Solubility of jarosite solid solutions precipitated from acid mine waters, Iron Mountain, California

USGS Publications Warehouse

Alpers, Charles N.; Nordstrom, D. Kirk; Ball, J.W.

1989-01-01

Because of the common occurrence of 15 to 25 mole percent hydronium substitution on the alkali site in jarosites, it is necessary to consider the hydronium content of jarosites in any attempt at rigorous evaluation of jarosite solubility or of the saturation state of natural waters with respect to jarosite. A Gibbs free energy of 3293.5±2.1 kJ mol-1 is recommended for a jarosite solid solution of composition K.77Na.03(H3O).20Fe3(SO4)2(OH)6. Solubility determinations for a wider range of natural and synthetic jarosite solid solutions will be necessary to quantify the binary and ternary mixing parameters in the (K-Na-H3O) system. In the absence of such studies, molar volume data for endmember minerals indicate that the K-H3O substitution in jarosite is probably closer to ideal mixing than either the Na-K or Na-H3O substitution.

Theoretical Analysis of Drug Dissolution: I. Solubility and Intrinsic Dissolution Rate.

PubMed

Shekunov, Boris; Montgomery, Eda Ross

2016-09-01

The first-principles approach presented in this work combines surface kinetics and convective diffusion modeling applied to compounds with pH-dependent solubility and in different dissolution media. This analysis is based on experimental data available for approximately 100 compounds of pharmaceutical interest. Overall, there is a linear relationship between the drug solubility and intrinsic dissolution rate expressed through the total kinetic coefficient of dissolution and dimensionless numbers defining the mass transfer regime. The contribution of surface kinetics appears to be significant constituting on average ∼20% resistance to the dissolution flux in the compendial rotating disk apparatus at 100 rpm. The surface kinetics contribution becomes more dominant under conditions of fast laminar or turbulent flows or in cases when the surface kinetic coefficient may decrease as a function of solution composition or pH. Limitations of the well-known convective diffusion equation for rotating disk by Levich are examined using direct computational modeling with simultaneous dissociation and acid-base reactions in which intrinsic dissolution rate is strongly dependent on pH profile and solution ionic strength. It is shown that concept of diffusion boundary layer does not strictly apply for reacting/interacting species and that thin-film diffusion models cannot be used quantitatively in general case. Copyright © 2016. Published by Elsevier Inc.

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

NASA Astrophysics Data System (ADS)

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; Chorover, Jon; O'Day, Peggy A.

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium (U) concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this work, the dissolution rates of K- and Na-compreignacite (K2(UO2)6O4(OH)6·8H2O and Na2(UO2)6O4(OH)6·8H2O, respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved carbonate concentration (ca. 0.2 and 2.8 mmol L-1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area, and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total U mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved U was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

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

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE PAGES

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; ...

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered

From Nm-Scale Measurements Of Mineral Dissolution Rate To Overall Dissolution Rate Laws: A Case Study Based On Diopside

NASA Astrophysics Data System (ADS)

Daval, D.; Saldi, G.; Hellmann, R.; Knauss, K.

2011-12-01

While we expect conventional reactive transport simulations to provide reliable estimations of the evolution of fluid-rock interactions over time scales of centuries and even more, recent experimental studies showed that they could hardly be satisfactorily used on simplified systems (e.g. batch carbonation experiments on single minerals), on time scales of weeks [1]. Among the reasons for such inconsistencies is the nature of the rate laws used in the geochemical codes, which heavily relies on our description of the fundamental mechanisms involved during water(-CO2)-mineral reactions. Silicate dissolution constitutes a key step of GCS processes. Whereas the dissolution rate of silicate minerals has been extensively studied at far-from-equilibrium conditions, extrapolating such rates over a broad range of solution composition relevant for GCS has proven challenging. Regarding diopside, recent studies [2, 3] suggested that below 125 °C, an unexpected drop of the rate occurred for Gibbs free energies of reaction (ΔGr) as low as -76 kJ.mol-1, with severe consequences on our ability to predict the rate of complex processes such as carbonation reactions [3]. The mechanism responsible for such a drop remains unclear and therefore needs to be deciphered. An examination of our previous data [3] led us to envisage that two different, non-exclusive aspects were worth investigating: (i) the possible passivating ability of interfacial, nm-thick Si-rich layers developed on weathered silicate surface, and (ii) the stop of etch pits formation on crystal surface, each mechanism being found to be responsible for drops of olivine [1] and albite [4] dissolution rates, respectively. Our ongoing experiments aim at better constraining these two mechanisms, and determining in turn whether one of them could explain the above-mentioned drop of diopside dissolution rate. Classical flow-through experiments with controlled SiO2(aq) concentrations are combined with both ex situ AFM and VSI

Reduction of jarosite by Shewanella oneidensis MR-1 and secondary mineralization

NASA Astrophysics Data System (ADS)

Bingjie, Ouyang; Xiancai, Lu; Huan, Liu; Juan, Li; Tingting, Zhu; Xiangyu, Zhu; Jianjun, Lu; Rucheng, Wang

2014-01-01

Jarosite is a common mineral in a variety of environments formed by the oxidation of iron sulfide normally accompanying with the generation of acid mine drainage (AMD) in mining areas or acid rock drainages (ARD) in many localities. Decomposition of jarosite by dissimilatory iron reducing bacteria (DIRB) influences the mobility of many heavy metals generally accommodated in natural jarosite. This study examined the anaerobic reduction of synthesized jarosite by Shewanella oneidensis strain MR-1, a typical facultative bacteria. The release of ferrous and ferric ion, as well as sulfate and potassium, in the inoculated experimental group lasting 80 days is much higher than that in abiotic control groups. The detection of bicarbonate and acetate in experimental solution further confirms the mechanism of microbial reduction of jarosite, in which lactate acts as the electron donor. The produced ferrous iron stimulates the subsequent secondary mineralization, leading to precipitation and transformation of various iron-containing minerals. Green rust and goethite are the intermediate minerals of the microbial reduction process under anoxic conditions, and the end products include magnetite and siderite. In aerobic environments, goethite, magnetite and siderite were also detected, but the contents were relatively lower. While in abiotic experiments, only goethite has been detected as a product. Thus, the microbial reduction and subsequent mineral transformation can remarkably influence the geochemical cycling of iron and sulfur in supergene environments, as well as the mobility of heavy metals commonly accommodated in jarosite.

CALCIUM CARBONATE DISSOLUTION RATE IN LIMESTONE CONTACTORS

EPA Science Inventory

The rate of carbonate mineral dissolution from limestone was studied using a rotating disk apparatus and samples of limestone of varied composition. The purpose of this study was to determine the effect of limestone composition on the kinetics of carbonate mineral dissolution. Th...

The origin of jarosite associated with a gossan on Archean gneiss in Southwest Greenland

NASA Astrophysics Data System (ADS)

Peng, Y.; Pratt, L. M.; Young, S. A.; Cadieux, S. B.; White, J. R.

2013-12-01

The mineral Jarosite [KFe3(SO4)2(OH)6] since its discovery, by Opportunity rover at Meridiani Planum on Mars, has been the subject of intense geochemical and environmental study over the last 5-10 years. Jarosite requires highly acidic, K-enriched, and oxidizing aqueous conditions for formation. Stable isotopes of O, H, and S of jarosite have the ability to record the temperatures of formation, environments of deposition, fluids, and fluid/atmospheric interactions. Therefore, the origin of jarosite is important for understanding present and past environmental conditions on Mars. Unfortunately, the origin of jarosite on Mars remains unclear. Jarosite is commonly found on Earth in the weathering zones of pyrite-bearing ore deposits, near-surface playa sediments in acid-saline lakes, or epithermal environments and hot springs. Here, we report the occurrence of jarosite in association with a gossan overlying weathered Archean gneiss and Paleoproterozoic mafic dikes at the ice-free margin of southwestern Greenland. In our 2012 field campaign, we excavated soil pits to a depth of 40 cm with a high vertical sampling resolution. No visible pyrite was found in the nearby outcroppings of gneiss in the field. XRD data show that all samples were composed of anorthite, quartz, albite, jarosite, muscovite, and microcline. Jarosite was the only sulfur-bearing mineral identified by XRD, with abundance of jarosite increasing with depth (up to 8.4 wt. %) in the soil pits. Water soluble and acid soluble sulfate were sequentially extracted using 10% NaCl and 2N HCl solutions, respectively. Pyrite was then subsequently extracted from insoluble residues by a chromium reduction method. The average abundance of water soluble sulfate, acid soluble sulfate, and pyrite were 100 ppm, 7 wt. %, and 10 ppm, respectively. The δ34S values of water soluble sulfate, acid soluble sulfate, and pyrite range from -0.7‰ to 3.1‰ (average= 1.5‰), -1.2 to 1.5‰ (average= 0.7‰), and 0.3‰ to 6.7�

Kagomé lattices as cathode: Effect of particle size and fluoride substitution on electrochemical lithium insertion in sodium- and ammonium Jarosites

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

Sandineni, Prashanth; Yaghoobnejad Asl, Hooman; Choudhury, Amitava, E-mail: choudhurya@mst.edu

Highly crystalline sodium and ammonium Jarosites, NaFe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6} and NH{sub 4}Fe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6}, have been synthesized employing hydrothermal synthesis routes. The structures consist of anionic layers of vertex-sharing FeO{sub 6} octahedra and SO{sub 4} tetrahedral units with interlayer space occupied by Na and ammonium ions, respectively. The corner-sharing FeO{sub 6} octahedral units form six and three rings similar to hexagonal tungsten bronze sheets also known as kagomé lattice. These sodium and ammonium Jarosites are thermally stable up to 400 °C and undergo facile electrochemical lithium insertion through the reduction of Fe{sup 3+} to Fe{sup 2+}.more » Galvanostatic charge–discharge indicates that up to 2.25 and 2 lithium ions per formula unit can be inserted at an average voltage of 2.49 and 2.26 V to the sodium and the ammonium Jarosites, respectively, under slow discharge rate of C/50. The cycle-life and experimental achievable capacity show strong dependence on particle sizes and synthesis conditions. A small amount of fluoride substitution improves both achievable capacity and average voltage. - Graphical abstract: Discharge capacity of jarosite phases as a function of particle size and fluoride substitution. - Highlights: • Synthesis of natro- and ammonium Jarosites. • Jarosites as cathodes for lithium ion batteries. • Li-ion electrochemistry of Jarosites. • Mössbauer spectroscopy of Jarosites.« less

Effects of Bacillus subtilis endospore surface reactivity on the rate of forsterite dissolution

NASA Astrophysics Data System (ADS)

Harrold, Z.; Gorman-Lewis, D.

2013-12-01

Primary mineral dissolution products, such as silica (Si), calcium (Ca) and magnesium (Mg), play an important role in numerous biologic and geochemical cycles including microbial metabolism, plant growth and secondary mineral precipitation. The flux of these and other dissolution products into the environment is largely controlled by the rate of primary silicate mineral dissolution. Bacteria, a ubiquitous component in water-rock systems, are known to facilitate mineral dissolution and may play a substantial role in determining the overall flux of dissolution products into the environment. Bacterial cell walls are complex and highly reactive organic surfaces that can affect mineral dissolution rates directly through microbe-mineral adsorption or indirectly by complexing dissolution products. The effect of bacterial surface adsorption on chemical weathering rates may even outweigh the influence of active processes in environments where a high proportion of cells are metabolically dormant or cell metabolism is slow. Complications associated with eliminating or accounting for ongoing metabolic processes in long-term dissolution studies have made it challenging to isolate the influence of cell wall interactions on mineral dissolution rates. We utilized Bacillus subtilis endospores, a robust and metabolically dormant cell type, to isolate and quantify the effects of bacterial surface reactivity on forsterite (Mg2SiO4) dissolution rates. We measured the influence of both direct and indirect microbe-mineral interactions on forsterite dissolution. Indirect pathways were isolated using dialysis tubing to prevent mineral-microbe contact while allowing free exchange of dissolved mineral products and endospore-ion adsorption. Homogenous experimental assays allowed both direct microbe-mineral and indirect microbe-ion interactions to affect forsterite dissolution rates. Dissolution rates were calculated based on silica concentrations and zero-order dissolution kinetics

Effect of oxalate on the dissolution rates of oligoclase and tremolite

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

Mast, M.A.; Drever, J.I.

