrams and PHREEQC calculations indicate that mixing and dilution affect the concentrations of all dissolved elements in the reach, and are the dominant processes controlling dissolved Ca, K, Li, Mn and SO4 concentrations. Additionally, dissolved Al and Fe concentrations decrease due to mineral precipitation (gibbsite, schwertmannite and ferrihydrite), whereas dissolved concentrations of Cd, Co, Cu, Ni, Pb and Zn decrease due to adsorption onto newly formed Fe precipitates. The uptake of dissolved metals by aquatic organisms is dependent on the aqueous speciation of the metals and kinetics of complexation reactions between metals, ligands and solid surfaces. Dissolved speciation of Cd, Cu, Ni and Zn in the mixing and reaction zone is assessed using the diffusive gradients in thin films (DGT) technique and results of speciation calculations using the Biotic Ligand Model (BLM). Data from open and restricted pore DGT units indicate that almost all dissolved metal species are inorganic and that aqueous labile or DGT available metal concentrations are generally equal to total dissolved concentrations in the mixing zone. Exceptions occur when labile metal concentrations are underestimated due to competition between H+ and metal ions for Chelex-100 binding sites in the DGT units at low pH values. Calculations using the BLM indicate that dissolved Cd and Zn species in the mixing and reaction zone are predominantly inorganic, which is consistent with the DGT results. Although the DGT method indicates that the majority of aqueous Cu species are inorganic, BLM calculations indicate that dissolved Cu is inorganic at pH 5.5. Integrated dissolved labile concentrations of Cd, Cu and Zn in the mixing and reaction zone are compared to calculated acute toxicity concentrations (LC50 values) for fathead minnows (Pimephales promelas) (Cd, Cu and Zn) and water fleas (Ceriodaphnia dubia) (Cd and Cu) using the BLM, and to national recommended water quality criteria [i.e., criteria maximum concentration (CMC) and criterion continuous concentration (CCC)]. Observed labile concentrations of Cd and Zn are below LC50 values and CMC for Cd, but above CCC and CMC for Zn at sites <30 m downstream of the confluence. In contrast, labile Cu concentrations exceed LC50 values for the organisms as well as CCC and CMC at sites <30 m downstream of the confluence. These results suggest that environmental conditions at sites closest to the confluence of the river and acid-mine drainage should not support healthy aquatic organisms. ?? 2007 Elsevier Ltd. All rights reserved.

Depositional setting, petrology and chemistry of Permian coals from the Paraná Basin: 2. South Santa Catarina Coalfield, Brazil

USGS Publications Warehouse

Kalkreuth, W.; Holz, M.; Mexias, A.; Balbinot, M.; Levandowski, J.; Willett, J.; Finkelman, R.; Burger, H.

2010-01-01

In Brazil economically important coal deposits occur in the southern part of the Paran?? Basin, where coal seams occur in the Permian Rio Bonito Formation, with major coal development in the states of Rio Grande de Sul and Santa Catarina. The current paper presents results on sequence stratigraphic interpretation of the coal-bearing strata, and petrological and geochemical coal seam characterization from the South Santa Catarina Coalfield, Paran?? Basin.In terms of sequence stratigraphic interpretation the precursor mires of the Santa Catarina coal seams formed in an estuarine-barrier shoreface depositional environment, with major peat accumulation in a high stand systems tract (Pre-Bonito and Bonito seams), a lowstand systems tract (Ponta Alta seam, seam A, seam B) and a transgressive systems tract (Irapu??, Barro Branco and Treviso seams).Seam thicknesses range from 1.70 to 2.39. m, but high proportions of impure coal (coaly shale and shaley coal), carbonaceous shale and partings reduce the net coal thickness significantly. Coal lithoypes are variable, with banded coal predominant in the Barro Branco seam, and banded dull and dull coal predominantly in Bonito and Irapu?? seams, respectively. Results from petrographic analyses indicate a vitrinite reflectance range from 0.76 to 1.63 %Rrandom (HVB A to LVB coal). Maceral group distribution varies significantly, with the Barro Branco seam having the highest vitrinite content (mean 67.5 vol%), whereas the Irapu?? seam has the highest inertinite content (33.8. vol%). Liptinite mean values range from 7.8. vol% (Barro Branco seam) to 22.5. vol% (Irapu?? seam).Results from proximate analyses indicate for the three seams high ash yields (50.2 - 64.2wt.%). Considering the International Classification of in-Seam Coals, all samples are in fact classified as carbonaceous rocks (>50wt.% ash). Sulfur contents range from 3.4 to 7.7 wt.%, of which the major part occurs as pyritic sulfur. Results of X-ray diffraction indicate the predominance of quartz and kaolinite (also pyrite). Gypsum, gibbsite, jarosite and calcite were also identified in some samples. Feldspar was noted but is rare. The major element distribution in the three seams (coal basis) is dominated by SiO2 (31.3wt.%, mean value), Al2O3 (14.5wt.%, mean value) and Fe2O3 (6.9 wt.%, mean value). Considering the concentrations of trace elements that are of potential environmental hazards the Barro Branco, Bonito and Irapu?? seams (coal base) are significantly enriched in Co (15.7ppm), Cr (54.5ppm), Li (59.3ppm), Mn (150.4ppm), Pb (58.0ppm) and V (99.6ppm), when compared to average trace elements contents reported for U. S. coals.Hierarchical cluster analysis identified, based on similarity levels, three groups of major elements and seven groups of trace elements. Applying discriminant analyses using trace and major element distribution, it could be demonstrated that the three seams from Santa Catarina show distinct populations in the discriminant analyses plots, and also differ from the coals of Rio Grande do Sul analyzed in a previous study. ?? 2010 Elsevier B.V.

Transformation of nanosilver in oxidized and reduced soils

NASA Astrophysics Data System (ADS)

Hashimoto, Y.; Mitsunobu, S.; Yamaguchi, N.

2013-12-01

A recent development in the manufacturing of consumer products has been the incorporation of nano-sized (< 100 nm) particles. Because of their antimicrobial properties, Ag nanoparticles (NPs) have been used in many purposes including medical devices, foodstorage containers, soaps and sanitizers, wound dressings, and fabrics. Textiles enhanced with AgNPs (e.g., socks) may leach Ag(I) and nanoparticles as they are washed. These nanoparticles are either deposited directly to land or gradually washed away in household wastewater. The AgNPs, similar to Ag(I), will partition to sludge in a wastewater treatment plant, and the sewage sludge may be applied as a land amendment to agricultural fields and urban landscapes. As a consequence, the concentration of Ag in soils can increase gradually for a long period of Ag-containing sludge. Because of their antimicrobial properties, the presence of Ag in the soil adversely affects soil's biologically-mediated functions such as nutrient cycling. In many of previous studies, however, it was not clear if toxicity was caused by the AgNPs themselves or Ag ions released as the result of oxidation and dissolution. Also, mobility and fate of Ag in the environment remain little known. To understand toxicological properties and fate of Ag in soils, chemical speciation of Ag is the critical information. The objective of this study was to determine chemical speciation of Ag derived from AgNP (Ago) and Ag chemicals (AgNO3) in oxidized and reduced soils. We employed X-ray absorption fine structure (XAFS) spectroscopy to identify Ag species and probable hosting phases in soils, and the study was focused on how the soil redox condition transforms AgNP into Ag(I) and vice versa. A soil incubation study was conducted using a volcanic ash soil amended with AgNO3 and AgNPs up to the levels of 1000 mg kg-1 soil. The soil water content was adjusted to the levels of field capacity (oxidized) and saturated (reduced) condition. After 30 days of incubation at 25 C, the soils were collected and analyzed for Ag by sequential extraction and Ag K-edge XAFS spectroscopy. To find probable Ag species in the soils, linear combination fitting was performed on Ag EXAFS data of soils using known reference Ag chemicals and sorption phases. According to the EXAFS analysis, AgNO3 did not exist and was transformed into humus and phyllosilicate-associated phases in the oxidized soil. In the reduced soils, AgNO3 was completely transformed into other compounds including Ago and Ag associated with soil colloids (phyllosilicate and gibbsite). The redox potential of this soil remained oxic levels (457 mV) due to extremely high Ag+ concentration, and the redox condition was not low enough to form sulfide Ag species. About 90% of AgNPs remained persistent in the oxidized soil. In contrast, AgNPs was transformed mainly into Ag2S in the reduced soil. Our study found that AgNPs remained persistent in oxidized soils but can be transformed into sulfide-associated forms in reduced soils.

REE in karst bauxites: the Campania example (southern Italy)

NASA Astrophysics Data System (ADS)

Mondillo, N.; Boni, M.; Balassone, G.; Rollinson, G.

2012-04-01

Global production of Rare Earth Element (REE) has dramatically increased in the last years, hence the strong interest to identify new deposits and to understand the processes responsible for their formation. Among REE concentrations related to weathering, the current targets are represented by the ion-adsorption deposit-types, occurring in China, in which REEs are adsorbed onto the surface of clays. Laterites have been also intensively investigated since the discovery of the secondary deposit of Mount Weld (Australia). Most REEs behave as immobile elements in laterites, and tend to be enriched compared to the underlying parent rocks. Many authors debate on a possible REE fractionation along the laterite profiles, resulting in the formation of supergene LREE-minerals. Bauxites are economic Al accumulations, derived from the weathering of alumosilicate-rich parent rocks resulting in the development of laterite profiles. Components as Ca, Mg, K, Si are leached and residual Fe, Al and Ti precipitate in form of hematite>>goethite, gibbsite [Al(OH)3] or amorphous Al hydroxides and anatase. Metabauxites can contain boehmite or diaspore [AlO(OH)]. Chemical composition (including REEs content) of lateritic bauxites generally mirrors the original composition of the parent rock. Geochemistry of REEs in karst bauxites, which lay on carbonate bedrocks and may be also allochthonous to them, is not so straightforward. Cretaceous karst bauxite deposits in the Apennine chain (Southern Italy) are presently uneconomic. A full mineralogical and geochemical study has been performed on several deposits of the Campania district, and three representative profiles have been sampled. In all deposits the bauxite ore has an oolitic-pisolitic texture, but contains also detrital intervals. The mineral association consists of boehmite, kaolinite and hematite, with less goethite and anatase. The main REE-bearing mineral is detrital monazite. In detail, we could detect (SEM) other LREE-phosphates (florencite type minerals) in the Regia Piana deposit and possibly LREE-enriched goethite at Dragoni. QEMSCAN® analysis allowed the identification and location of discrete particles of monazite and xenotime, but because of their very small dimensions (typically <10 microns) it was difficult to determine the exact chemical composition without further investigation. Chemical analyses have shown a total REEs content of 620 ppm on average in all bauxite deposits, with a maximum value of 1454 ppm of total REEs at the top of the Regia Piana profile. The LREE (La-Eu) contents in the samples vary between 200 and 1400 ppm, with positive Ce and La anomalies. The HREE (Gd-Lu) contents are always around 40-60 ppm. The relationship between REEs and the Al and/or Fe values is not clear, probably because the REE content may be slightly biased by the detrital characteristics of the bauxite. The higher Ce and other LREE values, detected at the top of several deposits rather than at the bottom, can be related to LREE supergene minerals occurrence in the higher parts of profile. The Campania deposits represent an interesting case study for REE concentration in karst bauxites. A similar LREE fractionation process could be applied to other bauxite deposits, though related to more favorable parent rocks with sub-economic REE-grades.

Molecular dynamics simulation of water at mineral surfaces: Structure, dynamics, energetics and hydrogen bonding

NASA Astrophysics Data System (ADS)

Kalinichev, A. G.; Wang, J.; Kirkpatrick, R.

