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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Mobility of heavy metals through granitic soils using mini column infiltration test

This study is about the mobility of cadmium through compacted granitic soils. Two granitic soils namely the Broga (BGR) and Kajang (KGR) granitic soils were collected in Selangor, Malaysia. Physical and chemical tests were applied for both granitic soils to determine the physical and chemical properties of soil materials. Physical test results shows granitic soils (BGR and KGR) have high percentage of sand ranging between 54%–63% and 46%–54% respectively, an intermediate and intermediate to high plasticity index as well as high specific gravity ie; 2.50–2.59 and 2.45–2.66 respectively. For chemical test, granitic soils shows acidic pH values ranged from 5.35–5.85 for BGR and pH 5.32–5.54 for KGR. For organic matter, SSA and CEC test, it shows low values ranged from 0.22%–0.34% and 0.39%– 0.50% respectively for organic matter test, 17.96 m{sup 2}/g–21.93 m{sup 2}/g and 25.76 m{sup 2}/g–26.83 m{sup 2}/g respectively for SSA test and 0.79 meq/100g–1.35 meq/100g and 1.31 meq/100g–1.35 meq/100g respectively for CEC test. Mini column infiltration test was conducted to determine the retention of cadmium while flowing through granite soils. This test conducted based on the falling head permeability concepts. Different G-force ranging from 231G to 1442G was used in this test. The breakthrough curves show the concentration of Cd becomes higher with the increasing of G-force for both granitic samples (BGR and KGR). The selectivity sorption for both granites ranked in the following decreasing order of; 231G>519G>923G>1442G. Results demonstrated that granitic soils also have low buffering capacity due to low resist of pH changes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2012

Crystallographic study of red fluorescent protein eqFP578 and its far-red variant Katushka reveals opposite pH-induced isomerization of chromophore

The wild type red fluorescent protein eqFP578 (from sea anemone Entacmaea quadricolor, {lambda}{sub ex} = 552 nm, {lambda}{sub em} = 578 nm) and its bright far-red fluorescent variant Katushka ({lambda}{sub ex} = 588 nm, {lambda}{sub em} = 635 nm) are characterized by the pronounced pH dependence of their fluorescence. The crystal structures of eqFP578f (eqFP578 with two point mutations improving the protein folding) and Katushka have been determined at the resolution ranging from 1.15 to 1.85 {angstrom} at two pH values, corresponding to low and high level of fluorescence. The observed extinguishing of fluorescence upon reducing pH in eqFP578f and Katushka has been shown to be accompanied by the opposite trans-cis and cis-trans chromophore isomerization, respectively. Asn143, Ser158, His197 and Ser143, Leu174, and Arg197 have been shown to stabilize the respective trans and cis fluorescent states of the chromophores in eqFP578f and Katushka at higher pH. The cis state has been suggested as being primarily responsible for the observed far-red shift of the emission maximum of Katushka relative to that of eqFP578f.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2011

The Effect of Crystallizing and Non-crystallizing Cosolutes on Succinate Buffer Crystallization and the Consequent pH Shift in Frozen Solutions

To effectively inhibit succinate buffer crystallization and the consequent pH changes in frozen solutions. Using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD), the crystallization behavior of succinate buffer in the presence of either (i) a crystallizing (glycine, mannitol, trehalose) or (ii) a non-crystallizing cosolute (sucrose) was evaluated. Aqueous succinate buffer solutions, 50 or 200 mM, at pH values 4.0 or 6.0 were cooled from room temperature to -25 C at 0.5 C/min. The pH of the solution was measured as a function of temperature using a probe designed to function at low temperatures. The final lyophiles prepared from these solutions were characterized using synchrotron radiation. When the succinic acid solution buffered to pH 4.0, in the absence of a cosolute, was cooled, there was a pronounced shift in the freeze-concentrate pH. Glycine and mannitol, which have a tendency to crystallize in frozen solutions, remained amorphous when the initial pH was 6.0. Under this condition, they also inhibited buffer crystallization and prevented pH change. At pH 4.0 (50 mM initial concentration), glycine and mannitol crystallized and did not prevent pH change in frozen solutions. While sucrose, a non-crystallizing cosolute, did not completely prevent buffer crystallization, the extent of crystallization was reduced. Sucrose decomposition, based on XRD peaks attributable to {beta}-D-glucose, was observed in frozen buffer solutions with an initial pH of 4.0. Trehalose completely inhibited crystallization of the buffer components when the initial pH was 6.0 but not at pH 4.0. At the lower pH, the crystallization of both trehalose dihydrate and buffer components was evident. When retained amorphous, sucrose and trehalose effectively inhibited succinate buffer component crystallization and the consequent pH shift. However, when trehalose crystallized or sucrose degraded to yield a crystalline decomposition product, crystallization of buffer was observed. Similarly, glycine and mannitol, two widely used bulking agents, inhibited buffer component crystallization only when retained amorphous. In addition to stabilizing the active pharmaceutical ingredient, lyoprotectants may prevent solution pH shift by inhibiting buffer crystallization.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Simultaneous recovery of Zn and Mn from used batteries in acidic and alkaline mediums: A comparative study