1987-09-01

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22/sup 0/C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of release ofmore » Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si. Large transient spikes of Al or Si are observed when oxalate is added to or removed from the system. The cause of the spikes is unknown; the authors suggest adsorption feldspar surfaces away from sites of active dissolution as a possibility. The rate of dissolution of tremolite is independent of pH over the pH range 2-5, and decreases at higher pH. The rate of dissolution of oligoclase in these experiments was independent of pH over the pH range 4-9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.« less

Estimation of dissolution rate from in vivo studies of synthetic vitreous fibers.

PubMed

Eastes, W; Potter, R M; Hadley, J G

2000-11-01

Although the dissolution rate of a fiber was originally defined by a measurement of dissolution in simulated lung fluid in vitro, it is feasible to determine it from animal studies as well. The dissolution rate constant for a fiber may be extracted from the decrease in long fiber diameter observed in certain intratracheal instillation experiments or from the observed long fiber retention in short-term biopersistence studies. These in vivo dissolution rates agree well with those measured in vitro for the same fibers. For those special types of fibers, the high-alumina rock wool fibers that could not be measured in vitro, the method provides a way of obtaining a chemical dissolution rate constant from an animal study. The inverse of the in vivo dissolution rate, the fiber dissolution time, correlates well with the weighted half life of long fibers in a biopersistence study, and the in vivo dissolution rate may be estimated accurately from this weighted half-life.

Feldspar dissolution rates in the Topopah Spring Tuff, Yucca Mountain, Nevada

USGS Publications Warehouse

Bryan, C.R.; Helean, K.B.; Marshall, B.D.; Brady, P.V.

2009-01-01

Two different field-based methods are used here to calculate feldspar dissolution rates in the Topopah Spring Tuff, the host rock for the proposed nuclear waste repository at Yucca Mountain, Nevada. The center of the tuff is a high silica rhyolite, consisting largely of alkali feldspar (???60 wt%) and quartz polymorphs (???35 wt%) that formed by devitrification of rhyolitic glass as the tuff cooled. First, the abundance of secondary aluminosilicates is used to estimate the cumulative amount of feldspar dissolution over the history of the tuff, and an ambient dissolution rate is calculated by using the estimated thermal history. Second, the feldspar dissolution rate is calculated by using measured Sr isotope compositions for the pore water and rock. Pore waters display systematic changes in Sr isotopic composition with depth that are caused by feldspar dissolution. The range in dissolution rates determined from secondary mineral abundances varies from 10-16 to 10-17 mol s-1 kg tuff-1 with the largest uncertainty being the effect of the early thermal history of the tuff. Dissolution rates based on pore water Sr isotopic data were calculated by treating percolation flux parametrically, and vary from 10-15 to 10-16 mol s-1 kg tuff-1 for percolation fluxes of 15 mm a-1 and 1 mm a-1, respectively. Reconciling the rates from the two methods requires that percolation fluxes at the sampled locations be a few mm a-1 or less. The calculated feldspar dissolution rates are low relative to other measured field-based feldspar dissolution rates, possibly due to the age (12.8 Ma) of the unsaturated system at Yucca Mountain; because oxidizing and organic-poor conditions limit biological activity; and/or because elevated silica concentrations in the pore waters (???50 mg L-1) may inhibit feldspar dissolution. ?? 2009 Elsevier Ltd. All rights reserved.

Stable Isotope Characteristics of Jarosite: The Acidic Aqueous History of Mars

NASA Technical Reports Server (NTRS)

Earl, Lyndsey D.

2005-01-01

The Mars Rover Opportunity found jarosite (Na(+) or K(+))Fe3SO4(OH)6 at the Meridiani Planum site. This mineral forms from the evaporation of an aqueous acidic sulfate brine. Oxygen isotope compositions may characterize formation conditions but subsequent isotope exchange may have occurred between the sulfate and hydroxide of jarosite and water. The rate of oxygen isotope exchange depends on the acidity and temperature of the brine, but it has not been investigated in detail. We performed laboratory experiments to determine the rate of oxygen isotope exchange under varying acidities and temperatures to learn more about this process. Barium sulfate samples were precipitated weekly from acidic sodium sulfate brines. The oxygen isotope composition of the precipitated sulfate was obtained using a Finnigan MAT253 Isotope Ratio Mass-Spectrometer. The results show that water was trapped in barium sulfate during precipitation. Trapped water may exchange with sulfate when exposed to high temperatures, thus changing the isotope composition of sulfate and the observed fractionation factor of oxygen isotope exchange between sulfate and water. The results of our research will contribute to the understanding of oxygen isotope exchange rates between water and sulfate under acidic conditions and provide experimental knowledge for the dehydration of barium sulfate samples.

Revisiting classical silicate dissolution rate laws under hydrothermal conditions

NASA Astrophysics Data System (ADS)

Pollet-Villard, Marion; Daval, Damien; Saldi, Giuseppe; Knauss, Kevin; Wild, Bastien; Fritz, Bertrand

2015-04-01

In the context of geothermal energy, the relative intensities of primary mineral leaching and secondary mineral precipitation can affect porosity and permeability of the reservoir, thereby influencing its hydraulic performance and the efficiency of the geothermal power station. That is why the prediction of reaction kinetics of fluid/rock interactions represents a critical issue in this context. Moreover, in several geothermal systems such as the one of Soultz-sous-Forêts (Alsace, France), the circulation of aqueous fluids induces only modest modifications of their chemical composition. Therefore, fluid-rock interactions take place at close-to-equilibrium conditions, where the rate-affinity relations are poorly known and intensively debated [1]. To describe more precisely the dissolution processes, our strategy consists in investigating the dissolution of the main cleavages of K-spar minerals (one of the prevalent primary minerals in the reservoir of Soultz-sous-Forêts geothermal system) over a wide range of Gibbs free energy (ΔG) conditions. The aims are to decipher the impact of crystallographic orientation and microstructural surface modifications on the dissolution kinetics and to propose a relation between K-spar dissolution rate and ΔG. Our experimental work relies on a coupled approach which combines classical experiments of K-spar dissolution monitored by aqueous chemical analyses (ICP-AES) and innovative techniques of nm- to μm-scale characterization of solid surface (SEM, AFM, VSI) [2]. Our results confirm that K-spar dissolution is an anisotropic process: we measure a tenfold factor between the slowest and the fastest-dissolving surfaces. Moreover, the formation of etch pits on surfaces during their alteration has been evidenced on all of the different faces that have been studied. This complex evolution of the surface topography casts doubt of the relevance of a surface model based on shrinking particles and represents a possible cause of an

Calcite dissolution rate spectra measured by in situ digital holographic microscopy.

PubMed

Brand, Alexander S; Feng, Pan; Bullard, Jeffrey W

2017-09-01

Digital holographic microscopy in reflection mode is used to track in situ , real-time nanoscale topography evolution of cleaved (104) calcite surfaces exposed to flowing or static deionized water. The method captures full-field holograms of the surface at frame rates of up to 12.5 s -1 . Numerical reconstruction provides 3D surface topography with vertical resolution of a few nanometers and enables measurement of time-dependent local dissolution fluxes. A statistical distribution, or spectrum, of dissolution rates is generated by sampling multiple area domains on multiple crystals. The data show, as has been demonstrated by Fischer et al. (2012), that dissolution is most fully described by a rate spectrum, although the modal dissolution rate agrees well with published mean dissolution rates ( e.g. , 0.1 µmol m -2 s -1 to 0.3 µmol m -2 s -1 ). Rhombohedral etch pits and other morphological features resulting from rapid local dissolution appear at different times and are heterogeneously distributed across the surface and through the depth. This makes the distribution in rates measured on a single crystal dependent both on the sample observation field size and on time, even at nominally constant undersaturation. Statistical analysis of the inherent noise in the DHM measurements indicates that the technique is robust and that it likely can be applied to quantify and interpret rate spectra for the dissolution or growth of other minerals.

Dissolution Rates of Biogenic Carbonate Sediments from the Bermuda Platform

NASA Astrophysics Data System (ADS)

Finlay, A. J.; Andersson, A. J.

2016-02-01

The contribution of biogenic carbonate sediment dissolution rates to overall net reef accretion/erosion (under both present and future oceanic pCO2 levels) has been strikingly neglected, despite experimental results indicating that sediment dissolution might be more sensitive to ocean acidification (OA) than calcification. Dissolution of carbonate sediments could impact net reef accretion rates as well as the formation and preservation of valuable marine and terrestrial ecosystems. Bulk sediment dissolution rates of samples from the Bermuda carbonate platform were measured in natural seawater at pCO2 values ranging from approximately 3500 μatm to 9000 μatm. This range of pCO2 levels incorporates values currently observed in porewaters on the Bermuda carbonate platform as well as a potential future increase in porewater pCO2 levels due to OA. Sediment samples from two different stations on the reef platform were analyzed for grain size and mineralogy. Dissolution rates of sediments in the dominant grain size fraction of the platform (500-1000 μm) from both stations ranged between 16.25 and 47.19 (± 0.27 to 0.79) μmoles g-1 hr-1 and are comparable to rates previously obtained from laboratory experiments on other natural carbonate sediments. At a pCO2 of 3500 μatm, rates from both samples were similar, despite their differing mineralogy. However, at pCO2 levels above 3500 μatm, the sediment sample with a greater weight percent of Mg-calcite had slightly higher dissolution rates. Despite many laboratory studies on biogenic carbonate dissolution, a significant disparity still exists between laboratory measurements and field observations. Performing additional controlled, laboratory experiments on natural sediment may help to elucidate the reasons for this disparity.

Estimating rock and slag wool fiber dissolution rate from composition.

PubMed

Eastes, W; Potter, R M; Hadley, J G

2000-12-01

A method was tested for calculating the dissolution rate constant in the lung for a wide variety of synthetic vitreous silicate fibers from the oxide composition in weight percent. It is based upon expressing the logarithm of the dissolution rate as a linear function of the composition and using a different set of coefficients for different types of fibers. The method was applied to 29 fiber compositions including rock and slag fibers as well as refractory ceramic and special-purpose, thin E-glass fibers and borosilicate glass fibers for which in vivo measurements have been carried out. These fibers had dissolution rates that ranged over a factor of about 400, and the calculated dissolution rates agreed with the in vivo values typically within a factor of 4. The method presented here is similar to one developed previously for borosilicate glass fibers that was accurate to a factor of 1.25. The present coefficients work over a much broader range of composition than the borosilicate ones but with less accuracy. The dissolution rate constant of a fiber may be used to estimate whether disease would occur in animal inhalation or intraperitoneal injection studies of that fiber.

Anglesite and silver recovery from jarosite residues through roasting and sulfidization-flotation in zinc hydrometallurgy.