2006-05-01

Fundamental molecular-level understanding of the properties of aqueous mineral interfaces is of great importance for many geochemical and environmental systems. Interaction between water and mineral surfaces substantially affects the properties of both phases, including the reactivity and functionality of the substrate surface, and the structure, dynamics, and energetics of the near surface aqueous phase. Experimental studies of interfacial water structure and dynamics using surface-sensitive techniques such as sum-frequency vibrational spectroscopy or X-ray and neutron reflectivity are not always possible for many practically important substrates, and their results often require interpretation concerning the atomistic mechanisms responsible for the observed behavior. Molecular computer simulations can provide new insight into the underlying molecular- level relationships between the inorganic substrate structure and composition and the structure, ordering, and dynamics of interfacial water. We have performed a series of molecular dynamics (MD) computer simulations of aqueous interfaces with several silicates (quartz, muscovite, and talc) and hydroxides (brucite, portlandite, gibbsite, Ca/Al and Mg/Al double hydroxides) to quantify the effects of the substrate mineral structure and composition on the structural, transport, and thermodynamic properties of water on these mineral surfaces. Due to the prevalent effects of the development of well-interconnected H-bonding networks across the mineral- water interfaces, all the hydroxide surfaces (including a fully hydroxylated quartz surface) show very similar H2O density profiles perpendicular to the interface. However, the predominant orientations of the interfacial H2O molecules and their detailed 2-dimensional near-surface structure and dynamics parallel to the interface are quite different reflecting the differences in the substrate structural charge distribution and the density and orientations of the surface OH groups. The H2O density profiles and other structural and dynamic characteristics of water at the two siloxane surfaces are very different from each other and from the hydroxide surfaces, since the muscovite surface is negatively charged and hydrophilic, while the talc surface is electrostatically neutral and hydrophobic. In general, at hydrophilic neutral surfaces both donating and accepting H-bonds from the H2O molecules are contributing to the development of the interfacial H-bond network, whereas at hydrophilic but charged surfaces only accepting or donating H-bonds with H2O molecules are possible. At the hydrophobic talc surface H-bonds among H2O molecules dominate the interfacial H-bond network and the water-surface interactions are very weak. The first water layer at all substrates is well ordered parallel to the surface, reflecting substrate crystal structures and indicating the reduced translational and orientational mobility of interfacial H2O molecules. At longer time scale (~100ps) their dynamics can be decomposed into a slow, virtually frozen, regime due to the substrate- bound H2O and a faster regime of almost free water reflecting the dynamics far from the surface. At shorter times (>10ps) the two dynamical regimes are superimposed. The much higher ordering of interfacial water (compared to bulk liquid) can not be adequately described as simply "ice-like". To some extent, it rather resembles the behavior of supercooled water.

Impact of Acid Mine Drainage on the hydrogeological system at Sia, Cyprus

NASA Astrophysics Data System (ADS)

Ng, Stephen; Malpas, John

2013-04-01

Discontinued mining of the volcanogenic massive sulphide ore bodies of Cyprus has left significant environmental concerns including Acid Mine Drainage. Remnant sulphide ore and tailings in waste dumps react with oxygenated rainwater to produce sulphuric acid, a process which is multiplied when metal-loving acidophilic bacteria are present. Given that Cyprus has a Mediterranean climate, characterized by its warm and dry summers and cool and wet winters, the low pH effluent with high levels of trace elements, particularly metals, is leached out of the waste tips particularly during the wet season. The Sia site includes an open mine-pit lake, waste rock and tailings dumps, a river leading to a downstream dam-lake, and a localised groundwater system. The study intends to: identify the point source and nature of contamination; analyze the mechanism and results of local acid generation; and understand how the hydrogeological system responds to seasonal variations. During two sampling campaigns, in the wet and dry seasons of 2011, water samples were collected from the mine pit lake, from upstream of the adjacent river down to the dam catchment, and from various boreholes close to the sulphide mine. The concentration of ions in waters varies between wet and dry seasons but, in both, relative amounts are directly related to pH. In the mine-pit lake, Fe, Mn, Mg, Cu, Pb, Zn, Ni, Co and Cd are found in higher concentrations in the dry season, as a result of substantial evaporation of water. The Sia River runs continuously in the wet season, and waters collected close to the waste tips have pH as low as 2.5 and higher concentrations of Al, Cu, Fe and Zn. Further downstream there is a significant decrease in trace metal contents with a concomitant rise of pH. Al and Fe dominate total cation content when pH is lower than 4. Al is derived from the weathering of clay minerals, especially during the wet season. Fe is derived from the oxidation of pyrite. Once pH's exceed 4, a white precipitate of gibbsite (Al(OH)3) settles to the stream bed removing Al from the water. This is finely laminated together with orange-brown layers of similarly precipitated Fe(OH)3. During the dry season the Sia River dries up and the mine-pit lake is greatly reduced in surface area leading to the crystallisation of a variety of multi-coloured salts, which form on the muddy substrate through capillary action. These include large amounts of gypsum and hexahydrite, and lesser amounts of chalcanthite, jarosite, wupatkiite, halotrichite, malachite, etc. These are ephemeral in nature being quickly dissolved by early rains of the wet season that, in the stream waters, produces short-lived toxic concentrations of metals. Groundwaters sampled directly at the mine site show the influence of drainage from the waste tips. Elsewhere, apart from sporadic high Boron concentrations, there is no evidence of contamination from the mine workings. The origin of Boron is a problem that arises at a number of sites throughout Cyprus, especially on the Mesaoria Plain and in the Troodos Complex.

Role of soil mineral components in the stabilization of organic matter in Umbric Ferralsols of South Brazil

NASA Astrophysics Data System (ADS)

Velasco-Molina, Marta; Berns, Anne E.; Macias, Felipe; Knicker, Heike

2013-04-01

Climatic conditions of subtropical and tropical regions support fast carbon (C) mineralization, and thus an accelerated degradation of soil organic matter (SOM) if compared to temperate region (Sánchez & Logan, 1992). However, even in those regions, there are still soil horizons that show notable C accumulation. Examples for the latter are umbric horizons in typical tropical soils, such as Ferralsols. The occurrence of this soils with thick umbric epipedons (× 100 cm thickness) in areas of South Brazil is a paradox, that still needs a better understanding (Marques et al., 2011), in particular since the processes that are responsible for the thickness and darkness of the umbric horizons are of special interest with respect to the role of soils as carbon sink. One major contributor to SOM stabilization represents the soil mineral phase. Therefore the main goal of this work its to study the impact of this factor on the SOM sequestration in Umbric Ferralsols from Atibaia, Campinas (São Paulo State) and Chapecó (Santa Catarina State) developed under different environmental conditions. With this objective the mineral fractions have been isolated by selective extraction of iron and aluminium oxides with different extracting solutions (sodium pyrophosphate, ammonium oxalate and dithionite-citrate-bicarbonate solution) and related to SOM quality and quantity. The latter was studied by the use of solid-state cross polarisation (CPMAS) 13C NMR spectroscopy after demineralization with hydrofluoric acid (Gonçalves et al., 2003). Quantification of the NMR spectra was performed by integration of the respective chemical shift regions under consideration of the contribution of spinning side bands. For our study the following regions were distinguished (Knicker & Lüdemann, 1995): alkyl C (0-45 ppm), N-alkyl C (45-60ppm), O-alkyl C (60-110 ppm), aryl C (110-160 ppm), carbonyl C (160-245 ppm). Preliminary results show that, the minimum vertical variation of total Fe into the profile is classical in Ferralsols and the behavior of Al points to the high presence of gibbsite in the clay fractions of the deeper horizon of the Campinas soils. The (AlP+FeP)/C ratios, obtained after extraction of the Al and Fe forms with a sodium pyrophosphate solution, were above 0.03 throughout the studied profile. According to Nierop et al. (2002) this points towards the existence of organic-metallic compounds. Most tentatively, they precipitated due to saturation of adsorption site. The solid-state 13C NMR spectra of the Chapecó samples showed that the preserved organic C is dominated by a alkyl C in lipids and amino acids (45 - 0 ppm). Other major intensities are observed between 110 and 45 ppm, in the region of O/N-alkyl C (carbohydrates, amino acids) and carboxyl C (220 to 160 ppm). The missing of a clear signal in the region between 160 and 110 ppm (signal derives from aromatic or olefinic C) indicates that in this soil lignin has minor contributions to its aromatic C content.

EFRT M12 Issue Resolution: Comparison of PEP and Bench-Scale Oxidative Leaching Results

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

Rapko, Brian M.; Brown, Christopher F.; Eslinger, Paul W.

2009-08-14

Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed and constructed and is to be operated as part of a plan to respond to issue M12, “Undemonstrated Leaching Processes.” The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processesmore » using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing. Two operating scenarios are currently being evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario has caustic leaching performed in the UFP-2 ultrafiltration feed vessels (i.e., vessel UFP-VSL-T02A in the PEP; and vessels UFP-VSL-00002A and B in the WTP PTF). The second scenario has caustic leaching conducted in the UFP-1 ultrafiltration feed preparation vessels (i.e., vessels UFP-VSL-T01A and B in the PEP; vessels UFP-VSL-00001A and B in the WTP PTF). In both scenarios, 19-M sodium hydroxide solution (NaOH, caustic) is added to the waste slurry in the vessels to dissolve solid aluminum compounds (e.g., gibbsite, boehmite). Caustic addition is followed by a heating step that uses direct steam injection to accelerate the leaching process. Following the caustic leach, the vessel contents are cooled using vessel cooling jackets and/or external heat exchangers. The main difference between the two scenarios is that for leaching in UFP1, the 19-M NaOH is added to un-concentrated waste slurry (3 to 8 wt% solids), while for leaching in UFP2, the slurry is concentrated to nominally 20 wt% solids using cross-flow ultrafiltration before the addition of caustic. For wastes that have significantly high chromium content, the caustic leaching and slurry dewatering is followed by adding sodium permanganate to UFP-VSL-T02A, and the slurry is subjected to oxidative leaching at nominally ambient temperature. The purpose of the oxidative leaching is to selectively oxidize the poorly alkaline-soluble Cr(III) believed to be the insoluble form in Hanford tank sludge to the much more alkaline-soluble Cr(VI), e.g., chromate. The work described in this report provides the test results that are related to the efficiency of the oxidative leaching process to support process modeling based on tests performed with a Hanford waste simulant. The tests were completed both at the lab-bench scale and in the PEP. The purpose of this report is to summarize the results from both scales that are related to oxidative leaching chemistry to support a scale factor for the submodels to be used in the G2 model, which predicts WTP operating performance. Owing to schedule constraints, the PEP test data to be included in this report are limited to those from Integrated Tests A (T01 A/B caustic leaching) and B (T02A caustic leaching).« less

Enhancing the hydrogeological landscape (HGL) characterisation of the Greater Launceston area (GLA) through better understanding of dolerite weathering, stream water properties and a revised landscape evolution model

NASA Astrophysics Data System (ADS)