Highlights: • Leaching processes of waste from alkaline batteries are reviewed and compared. • The recovery of Zn and Mn by electrolysis in acid medium is highly dependent on pH. • Reaction of Zn with the O{sub 2} is released at the anode in the electrodeposition of Zn. • Zn is recovered as ZnO in a single step by acidifying the basic leachate with HCl. - Abstract: A parallel study of acidic and alkaline leaching for the recovery of Mn and Zn from spent alkaline batteries is outlined. Using H{sub 2}SO{sub 4} as solvent and selecting appropriate conditions of temperature and concentration, all residues were dissolved except carbon. The separation and recovery of the two components were performed by electrodeposition with satisfactory results at pH values above 4 (current efficiency above 70% for Zn and Mn) but rather lower efficiencies as the pH decreased. Most of the Zn was selectively dissolved by alkaline leaching using a 6.5 M NaOH solution, and its recovery was examined by means of both electrochemical and chemical processes. The expected formation of pure Zn by electrowinning failed due to the formation of ZnO, the content of which was highly dependent on the electrodeposition time. For short periods, Zn was the main component. For longer periods the electrodeposit consisted of agglomerated microparticles of ZnO with a minor fraction of Zn metal (barely 3% as measured by X-ray diffraction). A chemical reaction of the element with oxygen released at the anode surface might be responsible for its conversion to ZnO. A simple chemical route is described for the first time for the direct conversion of Zn(OH){sub 4}{sup 2−} solution to nanostructured ZnO by lowering the pH to values around 12 using 2 M HCl solution.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Comparison of the Kinetic Rate Law Parameters for the Dissolution of Natural and Synthetic Autunite in the Presence of Aqueous Bicarbonate Ions

Bicarbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, bicarbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous bicarbonate concentration to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate (0.0005-0.003 M) under the pH range of 6-11 and a temperature range of 5-60oC. Consistent with the results of previous investigation, the rate of uranium release exhibited minimal dependency on temperature; but were strongly dependent on pH. Increasing aqueous bicarbonate concentrations afforded comparable increases in the rate of release of uranium. Most notably under low pH conditions the aqueous bicarbonate resulted in up to 370 fold increases in the rate of uranium release in relative to the rate of uranium release in the absence of bicarbonate. However, the effect of aqueous bicarbonate on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release.

Gudavalli, Ravi↗
DOE OSTI2019

Study of the Influence of Xanthate Derivative Structures on Copper Sulfide Mineral Adsorption Under Acidic Conditions

Adsorption of commercial xanthate derivatives on copper sulfide mineral (covellite, CuS) was studied by kinetics and isotherm adsorption experiments. The adsorption of xanthate derivatives was confirmed by FTIR (Fourier transform infrared spectroscopy) and XPS (X-ray photoelectron spectroscopy) results. Experiments were performed with two different xanthate derivatives, C-4410 (O-pentyl S-2-propenyl ester) and C-4940 (isobutyl xanthogen ethyl formate), on individual doses of 0.05 g of powdered covellite. It was found that the equilibrium times at pH 2, 4, and 6 were different for both xanthate derivatives. The shortest times were achieved at pH 2 and 4. The results suggest that C-4110 can be used as collector in a wide range of pH, while C-4940 is limited to lower pH values. Pseudo first- and pseudo second-order kinetics models were thus applied to the experimental data for pH 2. The information obtained from the kinetics models combined with XPS allowed proposing the adsorption mechanism for the covellite-xanthate derivative pair. The adsorption takes place through a non-covalent interaction for C-4410 and chemisorption process for C-4940. The best-fitting isotherm models for C-4410 and C-4940 adsorption were Redlich–Peterson and Freundlich, respectively, which yield a maximum adsorption capacity of 57.07 mg g{sup −1} for C-4410 and 44.62 mg g{sup −1} for C-4940.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Effects of cell condition, pH, and temperature on lead, zinc, and copper sorption to Acidithiobacillus caldus strain BC13