PubMed

Han, Haisheng; Sun, Wei; Hu, Yuehua; Jia, Baoliang; Tang, Honghu

2014-08-15

Hazardous jarosite residues contain abundant valuable minerals that are difficult to be recovered by traditional flotation process. This study presents a new route, roasting combined with sulfidization-flotation, for the recovery of anglesite and silver from jarosite residues of zinc hydrometallurgy. Surface appearance and elemental distribution of jarosite residues was examined by scanning electron microscopy and energy dispersive X-ray spectrometry analysis, respectively. Decomposition and transformation mechanisms of jarosite residues were illustrated by differential thermal analysis. Results showed that after roasting combined with flotation, the grade and recovery of lead were 43.89% and 66.86%, respectively, and those of silver were 1.3 kg/t and 81.60%, respectively. At 600-700 °C, jarosite was decomposed to release encapsulated valuable minerals such as anglesite (PbSO4) and silver mineral; silver jarosite decomposed into silver sulfate (Ag2SO4); and zinc ferrite (ZnO · Fe2O3) decomposed into zinc sulfate (ZnSO4) and hematite (Fe2O3). Bared anglesite and silver minerals were modified by sodium sulfide and easily collected by flotation collectors. This study demonstrates that the combination of roasting and sulfidization-flotation provides a promising process for the recovery of zinc, lead, and silver from jarosite residues of zinc hydrometallurgy. Copyright © 2014 Elsevier B.V. All rights reserved.

Calcite dissolution rate spectra measured by in situ digital holographic microscopy

NASA Astrophysics Data System (ADS)

Brand, Alexander S.; Feng, Pan; Bullard, Jeffrey W.

2017-09-01

Digital holographic microscopy in reflection mode is used to track in situ, real-time nanoscale topography evolution of cleaved (104) calcite surfaces exposed to flowing or static deionized water. The method captures full-field holograms of the surface at frame rates of up to 12.5 s-1. Numerical reconstruction provides 3D surface topography with vertical resolution of a few nanometers and enables measurement of time-dependent local dissolution fluxes. A statistical distribution, or spectrum, of dissolution rates is generated by sampling multiple area domains on multiple crystals. The data show, as has been demonstrated by Fischer et al. (2012), that dissolution is most fully described by a rate spectrum, although the modal dissolution rate agrees well with published mean dissolution rates (e.g., 0.1 μmol m-2 s-1 to 0.3 μmol m-2 s-1). Rhombohedral etch pits and other morphological features resulting from rapid local dissolution appear at different times and are heterogeneously distributed across the surface and through the depth. This makes the distribution in rates measured on a single crystal dependent both on the sample observation field size and on time, even at nominally constant undersaturation. Statistical analysis of the inherent noise in the DHM measurements indicates that the technique is robust and that it likely can be applied to quantify and interpret rate spectra for the dissolution or growth of other minerals.

The Positive Environmental Contribution of Jarosite by Retaining Lead in Acid Mine Drainage Areas

PubMed Central

Figueiredo, Maria-Ondina; da Silva, Teresa Pereira

2011-01-01

Jarosite, KFe3(SO4)2(OH)6, is a secondary iron sulphate often found in acid mine drainage (AMD) environments, particularly in mining wastes from polymetallic sulphide ore deposits. Despite the negative environmental connotation usually ascribed to secondary sulphate minerals due to the release of hazardous elements to aquifers and soils, jarosite acts as an efficient remover and immobilizer of such metals, particularly lead. The mineral chemistry of jarosite is reviewed and the results of a Fe K-edge XANES (X-Ray Absorption Near-Edge Structure) study of K-, Na- and Pb-jarosite are described and discussed within the context of the abandoned old mines of São Domingos and Aljustrel located in southern Portugal, in the Iberian Pyrite Belt (IPB). PMID:21655138

An upscaled rate law for magnesite dissolution in heterogeneous porous media

NASA Astrophysics Data System (ADS)

Wen, Hang; Li, Li

2017-08-01

Spatial heterogeneity in natural subsurface systems governs water fluxes and residence time in reactive zones and therefore determines effective rates of mineral dissolution. Extensive studies have documented mineral dissolution rates in natural systems, although a general rate law has remain elusive. Here we fill this gap by answering two questions: (1) how and to what extent does spatial heterogeneity affect water residence time and effectively-dissolving surface area? (2) what is the upscaled rate law that quantifies effective dissolution rates in natural, heterogeneous media? With data constraints from experimental work, 240 Monte-Carlo numerical experiments of magnesite dissolution within quartz matrix were run with spatial distributions characterized by a range of permeability variance σ2lnκ (0.5-6.0) and correlation length (2-50 cm). Although the total surface area and global residence time (τa) are the same in all experiments, the water fluxes through reactive magnesite zones varies between 0.7 and 72.8% of the total water fluxes. Highly heterogeneous media with large σ2lnκ and long λ divert water mostly into non-reactive preferential flow paths, therefore bypassing and minimizing flow in low permeability magnesite zones. As a result, the water residence time in magnesite zones (i.e., reactive residence time τa,r) is long and magnesite dissolution quickly reaches local equilibrium, which leads to small effective surface area and low dissolution rates. Magnesite dissolution rates in heterogeneous media vary from 2.7 to 100% of the rates in the equivalent homogeneous media, with effectively-dissolving surface area varying from 0.18 to 6.83 m2 (out of 51.71 m2 total magnesite surface area). Based on 240 numerical experiments and 45 column experiments, a general upscaled rate law in heterogeneous media, RMgCO3,ht =kAe,hm(1 - exp(-τa/τa,r))α, was derived to quantify effective dissolution rates. The dissolution rates in heterogeneous media are a

Charge transfer between biogenic jarosite derived Fe3+and TiO2 enhances visible light photocatalytic activity of TiO2.

PubMed

Chowdhury, Mahabubur; Shoko, Sipiwe; Cummings, Fransciuos; Fester, Veruscha; Ojumu, Tunde Victor

2017-04-01

In this work, we have shown that mining waste derived Fe 3+ can be used to enhance the photocatalytic activity of TiO 2 . This will allow us to harness a waste product from the mines, and utilize it to enhance TiO 2 photocatalytic waste water treatment efficiency. An organic linker mediated route was utilized to create a composite of TiO 2 and biogenic jarosite. Evidence of FeOTi bonding in the TiO 2 /jarosite composite was apparent from the FTIR, EFTEM, EELS and ELNEFS analysis. The as prepared material showed enhanced photocatalytic activity compared to pristine TiO 2 , biogenic jarosite and mechanically mixed sample of jarosite and TiO 2 under both simulated and natural solar irradiation. The prepared material can reduce the electrical energy consumption by 4 times compared to pristine P25 for degradation of organic pollutant in water. The material also showed good recyclability. Results obtained from sedimentation experiments showed that the larger sized jarosite material provided the surface to TiO 2 nanoparticles, which increases the settling rate of the materials. This allowed simple and efficient recovery of the catalyst from the reaction system after completion of photocatalysis. Enhanced photocatalytic activity of the composite material was due to effective charge transfer between TiO 2 and jarosite derived Fe 3+ as was shown from the EELS and ELNEFS. Generation of OH was supported by photoluminesence (PL) experiments. Copyright © 2016. Published by Elsevier B.V.

Effect of oxalate on the dissolution rates of oligoclase and tremolite (journal version)

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

Mast, M.A.; Drever, J.I.

1987-01-01

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22 deg C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of releasemore » of Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si. The rate of dissolution of tremolite is independent of pH over the pH range 2-5, and decreases at higher pH. The rate of dissolution of oligoclase was independent of pH over the pH range 4-9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.« less

Thermodynamics and nucleation mechanism of ammonium jarosite in sulfuric acid solution

NASA Astrophysics Data System (ADS)

Liu, PengFei; Zhang, YiFei; Wang, Li; You, ShaoWei; Bo, Jing

2017-11-01

Jarosite process is one of the most widely used methods in removing Fe, but in which the nucleation mechanism of ammonium jarosite has not been reported. Solubilities of the ammonium jarosite crystals under different Fe2(SO4)3 and (NH4)2SO4 concentrations and under different temperatures were measured, and the experiments of induction periods were systematically investigated in different temperatures (348 k, 358 k and 368 k) and H2SO4 concentrations (9 g/L, 10.8 g/L and 12.6 g/L) by reaction crystallization process based on the thermodynamic equilibrium data. According to the model of classical nucleation theory, the interfacial tension and the surface entropy factors in different conditions were calculated as 1.21 mJ/m2, 1.85 mJ/m2, 1.71 mJ/m2 and 1.51, 1.27, 1.17. The SEM photographs of (H3O, NH4)Fe3(SO4)2(OH)6 approved that the ammonium jarosite crystals were clearly grown by the two-dimensional nucleation mechanism and/or the spiral growth mechanism. But the growth mechanism of (H3O, NH4)Fe3(SO4)2(OH)6 had been determined to be the continuous growth by the surface entropy factor.

Enhancement of Loperamide Dissolution Rate by Liquisolid Compact Technique.

PubMed

Venkateswarlu, Kambham; Preethi, Jami Komala; Chandrasekhar, Kothapalli Bonnoth

2016-09-01

Purpose: The aim of present study was to improve the dissolution rate of poorly soluble drug Loperamide (LPM) by liquisolid compact technique. Methods: Liquisolid compacts of LPM were prepared using Propylene glycol (PG) as a solvent, Avicel pH 102 as carrier, Aerosil as coating material and Sodium Starch Glycolate (SSG) as superdisintegrant. Interactions between the drug and excipients were examined by Fourier Transform Infrared (FTIR) spectroscopy. The dissolution studies for LPM liquisolid formulation, marketed product and pure drug were carried out in pH 1.2 HCl buffer as dissolution media. Results: Results confirmed the absence of chemical interactions between the drug and excipients. From the solubility studies, it was observed the LPM was highly soluble in PG thereby it was selected as a solvent. The dissolution efficiency of LPM at 15 min was increased from 9.99 % for pure drug and 54.57% for marketed product to 86.81% for the tablets prepared by liquisolid compact technique. Stability studies showed no significant change in percent cumulative drug release, hardness, disintegration time, friability and drug content for 3 months. Conclusion: Formulation F2 showed significant increase in dissolution rate compared to the marketed product at pH 1.2 where LPM is largely absorbed. Around 90% of the drug was released from F2 in 30 min compared to the marketed product and it might be due to the increased wetting and surface area of the particles. Hence, the liquisolid compact technique appears to be a promising approach for improving the dissolution rate of poorly soluble drug.

Elevated CO2 affects shell dissolution rate but not calcification rate in a marine snail.

PubMed

Nienhuis, Sarah; Palmer, A Richard; Harley, Christopher D G

2010-08-22

As CO(2) levels increase in the atmosphere, so too do they in the sea. Although direct effects of moderately elevated CO(2) in sea water may be of little consequence, indirect effects may be profound. For example, lowered pH and calcium carbonate saturation states may influence both deposition and dissolution rates of mineralized skeletons in many marine organisms. The relative impact of elevated CO(2) on deposition and dissolution rates are not known for many large-bodied organisms. We therefore tested the effects of increased CO(2) levels--those forecast to occur in roughly 100 and 200 years--on both shell deposition rate and shell dissolution rate in a rocky intertidal snail, Nucella lamellosa. Shell weight gain per day in live snails decreased linearly with increasing CO(2) levels. However, this trend was paralleled by shell weight loss per day in empty shells, suggesting that these declines in shell weight gain observed in live snails were due to increased dissolution of existing shell material, rather than reduced production of new shell material. Ocean acidification may therefore have a greater effect on shell dissolution than on shell deposition, at least in temperate marine molluscs.