Moore, Leah; Nicholson, Allan; Cook, Wayne; Sweeney, Margaret

2014-05-01

In the Greater Launceston Area (GLA) in northern Tasmania, Australia, there is a widespread urban salinity problem with severe impacts on urban/peri-urban infrastructure in localised areas. Salinity patterns in the landscape (elevated flux to waterways; salt efflorescence at the land surface) could be related to: the underlying rock type, the thickness of regolith materials and hence the volume of the salt store, the landforms present and the amount of water passing over and through the landscape. In northern Tasmania secondary mineralogy on dolerite typically includes formation of Fe/Ca smectite phases (e.g. nontronite, saponite) and Fe-Ti oxides/sesquioxides (e.g. hematite, goethite) with some primary phases (e.g. Ca-plagioclase feldspar, augite) weathering through to a suite dominated by kaolinite clay and Fe-Ti oxides/sesquioxides. Deeply weathered profiles in the GLA have weathered to the kaolintite-clay dominant mineralogy and in places there are gibbsite/beidellite/hematite/goethite bauxites developed. Most existing salinity mapping emphasises salt manifestation over paleo-estuarine sediments of the Paleogene Tamar-Esk River system, so incorporation of deeply weathered Jurassic dolerite materials into the salt budget considerably augments the estimated potential hazard. Rapid stream surveys provide a snapshot of stream electrical conductivity (EC) over the study area at regular intervals allowing a broad evaluation of salt flux patterns in surfaces waters. Higher EC readings were obtained from selected streams draining: deeply weathered dolerite profiles (0.37 1.86 dS/m) and deeply weathered Paleogene paleo-estuarine sediments (0.49 to 1.16 dS/m). Lower values were measured on up-faulted dolerite blocks (<0.10 dS/m); moderately weathered, high relief dolerite (<0.03 dS/m), and in incised streams flowing over a rocky dolerite substrate (<0.03 dS/m). The patterns of stream EC reflect the nature of the regolith materials the streams drain, and match mapped patterns for distribution of deeply weathered Jurassic dolerite and moderately to deeply weathered bedded paleo-estuarine sediments of the Paleogene Tamar-Esk river system, some Quaternary terrace deposits along the Tamar and Esk Rivers; and some Holocene estuarine sediments. Recent geomorphic mapping has enabled development of a more comprehensive and consistent landscape evolution model that builds on existing knowledge. This model describes the influence of a progressively incising Tamar-Esk river system in response to episodic lowering of the local base level, with multiple episodes of valley widening as the river system stabilised after incision. Successive lowering events dissected earlier landforms, but locally remnant surfaces are preserved that represent former fluvial plain and terrace features. These processes were partially controlled by the structural configuration and contrasting resistance of the underlying lithologies, influencing the planform geometries of the rivers, and consequently the potential to preserve paleo-fluvial features. Because the Tamar River is an estuarine system, some of the lowermost preserved surfaces are likely to reflect marine processes (e.g. 5-7m; 10-12m ASL). The geomorphic mapping was conducted independently of the hydrogeological landscape (HGL) characterisation in the GLA, but there is strong correlation between the areas identified as having elevated salinity hazard (HGL) and newly mapped remnant surfaces in this landscape. This work complements HGL research and supports development of an increasingly rigorous evidence-based framework for GLA salinity hazard management.

DWPF Recycle Evaporator Simulant Tests

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

Stone, M

2005-04-05

Testing was performed to determine the feasibility and processing characteristics of an evaporation process to reduce the volume of the recycle stream from the Defense Waste Processing Facility (DWPF). The concentrated recycle would be returned to DWPF while the overhead condensate would be transferred to the Effluent Treatment Plant. Various blends of evaporator feed were tested using simulants developed from characterization of actual recycle streams from DWPF and input from DWPF-Engineering. The simulated feed was evaporated in laboratory scale apparatus to target a 30X volume reduction. Condensate and concentrate samples from each run were analyzed and the process characteristics (foaming,more » scaling, etc) were visually monitored during each run. The following conclusions were made from the testing: Concentration of the ''typical'' recycle stream in DWPF by 30X was feasible. The addition of DWTT recycle streams to the typical recycle stream raises the solids content of the evaporator feed considerably and lowers the amount of concentration that can be achieved. Foaming was noted during all evaporation tests and must be addressed prior to operation of the full-scale evaporator. Tests were conducted that identified Dow Corning 2210 as an antifoam candidate that warrants further evaluation. The condensate has the potential to exceed the ETP WAC for mercury, silicon, and TOC. Controlling the amount of equipment decontamination recycle in the evaporator blend would help meet the TOC limits. The evaporator condensate will be saturated with mercury and elemental mercury will collect in the evaporator condensate collection vessel. No scaling on heating surfaces was noted during the tests, but splatter onto the walls of the evaporation vessels led to a buildup of solids. These solids were difficult to remove with 2M nitric acid. Precipitation of solids was not noted during the testing. Some of the aluminum present in the recycle streams was converted from gibbsite to aluminum oxide during the evaporation process. The following recommendations were made: Recycle from the DWTT should be metered in slowly to the ''typical'' recycle streams to avoid spikes in solids content to allow consistent processing and avoid process upsets. Additional studies should be conducted to determine acceptable volume ratios for the HEME dissolution and decontamination solutions in the evaporator feed. Dow Corning 2210 antifoam should be evaluated for use to control foaming. Additional tests are required to determine the concentration of antifoam required to prevent foaming during startup, the frequency of antifoam additions required to control foaming during steady state processing, and the ability of the antifoam to control foam over a range of potential feed compositions. This evaluation should also include evaluation of the degradation of the antifoam and impact on the silicon and TOC content of the condensate. The caustic HEME dissolution recycle stream should be neutralized to at least pH of 7 prior to blending with the acidic recycle streams. Dow Corning 2210 should be used during the evaporation testing using the radioactive recycle samples received from DWPF. Evaluation of additional antifoam candidates should be conducted as a backup for Dow Corning 2210. A camera and/or foam detection instrument should be included in the evaporator design to allow monitoring of the foaming behavior during operation. The potential for foam formation and high solids content should be considered during the design of the evaporator vessel.« less

A lithofacies terrain model for the Blantyre Region: Implications for the interpretation of palaeosavanna depositional systems and for environmental geology and economic geology in southern Malawi

NASA Astrophysics Data System (ADS)

Dill, H. G.; Ludwig, R.-R.; Kathewera, A.; Mwenelupembe, J.

2005-06-01

The Blantyre City Area is part of the African savanna in southern Malawi. Sedimentological, geomorphological, chemical and mineralogical studies were conducted to create a lithofacies terrain model. The project involves mapping, cross-sectioning, grain size, heavy mineral analysis, XRD and the study of sedimentary textures under the petrographic microscope. These classical techniques were combined with GIS-based field and office works. The combined efforts led to 2-D maps and 3-D block diagrams that illustrate the geomorphological and sedimentological evolution of the landscape in southern Malawi during the late Mesozoic and Cenozoic. The results obtained through integrated geomorphological-sedimentological studies form the basis for land management (planning of residential areas, waste disposal sites, assessment of bearing capacity of rocks), geohazard prediction (delineation of high risk zones in terms of mass flow and inundation) and the evaluation of high-place (ceramic raw materials) and high-unit value (placers of precious metals and gemstones) mineral commodities in the study area. The study addresses regional and general aspects alike. In regional terms, the study aimed at unraveling the evolution of landforms at the southern end of the East African Rift System during the most recent parts of the geological past. Four stages of peneplanation were established in the working area. Planation was active from the Cretaceous to the Quaternary (stage I: early to mid-Cretaceous, stage II: early Tertiary, stage III: early to mid-Tertiary, stage IV: mid- to late Tertiary). During the most recent parts of the Quaternary, strong fluvial incision was triggered by the base-level lowering of the Shire River. Geomorphological alteration of the landscape goes along with a phyllosilicate-sesquioxide transformation from minerals indicative of more acidic meteoric fluids (e.g., gibbsite, kaolinite) to those typical of more alkaline conditions (e.g. smectite, vermiculite, hydrobiotite). In addition, the investigation is to provide some characteristic features suitable for the recognition and interpretation of terrestrial environments resembling the present-day savanna in the ancient sedimentary record: Conspicuous bimodality in the grain-size distribution. High degree of gravel roundness. Boulder fields (basal conglomerates) with fitting breccias and no rotation of structural elements. Poor to very poor sorting of siliciclastics. Stratification is rare; if present only in sandy beds with antidune and tabular cross-bedding at low angle prevailing over cross-bedding at high angle. Grading rare; in arenaceous deposits poorly developed FU sequences, in rudites poorly developed CU sequences, locally with surface armoring. Directional sedimentary structures in coarse-grained deposits are unimodal. Fabric types: a(t)b(i) and a(p)b(i); shear planes indicative of slide may be present. Ribbon-shaped architectural elements prevail over channel-like types. Bounding surfaces/unconformities are uneven to wavy and more widespread than scour-and-pool structures. Fine-grained carbonaceous interbeds are restricted to shallow depressions. Etch marks such as tafonis, flutes, honeycomb textures are common. Placer deposits of metallic and non-metallic mineral commodities are abundant. Alucretes and ferricretes of bog iron (ferrihydrite > goethite) and lateritic (goethite > ferrihydrite) types are common, calcitic freshwater limestones and gypcretes are scarce. Kandite-group minerals "in" (relic), smectite-group minerals "in", vermiculite "in" (recent), mica-group minerals "out".

Quantifying chemical weathering rates along a precipitation gradient on Basse-Terre Island, French Guadeloupe: New insight from U-series isotopes in weathering rinds

NASA Astrophysics Data System (ADS)

Engel, Jacqueline M.; Ma, Lin; Sak, Peter B.; Gaillardet, Jerome; Ren, Minghua; Engle, Mark A.; Brantley, Susan L.

2016-12-01

Inside soil and saprolite, rock fragments can form weathering clasts (alteration rinds surrounding an unweathered core) and these weathering rinds provide an excellent field system for investigating the initiation of weathering and long term weathering rates. Recently, uranium-series (U-series) disequilibria have shown great potential for determining rind formation rates and quantifying factors controlling weathering advance rates in weathering rinds. To further investigate whether the U-series isotope technique can document differences in long term weathering rates as a function of precipitation, we conducted a new weathering rind study on tropical volcanic Basse-Terre Island in the Lesser Antilles Archipelago. In this study, for the first time we characterized weathering reactions and quantified weathering advance rates in multiple weathering rinds across a steep precipitation gradient. Electron microprobe (EMP) point measurements, bulk major element contents, and U-series isotope compositions were determined in two weathering clasts from the Deshaies watershed with mean annual precipitation (MAP) = 1800 mm and temperature (MAT) = 23 °C. On these clasts, five core-rind transects were measured for locations with different curvature (high, medium, and low) of the rind-core boundary. Results reveal that during rind formation the fraction of elemental loss decreases in the order: Ca ≈ Na > K ≈ Mg > Si ≈ Al > Zr ≈ Ti ≈ Fe. Such observations are consistent with the sequence of reactions after the initiation of weathering: specifically, glass matrix and primary minerals (plagioclase, pyroxene) weather to produce Fe oxyhydroxides, gibbsite and minor kaolinite. Uranium shows addition profiles in the rind due to the infiltration of U-containing soil pore water into the rind as dissolved U phases. U is then incorporated into the rind as Fe-Al oxides precipitate. Such processes lead to significant U-series isotope disequilibria in the rinds. This is the first time that multiple weathering clasts from the same watershed were analyzed for U-series isotope disequlibrian and show consistent results. The U-series disequilibria allowed for the determination of rind formation ages and weathering advance rates with a U-series mass balance model. The weathering advance rates generally decreased with decreasing curvature: ∼0.17 ± 0.10 mm/kyr for high curvature, ∼0.12 ± 0.05 mm/kyr for medium curvature, and ∼0.11 ± 0.04, 0.08 ± 0.03, 0.06 ± 0.03 mm/kyr for low curvature locations. The observed positive correlation between the curvature and the weathering rates is well supported by predictions of weathering models, i.e., that the curvature of the rind-core boundary controls the porosity creation and weathering advance rates at the clast scale. At the watershed scale, the new weathering advance rates derived on the low curvature transects for the relatively dry Deshaies watershed (average rate of 0.08 mm/kyr; MAP = 1800 mm and MAT = 23 °C) are ∼60% slower than the rind formation rates previously determined in the much wetter Bras David watershed (∼0.18 mm/kyr, low curvature transect; MAP = 3400 mm and MAT = 23 °C) also on Basse-Terre Island. Thus, a doubling of MAP roughly correlates with a doubling of weathering advance rate. The new rind study highlights the effect of precipitation on weathering rates over a time scale of ∼100 kyr. Weathering rinds are thus a suitable system for investigating long-term chemical weathering across environmental gradients, complementing short-term riverine solute fluxes.