This study describes the effects of cell condition, pH, and temperature on lead, zinc, and copper sorption to Acidithiobacillus caldus strain BC13 with a Langmuir model. Copper exhibited the highest loading capacity, 4.76 ± 0.28 mmol g-1, to viable cells at pH 5.5. The highest kL (binding-site affinity) observed was 61.2 ± 3.0 L mmol-1 to dehydrated cells at pH 4.0. The pHs that maximized loading capacities and binding-site affinities were generally between 4.0 and 5.5, where the sum of free-proton and complexed-metal concentrations was near a minimum. Of additional importance, lead, zinc, and copper sorbed to viable cells at pH values as low as 1.5. Previous studies with other acidithiobacilli did not measure viable-cell sorption below pH 4.0. In separate experiments, desorption studies showed that far less copper was recovered from viable cells than any other metal or cell condition, suggesting that uptake may play an important role in copper sorption by At. caldus strain BC13. To reflect an applied system, the sorption of metal mixtures was also studied. In these experiments, lead, zinc, and copper sorption from a tertiary mixture were 40.2 ± 4.3%, 28.7 ± 3.8%, and 91.3 ± 3.0%, respectively, of that sorbed in single-metal systems.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2011

Grinding Wear Behaviour of Stepped Austempered Ductile Iron as Media Material During Comminution of Iron Ore in Ball Mills

An attempt has been made to evaluate the suitability of austempered ductile iron (ADI) as media material for grinding iron ore in a ball mill. Spheroidal graphite (S.G) iron balls are austenitised at 900 deg. C for 60 minutes and given stepped austempering treatment at 280 deg. C for 30 minutes and 60 minutes followed by 380 deg. C for 60 minutes in each case. These materials are characterised by measuring hardness, analysing X-ray diffraction (X-RD), studying microstructure using optical and scanning electron microscope (SEM). Grinding wear behaviour of these materials was assessed for wear loss in wet condition at different pH value of the mineral slurry and found that the wear rate of grinding media material decreases with increase in pH of the slurry. The wear resistance of ADI balls were compared with forged En31 steel balls and found that the stepped austempered ductile iron is superior to forged En31 steel balls.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Leaching behaviour of low Ca:Si ratio CaO–SiO{sub 2}–H{sub 2}O systems

A dynamic leaching study of the dissolution of low calcium to silicon ratio (C/S) calcium–silicate–hydrate (C–S–H) systems with initial C/S ranging from 0.2 to 0.6 has been undertaken. Dissolution was studied in demineralised water at 25 °C to a degree of leaching of 2.5 m{sup 3} kg{sup −1}. These C–S–H gels show remarkably similar behaviour during early leaching stages, giving an equilibrated pH of ~ 9.9 and a solution phase C/S of ~ 0.29. Over longer times, C–S–H gels with C/S > 0.29 evolve, on leaching, towards a congruent dissolution point with a solid C/S close to 0.84 (consistent with tobermorite) and pH ~ 10.8. C–S–H gels with C/S < 0.29 become increasingly silica-rich on leaching but maintain an alkaline pH > 9.5 down to at least C/S = 0.07 (the lowest ratio reached). For C/S < 0.7, chemical modelling and X-ray diffraction data support an explanation of the incongruent dissolution behaviour of the low C/S C–S–H gels based on the congruent dissolution of distinct amorphous silica and tobermorite-like C–S–H phases. Above C/S of 0.7, the dissolution data are well described by an ideal solid solution model for the C–S–H phases. These results are of relevance to the consideration of the disposal of silica-rich vitrified intermediate-level radioactive wastes in cement-based concepts for geological disposal, where maintenance of alkaline pH values forms a key component of the chemical barrier to radionuclide migration. The implications are that the long-term pH buffering capacity provided by cementitious backfill materials would not be significantly affected by interactions with silica-rich wasteforms, which may lower the net C/S ratio of C–S–H phases, due to the natural tendency of these systems to restore congruent dissolution at pH 10.8.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Photocatalytic activity of 3D flower-like MoS2 hemispheres