Alkaline decomposition of synthetic jarosite with arsenic

PubMed Central

2013-01-01

The widespread use of jarosite-type compounds to eliminate impurities in the hydrometallurgical industry is due to their capability to incorporate several elements into their structures. Some of these elements are of environmental importance (Pb2+, Cr6+, As5+, Cd2+, Hg2+). For the present paper, AsO43- was incorporated into the lattice of synthetic jarosite in order to carry out a reactivity study. Alkaline decomposition is characterized by removal of sulfate and potassium ions from the lattice and formation of a gel consisting of iron hydroxides with absorbed arsenate. Decomposition curves show an induction period followed by a conversion period. The induction period is independent of particle size and exponentially decreases with temperature. The conversion period is characterized by formation of a hydroxide halo that surrounds an unreacted jarosite core. During the conversion period in NaOH media for [OH-] > 8 × 10-3 mol L-1, the process showed a reaction order of 1.86, and an apparent activation energy of 60.3 kJ mol-1 was obtained. On the other hand, during the conversion period in Ca(OH)2 media for [OH-] > 1.90 × 10-2 mol L-1, the reaction order was 1.15, and an apparent activation energy of 74.4 kJ mol-1 was obtained. The results are consistent with the spherical particle model with decreasing core and chemical control. PMID:23566061

The Preservation and Detection of Organic Matter within Jarosite

NASA Astrophysics Data System (ADS)

Lewis, J. M. T.; Eigenbrode, J. L.; McAdam, A.; Andrejkovicova, S. C.; Knudson, C. A.; Wong, G. M.; Millan, M.; Freissinet, C.; Szopa, C.; Li, X.; Bower, D. M.

2017-12-01

Since its arrival at Mt. Sharp in 2014 the Mars Science Laboratory Curiosity rover has been examining the mountain's lower stratigraphy, which shows a progression from clay-bearing to sulfate-bearing strata. Clay minerals are known to be effective long-term preservers of organic matter [1], but it is important to also consider the potential for Martian sulfate minerals to host organic molecules. The Sample Analysis at Mars (SAM) instrument suite on board the rover uses pyrolysis to liberate organic fragments from sampled materials [2]. However, the surface of Mars hosts widespread oxychlorine phases, which thermally decompose to release oxygen and chlorine that can degrade and destroy organic signals [3]. Francois et al. (2016) demonstrated that synthetic magnesium sulfate can incorporate phthalic acid and protect it from oxychlorine phases during pyrolysis [4]. Magnesium sulfate as well as calcium sulfate and jarosite have all been observed by instruments on the rover. The addition of organic standards to the starting materials in jarosite synthesis reactions has conclusively demonstrated that jarosite can incorporate organic molecules. The samples were analyzed by SAM-like evolved gas analysis (EGA) and gas chromatography-mass spectrometry (GC-MS) and the influence of perchlorates assessed. Jarosite has been observed by multiple missions to the Martian surface and from orbit, thus the probability of future organic detection missions encountering the mineral is high. Samples from this study were examined by laser desorption/ionization mass spectrometry and Raman spectroscopy, which will be utilized by the ExoMars rover and Mars 2020 rover respectively. The data inform the sampling and analysis strategies for sulfate-rich regions of Mars for present and future organic-detection missions. [1] Farmer & Des Marais (1999) JGR: Planets 104, [2] Mahaffy et al., (2012) Space Science Reviews 170 [3] Glavin et al., (2013) JGR: Planets 118 [4] Francois et al., (2016) JGR

Glycine identification in natural jarosites using laser desorption Fourier transform mass spectrometry: implications for the search for life on Mars.

PubMed

Kotler, J Michelle; Hinman, Nancy W; Yan, Beizhan; Stoner, Daphne L; Scott, Jill R

2008-04-01

The jarosite group minerals have received increasing attention since the discovery of jarosite on the martian surface by the Mars Exploration Rover Opportunity. Given that jarosite can incorporate foreign ions within its structure, we have investigated the use of jarosite as an indicator of aqueous and biological processes on Earth and Mars. The use of laser desorption Fourier transform mass spectrometry has revealed the presence of organic matter in several jarosite samples from various locations worldwide. One of the ions from the natural jarosites has been attributed to glycine because it was systematically observed in combinations of glycine with synthetic ammonium and potassium jarosites, Na(2)SO(4) and K(2)SO(4). The ability to observe these organic signatures in jarosite samples with an in situ instrumental technique, such as the one employed in this study, furthers the goals of planetary geologists to determine whether signs of life (e.g., the presence of biomolecules or biomolecule precursors) can be detected in the rock record of terrestrial and extraterrestrial samples.

Dissolution Rates and Mineral Lifetimes of Phosphate Containing Minerals and Implications for Mars

NASA Astrophysics Data System (ADS)

Adcock, C. T.; Hausrath, E.

2011-12-01

The objectives of NASA's Mars Exploration Program include exploring the planet's habitability and the possibility of past, present, or future life. This includes investigating "possible supplies of bioessential elements" [1]. Phosphate is one such bioessential element for life as we understand it. Phosphate is also abundant on Mars [2], and the phosphate rich minerals chlorapatite, fluorapatite, and merrillite have been observed in Martian meteorites [3]. Surface rock analyses from the MER Spirit also show the loss of a phosphate rich mineral from the rocks Wishstone and Watchtower at Gusev Crater [4,5], implying mineral dissolution. Dissolution rates of phosphate containing minerals are therefore important for characterizing phosphate mobility and bioavailability on Mars. Previous studies have measured dissolution rates of fluorapatite [6-8]. However, chlorapatite and merrillite (a non-terrestrial mineral similar to whitlockite) are more common phosphate minerals found in Martian meteorites [3], and few dissolution data exist for these minerals. We have begun batch dissolution experiments on chlorapatite, synthesized using methods of [9], and whitlockite, synthesized using a method modified from [10]. Additionally, we are dissolving Durango fluorapatite to compare to dissolution rates in literature, and natural Palermo whitlockite to compare to dissolution rates of our synthesized whitlockite. Batch dissolution experiments were performed after [8], using a 0.01 molar KNO3 solution with 0.1500g-0.3000g mineral powders and starting solution volumes of 180ml in LDPE reaction vessels. HNO3 or KOH were used to adjust initial pH as required. Dissolution rates are calculated from the rate of change of elemental concentration in solution as a function of time, and normalized to the mineral surface area as measured by BET. Resulting rates will be used to calculate mineral lifetimes for the different phosphate minerals under potential Mars-like aqueous conditions, and in

Control of Drug Dissolution Rate from Film Dosage Forms Containing Valsartan.

PubMed

Murata, Yoshifumi; Kofuji, Kyoko; Maida, Chieko

2016-01-01

Film dosage forms (FDs) containing valsartan (VST), a popular antihypertensive drug, were prepared using a casting method with sodium alginate and other polysaccharides as the film base. Drug dissolution profiles of the FDs were investigated in limited medium. The FDs were 170-200 μm thick and were easy to handle. All FDs immediately swelled and disintegrated in the medium. About 23% of the VST incorporated into the FD prepared with 1.5% sodium alginate dissolved at 5 min. The initial dissolution rate of VST increased upon the addition of chitosan to the film base; this effect was not observed in the case of chitin. On the other hand, the rate apparently decreased upon modification with alginic acid. In addition, the solubility of VST in the dissolution medium was changed by the addition of chitosan or alginic acid. FDs prepared with polysaccharides are useful for simplifying the administration of drugs to patients, and the drug dissolution rate from FDs can be controlled by modification.

Rate of production, dissolution and accumulation of biogenic solids in the ocean

NASA Technical Reports Server (NTRS)

Arrhenius, G.

1988-01-01

The equatorial current system, by its response to global circulation changes, provides a unique recording mechanism for long range climatic oscillations. A permanent record of the changes in rate of upwelling and organic production is generated in the equatorial deep sea sediments, particularly by such biogenic components which are unaffected by secondary dissolution. In order to determine the rates of accumulation of various sedimentary components, a reliable differential measurement of age of the strata must be obtained. Various approaches to this problem are reviewed, and sources of error discussed. Secondary dissolution of calcium carbonate introduces a substantial and variable difference between the dissolution-modified, and hence a priori unknown, rate of deposition on one hand and the rate of accumulation, derivable from the observed concentration, on the other. The cause and magnitude of these variations are of importance, particularly since some current dating schemes are based on assumed constancy in the rate of accumulation of this and, in some cases, also all other sedimentary components. The concepts used in rate evaluation are discussed with emphasis on the difference between the state of dissolution, an observable property of the sediment, and the rate of dissolution, a parameter that requires deduction of the carbonate fraction dissolved, and of the time differential. As a most likely cause of the enhanced state of dissolution of the interglacial carbonate sediments is proposed the lowered rates of biogenic production and deposition, which cause longer exposure of the carbonate microfossils to corrosion in the bioturbated surface layer of the sediment. Historical perspective is included in the discussion in view of the dedication of the Symposium to Hans Pettersson, the leader of the Swedish Deep Sea Expedition 1947-1948, an undertaking that opened a new era in deep sea research and planetary dynamics.

The use of ordered mixtures for improving the dissolution rate of low solubility compounds.

PubMed

Nyström, C; Westerberg, M

1986-03-01

The dissolution rate of micronized griseofulvin has been investigated, both for the agglomerated raw material and the material formulated as an ordered mixture, by means of the USP XX paddle method. During the experiments, which were performed at sink condition and constant temperature, the effects of adding a surfactant and of agitation were tested. The ordered mixture with sodium chloride gave a fast dissolution rate, practically independent of the test parameters. Micronized griseofulvin alone gave dissolution profiles that were improved by adding polysorbate 80 and by increased agitation, but the dissolution rates obtained were much lower than those for the ordered mixture. It was concluded that the rate limiting step in the dissolution of griseofulvin as the raw material is the penetration of the dissolution medium into the agglomerates. With an ordered mixture, these agglomerates were deaggregated during the mixing process, producing a system in which the entire external surface area of the primary particles was exposed to the dissolution medium. This conclusion was supported by calculation of the contact surface areas taking part in the dissolution process for the systems tested. The procedure developed in this study could be applied to preformulation work where a cohesive, low solubility drug of hydrophobic nature is to be formulated.

The composition of coexisting jarosite-group minerals and water from the Richmond mine, Iron Mountain, California

USGS Publications Warehouse

Jamieson, Heather E.; Robinson, Clare; Alpers, Charles N.; Nordstrom, D. Kirk; Poustovetov, Alexei; Lowers, Heather A.

2005-01-01

Jarosite-group minerals accumulate in the form of stalactites and fine-grained mud on massive pyrite in the D drift of the Richmond mine, Iron Mountain, California. Water samples were collected by placing beakers under the dripping stalactites and by extracting pore water from the mud using a centrifuge. The water is rich in Fe3+ and SO4 2−, with a pH of approximately 2.1, which is significantly higher than the extremely acidic waters found elsewhere in the mine. Electron-microprobe analysis and X-ray mapping indicate that the small crystals (<10 μm in diameter) are compositionally zoned with respect to Na and K, and include hydronium jarosite corresponding to the formula (H3O)0.6K0.3Na0.1Fe3 3+(SO4)2(OH)6. The proton-microprobe analyses indicate that the jarosite-group minerals contain significant amounts of As, Pb and Zn, and minor levels of Bi, Rb, Sb, Se, Sn and Sr. Speciation modeling indicates that the drip waters are supersaturated with respect to jarosite-group minerals. The expected range in composition of jarosite-group solid-solution in equilibrium with the pore water extracted from the mud was found to be consistent with the observed range in composition.

Diurnal variation in rates of calcification and carbonate sediment dissolution in Florida Bay

USGS Publications Warehouse

Yates, K.K.; Halley, R.B.