Using Uranium-series isotopes to understand processes of rapid soil formation in tropical volcanic settings: an example from Basse-Terre, French Guadeloupe

NASA Astrophysics Data System (ADS)

Ma, Lin

2015-04-01

Lin Ma1, Yvette Pereyra1, Peter B Sak2, Jerome Gaillardet3, Heather L Buss4 and Susan L Brantley5, (1) University of Texas at El Paso, El Paso, TX, United States, (2) Dickinson College, Carlisle, PA, United States, (3) Institute de Physique d Globe Paris, Paris, France, (4) University of Bristol, Bristol, United Kingdom, (5) Pennsylvania State University Main Campus, University Park, PA, United States Uranium-series isotopes fractionate during chemical weathering and their activity ratios can be used to determine timescales and rates of soil formation. Such soil formation rates provide important information to understand processes related to rapid soil formation in tropical volcanic settings, especially with respect to their fertility and erosion. Recent studies also highlighted the use of U-series isotopes to trace and quantify atmospheric inputs to surface soils. Such a process is particularly important in providing mineral nutrients to ecosystems in highly depleted soil systems such as the tropical soils. Here, we report U-series isotope compositions in thick soil profiles (>10 m) developed on andesitic pyroclastic flows in Basse-Terre Island of French Guadeloupe. Field observations have shown heterogeneity in color and texture in these thick profiles. However, major element chemistry and mineralogy show some general depth trends. The main minerals present throughout the soil profile are halloysite and gibbsite. Chemically immobile elements such as Al, Fe, and Ti show a depletion profile relative to Th while elements such as K, Mn, and Si show a partial depletion profile at depth. Mobile elements such as Ca, Mg, and Sr have undergone intensive weathering at depths, and an addition profile near the surface, most likely related to atmospheric inputs. (238U/232Th) activity ratios in one soil profile from the Brad David watershed in this study ranged from 0.374 to 1.696, while the (230Th/232Th) ratios ranged from 0.367 to 1.701. A decrease of (238U/232Th) in the deep soil profile depth is observed, and then an increase to the surface. The (230Th /232Th) ratios showed a similar trend as (238U/232Th). Marine aerosols and atmospheric dust from the Sahara region are most likely responsible for the addition of U in shallow soils. Intensive chemical weathering is responsible for the loss of U at depth, consistent with these observations of major element chemistry and mineralogy. Furthermore, U-series chemical weathering model suggests that the weathering duration from 12m to 4m depth in this profile is about 250kyr, with a weathering advancing rate of ~30 m/Ma. The rate is also about one order of magnitude lower than the weathering rate (~300 m/Ma) determined by river chemistry for this watershed. In this profile, the augered core didn't reach the unweathered bedrock. Hence, the derived slow weathering rate most likely represents the intensive weathering of clay minerals, while the transformation of fresh bedrock to regolith occurs at much great depth beneath the thick regolith. The marine aerosols and atmospheric dust are important sources of mineral nutrients for highly depleted surface soils.

EDITORIAL: Colloidal suspensions Colloidal suspensions

NASA Astrophysics Data System (ADS)

Petukhov, Andrei; Kegel, Willem; van Duijneveldt, Jeroen

2011-05-01

Special issue in honour of Henk Lekkerkerker's 65th birthday Professor Henk N W Lekkerkerker is a world-leading authority in the field of experimental and theoretical soft condensed matter. On the occasion of his 65th birthday in the summer of 2011, this special issue celebrates his many contributions to science. Henk Lekkerkerker obtained his undergraduate degree in chemistry at the University of Utrecht (1968) and moved to Calgary where he received his PhD in 1971. He moved to Brussels as a NATO fellow at the Université Libre de Bruxelles and was appointed to an assistant professorship (1974), an associate professorship (1977) and a full professorship (1980) in physical chemistry at the Vrije Universiteit Brussel. In 1985 he returned to The Netherlands to take up a professorship at the Van 't Hoff Laboratory, where he has been ever since. He has received a series of awards during his career, including the Onsager Medal (1999) of the University of Trondheim, the Bakhuys Roozeboom Gold Medal (2003) of the Royal Dutch Academy of Arts and Sciences (KNAW), the ECIS-Rhodia European Colloid and Interface Prize (2003), and the Liquid Matter Prize of the European Physical Society (2008). He was elected a member of KNAW in 1996, was awarded an Academy Chair position in 2005, and has held several visiting lectureships. Henk's work focuses on phase transitions in soft condensed matter, and he has made seminal contributions to both the theoretical and experimental aspects of this field. Here we highlight three major themes running through his work, and a few selected publications. So-called depletion interactions may lead to phase separation in colloid-polymer mixtures, and Henk realised that the partitioning of polymer needs to be taken into account to describe the phase behaviour correctly [1]. Colloidal suspensions can be used as model fluids, with the time- and length-scales involved leading to novel opportunities, notably the direct observation of capillary waves at a fluid-fluid interface [2]. Together with Remco Tuinier, Henk has recently completed a book in this area which is to appear later this year. A major theme in Henk's research is that of phase transitions in lyotropic liquid crystals. Henk, together with Daan Frenkel and Alain Stroobants, realized in the 1980s that a smectic phase in dispersions of rod-like particles can be stable without the presence of attractive interactions, similar to nematic ordering as predicted earlier by Onsager [3]. Together with Gert-Jan Vroege he wrote a seminal review in this area [4]. Henk once said that 'one can only truly develop one colloidal model system in one's career' and in his case this must be that of gibbsite platelets. Initially Henk's group pursued another polymorph of aluminium hydroxide, boehmite, which forms rod-like particles [5], which already displayed nematic liquid crystal phases. The real breakthrough came when the same precursors treated the produced gibbsite platelets slightly differently. These reliably form a discotic nematic phase [6] and, despite the polydispersity in their diameter, a columnar phase [7]. A theme encompassing a wide range of soft matter systems is that of colloidal dynamics and phase transition kinetics. Many colloidal systems have a tendency to get stuck in metastable states, such as gels or glasses. This is a nuisance if one wishes to study phase transitions, but it is of great practical significance. Such issues feature in many of Henk's publications, and with Valerie Anderson he wrote a highly cited review in this area [8]. Henk Lekkerkerker has also invested significant effort into the promotion of synchrotron radiation studies of colloidal suspensions. He was one of the great supporters of the Dutch-Belgian beamline 'DUBBLE' project at the ESRF [9]. He attended one of the very first experiments in Grenoble in 1999, which led to a Nature publication [7]. He was strongly involved in many other experiments which followed and also has been a member of the beam line board. The most recent synchotron data are reported in this issue and Henk is a co-author on the paper. Henk's international leadership in the soft condensed matter field is also illustrated by some of the various roles he has held over the years, such as that of president of the European Colloid and Interface Society 1995-6. He was the heart and soul of the 6th Liquid Matter Conference in Utrecht (2005). For many years he acted as consultant to Schlumberger Cambridge Research. Henk is a towering figure in the scientific community, not just physically but in particular through his intellectual rigour. Henk also took on administrative roles, notably as dean of the chemistry department in Utrecht University and as scientific director of the Debye Institute, and he did these tasks thoroughly and effectively. Henk is an inspiring teacher and his lectures and notes are always of outstanding clarity. Henk has supervised a series of PhD students and postdoctoral researchers, several of whom have taken up academic positions since. A particular strength of Henk is his phenomenal command of the scientific literature which translates into authoritative introductions to his publications. For example, one of us once came to him saying that he had calculated the scattering profiles for a simple one-dimensional model, which can be applied to describe intra-columnar scattering from a columnar phase of gibbsite platelets. After seeing what the model assumptions were, Henk immediately opened his drawer and quickly found a paper of Zernike and Prins dated 1927 [10]. 'Is this the model you are talking about?' he asked. Of course it was. This was a great lesson, which not only demonstrated Henk's familiarity with the literature but also the effectiveness of his filing system. A favourite tool of Henk's trade is that of the (mostly handwritten) 'notities' (notes) he would hand or send to his students and collaborators to feed scientific discussions. We have been the grateful recipients of many such notes ourselves. Visitors to Henk's office would often be treated to a demonstration experiment (for instance, birefringent suspensions) and a range of hand-made models designed to illustrate complex concepts (such as multidimensional phase diagrams). Henk's relationship with his students usually extends well after graduation, and many have benefitted from Henk's advice as a mentor. In spite of his scientific standing, Henk is down to earth; he is a pleasant and warm person, with a deep interest in people. He has many friends all over the world. At the same time, he does not eschew scientific debate. He takes a dim view of pretentious work, especially when it seems that inconvenient data has been neglected. Typically though he will comment in a way that avoids embarrassment and that motivates a redoubled effort. Henk's career will be celebrated at a symposium to be held in Amsterdam in June 2011. This special issue contains invited contributions by speakers at this symposium, as well as by other collaborators, colleagues, former students, and friends. The authors were free to choose their topics. We have grouped their contributions into a number of themes. The wide range of subjects mirrors Henk's interests and the research themes reviewed above are well represented. Henk, this special issue is for you—we hope you will enjoy it! References [1] Lekkerkerker H N W, Poon W C-K, Pusey P N, Stroobants A and Warren P B 1992 Europhys. Lett. 20 559 [2] Aarts D G A L, Schmidt M and Lekkerkerker H N W 2004 Science 304 847 [3] Frenkel D, Lekkerkerker H N W and Stroobants A 1988 Nature 332 822 [4] Vroege G J and Lekkerkerker H N W 1992 Rep. Prog. Phys. 55 1241 [5] Buining P A, Pathmamanoharan C, Jansen J B H and Lekkerkerker H N W 1991 J. Am. Ceram. Soc. 74 1303 [6] van der Kooij F M and Lekkerkerker H N W 1998 J. Phys. Chem. B 102 7829 [7] van der Kooij F M, Kassapidou K and Lekkerkerker H N W 2000 Nature 406 868 [8] Anderson V J and Lekkerkerker H N W 2002 Nature 416 811 [9] Borsboom M et al 1998 J. Synchrotron Radiat. 5 518 [10] Zernike F and Prins J A 1927 Z. Phys. 41 184 Colloidal suspensions contents How much does the core structure of a three-phase contact line contribute to the line tension near a wetting transition? J O Indekeu, K Koga and B Widom A systematic coarse-graining strategy for semi-dilute copolymer solutions: from monomers to micelles Barbara Capone, Ivan Coluzza and Jean-Pierre Hansen Structural searches using isopointal sets as generators: densest packings for binary hard sphere mixtures Toby S Hudson and Peter Harrowell The theory of delamination during drying of confined colloidal suspensions K J Wallenstein and W B Russel Electrostatics Modeling of equilibrium hollow objects stabilized by electrostatics Ethayaraja Mani, Jan Groenewold and Willem K Kegel The Donnan equilibrium: I. On the thermodynamic foundation of the Donnan equation of state A Philipse and A Vrij Colloidal rods and platelets Cholesteric order in systems of helical Yukawa rods H H Wensink and G Jackson Magnetic-field-induced nematic-nematic phase separation and droplet formation in colloidal goethite E van den Pol, A A Verhoeff, A Lupascu, M A Diaconeasa, P Davidson, I Dozov, B W M Kuipers, D M E Thies-Weesie and G J Vroege Structure of colloidal sphere-plate mixtures N Doshi, G Cinacchi, J S van Duijneveldt, T Cosgrove, S W Prescott, I Grillo, J Phipps and D I Gittins 3D structure of nematic and columnar phases of hard colloidal platelets A B G M Leferink op Reinink, J M Meijer, D Kleshchanok, D V Byelov, G J Vroege, A V Petukhov and H N W Lekkerkerker Phase behaviour of binary mixtures of diamagnetic colloidal platelets in an external magnetic field Jonathan Phillips and Matthias Schmidt Rheo-SAXS investigation of shear-thinning behaviour of very anisometric repulsive disc-like clay suspensions A M Philippe, C Baravian, M Imperor-Clerc, J De Silva, E Paineau, I Bihannic, P Davidson, F Meneau, P Levitz and L J Michot Colloid-polymer mixtures and depletion interactions Phase stability of a reversible supramolecular polymer solution mixed with nanospheres Remco Tuinier When depletion goes critical Roberto Piazza, Stefano Buzzaccaro, Alberto Parola and Jader Colombo Tuning the demixing of colloid-polymer systems through the dispersing solvent E A G Jamie, R P A Dullens and D G A L Aarts Polydispersity effects in colloid-polymer mixtures S M Liddle, T Narayanan and W C K Poon Colloidal dynamics and crystallization Crystallization and aging in hard-sphere glasses C Valeriani, E Sanz, E Zaccarelli, W C K Poon, M E Cates and P N Pusey Real-time monitoring of complex moduli from micro-rheology Taiki Yanagishima, Daan Frenkel, Jurij Kotar and Erika Eiser Brownian motion of a self-propelled particle B ten Hagen, S van Teeffelen and H Löwen Crystallization in suspensions of hard spheres: a Monte Carlo and molecular dynamics simulation study T Schilling, S Dorosz, H J Schöpe and G Opletal Structural signature of slow dynamics and dynamic heterogeneity in two-dimensional colloidal liquids: glassy structural order Takeshi Kawasaki and Hajime Tanaka

Quantifying chemical weathering rates along a precipitation gradient on Basse-Terre Island, French Guadeloupe: new insight from U-series isotopes in weathering rinds

USGS Publications Warehouse

Engel, Jacqueline M.; May, Linda; Sak, Peter B.; Gaillardet, Jerome; Ren, Minghua; Engle, Mark A.; Brantley, Susan L.