Highlights: • The ultrathin MoS{sub 2} nano-sheet assembled 3D flower-like MoS{sub 2} hemispheres were prepared via hydrothermal method. • The bandgap of as-synthesized MoS{sub 2} is about 2.05 eV, resulting in a broad absorption in the visible range. • The photocatalyst of MoS{sub 2} present the optimal catalytic property under mild acidity. - Abstract: The novel 3D flower-like MoS{sub 2} hemispheres assembled by ultrathin MoS{sub 2} nano-sheet petals have been successfully prepared via a facile hydrothermal method using CTAB as surfactant. The crystal structure and morphology of the as-synthesized MoS{sub 2} samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR), Raman spectra and scanning electron microscopy (SEM). Moreover the microstructure and the optical properties of MoS{sub 2} samples were also measured by transmission electron microscopy (TEM) and the UV–vis diffuse reflectance spectra (DRS). The photocatalytic performance of the flower-like MoS{sub 2} hemispheres were evaluated through the degradation of Rhodamine (RhB) and methylene blue (MB) solutions, and the stabilities of photo-catalysts were also studied through the three cycles of experiments. The effects on photo-catalytic performance from the initial pH values (3–9) of RhB and MB solutions were also investigated, indicating the samples present the optimal catalytic property at pH = 5.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Photocatalytic hydrogen generation over porous ZnIn{sub 2}S{sub 4} microspheres synthesized via a CPBr-assisted hydrothermal method

Graphical abstract: ZnIn{sub 2}S{sub 4} porous microspheres were synthesized via a cetylpyridinium bromide (CPBr)-assisted hydrothermal method. It could be seen from the SEM image that the flowerlike microspheres were composed of numerous nanosheets. Many slit-like pores were formed among the curved nanosheets. The porous structure benefited the adsorption of reactants, the diffuseness of products, the charge separation on surface, the transfer of the interfacial charge carriers and the charge carrier trapping. And porous ZnIn{sub 2}S{sub 4} photocatalyst exhibited higher photocatalytic activity than nonporous ZnIn{sub 2}S{sub 4} material. Highlights: {yields} A series of unique flower-like porous ZnIn{sub 2}S{sub 4} microspheres of hexagonal crystal phase as efficient visible-light photocatalysts have been synthesized through CPBr-assisted hydrothermal method. {yields} The CPBr addition would visibly influence the self-assemble growing and the crystal structure including the position and intensity of some peaks. {yields} We also found that the pH value plays a crucial role in the formation of ZnIn{sub 2}S{sub 4} porous microspheres and the influence of the pH on the structure of product has been first reported in our paper. {yields} The results showed that our as-synthesized porous ZnIn{sub 2}S{sub 4} microspheres possessed a specific surface area of 165.4 m{sup 2} g{sup -1} and performed higher visible-light photocatalytic activity than bulk ZnIn{sub 2}S{sub 4} for hydrogen evolution. The maximum H{sub 2} evolution rate of ZnIn{sub 2}S{sub 4} reaches 1544.8 {mu}mol/(h g). -- Abstract: Hexagonal ZnIn{sub 2}S{sub 4} porous microspheres were synthesized via a cetylpyridinium bromide (CPBr)-assisted hydrothermal method. The structure, morphology and optical property of these prepared products were characterized by wide angle X-ray diffraction (WAXRD), small angle X-ray diffraction (SAXRD), UV-Vis diffusive reflectance spectroscopy (DRS), field emission scanning electron microscopy (FESEM), energy dispersive X-ray analyzer (EDX) and nitrogen sorption analysis. The effects of CPBr and pH on the crystal structure, morphology and photocatalytic activity of ZnIn{sub 2}S{sub 4} products were studied. The results demonstrated that the flowerlike ZnIn{sub 2}S{sub 4} microspheres, which were composed of numerous nanosheets, performed higher visible-light photocatalytic activity than bulk ZnIn{sub 2}S{sub 4} for hydrogen evolution. The CPBr addition influenced the crystal structure including the position and intensity of some peaks. Furthermore, the pH played a crucial role in the formation of ZnIn{sub 2}S{sub 4} porous microspheres. The as-synthesized porous ZnIn{sub 2}S{sub 4} microspheres possessed the specific surface area of 165.4 m{sup 2} g{sup -1} and the slit-like porous configuration, which was beneficial to photocatalytic reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Polyethyleneimine modified bentonite for the adsorption of amino black 10B