2006-01-01

Water quality and circulation in Florida Bay (a shallow, subtropical estuary in south Florida) are highly dependent upon the development and evolution of carbonate mud banks distributed throughout the Bay. Predicting the effect of natural and anthropogenic perturbations on carbonate sedimentation requires an understanding of annual, seasonal, and daily variations in the biogenic and inorganic processes affecting carbonate sediment precipitation and dissolution. In this study, net calcification rates were measured over diurnal cycles on 27 d during summer and winter from 1999 to 2003 on mud banks and four representative substrate types located within basins between mud banks. Substrate types that were measured in basins include seagrass beds of sparse and intermediate density Thalassia sp., mud bottom, and hard bottom communities. Changes in total alkalinity were used as a proxy for calcification and dissolution. On 22 d (81%), diurnal variation in rates of net calcification was observed. The highest rates of net carbonate sediment production (or lowest rates of net dissolution) generally occurred during daylight hours and ranged from 2.900 to -0.410 g CaCO3 m-2 d-1. The lowest rates of carbonate sediment production (or net sediment dissolution) occurred at night and ranged from 0.210 to -1.900 g CaCO3 m -2 night-1. During typical diurnal cycles, dissolution during the night consumed an average of 29% of sediment produced during the day on banks and 68% of sediment produced during the day in basins. Net sediment dissolution also occurred during daylight, but only when there was total cloud cover, high turbidity, or hypersalinity. Diurnal variation in calcification and dissolution in surface waters and surface sediments of Florida Bay is linked to cycling of carbon dioxide through photosynthesis and respiration. Estimation of long-term sediment accumulation rates from diurnal rates of carbonate sediment production measured in this study indicates an overall average

Illite Dissolution Rates and Equation (100 to 280 dec C)

DOE Data Explorer

Carroll, Susan

2014-10-17

The objective of this suite of experiments was to develop a useful kinetic dissolution expression for illite applicable over an expanded range of solution pH and temperature conditions representative of subsurface conditions in natural and/or engineered geothermal reservoirs. Using our new data, the resulting rate equation is dependent on both pH and temperature and utilizes two specific dissolution mechanisms (a “neutral” and a “basic” mechanism). The form of this rate equation should be easily incorporated into most existing reactive transport codes for to predict rock-water interactions in EGS shear zones.

Improving the API dissolution rate during pharmaceutical hot-melt extrusion I: Effect of the API particle size, and the co-rotating, twin-screw extruder screw configuration on the API dissolution rate.

PubMed

Li, Meng; Gogos, Costas G; Ioannidis, Nicolas

2015-01-15

The dissolution rate of the active pharmaceutical ingredients in pharmaceutical hot-melt extrusion is the most critical elementary step during the extrusion of amorphous solid solutions - total dissolution has to be achieved within the short residence time in the extruder. Dissolution and dissolution rates are affected by process, material and equipment variables. In this work, we examine the effect of one of the material variables and one of the equipment variables, namely, the API particle size and extruder screw configuration on the API dissolution rate, in a co-rotating, twin-screw extruder. By rapidly removing the extruder screws from the barrel after achieving a steady state, we collected samples along the length of the extruder screws that were characterized by polarized optical microscopy (POM) and differential scanning calorimetry (DSC) to determine the amount of undissolved API. Analyses of samples indicate that reduction of particle size of the API and appropriate selection of screw design can markedly improve the dissolution rate of the API during extrusion. In addition, angle of repose measurements and light microscopy images show that the reduction of particle size of the API can improve the flowability of the physical mixture feed and the adhesiveness between its components, respectively, through dry coating of the polymer particles by the API particles. Copyright © 2014. Published by Elsevier B.V.

Discovery of jarosite within the Mawrth Vallis region of Mars: Implications for the geologic history of the region

NASA Astrophysics Data System (ADS)

Farrand, William H.; Glotch, Timothy D.; Rice, James W.; Hurowitz, Joel A.; Swayze, Gregg A.

2009-12-01

Analysis of visible to near infrared reflectance data from the MRO CRISM hyperspectral imager has revealed the presence of an ovoid-shaped landform, approximately 3 by 5 km in size, within the layered terrains surrounding the Mawrth Vallis outflow channel. This feature has spectral absorption features consistent with the presence of the ferric sulfate mineral jarosite, specifically a K-bearing jarosite (KFe 3(SO 4) 2(OH) 6). Terrestrial jarosite is formed through the oxidation of iron sulfides in acidic environments or from basaltic precursor minerals with the addition of sulfur. Previously identified phyllosilicates in the Mawrth Vallis layered terrains include a basal sequence of layers containing Fe-Mg smectites and an upper set of layers of hydrated silica and aluminous phyllosilicates. In terms of its fine scale morphology revealed by MRO HiRISE imagery, the jarosite-bearing unit has fracture patterns very similar to that observed in Fe-Mg smectite-bearing layers, but unlike that observed in the Al-bearing phyllosilicate unit. The ovoid-shaped landform is situated in an east-west bowl-shaped depression superposed on a north sloping surface. Spectra of the ovoid-shaped jarosite-bearing landform also display an anomalously high 600 nm shoulder, which may be consistent with the presence of goethite and a 1.92 μm absorption which could indicate the presence of ferrihydrite. Goethite, jarosite, and ferrihydrite can be co-precipitated and/or form through transformation of schwertmannite, both processes generally occurring under low pH conditions (pH 2-4). To date, this location appears to be unique in the Mawrth Vallis region and could represent precipitation of jarosite in acidic, sulfur-rich ponded water during the waning stages of drying.

Discovery of jarosite within the Mawrth Vallis region of Mars: Implications for the geologic history of the region

USGS Publications Warehouse

Farrand, W. H.; Glotch, T.D.; Rice, J. W.; Hurowitz, J.A.; Swayze, G.A.

2009-01-01

Analysis of visible to near infrared reflectance data from the MRO CRISM hyperspectral imager has revealed the presence of an ovoid-shaped landform, approximately 3 by 5 km in size, within the layered terrains surrounding the Mawrth Vallis outflow channel. This feature has spectral absorption features consistent with the presence of the ferric sulfate mineral jarosite, specifically a K-bearing jarosite (KFe3(SO4)2(OH)6). Terrestrial jarosite is formed through the oxidation of iron sulfides in acidic environments or from basaltic precursor minerals with the addition of sulfur. Previously identified phyllosilicates in the Mawrth Vallis layered terrains include a basal sequence of layers containing Fe-Mg smectites and an upper set of layers of hydrated silica and aluminous phyllosilicates. In terms of its fine scale morphology revealed by MRO HiRISE imagery, the jarosite-bearing unit has fracture patterns very similar to that observed in Fe-Mg smectite-bearing layers, but unlike that observed in the Al-bearing phyllosilicate unit. The ovoid-shaped landform is situated in an east-west bowl-shaped depression superposed on a north sloping surface. Spectra of the ovoid-shaped jarosite-bearing landform also display an anomalously high 600 nm shoulder, which may be consistent with the presence of goethite and a 1.92 ??m absorption which could indicate the presence of ferrihydrite. Goethite, jarosite, and ferrihydrite can be co-precipitated and/or form through transformation of schwertmannite, both processes generally occurring under low pH conditions (pH 2-4). To date, this location appears to be unique in the Mawrth Vallis region and could represent precipitation of jarosite in acidic, sulfur-rich ponded water during the waning stages of drying. ?? 2009 Elsevier Inc. All rights reserved.

Shining a light on Jarosite: formation, alteration and stability studies using in situ experimental synchrotron and neutron techniques.

NASA Astrophysics Data System (ADS)

Brand, H. E. A.; Scarlett, N. V. Y.; Wilson, S. A.; Frierdich, A. J.; Grey, I. E.

2016-12-01

Jarosites and related minerals are critical to a range of mineral processing and research applications. They are used in the removal of iron species from smelting processes; they occur in metal bioleaching systems, and they are present in acid mine drainage environments. There has been a recent resurgence in interest in jarosites since their detection on Mars. In this context, the presence of jarosite has been recognised as a likely indicator of liquid water at the surface of Mars in the past & it is thought that their study will provide insight into the environmental history of Mars. Acid sulfate soils cover large areas of the Australian coastline and are likely to be a major constituent of the Martian environment. The oxidation of acid sulfate soils, coupled with potential release of heavy metals and acidic groundwaters, can have serious consequences for fragile ecosystems. Understanding these sediments will provide insight into the biogeochemical processes that affect the lifetimes of transient mineral species on Earth, and may be used to better understand soil acidification, contaminant mobility at sites affected by acid and metalliferous drainage, and even constrain past weathering and putative biosignatures on Mars. Knowledge of the behaviour of jarosite minerals under the actual conditions that they are found in is crucial to understanding their potential environmental impacts on both Earth and Mars. To this end, we are engaged in a program to study the formation, stability and alteration of natural and synthetic jarosite minerals using a complementary suite of in situ synchrotron and neutron techniques. There are 3 sections to this work that will introduce the experimental techniques and sample environments that make these measurements possible: Studying the nucleation and growth of jarosites under laboratory conditions. The experimentation consisted of time-resolved synchrotron small angle X-ray scattering and X-ray diffraction. Studying the stability of

Dissolution Rate Enhancement of Repaglinide Using Dietary Fiber as a Promising Carrier.

PubMed

Chatap, Vivekanand K; Patil, Savita D

2016-01-01

In present investigation, an innovative attempt has been made to enhance the solubility and dissolution rate of Repaglinide (RPGD) using hydrothermally treated water insoluble dietary bamboo fibers (HVBF) as potential nutraceutical used in the treatment of diabetes mellitus. RPGD was selected as a model drug due to its low aqueous solubility and dissolution rate. Characterization of HVBF demonstrated the outstanding features like high surface area, maximum drug loading and increase dissolution rate and making HVBF as an excellent drug carrier. RHVBF (Repaglinide loaded HVBF) tablets were prepared using direct compression method. Pre and post-compression parameters for blend and tablets were studied and found within acceptable limits. RHVBF and tablet showed significantly improved dissolution rate, when compared with pure crystalline RPGD, physical mixture, RVBF and commercial marketed tablet. This fact was further supported by FT-IR, DSC, XRPD and FESEM studies followed by in-vitro drug release profile. Stability studies showed no changes after exposing to accelerated conditions for a period of 3 months with respect to physical characteristics and in-vitro drug release studies. In a nut shell, it can be concluded that HVBF is a novel, smart and promising carrier for poorly water soluble drugs, when administered orally.

Controlled precipitation for enhanced dissolution rate of flurbiprofen: development of rapidly disintegrating tablets.

PubMed

Essa, Ebtessam A; Elmarakby, Amira O; Donia, Ahmed M A; El Maghraby, Gamal M

2017-09-01

The aim of this work was to investigate the potential of controlled precipitation of flurbiprofen on solid surface, in the presence or absence of hydrophilic polymers, as a tool for enhanced dissolution rate of the drug. The work was extended to develop rapidly disintegrated tablets. This strategy provides simple technique for dissolution enhancement of slowly dissolving drugs with high scaling up potential. Aerosil was dispersed in ethanolic solution of flurbiprofen in the presence and absence of hydrophilic polymers. Acidified water was added as antisolvent to produce controlled precipitation. The resultant particles were centrifuged and dried at ambient temperature before monitoring the dissolution pattern. The particles were also subjected to FTIR spectroscopic, X-ray diffraction and thermal analyses. The FTIR spectroscopy excluded any interaction between flurbiprofen and excipients. The thermal analysis reflected possible change in the crystalline structure and or crystal size of the drug after controlled precipitation in the presence of hydrophilic polymers. This was further confirmed by X-ray diffraction. The modulation in the crystalline structure and size was associated with a significant enhancement in the dissolution rate of flurbiprofen. Optimum formulations were successfully formulated as rapidly disintegrating tablet with subsequent fast dissolution. Precipitation on a large solid surface area is a promising strategy for enhanced dissolution rate with the presence of hydrophilic polymers during precipitation process improving the efficiency.

Comparison on Response and Dissolution Rates Between Ursodeoxycholic Acid Alone or in Combination With Chenodeoxycholic Acid for Gallstone Dissolution According to Stone Density on CT Scan: Strobe Compliant Observation Study.