2016-01-01

Inside soil and saprolite, rock fragments can form weathering clasts (alteration rinds surrounding an unweathered core) and these weathering rinds provide an excellent field system for investigating the initiation of weathering and long term weathering rates. Recently, uranium-series (U-series) disequilibria have shown great potential for determining rind formation rates and quantifying factors controlling weathering advance rates in weathering rinds. To further investigate whether the U-series isotope technique can document differences in long term weathering rates as a function of precipitation, we conducted a new weathering rind study on tropical volcanic Basse-Terre Island in the Lesser Antilles Archipelago. In this study, for the first time we characterized weathering reactions and quantified weathering advance rates in multiple weathering rinds across a steep precipitation gradient. Electron microprobe (EMP) point measurements, bulk major element contents, and U-series isotope compositions were determined in two weathering clasts from the Deshaies watershed with mean annual precipitation (MAP) = 1800 mm and temperature (MAT) = 23 °C. On these clasts, five core-rind transects were measured for locations with different curvature (high, medium, and low) of the rind-core boundary. Results reveal that during rind formation the fraction of elemental loss decreases in the order: Ca ≈ Na > K ≈ Mg > Si ≈ Al > Zr ≈ Ti ≈ Fe. Such observations are consistent with the sequence of reactions after the initiation of weathering: specifically, glass matrix and primary minerals (plagioclase, pyroxene) weather to produce Fe oxyhydroxides, gibbsite and minor kaolinite.Uranium shows addition profiles in the rind due to the infiltration of U-containing soil pore water into the rind as dissolved U phases. U is then incorporated into the rind as Fe-Al oxides precipitate. Such processes lead to significant U-series isotope disequilibria in the rinds. This is the first time that multiple weathering clasts from the same watershed were analyzed for U-series isotope disequlibrian and show consistent results. The U-series disequilibria allowed for the determination of rind formation ages and weathering advance rates with a U-series mass balance model. The weathering advance rates generally decreased with decreasing curvature: ∼0.17 ± 0.10 mm/kyr for high curvature, ∼0.12 ± 0.05 mm/kyr for medium curvature, and ∼0.11 ± 0.04, 0.08 ± 0.03, 0.06 ± 0.03 mm/kyr for low curvature locations. The observed positive correlation between the curvature and the weathering rates is well supported by predictions of weathering models, i.e., that the curvature of the rind-core boundary controls the porosity creation and weathering advance rates at the clast scale.At the watershed scale, the new weathering advance rates derived on the low curvature transects for the relatively dry Deshaies watershed (average rate of 0.08 mm/kyr; MAP = 1800 mm and MAT = 23 °C) are ∼60% slower than the rind formation rates previously determined in the much wetter Bras David watershed (∼0.18 mm/kyr, low curvature transect; MAP = 3400 mm and MAT = 23 °C) also on Basse-Terre Island. Thus, a doubling of MAP roughly correlates with a doubling of weathering advance rate. The new rind study highlights the effect of precipitation on weathering rates over a time scale of ∼100 kyr. Weathering rinds are thus a suitable system for investigating long-term chemical weathering across environmental gradients, complementing short-term riverine solute fluxes.

Potential Chemical Effects of Changes in the Source of Water Supply for the Albuquerque Bernalillo County Water Utility Authority

USGS Publications Warehouse

Bexfield, Laura M.; Anderholm, Scott K.

2008-01-01

Chemical modeling was used by the U.S. Geological Survey, in cooperation with the Albuquerque Bernalillo County Water Utility Authority (henceforth, Authority), to gain insight into the potential chemical effects that could occur in the Authority's water distribution system as a result of changing the source of water used for municipal and industrial supply from ground water to surface water, or to some mixture of the two sources. From historical data, representative samples of ground-water and surface-water chemistry were selected for modeling under a range of environmental conditions anticipated to be present in the distribution system. Mineral phases calculated to have the potential to precipitate from ground water were compared with the compositions of precipitate samples collected from the current water distribution system and with mineral phases calculated to have the potential to precipitate from surface water and ground-water/surface-water mixtures. Several minerals that were calculated to have the potential to precipitate from ground water in the current distribution system were identified in precipitate samples from pipes, reservoirs, and water heaters. These minerals were the calcium carbonates aragonite and calcite, and the iron oxides/hydroxides goethite, hematite, and lepidocrocite. Several other minerals that were indicated by modeling to have the potential to precipitate were not found in precipitate samples. For most of these minerals, either the kinetics of formation were known to be unfavorable under conditions present in the distribution system or the minerals typically are not formed through direct precipitation from aqueous solutions. The minerals with potential to precipitate as simulated for surface-water samples and ground-water/surface-water mixtures were quite similar to the minerals with potential to precipitate from ground-water samples. Based on the modeling results along with kinetic considerations, minerals that appear most likely to either dissolve or newly precipitate when surface water or ground-water/surface-water mixtures are delivered through the Authority's current distribution system are carbonates (particularly aragonite and calcite). Other types of minerals having the potential to dissolve or newly precipitate under conditions present throughout most of the distribution system include a form of silica, an aluminum hyroxide (gibbsite or diaspore), or the Fe-containing mineral Fe3(OH)8. Dissolution of most of these minerals (except perhaps the Fe-containing minerals) is not likely to substantially affect trace-element concentrations or aesthetic characteristics of delivered water, except perhaps hardness. Precipitation of these minerals would probably be of concern only if the quantities of material involved were large enough to clog pipes or fixtures. The mineral Fe3(OH)8 was not found in the current distribution system. Some Fe-containing minerals that were identified in the distribution system were associated with relatively high contents of selected elements, including As, Cr, Cu, Mn, Pb, and Zn. However, these Fe-containing minerals were not identified as minerals likely to dissolve when the source of water was changed from ground water to surface water or a ground-water/surface-water mixture. Based on the modeled potential for calcite precipitation and additional calculations of corrosion indices ground water, surface water, and ground-water/surface-water mixtures are not likely to differ greatly in corrosion potential. In particular, surface water and ground-water/surface-water mixtures do not appear likely to dissolve large quantities of existing calcite and expose metal surfaces in the distribution system to substantially increased corrosion. Instead, modeling calculations indicate that somewhat larger masses of material would tend to precipitate from surface water or ground-water/surface-water mixtures compared to ground water alone.

Hydrogeology and geochemistry of acid mine drainage in ground water in the vicinity of Penn Mine and Camanche Reservoir, Calaveras County, California; first-year summary

USGS Publications Warehouse

Hamlin, S.N.; Alpers, Charles N.

1995-01-01

Acid drainage from the Penn Mine in Calaveras County, California, has caused contamination of ground water between Mine Run Dam and Camanche Reservoir. The Penn Mine was first developed in the 1860's primarily for copper and later produced lesser amounts of zinc, lead, silver, and gold from steeply dipping massive sulfide lenses in metamorphic rocks. Surface disposal of sulfidic waste rock and tailings from mine operations has produced acidic drainage with pH values between 2.3 and 2.7 and elevated concentrations of sulfate and metals, including copper, zinc, cadmium, iron, and aluminum. During the mine's operation and after its subsequent abandonment in the late 1950's, acid mine drainage flowed down Mine Run into the Mokelumne River. Construction of Camanche Dam in 1963 flooded part of the Mokelumne River adjacent to Penn Mine. Surface-water diversions and unlined impoundments were constructed at Penn Mine in 1979 to reduce runoff from the mine, collect contaminated surface water, and enhance evaporation. Some of the contaminated surface water infiltrates the ground water and flows toward Camanche Reservoir. Ground- water flow in the study area is controlled by the local hydraulic gradient and the hydraulic characteristics of two principal rock types, a Jurassic metavolcanic unit and the underlying Salt Spring slate. The hydraulic gradient is west from Mine Run impoundment toward Camanche Reservoir. The median hydraulic conductivity was about 10 to 50 times higher in the metavolcanic rock (0.1 foot per day) than in the slate (0.002 to 0.01 foot per day); most flow occurs in the metavolcanic rock where hydraulic conductivity is as high as 50 feet per day in two locations. The contact between the two rock units is a fault plane that strikes N20?W, dips 20?NE, and is a likely conduit for ground-water flow, based on down-hole measurements with a heatpulse flowmeter. Analyses of water samples collected during April 1992 provide a comprehensive characterization of ground water below Mine Run Dam at the Penn Mine. Specific conductance of the samples ranged from 1,810 to 18,000 microsiemens per centimeter. pH values of sampled ground water ranged from 3.7 to 7.8. Dissolved constituents in ground water ranged from less than 0.010 to 86 milligrams per liter for copper, from less than 0.010 to 240 milligrams per liter for iron, from less than 0.01 to 250 milligrams per liter for aluminum, and from 0.020 to 600 milligrams per liter for zinc. A contaminated ground-water plume appears to originate in the metavolcanic unit along the north abutment of Mine Run Dam. The plume is characterized by low pH, high concentrations of sulfate and dissolved metals, and enrichment of the heavy stable isotopes of hydrogen and oxygen. Dissolved iron and sulfate correlate positively, suggesting pyrite as the probable source of these elements. The concentrations of some dissolved constituents apparently are controlled by equilibrium with solid mineral phases. Poorly crystalline hydrous ferric oxide and microcrystalline gibbsite are close to saturation in ground water with pH values between 4 and 7.8 and probably control the solubility of Fe3+ and Al3+, respectively. Using a range of bulk hydraulic conductivity values for the metavolcanic unit from the median value (0.1 foot per day) to the highest values (50 feet per day), together with a representative cross-sectional area (3,000 square feet) for the contaminated ground-water plume and a hydraulic gradient of 0.14 from August 1992, the following range in ground-water flow rates is estimated by Darcy's law: 42 to 21,000 cubic feet per day, or 105 to 5x107 gallons per year. Multiplying this estimated range in ground-water flow by representative metal concentrations from the contaminated plume gives the following estimates for annual metal transport to Camanche Reservoir by ground water: 86 to 42,000 pounds of copper; 310 to 150,000 pounds of zinc; and 1.5 to 750 pounds of cadmium. These crude preliminary es

The Natural Enrichment of Stable Cesium in Weathered Micaceous Materials and Its Implications for 137Cs Sorption.