The modified bentonite with a graft amount of 30% was prepared by polyethylenimine reacting with the epoxy bonds on the molecular of (3-Glycidyloxypropyl) trimethoxysilane and being grafted on the bentonite to remove amino black10B. The effects of pH, time, temperature and concentration on the adsorption capacity were studied. As the pH value increases from 3 to 10, the adsorption capacity decreased from 264.5 to 140.4 mg/g. The adsorption process reached equilibrium at 90 min when pH=3. The adsorption kinetics indicates that the adsorption process was very fast and in accordance with the secondary adsorption kinetics. The data about thermodynamic equilibrium was consistent with the Langmuir model. The adsorption process mainly depended on electrostatic attraction and hydrogen bonding and the adsorption data of Bent-PGLYMO-PEI showed that the maximum adsorption capacity reached 327.7 mg/g. - Graphical abstract: Bent-PGLYMO-PEI has been synthesized and exhibited a high adsorption capacity on amino black 10B due to electrostatic interaction between polyethyleneimine and amino black 10B. Display Omitted - Highlights: • The composite material is covalently bonded and stable. • Each repeating unit of polyethyleneimine has a plurality of adsorption sites. • Bent-GLYMO-PEI has a faster adsorption rate and a higher adsorption capacity for amino black 10B.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Examination of Simulated Non-Compliant Waste from Hanford Single-Shell Tanks

This report summarizes the electrochemical testing results for the aggressive layers testing recommended by the single-shell tank integrity expert panel. From single-shell chemistry data, 39 layers were identified as possible aggressive waste layers and were grouped by aggressive ion and inhibitor ions. From those groups 18 segments were identified as representative segments and tested. The testing reported here showed pitting corrosion for six aggressive layers, and one layer showed a propensity for crevice corrosion. In these cases there was a lack of inhibitors, an abundance of aggressive ions, or both. A good prediction for pitting corrosion could be made by considering the pH value of the layer. When the pH was less than 12, there was a high probability for pitting to occur. However, the pH of the solution was not always an indicator, and the inhibitor ion and aggressive ion concentrations then needed to be considered.

Wyrwas, Richard↗
NASA NTRS1985

Dicyclohexylcarbodiimide-sensitive ATPase in Halobacterium saccharovorum

Membranes from Halobacterium saccharovorum contained a cryptic ATPase which required Mg(2+) or Mn(2+) and was activated by Triton X-100. The optimal pH for ATP hydrolysis was 9-10. ATP or GTP were hydrolyzed at the same rate while ITP, CTP, and UTP were hydrolyzed at about half that rate. The products of ATP hydrolysis were ADP and phosphate. The ATPase required high concentrations (3.5 M) of NaCl for maximum activity. ADP was a competitive inhibitor of the activity, with an apparent Ki of 50 micro-M. Dicyclohexylcarbodiimide (DCCD) inhibited ATP hydrolysis. The inhibition was marginal at the optimum pH of the enzyme. When the ATPase was preincubated with DCCD at varying pH values, but assayed at the optimal pH for activity, DCCD inhibition was observed to increase with increasing acidity of the preincubation medium. DCCD inhibition was also dependent on time of preincubation, and protein and DCCD concentrations. When preincubated at pH 6.0 for 4 h at a protein:DCCD ratio of 40 (w/w), ATPase activity was inhibited 90 percent.