PubMed

Lee, Jae Min; Hyun, Jong Jin; Choi, In Young; Yeom, Suk Keu; Kim, Seung Young; Jung, Sung Woo; Jung, Young Kul; Koo, Ja Seol; Yim, Hyung Joon; Lee, Hong Sik; Lee, Sang Woo; Kim, Chang Duck

2015-12-01

Medical dissolution of gallstone is usually performed on radiolucent gallstones in a functioning gallbladder. However, absence of visible gallstone on plain abdominal x-ray does not always preclude calcification. This study aims to compare the response and dissolution rates between ursodeoxycholic acid (UDCA) alone or in combination with chenodeoxycholic acid (CDCA) according to stone density on computed tomography (CT) scan. A total of 126 patients underwent dissolution therapy with either UDCA alone or combination of CDCA and UDCA (CNU) from December 2010 to March 2014 at Korea University Ansan Hospital. In the end, 81 patients (CNU group = 44, UDCA group = 37) completed dissolution therapy for 6 months. Dissolution rate (percentage reduction in the gallstone volume) and response to therapy (complete dissolution or partial dissolution defined as reduction in stone volume of >50%) were compared between the 2 groups. Dissolution and response rates of sludge was also compared between the 2 groups. The overall response rate was 50.6% (CNU group 43.2% vs UDCA group 59.5%, P = 0.14), and the overall dissolution rate was 48.34% (CNU group 41.5% vs UDCA group 56.5%, P = 0.13). When analyzed according to stone density, response rate was 33.3%, 87.1%, 30.0%, and 6.2% for hypodense, isodense, hyperdense, and calcified stones, respectively. Response rate (85.7% vs 88.2%, P = 0.83) and dissolution rate (81.01% vs 85.38%, P = 0.17) of isodense stones were similar between CNU and UDCA group. When only sludge was considered, the overall response rate was 87.5% (CNU group 71.4% vs UDCA group 94.1%, P = 0.19), and the overall dissolution rate was 85.42% (CNU group 67.9% vs UDCA group 92.7%, P = 0.23). Patients with isodense gallstones and sludge showed much better response to dissolution therapy with CNU and UDCA showing comparable efficacy. Therefore, CT scan should be performed before medication therapy if stone dissolution is intended.

Carbonate dissolution rates in high salinity brines: Implications for post-Noachian chemical weathering on Mars

NASA Astrophysics Data System (ADS)

Phillips-Lander, Charity M.; Parnell, S. R.; McGraw, L. E.; Elwood Madden, M. E.

2018-06-01

A diverse suite of carbonate minerals including calcite (CaCO3) and magnesite (MgCO3) have been observed on the martian surface and in meteorites. Terrestrial carbonates usually form via aqueous processes and often record information about the environment in which they formed, including chemical and textural biosignatures. In addition, terrestrial carbonates are often found in association with evaporite deposits on Earth. Similar high salinity environments and processes were likely active on Mars and some areas may contain active high salinity brines today. In this study, we directly compare calcite and magnesite dissolution in ultrapure water, dilute sulfate and chloride solutions, as well as near-saturated sulfate and chloride brines with known activity of water (aH2O) to determine how dissolution rates vary with mineralogy and aH2O, as well as aqueous cation and anion chemistry to better understand how high salinity fluids may have altered carbonate deposits on Mars. We measured both calcite and magnesite initial dissolution rates at 298 K and near neutral pH (6-8) in unbuffered solutions containing ultrapure water (18 MΩ cm-1 UPW; aH2O = 1), dilute (0.1 mol kg-1; aH2O = 1) and near-saturated Na2SO4 (2.5 mol kg-1, aH2O = 0.92), dilute (0.1 mol kg-1, aH2O = 1) and near-saturated NaCl (5.7 mol kg-1, aH2O = 0.75). Calcite dissolution rates were also measured in dilute and near-saturated MgSO4 (0.1 mol kg-1, aH2O = 1 and 2.7 mol kg-1, aH2O = 0.92, respectively) and MgCl2 (0.1 mol kg-1, aH2O = 1 and 3 mol kg-1, aH2O = 0.73, respectively), while magnesite dissolution rates were measured in dilute and near-saturated CaCl2 (0.1 mol kg-1, aH2O = 1 and 9 mol kg-1, aH2O = 0.35). Initial calcite dissolution rates were fastest in near-saturated MgCl2 brine, while magnesite dissolution rates were fastest in dilute (0.1 mol kg-1) NaCl and CaCl2 solutions. Calcite dissolution rates in near-saturated Na2SO4 were similar to those observed in the dilute solutions (-8.00 ± 0

Chemical, crystallographic and stable isotopic properties of alunite and jarosite from acid-Hypersaline Australian lakes

USGS Publications Warehouse

Alpers, Charles N.; Rye, R.O.; Nordstrom, D. Kirk; White, L.D.; King, B.-S.

1992-01-01

Chemical, crystallographic and isotopic analyses were made on samples containing alunite and jarosite from the sediments of four acid, hypersaline lakes in southeastern and southwestern Australia. The alunite and jarosite are K-rich with relatively low Na contents based on chemical analysis and determination of unit cell dimensions by powder X-ray diffraction. Correcting the chemical analyses of fine-grained mineral concentrates from Lake Tyrrell, Victoria, for the presence of halite, silica and poorly crystalline aluminosilicates, the following formulas indicate best estimates for solid-solution compositions: for alunite, K0.87Na0.04(H3O)0.09(Al 0.92Fe0.08)3(SO4)2(OH) 6 and for jarosite, K0.89Na0.07(H3O)0.04(Fe 0.80Al0.20)3(SO4)2(OH) 6. The ??D-values of alunite are notably larger than those for jarosite from Lake Tyrrell and it appears that the minerals have closely approached hydrogen isotope equilibrium with the acidic regional groundwaters. The ??D results are consistent with a fractionation ???60-70??? between alunite and jarosite observed in other areas. However, interpretation of ??D results is complicated by large variability in fluid ??DH2O from evaporation, mixing and possible ion hydration effects in the brine. ??D-values of water derived from jarosite by step-wise heating tend to be smaller at 250??C, at which temperature hydronium and other non-hydroxyl water is liberated, than at 550??C, where water is derived from the hydroxyl site, but the differences are not sufficiently different to invalidate measurements of total ??D obtained by conventional, single-step heating methods. ??34S-values for alunite and jarosite from the four lakes (+19.7 to +21.2??? CDT) and for aqueous sulfate from Lake Tyrrell (+18.3 to +19.8???) are close to the values for modern evaporites (+21.5 ??0.3???) and seawater (+20??0.5???) and are probably typical of seawater-derived aerosols in arid coastal environments. ??34-S-values slightly smaller than that for seawater may

Spectral and chemical characterization of jarosite in a palaeolacustrine depositional environment in Warkalli Formation in Kerala, South India and its implications

NASA Astrophysics Data System (ADS)

Singh, Mahima; Rajesh, V. J.; Sajinkumar, K. S.; Sajeev, K.; Kumar, S. N.

2016-11-01

Coastal cliffs fringing the Arabian Sea near Varkala exhibits the Warkalli Formation of the Tertiary sequence of Kerala, South India, with well-marked occurrence of jarosite associated with other hydrous mineral phases of phyllosilicate family in a palaeo-lacustrine depositional environment. Sandy phyllosilicates dominate the mineral assemblage, but jarosite occurs as a prominent secondary phase formed during acid-sulphate alteration of iron sulphide in this area. Here, we discuss about the potentiality of spectroscopic techniques to identify the possible mineral phases in the collected samples. The samples from the coastal cliffs have been characterized by hyperspectral analysis (VIS-NIR-SWIR), X-ray Diffraction (XRD), Fourier Transform Infra-red Reflectance (FTIR), Electron Probe Microanalysis (EPMA) and Laser Raman spectroscopy. The spectral and chemical analyses have confirmed the jarosite as natrojarosite and phyllosilicate as kaolinite. Other accessory phases have also been identified through XRD. FTIR spectroscopy has played a major role in identifying the major hydrous bonds between the minerals. VIS-NIR-SWIR spectra show several optimum spectral features at 910 nm, 1470 nm, 1849-1864 nm (in the form of a doublet), 1940 nm and 2270 nm, which could be utilised to locate jarosite in the remotely-sensed data. X-ray diffraction peaks helped in the identification of maximum number of minerals (kaolinite, smectite, quartz, feldspar, pyrite, marcasite and hematite) and the variation in jarosite content in the samples. We propose the formation of jarosite in the region by a seasonal, local and temporary development of acidic conditions. Abundance of organic matter in a fluvio-lacustrine environment has developed anaerobic conditions by removing available oxygen through decomposition of organic matter containing sulphur compounds. The sulphur thus liberated combines with hydrogen from water to develop acidic conditions and resulted in the formation of jarosite. The

Effects of ocean acidification on the dissolution rates of reef-coral skeletons.

PubMed

van Woesik, Robert; van Woesik, Kelly; van Woesik, Liana; van Woesik, Sandra

2013-01-01

Ocean acidification threatens the foundation of tropical coral reefs. This study investigated three aspects of ocean acidification: (i) the rates at which perforate and imperforate coral-colony skeletons passively dissolve when pH is 7.8, which is predicted to occur globally by 2100, (ii) the rates of passive dissolution of corals with respect to coral-colony surface areas, and (iii) the comparative rates of a vertical reef-growth model, incorporating passive dissolution rates, and predicted sea-level rise. By 2100, when the ocean pH is expected to be 7.8, perforate Montipora coral skeletons will lose on average 15 kg CaCO3 m(-2) y(-1), which is approximately -10.5 mm of vertical reduction of reef framework per year. This rate of passive dissolution is higher than the average rate of reef growth over the last several millennia and suggests that reefs composed of perforate Montipora coral skeletons will have trouble keeping up with sea-level rise under ocean acidification. Reefs composed of primarily imperforate coral skeletons will not likely dissolve as rapidly, but our model shows they will also have trouble keeping up with sea-level rise by 2050.

Kinetics of Alkaline Decomposition and Cyaniding of Argentian Rubidium Jarosite in NaOH Medium

NASA Astrophysics Data System (ADS)

Rodríguez, Eleazar Salinas; Sáenz, Eduardo Cerecedo; Ramírez, Marius; Cardona, Francisco Patiño; Labra, Miguel Pérez

2012-10-01

The alkaline decomposition of Argentian rubidium jarosite in NaOH media is characterized by an induction period and a progressive conversion period in which the sulfate and rubidium ions pass to the solution, leaving an amorphous iron hydroxide residue. The process is chemically controlled and the order of reaction with respect to hydroxide concentration in the range of 1.75 and 20.4 mol OH- m-3 is 0.94, while activation energy in the range of temperatures of 298 K to 328 K (25 °C to 55 °C) is 91.3 kJ mol-1. Cyaniding of Argentian rubidium jarosite in NaOH media presents a reaction order of 0 with respect to NaCN concentration (in the range of 5 to 41 mol m-3) and an order of reaction of 0.62 with respect to hydroxide concentration, in the range of 1.1 and 30 mol [OH-] m-3. In this case, the cyaniding process can be described, as in other jarosites, as the following two-step process: (1) a step (slow) of alkaline decomposition that controls the overall process followed by (2) a fast step of silver complexation. The activation energy during cyaniding in the range of temperatures of 298 K to 333 K (25 °C to 60 °C) is 43.5 kJ mol-1, which is characteristic of a process controlled by chemical reaction. These results are quite similar to that observed for several synthetic jarosites and that precipitated in a zinc hydrometallurgical plant (Industrial Minera México, San Luis Potosi).