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

Elliott, W. Crawford; Kahn, Bernd; Rosson, Robert

2011-11-14

In this exploratory project, we are testing two interrelated hypotheses about the sorption of Cs within weathered micaceous materials in subsurface regolith materials from the Savannah River Site (SRS) located on the Atlantic Coastal Plain: 1) that stable cesium has become significantly enriched relative to potassium in subsurface micaceous particles as a result of chemical weathering processes; and 2) that the Cs so present is sufficient to be a major factor determining the ability of the subsurface materials to take up and hold 137Cs. To test these hypotheses, we collected by hand augur soil samples corresponding to soils representative atmore » the SRS: upland regolith (Fuquay series); soils formed on Tobacco Road Sandstone; and, soils formed on Quaternary Alluvium. From our data, the quantification of the amounts of stable cesium concentrated in various sites within 2:1 phyllosilicates by natural processes is highly relevant toward understanding the future sorption of 137Cs by the mica, illite, vermiculite, and hydroxyl interstratified vermiculite (HIV) phases present in the subsurface at and in proximity to SRS. Studying sorption and fixation of Cs in these micaceous phases interlayers potentially leads to increased knowledge to the extent that stable Cs resists exchange with ion exchange cations (Mg, NH4, or even alkyl ammonium compounds) and to the extent that Cs can become fixed over the long term. Such knowledge will help in the development of 137Cs remediation strategies for the long-term, which is a critical aspect of the SBR goals. We characterized the mineralogy, K-Ar ages of the soil and soil clay fractions (before and after acid treatment), and alkali element chemistry (K, Rb, Cs) of the clay fractions of soils collected from these three different types of soils. The clay fractions of the Fuquay soils are composed of kaolinite, and hydroxy interstratified vermiculite (HIV). Kaolinite, HIV, quartz, gibbsite and illite are found in the quaternary soils. Leach experiments using 10% nitric acid and 50% nitric acid were performed on 62 mesh fractions to show the amounts of Cs and Rb relative to K (Cs/K, Rb/K) that are exchangeable in these soils compared to Coastal Plain micas and upper continental crust. The Cs/K and Rb/K of the leachates are considerably higher relative to both upper continental crust and relative to weathered micas found in Georgia Coast Plain sediments. The K-Ar ages of the clay fractions of five different SRS soil series were ca. 320 Ma. After leaching with nitric acid, the ages of the soil clay fractions were approximately the same as the unleached soil clays. Based on the similarity of these ages to the ages of Coastal Plain micas, the K and Ar remaining after treatment is believed to be enclosed in a relect mica in the HIV phases in the soils. The HIV is likely a mica-HIV intergrade. Based on these data, stable cesium has become significantly enriched relative to potassium in subsurface micaceous particles as a result of chemical weathering processes in the SRS Fuquay soils studied thus far. Our data permit the interpretation describing the sorption of Cs and Rb in an apex site or in a hard to reach hard-to-exchange sorption site during pedogenesis. In terms of testing the second hypothesis, our work is ongoing and we report some preliminary data on Cs-137 and Rb-85 exchange experiments on select SRS Fuquay soils (-2 mm). Our isotopic equilibration experiments using Cs and Rb isotopes in separate exchange experiments show only small amounts of Cs and Rb in the original sample is exchangeable isotopically for a period of a few weeks in acidified conditions. The isotope exchange experiments provide support for our interpretation that pedogenically accumulated Cs (and Rb) occupy sites that are unavailable to exchange or exchange slowly in acid conditions corresponding to present conditions in SRS soils. In more basic solutions, greater exchange isotopic exchange is noted and suggests an expansion of interlayer sites thereby permitting more isotopic exchange of Cs and Rb.« less

Geochemical study of stream waters affected by mining activities in the SE Spain

NASA Astrophysics Data System (ADS)

Garcia-Lorenzo, Maria Luz; Perez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Bech, Jaime

2015-04-01

Water pollution by dissolved metals in mining areas has mainly been associated with the oxidation of sulphide-bearing minerals exposed to weathering conditions, resulting in low quality effluents of acidic pH and containing a high level of dissolved metals. According to transport process, three types of pollution could be established: a) Primary contamination, formed by residues placed close to the contamination sources; b) Secondary contamination, produced as a result of transport out of its production areas; c) Tertiary contamination. The aim of this work was to study trace element in water samples affected by mining activities and to apply the MINTEQ model for calculating aqueous geochemical equilibria. The studied area constituted an important mining centre for more than 2500 years, ceasing activity in 1991. The ore deposits of this zone have iron, lead and zinc as the main metal components. As a result, a lot of contaminations sources, formed by mining steriles, waste piles and foundry residues are present. For this study, 36 surficial water samples were collected after a rain episode in 4 different areas. In these samples, the trace element content was determined by by flame atomic absorption spectrometry (Fe and Zn), electrothermal atomization atomic absorption spectrometry (Pb and Cd), atomic fluorescence spectrometry (As) and ICP-MS for Al. MINTEQA2 is a geochemical equilibrium speciation model capable of computing equilibria among the dissolved, adsorbed, solid, and gas phases in an environmental setting and was applied to collected waters. Zone A: A5 is strongly influenced by tailing dumps and showed high trace element content. In addition, is influenced by the sea water and then showed high bromide, chloride, sodium and magnesium content, together with a basic pH. The MINTEQ model application suggested that Zn and Cd could precipitate as carbonate (hidrocincite, smithsonite and otavite). A9 also showed acid pH and high trace element content; is influenced by tailing dumps and also by waters from gully watercourses, transporting materials from Sierra Minera. The MINTEQ simulation showed that Pb and Ca could precipitate as sulphates (anglesite and gypsum). Waters affected by secondary contamination have been mixed with carbonate materials, present in the zone increasing the pH. Some elements have precipitated, such as Cu and Pb, while Cd, Zn and As are soluble. The MINTEQ model results showed that in A10 and A14, Al could precipitate as diaspore but also carbonates could be formed, particularly dolomite. These model in A12 sample showed that soluble Zn could precipitate as carbonate and Al as oxyhydroxide, similarly than in A13. A2 and A6 waters are affected by tertiary contamination and showed basic pH, soluble carbonates and lower trace element content. Only Zn, Cd and Al are present. The speciation model showed that in A2, Cd and Zn could precipitate as carbonates while Al as oxihydroxide. In A6, the model suggested that soluble Pb could precipitate as carbonate (hidrocerusite and cerusite) or as hydroxide; Al as diaspore, Ca as calcite and Fe as hematite. Zone B: All waters are strongly affected by mining activities and showed acid pH, high trace element content and high content of soluble sulphates. The MINTEQ results showed that in B8, Fe could precipitate as hydroxychloride and in B12 could form alunite. In B9, B10, B13 y B14, the model estimates the precipitation of anglesite, gypsum and Fe hydroxichloride (B9 and B10), diaspore in B13 and B14, and gypsum and Fe hydroxychloride in B13. All the sampling points collected in Zone C are affected by primary contamination, because there are a lot of tailing dumps. C1 showed high trace element content because is a reception point of a lot of tailing dumps. Water samples from C3 to C8 also had acid pH and high trace element content, particularly As, Zn and Cd. In addition, they showed high soluble sulphates. C2 water showed neutral pH, soluble carbonate and low trace element content because is influenced by a stabilised tailing dump. In all samples, except C2, the MINTEQ model showed that a lot of efflorescences could be formed, mainly sulphates. Zone D: All waters collected in this zone showed acid pH and high trace element content, mainly Zn, Cd and As. MINTEQ model results showed that elements could precipitate as jarosite but also anglesite in D8 and gypsum in D9, D11 and D12. D1 is affected by secondary contamination, which showed higher pH (still acid) and lower content in soluble salts and trace elements. The MINTEQ model suggested that Al could precipitate as diaspore, gibbsite and alunite. The applied model is an appropriate tool for the analysis of waters affected by mining activities. The obtained simulations confirm natural attenuation processes.

Mineralogical and geochemical characteristics of the Noamundi-Koira basin iron ore deposits (India)

NASA Astrophysics Data System (ADS)

Mirza, Azimuddin; Alvi, Shabbar Habib; Ilbeyli, Nurdane

2015-04-01

India is one of the richest sources of iron ore deposits in the world; and one of them is located in the Noamundi-Koira basin, Singhbhum-Orissa craton. The geological comparative studies of banded iron formation (BIF) and associated iron ores of Noamundi-Koira iron ore deposits, belonging to the iron ore group in eastern India, focus on the study of mineralogy and major elemental compositions along with the geological evaluation of different iron ores. The basement of the Singhbhum-Orissa craton is metasedimentary rocks which can be traced in a broadly elliptical pattern of granitoids, surrounded by metasediments and metavolcanics of Greenstone Belt association. The Singhbhum granitoid is intrusive into these old rocks and to younger, mid Archaean metasediments, including iron formations, schists and metaquartzites and siliciclastics of the Precambrian Iron Ore Group (Saha et al., 1994; Sharma, 1994). The iron ore of Noamundi-Koira can be divided into seven categories (Van Schalkwyk and Beukes 1986). They are massive, hard laminated, soft laminated, martite-goethite, powdery blue dust and lateritic ore. Although it is more or less accepted that the parent rock of iron ore is banded hematite jasper (BHJ), the presence of disseminated martite in BHJ suggests that the magnetite of protore was converted to martite. In the study area, possible genesis of high-grade hematite ore could have occurred in two steps. In the first stage, shallow, meteoric fluids affect primary, unaltered BIF by simultaneously oxidizing magnetite to martite and replacing quartz with hydrous iron oxides. In the second stage of supergene processes, deep burial upgrades the hydrous iron oxides to microplaty hematite. Removal of silica from BIF and successive precipitation of iron resulted in the formation of martite- goethite ore. Soft laminated ores were formed where precipitation of iron was partial or absent. The leached out space remains with time and the interstitial space is generally filled with kaolinite and gibbsite, which make it low grade. Massive iron ores are devoid of any lamination and usually associated with BHJ and lower shale. The thickness of the massive ore layer varies with the location. The massive iron ore grades in to well-developed bedded BHJ in depth. Blue dust occurs in association with BHJ as pockets and layers. Although blue dust and friable ore are both powdery ores, and subjected to variable degree of deformation, leading to the formation of folding, faulting and joints of complex nature produce favourable channels. Percolating water play an important role in the formation of blue dust and the subterranean solution offers the necessary acidic environment for leaching of quartz from the BHJ. The dissolution of silica and other alkalis are responsible for the formation of blue dust. The friable and powdery ore on the other hand are formed by soft laminated ore. As it is formed from the soft laminated ore, its alumina content remains high similar to soft laminated ore compaired to blue dust. Mineralogy study suggests that magnetite was the principal iron oxide mineral, now a relict phase whose depositional history is preserved in BHJ, where it remains in the form of martite. The platy hematite is mainly the product of martite. The different types of iron ores are intricately related with the BHJ. Hard laminated ores, martite-goethite ore and soft laminated ore are resultant of desilicification process through the action of hydrothermal fluids. Geochemistry of banded iron-formations of the Noamundi-Koira iron ore deposits shows that they are detritus-free chemical precipitates. The mineralogical and geochemical data suggest that the hard laminated, massive, soft laminated ores and blue dust had a genetic lineage from BIF's aided with certain input from hydrothermal activity. The comparative study of major elemental composition of the basin samples and while plotting a binary diagram, it shows a relation between major oxides against iron oxides, in which iron oxides is taken as a reference oxide (Mirza, 2011). On the other hand, by plotting a binary diagram between chemical index of alteration (CIA) and other oxides while taking the samples of lower, middle and upper shales. It reflects an immobility and mobility of ions during partial and complete weathering processes (Mirza, 2011). Geochemical data indicate that BIF are in general detritus free chemical precipitates. Fe2O3 content of BHJ are varies in between 36.6% to 65.04%. In hard laminated ore, Fe2O3 content varies from 93.8% to 96.38%, Soft laminated ore varies from 83.64% to 89.5% and laterite ore varies from 53.5% to 79.11%. Fe2O3 content in Martite- Goethite ore varies from 86.38% to 89.42% and blue dust having 90.74% to 95.86% and all other oxides like SiO2, Al2O3, CaO, MgO, K2O, Na2O are decreases. Major part of the iron could have been added to the bottom sea water by hydrothermal solutions derived from hydrothermally active anoxic marine environments. The presence of intacalated tuffaceous shales pointing towards the genesis of iron, which could have leached from sea floor by volcanogenic process. Iron and silica of BIF were provided by the hydrothermal solutions emplaced at the vent sites situated at the Archean-Mid Oceanic Ridges. References: Mirza A (2011). Major element geochemistry of iron ore deposits in Noamundi-Koira basin of Singhbhum-Orissa craton (India). MSc thesis, Aligarh Muslim University, India. Saha AK (1994). Crustal evolution of Singhbhum, North Orissa, Eastern India; Geol. Soc. India Memoir 27 341. Sharma M, Basu AR and Ray SL (1994). Sm-Nd isotopic and geochemical study of the Archaean tonalite-amphibolite association from the eastern Indian craton. Contrib. Mineral Petrol. 117:45-55. Van Schalkwyk J and Beukes N J (1986). The Sishen iron ore deposit, Griqualand West; In: Mineral deposits of Southern Africa (eds) Annhaeusser C R and Maske S S, Geological Society of South Africa, Johannesburg, 931-956.