Kristjansson, H.↗
DOE OSTI2018

Reaction mechanism of magnesium potassium phosphate cement with high magnesium-to-phosphate ratio

Understanding reaction mechanisms of magnesium potassium phosphate (MKP) cement is of significant importance, as it is closely related to the optimum design of MKP cement-based materials. In this study, reaction mechanisms of MKP cements with a high magnesium-to-phosphate (Mg/PO{sub 4}) molar ratio of 8 were investigated at two different water-to-solid (w/s) ratios of 0.5 and 5. The experimental findings show that the use of this high Mg/PO{sub 4} molar ratio suppresses the formation of potassium-free magnesium phosphate hydrates. K-struvite is mainly formed with probably more phosphate than the theoretical value. Moreover, the w/s ratio plays a crucial role on governing the reaction path of MKP cements. The lower w/s ratio (w/s = 0.5) leads to higher potassium concentration and pH value, thus suppressing the formation of intermediate product, Mg{sub 2}KH(PO{sub 4}){sub 2}·15H{sub 2}O, which is formed at the higher w/s = 5. However, it causes the formation of minor amount of brucite at 28 d, which coexists with K-struvite in the paste.

36 MATERIALS SCIENCE↗
DOE OSTI2012

pH Dependence of the Photoactive Yellow Protein Photocycle Investigated by Time-Resolved Crystallography

Visualizing the three-dimensional structures of a protein during its biological activity is key to understanding its mechanism. In general, protein structure and function are pH-dependent. Changing the pH provides new insights into the mechanisms that are involved in protein activity. Photoactive yellow protein (PYP) is a signaling protein that serves as an ideal model for time-dependent studies on light-activated proteins. Its photocycle is studied extensively under different pH conditions. However, the structures of the intermediates remain unknown until time-resolved crystallography is employed. With the newest beamline developments, a comprehensive time series of Laue data can now be collected from a single protein crystal. This allows us to vary the pH. Here we present the first structure, to our knowledge, of a short-lived protein-inhibitor complex formed in the pB state of the PYP photocycle at pH 4. A water molecule that is transiently stabilized in the chromophore active site prevents the relaxation of the chromophore back to the trans configuration. As a result, the dark-state recovery is slowed down dramatically. At pH 9, PYP stops cycling through the pB state altogether. The electrostatic environment in the chromophore-binding site is the likely reason for this altered kinetics at different pH values.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Hydrothermal solubility of Dy hydroxide as a function of pH and stability of Dy hydroxyl aqueous complexes from 25 to 250 °C

The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize the thermodynamic properties of Dy 3+ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ f G° T ) derived for Dy 3+ and DyOH 2+ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO 4 solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K s0 ) and formation constants for the hydrolysis of Dy (β n with n = 1 to 3; Dy 3+ + nOH – = DyOH n 3-n ) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy 3+ aqua ions and the DyOH 2+ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.

58 GEOSCIENCES↗
DOE OSTI2016

Double-gated Si NW FET sensors: Low-frequency noise and photoelectric properties

The transport, noise, and photosensitivity properties of an array of silicon nanowire (NW) p{sup +}-p-p{sup +} field-effect transistors (FETs) are investigated. The peculiarities of photosensitivity and detectivity are analyzed over a wide spectrum range. The absorbance of p-Si NW shifts to the short wavelength region compared with bulk Si. The photocurrent and photosensitivity reach increased values in the UV range of the spectrum at 300 K. It is shown that sensitivity values can be tuned by the drain-source voltage and may reach record values of up to 2–4 A/W at a wavelength of 300 nm at room temperature. Low-frequency noise studies allow calculating the photodetectivity values, which increase with decreasing wavelength down to 300 nm. We show that the drain current of Si NW biochemical sensors substantially depends on pH value and the signal-to-noise ratio reaches the high value of 10{sup 5}. Increasing pH sensitivity with gate voltage is revealed for certain source-drain currents of pH-sensors based on Si NW FETs. The noise characteristic index decreases from 1.1 to 0.7 with the growth of the liquid gate voltage. Noise behavior is successfully explained in the framework of the correlated number-mobility unified fluctuation model. pH sensitivity increases as a result of the increase in liquid gate voltage, thus giving the opportunity to measure very low proton concentrations in the electrolyte medium at certain values of the liquid gate voltage.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