Calcite Dissolution Kinetics

NASA Astrophysics Data System (ADS)

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

2016-12-01

A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations <=0.04 g/L) to enhance the dissolution rate at low degrees of undersaturation by >500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state

Improving Dissolution Rate of Carbamazepine-Glutaric Acid Cocrystal Through Solubilization by Excess Coformer.

PubMed

Yamashita, Hiroyuki; Sun, Changquan Calvin

2017-12-29

The use of soluble cocrystals is a promising strategy for delivering poorly soluble drugs. However, precipitation of poorly soluble crystal form during dissolution hinders the successful tablet development of cocrystals. This work was aimed to understand the mechanisms for improving dissolution performance of a soluble cocrystals by using excess coformer. A highly soluble carbamazepine (CBZ) cocrystal with- glutaric acid (GLA) was studied. Impact of excess GLA on solubility and intrinsic dissolution rate (IDR) was assessed. Viscosity of GLA solutions was also measured. Solid form of powders and pellets was examined using powder X-ray diffractometry. IDRs of cocrystal and GLA mixtures in different ratios were measured to identify a suitable formulation for maintaining high dissolution rate of CBZ-GLA in an aqueous environment. IDR of CBZ-GLA in a pH 1.2 HCl solution was improved when GLA was present in the solution. Precipitation of CBZ·2H 2 O was eliminated when GLA concentration was ≥100 mg/mL. The improved IDR was accompanied by higher solubility of CBZ in GLA solution and increased solution viscosity. The trend in IDR profile matched well with the solubility profile normalized by solution viscosity. Mixture of cocrystal and GLA led to improved IDR in simulated intestinal fluid. The excess GLA increased the aqueous solubility of CBZ·2H 2 O and, thereby, reduced the propensity to precipitation of CBZ·2H 2 O during dissolution by lowering the degree of supersaturation. This strategy allowed development of a CBZ-GLA formulation with a significantly enhanced dissolution rate than CBZ-GLA.

Possible role of Rhodotorula sp. in the formation of jarosite in the AMD environment of Muskau Arch, Poland

NASA Astrophysics Data System (ADS)

Jakus, Natalia; Chlebicki, Andrzej; Bożęcki, Piotr; Manecki, Maciej

2016-04-01

The Muskau Arch is situated in the west of Poland and in the east of Germany. This region is a belt formed by push and frontal moraines during the Middle-Polish (Riss) glaciation, especially during the Wartanian glaciation. The occurrence of glacier caused folding and forming the glacitectonic type of lignit deposits which were mined for over 150 years. Both open pit and underground mining methods has exposed metal sulfides (mainly pyrite) to air and water causing bio-oxidation. Due to this process the acidity of many reservoirs have increased significantly (pH values between 2 and 4). As a consequence of changes in the environment, new mineral phases precipitated from highly acid waters rich in, among others, various forms of Fe and S. Precipitation of ochreous minerals such as schwertmannite, goethite and jarosite was partly catalyzed by many various acidophilic and acid-tolerant microorganisms: bacteria, archaea and probably yeasts. Jarosite KFe33+(OH)6(SO4)2 can be precipitated both in abiotic conditions and as a by-product of the activity of living organisms. The example of biomineralization induced by fungi Purpureocillium lilacinum in similar AMD environment of Rio Tinto is reported (Oggerin et al, 2014). Recently, jarosite is also considered as a possible biosignature of life on Mars. The assessment of microbial participation in formation of jarosite is an elementary step in geomicrobiological and astrobiological research. Isolated by us Rhodotorula sp. is an unicellular pigmented yeast. Fungi from the genus Rhodotorula F.C. Harrison belong to Sporidiobolalas part of phylum Basidiomycota. They are common environmental inhabitants. Some species, known from Rio Tinto, can live in extreme acidic soils at pH of about 2 (Lopez-Archila et al, 2004). For the first time, authors isolated strain Rhodotorula sp. from surface precipitates in Ł ęknica region (Muskau Arch). This ochreous precipitate contains jarosite. The yeast might be an important factor in indirect

Quartz dissolution. I - Negative crystal experiments and a rate law. II - Theory of rough and smooth surfaces

NASA Technical Reports Server (NTRS)

Gratz, Andrew J.; Bird, Peter

1993-01-01

The range of the measured quartz dissolution rates, as a function of temperature and pOH, extent of saturation, and ionic strength, is extended to cover a wider range of solution chemistries, using the negative crystal methodology of Gratz et al. (1990) to measure the dissolution rate. A simple rate law describing the quartz dissolution kinetics above the point of zero charge of quartz is derived for ionic strengths above 0.003 m. Measurements were performed on some defective crystals, and the mathematics of step motion was developed for quartz dissolution and was compared with rough-face behavior using two different models.

Chemical structure influence on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux

NASA Astrophysics Data System (ADS)

Padgett, Mark C.; Tick, Geoffrey R.; Carroll, Kenneth C.; Burke, William R.

2017-03-01

The influence of chemical structure on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux was examined. The variability of measured and UNIFAC modeled NAPL activity coefficients as a function of mole fraction was compared for two NAPL mixtures containing structurally-different contaminants of concern including toluene (TOL) or trichloroethene (TCE) within a hexadecane (HEXDEC) matrix. The results showed that dissolution from the NAPL mixtures transitioned from ideality for mole fractions > 0.05 to nonideality as mole fractions decreased. In particular, the TCE generally exhibited more ideal dissolution behavior except at lower mole fractions, and may indicate greater structural/polarity similarity between the two compounds. Raoult's Law and UNIFAC generally under-predicted the batch experiment results for TOL:HEXDEC mixtures especially for mole fractions ≤ 0.05. The dissolution rate coefficients were similar for both TOL and TCE over all mole fractions tested. Mass flux reduction (MFR) analysis showed that more efficient removal behavior occurred for TOL and TCE with larger mole fractions compared to the lower initial mole fraction mixtures (i.e. < 0.2). However, compared to TOL, TCE generally exhibited more efficient removal behavior over all mole fractions tested and may have been the result of structural and molecular property differences between the compounds. Activity coefficient variability as a function of mole fraction was quantified through regression analysis and incorporated into dissolution modeling analyses for the dynamic flushing experiments. TOL elution concentrations were modeled (predicted) reasonable well using ideal and equilibrium assumptions, but the TCE elution concentrations could not be predicted using the ideal model. Rather, the dissolution modeling demonstrated that TCE elution was better described by the nonideal model whereby NAPL-phase activity coefficient varied as a function of COC mole

Detection of Biosignatures in Natural and Microbial Cultured Jarosites Using Laser- Desorption Fourier Transform Mass Spectrometry: Implications for Astrobiology

NASA Astrophysics Data System (ADS)

Kotler, J.; Hinman, N. W.; Yan, B.; Stoner, D. L.; Scott, J. R.

2006-12-01

The jarosite group minerals have received increasing attention since the discovery by the Mars Exploration Rover-Opportunity of jarosite on the Martian surface. The general chemical formula for jarosite is XFe3(SO4)2(OH)6 where the X represents both monovalent and divalent cations that can occupy the axial positions in the crystal structure. Commonly found ions include K+, Na+, H3O+, NH4+, and Pb2+ with reports of other large ions occupying this position in the literature. Modeling efforts have been performed to confirm that jarosite has the ability to incorporate a variety of "foreign" cations. The minerals unique ability to incorporate various large ions in its structure and its association with biological activity in terrestrial environments has lead to investigations regarding its use as an indicator of aqueous and/or biological activity. The use of laser desorption Fourier transform mass spectrometry (LD-FTMS) has revealed the presence of organic matter including the amino acid, glycine, in several jarosite samples from various worldwide locations. Iron precipitates derived from acidophilic microbial cultures were also analyzed. Using attenuated total reflectance infrared spectroscopy (ATR-IR), signals indicative of microbes or microbial exudates were weak and ambiguous. In contrast, LD-FTMS clearly detected bioorganic constituents in some desorption spots. However, the signals were sporadic and required the laser scanning/imaging capability of our laboratory built system to locate the microbial signatures in the heterogeneous samples. The ability to observe these bioorganic signatures in jarosite samples using the instrumental technique employed in this study furthers the goals of planetary geologists to determine whether signs of life (e.g., presence of biomolecules or biomolecule precursors) can be detected in the rock record of terrestrial and extraterrestrial samples.

Improvement of the dissolution rate of artemisinin by means of supercritical fluid technology and solid dispersions.

PubMed

Van Nijlen, T; Brennan, K; Van den Mooter, G; Blaton, N; Kinget, R; Augustijns, P

2003-03-26

The purpose of this study was to enhance the dissolution rate of artemisinin in order to improve the intestinal absorption characteristics. The effect of: (1) micronisation and (2) formation of solid dispersions with PVPK25 was assessed in an in vitro dissolution system [dissolution medium: water (90%), ethanol (10%) and sodium lauryl sulphate (0.1%)]. Coulter counter analysis was used to measure particle size. X-ray diffraction and DSC were used to analyse the physical state of the powders. Micronisation by means of a jet mill and supercritical fluid technology resulted in a significant decrease in particle size as compared to untreated artemisinin. All powders appeared to be crystalline. The dissolution rate of the micronised forms improved in comparison to the untreated form, but showed no difference in comparison to mechanically ground artemisinin. Solid dispersions of artemisinin with PVPK25 as a carrier were prepared by the solvent method. Both X-ray diffraction and DSC showed that the amorphous state was reached when the amount of PVPK25 was increased to 67%. The dissolution rate of solid dispersions with at least 67% of PVPK25 was significantly improved in comparison to untreated and mechanically ground artemisinin. Modulation of the dissolution rate of artemisinin was obtained by both particle size reduction and formation of solid dispersions. The effect of particle size reduction on the dissolution rate was limited. Solid dispersions could be prepared by using a relatively small amount of PVPK25. The formation of solid dispersions with PVPK25 as a carrier appears to be a promising method to improve the intestinal absorption characteristics of artemisinin. Copyright 2003 Elsevier Science B.V.

Dissolution Rates and Reaction Products of Olivine Interaction with Ammonia-Rich Fluid

NASA Astrophysics Data System (ADS)

Zandanel, A. E.; Truche, L.; Hellmann, R.; Tobie, G.; Marrocchi, Y.

2018-05-01

Olivine dissolution rates and reaction products in NH3-rich fluids are determined from experiments simulating H2O-rock interaction on Enceladus. Kinetic rates are calculated from flow through experiments and reaction products from static experiments.

Effect of Phosphate, Fluoride, and Nitrate on Gibbsite Dissolution Rate and Solubility

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

Herting, Daniel L.

2014-01-29

Laboratory tests have been completed with simulated tank waste samples to investigate the effects of phosphate, fluoride, and nitrate on the dissolution rate and equilibrium solubility of gibbsite in sodium hydroxide solution at 22 and 40{degrees}C. Results are compared to relevant literature data and to computer model predictions. The presence of sodium nitrate (3 M) caused a reduction in the rate of gibbsite dissolution in NaOH, but a modest increase in the equilibrium solubility of aluminum. The increase in solubility was not as large, though, as the increase predicted by the computer model. The presence of phosphate, either as sodiummore » phosphate or sodium fluoride phosphate, had a negligible effect on the rate of gibbsite dissolution, but caused a slight increase in aluminum solubility. The magnitude of the increased solubility, relative to the increase caused by sodium nitrate, suggests that the increase is due to ionic strength (or water activity) effects, rather than being associated with the specific ion involved. The computer model predicted that phosphate would cause a slight decrease in aluminum solubility, suggesting some Al-PO4 interaction. No evidence was found of such an interaction.« less

The effect of a new formaldehyde-free binder on the dissolution rate of glass wool fibre in physiological saline solution.