Surficial geology and soils of the Elmira-Williamsport region, New York and Pennsylvania, with a section on forest regions and great soil groups

USGS Publications Warehouse

Denny, Charles Storrow; Lyford, Walter Henry; Goodlett, J.C.

1963-01-01

The Elmira-Williamsport region, lying south of the Finger Lakes in central New York and northern Pennsylvania, is part of the Appalachian Plateaus physiographic province. A small segment of the Valley and Ridge province is included near the south border. In 1953 and 1954, the authors, a geologist and a soil scientist, made a reconnaissance of about 5,000 square miles extending southward from the Finger Lakes, N.Y., to Williamsport, Pa., and eastward from Wellsboro, Pa., to Towanda, Pa. Glacial drift of Wisconsin age, covering the central and most of the northern parts of the region, belongs to the Olean substage of MacClintock and Apfel. This drift is thin and patchy, is composed of the relatively soft sandstones, siltstone, shales, and conglomerates of the plateaus, commonly has a low calcium carbonate content, and is deeply leached. Mantling its surface are extensive rubbly colluvial deposits. No conspicuous terminal moraine marks the relatively straight border of Olean drift. The Valley Heads moraine of Fairchild near the south ends of the Finger Lakes is composed of relatively thick drift containing a considerable amount of somewhat resistant sedimentary and crystalline rocks. Commonly this drift has a relatively high carbonate content and is leached to only shallow depths. The Valley Heads drift is younger than Olean, but its precise age is undetermined. The age of the Olean is perhaps between Sangamon and Farmdale, on the basis of, in part, a carbon-14 date from peat at Otto, N.Y. All differences in soil development on these two Wisconsin drifts are clearly related to the lithology of the parent material or the drainage, rather than to weathering differing in kind or in duration. The authors believe that the soils are relatively young, are in equilibrium with the present environment, and contain few, if any, features acquired during past weathering intervals. The effect of tree throw on soil profiles and the presence of soils on slopes clearly indicate that soils form rapidly. Sols Bruns Acides are the most extensive great soil group occurring throughout the region. Podzols and Gray-Brown Podzolic soils are also widespread, and on long, smooth slopes Low Humic-Gley soils are common. Organic soils are of small extent. South of the Wisconsin drift border, the surficial mantle consists chiefly of alluvial, colluvial, or residual deposits of Wisconsin or of Recent age, but there are many small isolated patches of older, strongly weathered materials of pre-Wisconsin age. Although such older materials are commonly overlain or mixed with less weathered mantle, the yellowish-red color, characteristic of the strongly weathered material, is generally not masked. Some of the older material is drift, presumed to be of Illionian age, that was probably strongly weathered to a considerable depth in Sangamon time and has been greatly eroded since the last interglacial period. No clear-cut exposure of Wisconsin drift resting on older drift or other strongly weathered mantle has been found. The old drift and the other strongly weathered materials apparently acquired their present red color in pre-Wisconsin time. Where exposed at the surface, such strongly weathered mantle is the parent material of modern Red-Yellow Podzolic soils. Sols Bruns Acides and Gray-Brown Podzolic soils, developed on slightly weathered parent materials, are found adjacent to these red soils. This suggests that these Red-Yellow Podzolic soils probably developed from strongly weathered parent materials. No buried soils were found nor were any soils recognized as relics from pre-Wisconsin time. Comparison of a map of the great soil groups with a map of the vegetation of the region, prepared by John C. Goodlett, does not reveal a close relation. Laboratory analyses of samples collected furnish data on textural, mineralogical, and chemical changes caused by weathering and soil formation. The results indicate that the amount of chemical weathering which the Wisconsin drift has undergone is slight. The Red-Yellow Podzolic soils on strongly weathered pre-Wisconsin drift have B2 horizons that have a finer texture than the A2 or C horizons. The parent materials of these soils seem to be strongly weathered because of the high chromas, reddish hues, friable condition of most rock fragments, relatively high kaolinite content, and presence of gibbsite in the clay fraction. Measurements at numerous localities show that the depth of leaching increases with decreasing carbonate content and is not a criterion of the age of the drift. Pebble counts of gravels also show that the depth of leaching of gravel is related to its limestone content. The location of the gravel deposits is probably due primarily to the presence of pebbles of resistant rock rather than to ice wastage involving abundant glacial melt water. The region is in the Susquehanna drainage basin except for its north fringe, which drains to Lake Ontario. Most of the region is a dissected plateau ranging in altitude from 700 to 2,500 feet and underlain by gently folded sedimentary rocks of Paleozoic age. Much of the region slopes moderately or steeply; the most extensive areas of gently sloping land are 011 the uplands. In the northern part are several straight and deep valleys the southern extension of the Finger Lakes basins separated by uplands with several low cuestas that face north. Similarly, some streams such as the Canisteo, Cohocton, and Chemung Rivers, and the part of the Susquehanna River that is in New York, trend at right angles to the Finger Lakes, flowing in valleys that parallel the regional strike of the bedrock. The Olean drift border is marked by a change from drift containing very few rounded or striated rock fragments to a mantle containing only angular rock fragments and traces of red, strongly weathered materials. A reconstruction of the surface of the ice sheet, at its maximum extent shows an inferred slope of its distal margin ranging from 100 to 500 feet per mile

Quantitative physical and chemical variables used to assess erosion and fertility loss in tropical Dominican and Haitian soils

NASA Astrophysics Data System (ADS)

Pastor, J.; Alexis, S.; Vizcayno, C.; Hernández, A. J.

2009-04-01

The Pedernales province (Dominican Republic) has the main part of the only Biosphere Reserve in that Caribbean Island, including the Bahoruco and Jaragua National Parks. In these Parks is possible to find almost the totality of tropical forest ecosystems (evergreen rain forest, latifoliated forest, dry forest and mangrove forest on mainland), as well as the most frequent soil uses in the Dominican country. The consulted bibliography about the soils is very scarce and it does not give any information relating to this natural resource, which is basic for a sustainable development management in this territory. When Christopher Columbus reached the island, its plant cover constituted 95% of the land. This was largely because the limited, rudimentary tools used by the Indians to exploit the soil, allowed them to maintain a well-balanced ecological system. The initial type of agriculture practised by the indigenous inhabitants was scarcely destructive and based on vegetatively reproducing crops propagated through cuttings, but later forest burning was an especially significant management practice aimed at releasing nutrients into the soil, in an environment in which under natural conditions, particularly those of the rainforest, these were mostly locked within plant structures. The colonial system, on the contrary, brought with it more elaborate methods and utensils enabling them to cultivate cereals (somewhat unknown to the native Indians) and to rear livestock (cows, goats) yet contributed to the growth of deforestation. Agricultural activities were not confined to the plains; even the virgin woods of the mountains were exploited. The monocrops grown across vast expanses rapidly rid the soil of its productive capacity. Cutting down and burning forest for agricultural uses, and also industrial exploitation of bauxite and limestone produced also important alterations in the soil processes. Agricultural activities were not confined to the plains; even the virgin woods of the mountains were exploited. The monocrops grown across vast expanses rapidly rid the soil of its productive capacity. The Factors affecting soil degradation in this territory may be generally divided into the three groups: physic-natural, political, and socio-economic. The climate and geomorphology are the natural factors mostly influencing the soils. Its relief means its soils are highly vulnerable and sensitive to erosion, and its different ecosystems are similarly sensitive to the actions of cyclones and hurricanes. Many of the lands have slopes exceeding 20%, and 40%. Since the colonisation another cause of the degradation of its soils has been a lack of political will to protect the natural resources. The situation of extreme poverty of the territory, especially in the rural areas, particularly affects plant resources and the soil: to meet needs, the population have to exploit the most marginal of territories rather than intensifying existing systems. Thus, the dynamics of poverty becomes a vicious cycle, with poverty as the cause and consequence of the deteriorated natural resources. As a consequence of all these factors, the expansion of agricultural boundaries following deforestation is one of the causes of soil erosion affecting mountain lands. On the other hand, climatic change including more irregular and less rainfall, along with an increased incidence of natural disasters (cyclones, hurricanes, floods), have placed this territory in a situation very difficult. Our recent discovery of important levels of Al, Pb, Zn, Cu, Cr and Cd in the territory, especially on the superficial layer of river Pedernales Basin soils (Dominican Republic-Haiti), made us to investigate about the possible effects of the soil degradation and erosion produced on the toxicity of these metals. The source of these metals is linked to geoedaphic processes more than to human impacts, in a region that comprises core, intensive agriculture and buffer areas of the reserve, harbouring mines (bauxite and limestone), crops and livestock. The hypothesis that heavy metals liberated by geochemical actions in some of these tropical ecosystems could be related both to productivity and to human and animal health, led us also to assess metal bioavailability in the area's main crops as the primary source of food or fodder. To establish the context of the heavy metal pollution, we characterized the geoedaphic features of the region. The predominant rocks are sedimentary limestones: with limestone colluvial deposits dominant in the tropical conifer forest and rain forest of the Sierra de Bahoruco; crystalline limestones in the tropical latifoliated forest; and Quaternary detritic rocks and reefs (carbonates overlying alterites) in the dry tropical forest. Across the territory, there is a marked predominance of soils that range from surface soils to shallow, poorly developed stony soils of low natural fertility. Most can be classified as entisols. Soils of recent alluvial origin lack pedogenetic horizons and are subjected to diverse humidity and temperature regimens. Slopes are pronounced and relief and altitudes vary. Their profiles include A-R horizons characterised by displaying an ochre epipedon over a fractured rock bed whose depth is shallow and A-C horizons of a sandy to clayey soil and subsoil texture, whose colours range from dark brown to grey and depths from very shallow to deep. Soils occur from the mountains to landscapes including rivers or sandy coasts. The ecosystems examined occur from an altitude of 1300-1200 m to sea level and the cultivated soils have the main food sources for human and animal consumption: bean, corn, sorghum, coffee, Guinea banana, fruit trees and tubers. We present these data for 79 soil samples according to the corresponding landscape units (forests) along with their dominant lithologies (crystalline limestones, carbonated limestones on alterites and coral limestones). Our study describes edaphic processes linked to physical and chemical erosion in this region. The main types of clay are: hematite, kaolin, bohemite (the most abundant) gibbsite and calcite. Textures range from sandy-silty to clayey. Sand and clay fractions seem more abundant than silt ones. Soil pHs are generally in the basic range with infrequent acid soils. OM and total Nitrogen levels are not low, especially OM in the dry forest and N in the latifoliated forest. Available K contents are low in mountain forests and high in dry forests. Available P contents are generally low to very low. The topsoil layers (0-20 cm) of different types of wet and dry tropical forests and agroecosystems were assessed in terms of several physical factors related to erosion. These factors were: particle size, aggregate structural instability index (Is), and soil physical degradation index, erodibility index and erosionability index. This study reports also fertility loss, OM and heavy metal data obtained in the topsoil samples from both natural ecosystems and agroecosystems. Soil fertility also needs to be assessed since has been severely compromised by changes in the physical and chemical properties of the soil induced by the felling and burning of trees to make way for crops. Acknowledgements: Projects CTM2005-02165/TECNO (MEC) & CTM2008-04827/TECNO (MceI). Program EIADES S-0505/AMB/0296 (CAM) and Project "Promoción de la calidad educativa y el desarrollo local en la provincia de Pedernales, R. Dominicana" (CAM & Centro Cultural Poveda of Sto. Domingo, Dominican Republic).

Surficial geology and geomorphology of Potter County, Pennsylvania

USGS Publications Warehouse

Denny, C.S.

1956-01-01

Potter County is located in the Appalachian Plateaus of north-central Pennsylvania and contains the headwaters of the Genesee River, the Allegheny River, and the Susquehanna River. Drift of Wisconsin age covers the northeastern part of the county. This study includes a detailed survev of the surficial deposits of the Genesee quadrangle in north-central Potter County and a reconnaissance of the remainder of the county; a soil survey and a botanical survey were carried on concurrently. The region is a deeply dissected plateau having extensive areas of steeply sloping land separated by narrow ridges and valleys; there is very little level land. Near the junction of the three watersheds the uplands rise to altitudes of more than 2,500 feet. The maximum relief in the Susquehanna drainage is more than 1,500 feet; in the Genesee and Allegheny drainage it. is about 800 feet. Valley walls are steep (15° to 30°), and the uplands have gentle slopes (0.5° to 10°). The drainage pattern is trellised. The climate is continental. Temperatures range from about -30° F. to more than 100° F. The average annual precipitation ranges approximately from 34 to 42 inches. Floods may occur at any season of the year. The large volumes of water from rain or melting snow carried by small streams come from springs. There is little precise data on frost in the ground, but it is probable that the ground seldom freezes in forested areas. The soils of Potter County have relatively immature profiles with poorly developed horizons that commonly have many characteristics inherited from their parent materials. At the great soil group level, the zonal soils are divided into Podzol soils and Brown Podzolic soils. Many soils have a high silt content in the upper part of the profile, apparently derived (at least partly) from a mantle of eolian silt. Mos~ of Potter County is covered by second-growth forests consisting of 40- to 60-year-old hardwood stands. The present forests growing on slopes and summits are composed approximately of 25 species of trees. The northern hardwood region includes most of the county, with an oak-forest region near the borders, principally along its southern margin. Potter County is underlain by sandstone, siltstone, shale, conglomerate, and minor amounts of coal and calcareous rock that range in age from Late Devonian to Pennsylvanian. These rocks form broad open folds that strike northeast. South of the border of the Wisconsin drift, and possibly at two localities inside the drift border, are scattered remnants of ancient soils (here called paleosol), that were formed in preWisconsin time-probably during the Sangamon interglacial stage. This paleosol ranges in texture from clay loam to silt loam, ranges in color from yellowish red to red, includes a few percent to more than 25 percent of rock fragments, and apparently contains a small percentage of gibbsite and varying amounts of kaolinite. Known thicknesses range from 1 to 33 feet. Paleosol was developed on diverse kinds of parent material, such as till, stratified drift, colluvium, and residuum, at altitudes ranging from a few hundred to 2,400 feet. The climatic conditions under which the paleosol formed are uncertain; however, these ancient soils may record an episode of subtropical climatic conditions during which lateritic soils were formed. Perhaps these soils are analogous to the Red-Yellow Podzolic soils of southeastern United States. Except for one possible remnant, no pre-Wisconsin drift has been recognized in Potter County. The Wisconsin glacial deposits of Potter County belong to either the Iowan or Tazewell substages and are dominantly till with minor amounts of glaciofluvial deposits. Erratics of igneous or metamorphic rock comprise less than 0.1 percent of the total number of rock fragments. The till is slightly weathered to depths ranging from 3 to about 12 feet. The drift border is indefinite and has been drawn at the southern limit of erratics or well-rounded or striated pebbles and is only locally marked by a terminal moraine or by a distinct change in the surficial deposits. The drift border is relatively straight and crosses the Genesee quadrangle in a northwesterly direction with little regard for the major topographic features, thus suggesting that the Wisconsin ice sheet had a relatively straight and steep front. Over most of the unglaciated part of Potter County, the bedrock is concealed beneath rubble that probably was formed during the Iowan or Tazewell substage, almost contemporaneously with the adjacent drift. In general, the rubble is thickest and most extensive within about 10 miles of the drift border, becoming thinner and less continuous farther away. The apparent parallelism between a belt of thick periglacial deposits and the drift border suggests that the deposits result from climatic factors in operation while the Wisconsin ice sheet was nearby. Ancient soil structures or patterned ground occur at, or near, the surface of both the periglacial deposits and the adjacent drift. These ancient soil structures are so similar to modern forms in arctic or alpine environments that they are considered to be the result of vigorous frost action. Many of the structures are believed to be a result of down-slope movement of debris by solifluction, facilitated by a frozen subsoil as much as 10 feet deep. Perennially frozen ground may have been present, but this is not a prerequisite. The periglacial deposits underlie long smooth slopes that extend from ridge crest to valley bottom. Flood plains are absent near the headwaters of many streams, the valley walls forming a V-shaped profile. While frost action was in progress, forests probably were restricted to flood plains, lower slopes, and scattered upland areas. Large parts of the upland were bare or partly covered by tundra vegetation; elsewhere, there were scattered trees but no dense forest. 1 2 SURFICIAL GEOLOGY AND GEOMORPHOLOGY OF POTTER COUNTY, PENNSYLVANIA Recent alluvium and alluvial fans include sand and sandy loams, 1 to 3 feet thick, that overlie gravel. The alluvium contains organic matter and lenses of finer materials. Thickness ranges from a few to more than 100 feet. Along the principal streams the alluvium probably overlies Pleistocene deposits. Most of the alluvial fans are composed of unstratified rubbly, pebbly, cobbly. or bouldery sandy loams to silty clay loams with local lenses of stratified sand and gravel. The alluvial fans mapped in the Genesee quadrangle probably include both Wisconsin stage and Recent deposits. The summits of the A.ppalachian Plateaus in north-central Pennsylvania have long been recognized as the remnants or traces of one or more peneplains. To test this hypothesis, a restored contour map was prepared to show the configuration of a supposed peneplain on the assumption that the plateau tops are remnants of such an old erosion surface. The restored contours delineate a surface that corresponds roughly to rock structure. In general, the uplands slope parallel to the dip of the bedrock. The major streams, such as the West Branch Susquehanna River, cross the ridges and valleys of the restored surface in such a way that it is difficult to suppose that the restored surface was ever graded to these streams. On the contrary, it is probable that the restored surface never existed and that the plateau tops are structurally controlled surfaces held up by sandstone and conglomerate beds in the Pottsville and Pocono formations. The plateau tops may have been lowered by erosion as much as 200 feet during the Pleistocene-in other words, after the major streams were incised. If this portion of the Appalachian Plateaus was ever reduced to a peneplain, such a hypothetical surface must have lain many hundreds of feet above the uplands of the present day. The only alternative that might involve peneplanation is the improbable hypothesis that the plateau tops are remnants of a slightly deformed peneplain and that the peneplain was folded along the axes of the Appalachian orogeny. This remote possibility is not supported by any known evidence. The geomorphic analysis yields no new data on the origin of the cross-axial drainage. Regardless of whether the plateaus are peneplain remnants or are structurally controlled surfaces, the beginning of the major southeastward-flowing streams long antedates the existing landscape. The geomorphic history of Potter County begins with an assumed long interval of erosion during the Mesozoic and early Cenozoic eras, for which no record remains in this area. The southeast master drainage was established by the latter part of the Tertiary period (perhaps at a much earlier date), probably as the result of the northwestward migration of the Atlanticinterior divide. In late Pliocene(?) time, areas adjacent to parts of the West Branch Susquehanna River-and probably elsewhere-had a moderate relief ranging from 300 to 700 feet. Some segments of the West Branch meandered across a broad valley that lay about 900 feet above the present streams. The landscape probably was covered by deep residual soils, perhaps by saprolite. The early Pleistocene history of Potter County is essentially unknown. No deposits of the Kansan stage are known except for a possible trace of pre-Illinoian drift on the uplands in central Potter County (Ayers Hill quadrangle). Some deposits in central and eastern Pennsylvania may be of Kansan age. It is probable that the assumed Aftonian regolith was removed by mass movements and other processes during the Kansan stage, thus resulting in a lowering of the plateau tops by as much as 10 feet. By the close of the Yarmouth(?) interglacial stage the major streams were incised to essentially their present depths. The climates of the Yarmouth interglacial stage probably produced deep residual soils over the landscape, parts of which may still be preserved in the paleosol remnants of the present day. No Illinoian drift is known in Potter County, but drift assigned to this stage occurs in areas to the northwest and to the southeast. Some valleys, such as Kettle Creek valley, were filled with sand and gravel alluvium to depths of as much as 150 feet above their present flood plains. It is assumed that the Yarmouth residual soils were removed by mass movements and other processes induced by a periglacial climate, thus lowering the plateau tops by as much as 10 feet. During the Sangamon interglacial stage, deep (10-to-20 foot) residual soils or paleosol were developed in Potter County and probably throughout much of Pennsylvania, perhaps as a result of lateritic weathering in a subtropical climate. It is possible that the paleosol was largely removed by mass movements and by running water during late Sangamon time. During either the Iowan or Tazewell substages of the Wisconsin (perhaps the Iowan), the ice sheet advanced into the northeastern part of Potter County. The drift is similar to the Olean drift (local usage). The paleosol was almost completely removed by mass movements and other processes induced· by a periglacial climate, prior to drift deposition. This removal probably resulted in a lowering of the plateau tops by as much as 10 feet since Sangamon time. Nearly contemporaneously with drift deposition, the periglacial deposits were formed by frost heaving, solifluction, and fluvial transport in areas outside the drift border. Soil structures or patterned ground were developed on both the drift and the periglacial deposits. It is probable that the forests in the periglacial area were greatly restricted and that large areas on the uplands were essentially treeless. Little is known about the history of Potter County in postOlean time. Presumably, forests completely covered the county by the onset of the next substage, during which the Binghamton drift of MacClintock and Apfel was deposited. This drift also is found in southern New York State. The formation of the alluvium and alluvial fans probably began in the Tazewell substage and continued during the Recent epoch. Since these deposits were formed there has been very little dissection. There is little, if any, difference between soils developed on periglacial deposits and soils developed on drift. The roots of fallen trees have disturbed the soil horizons, and it is unlikely that the existing soil profiles are more than 500 years old. The forested landscape of Potter County has a distinctive microrelief ranging from a few inches to a few feet of mounds and pits produced by the roots of fallen trees. Most mounds and pits range from 10 to 20 feet in length and from 6 to 15 feet in width. On level land, many mounds are oriented with their long axes trending northward, and in some areas the orientation is random. On slopes, the mounds are oriented with their long axes at right angles to the maximum slope as a result of trees falling downslope. The toppling of trees increases the permeability of surficial deposits and mixes and destroys the soil horizons. The microrelief is a factor in forest development. The toppling of trees on slopes is a significant agent of slope erosion. The process loosens, breaks up, or overturns the upper 2 to 3 feet of the forest soil, and it tends to make the surficial layer more stony and to produce features resembling soil structures.