PubMed

Potter, Russell M; Olang, Nassreen

2013-04-12

The in-vitro dissolution rate of fibres is a good predictor of the in-vivo behavior and potential health effects of inhaled fibres. This study examines the effect of a new formaldehyde-free carbohydrate-polycarboxylic acid binder on the in-vitro dissolution rate of biosoluble glass fibres. Dissolution rate measurements in pH 7.4 physiological saline solution show that the presence of the binder on wool insulation glass fibres has no effect on their dissolution. There is no measurable difference between the dissolution rates of continuous draw fibres before and after binder was applied by dipping. Nor is there a measurable difference between the dissolution rates of a production glass wool sample with binder and that same sample after removal of the binder by low-temperature ashing. Morphological examination shows that swelling of the binder in the solution is at least partially responsible for the development of open channels around the glass-binder interface early in the dissolution. These channels allow fluid to reach the entire glass surface under the binder coating. There is no evidence of any delay in the dissolution rate as a result of the binder coating.

The effect of a new formaldehyde-free binder on the dissolution rate of glass wool fibre in physiological saline solution

PubMed Central

2013-01-01

The in-vitro dissolution rate of fibres is a good predictor of the in-vivo behavior and potential health effects of inhaled fibres. This study examines the effect of a new formaldehyde-free carbohydrate-polycarboxylic acid binder on the in-vitro dissolution rate of biosoluble glass fibres. Dissolution rate measurements in pH 7.4 physiological saline solution show that the presence of the binder on wool insulation glass fibres has no effect on their dissolution. There is no measurable difference between the dissolution rates of continuous draw fibres before and after binder was applied by dipping. Nor is there a measurable difference between the dissolution rates of a production glass wool sample with binder and that same sample after removal of the binder by low-temperature ashing. Morphological examination shows that swelling of the binder in the solution is at least partially responsible for the development of open channels around the glass-binder interface early in the dissolution. These channels allow fluid to reach the entire glass surface under the binder coating. There is no evidence of any delay in the dissolution rate as a result of the binder coating. PMID:23587247

Chemical structure influence on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux.

PubMed

Padgett, Mark C; Tick, Geoffrey R; Carroll, Kenneth C; Burke, William R

2017-03-01

The influence of chemical structure on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux was examined. The variability of measured and UNIFAC modeled NAPL activity coefficients as a function of mole fraction was compared for two NAPL mixtures containing structurally-different contaminants of concern including toluene (TOL) or trichloroethene (TCE) within a hexadecane (HEXDEC) matrix. The results showed that dissolution from the NAPL mixtures transitioned from ideality for mole fractions >0.05 to nonideality as mole fractions decreased. In particular, the TCE generally exhibited more ideal dissolution behavior except at lower mole fractions, and may indicate greater structural/polarity similarity between the two compounds. Raoult's Law and UNIFAC generally under-predicted the batch experiment results for TOL:HEXDEC mixtures especially for mole fractions ≤0.05. The dissolution rate coefficients were similar for both TOL and TCE over all mole fractions tested. Mass flux reduction (MFR) analysis showed that more efficient removal behavior occurred for TOL and TCE with larger mole fractions compared to the lower initial mole fraction mixtures (i.e. <0.2). However, compared to TOL, TCE generally exhibited more efficient removal behavior over all mole fractions tested and may have been the result of structural and molecular property differences between the compounds. Activity coefficient variability as a function of mole fraction was quantified through regression analysis and incorporated into dissolution modeling analyses for the dynamic flushing experiments. TOL elution concentrations were modeled (predicted) reasonable well using ideal and equilibrium assumptions, but the TCE elution concentrations could not be predicted using the ideal model. Rather, the dissolution modeling demonstrated that TCE elution was better described by the nonideal model whereby NAPL-phase activity coefficient varied as a function of COC mole fraction

Examination of the jarosite-alunite precipitate addition in the raw meal for the production of sulfoaluminate cement clinker.

PubMed

Katsioti, M; Tsakiridis, P E; Leonardou-Agatzini, S; Oustadakis, P

2006-04-17

The aim of the present research work was to investigate the possibility of adding a jarosite-alunite chemical precipitate, a waste product of a new hydrometallurgical process developed to treat economically low-grade nickel oxides ores, in the raw meal for the production of sulfoaluminate cement clinker. For that reason, two samples of raw meals were prepared, one contained 20% gypsum, as a reference sample ((SAC)Ref) and another with 11.31% jarosite-alunite precipitate ((SAC)J/A). Both raw meals were sintered at 1300 degrees C. The results of chemical and mineralogical analyses as well as the microscopic examination showed that the use of the jarosite-alunite precipitate did not affect the mineralogical characteristics of the so produced sulfoaluminate cement clinker and there was confirmed the formation of the sulfoaluminate phase (C4A3S), the most typical phase of this cement type. Furthermore, both clinkers were tested by determining the grindability, setting time, compressive strength and expansibility. The hydration products were examined by XRD analysis at 2, 7, 28 and 90 days. The results of the physico-mechanical tests showed that the addition of jarosite-alunite precipitate did not negatively affect the quality of the produced cement.

The influence of co-formers on the dissolution rates of co-amorphous sulfamerazine/excipient systems.

PubMed

Gniado, Katarzyna; Löbmann, Korbinian; Rades, Thomas; Erxleben, Andrea

2016-05-17

A comprehensive study on the dissolution properties of three co-amorphous sulfamerazine/excipient systems, namely sulfamerazine/deoxycholic acid, sulfamerazine/citric acid and sulfamerazine/sodium taurocholate (SMZ/DA, SMZ/CA and SMZ/NaTC; 1:1 molar ratio), is reported. While all three co-formers stabilize the amorphous state during storage, only co-amorphization with NaTC provides a dissolution advantage over crystalline SMZ and the reasons for this were analyzed. In the case of SMZ/DA extensive gelation of DA protects the amorphous phase from crystallization upon contact with buffer, but at the same time prevents the release of SMZ into solution. Disk dissolution studies showed an improved dissolution behavior of SMZ/CA compared to crystalline SMZ. However, enhanced dissolution properties were not seen in powder dissolution testing due to poor dispersibility. Co-amorphization of SMZ and NaTC resulted in a significant increase in dissolution rate, both in powder and disk dissolution studies. Copyright © 2016. Published by Elsevier B.V.

Increased dissolution rates of tranilast solid dispersions extruded with inorganic excipients.

PubMed

Maniruzzaman, Mohammed; Ross, Steven A; Islam, Muhammad Tariqul; Scoutaris, Nikolaos; Nair, Arun; Douroumis, Dennis

2017-06-01

The purpose of this study was to evaluate the performance of Neusilin® (NEU) a synthetic magnesium aluminometasilicate as an inorganic drug carrier co-processed with the hydrophilic surfactants Labrasol and Labrafil to develop Tranilast (TLT)-based solid dispersions using continuous melt extrusion (HME) processing. Twin-screw extrusion was optimized to develop various TLT/excipient/surfactant formulations followed by continuous capsule filling in the absence of any downstream equipment. Physicochemical characterization showed the existence of TLT in partially crystalline state in the porous network of inorganic NEU for all extruded formulations. Furthermore, in-line NIR studies revealed a possible intermolecular H-bonding formation between the drug and the carrier resulting in the increase of TLT dissolution rates. The capsules containing TLT-extruded solid dispersions showed enhanced dissolution rates and compared with the marketed Rizaben ® product.

Improvement of the dissolution rate of poorly soluble drugs by solid crystal suspensions.

PubMed

Thommes, Markus; Ely, David R; Carvajal, M Teresa; Pinal, Rodolfo

2011-06-06

We present a novel extrusion based approach where the dissolution rate of poorly soluble drugs (griseofulvin, phenytoin and spironolactone) is significantly accelerated. The drug and highly soluble mannitol are coprocessed in a hot melt extrusion operation. The obtained product is an intimate mixture of the crystalline drug and crystalline excipient, with up to 50% (w/w) drug load. The in vitro drug release from the obtained solid crystalline suspensions is over 2 orders of magnitude faster than that of the pure drug. Since the resulting product is crystalline, the accelerated dissolution rate does not bear the physical stability concerns inherent to amorphous formulations. This approach is useful in situations where the drug is not a good glass former or in cases where it is difficult to stabilize the amorphous drug. Being thermodynamically stable, the dissolution profile and the solid state properties of the product are maintained after storage at 40 °C, 75% RH for at least 90 days.

Dissolution of Olivine, Siderite, and Basalt at 80 Deg C in 0.1 M H2SO4 in a Flow Through Process: Insights into Acidic Weathering on Mars

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, D. W.; Hausrath, E. M.; Morris, R. V.; Niles, P. B.; Achilles, C. N.; Ross, D. K.; Cooper, B. L.; Gonzalex, C. P.; Mertzman, S. A.

2012-01-01

The occurrence of jarosite, other sulfates (e.g., Mg-and Ca-sulfates), and hematite along with silicic-lastic materials in outcrops of sedimentary materials at Meridiani Planum (MP) and detection of silica rich deposits in Gusev crater, Mars, are strong indicators of local acidic aqueous processes [1,2,3,4,5]. The formation of sediments at Meridiani Planum may have involved the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [6,7]. Also, our previous work on acid weathering of basaltic materials in a closed hydro-thermal system was focused on the mineralogy of the acid weathering products including the formation of jarosite and gray hematite spherules [8,9,10]. The object of this re-search is to extend our earlier qualitative work on acidic weathering of rocks to determine acidic dissolution rates of Mars analog basaltic materials at 80 C using a flow-thru reactor. We also characterized residual phases, including poorly crystalline or amorphous phases and precipitates, that remained after the treatments of olivine, siderite, and basalt which represent likely MP source rocks. This study is a stepping stone for a future simulation of the formation of MP rocks under a range of T and P.

The effects of ion identity and ionic strength on the dissolution rate of a gibbsitic bauxite

NASA Astrophysics Data System (ADS)

Mogollón, José Luis; Pérez-Diaz, Alberto; Lo Monaco, Salvador

2000-03-01

The influence of cation and anion identity and concentration, on the far from equilibrium dissolution rate of gibbsite, was studied at 298°K. Input solutions, with initial pH = 3.5 and variable salt type and concentration, were flowed at different rates, through columns packed with a unconsolidated gibbsitic bauxite from Los Pijigüaos-Venezuela ore deposit. It was observed cations Na +, K +, Mg 2+ and Ca2+ have no influence on the far from equilibrium dissolution rate. Anions have two different effects: concentration increases of monovalent anions (Cl -, NO 3- and ClO 4-) causes a decrease in the rate, as a function of [anion] (-0.11 ± 0.01); and increases of sulfate concentration causes an increase in the rate as a function of [SO 4=] (0.4 ± 0.1). According to our calculations, these two effects have a remarkable influence upon the lifetime of gibbsite under weathering conditions. Based on Transition State Theory, it is proposed the experimental observations are due to an electrostatic effect on the activated complex (AC ♯) of the gibbsite dissolution reaction. For this AC ♯ the product of the charge of the involved chemical entities is negative. When SO 4= participates in the AC ♯ the product of the charges switches to positive and therefore, the electrostatic interaction increase the dissolution rate. The dissolution rates are independent of the solution saturation degree below ΔGr = - 0.74 kcal/mol. It is inferred that the critical ΔGr is a constant of the solid, not affected by the solution characteristics, e.g., pH, ionic strength, cation and anion identities.

Sensitivity of mineral dissolution rates to physical weathering : A modeling approach

NASA Astrophysics Data System (ADS)

Opolot, Emmanuel; Finke, Peter

2015-04-01

There is continued interest on accurate estimation of natural weathering rates owing to their importance in soil formation, nutrient cycling, estimation of acidification in soils, rivers and lakes, and in understanding the role of silicate weathering in carbon sequestration. At the same time a challenge does exist to reconcile discrepancies between laboratory-determined weathering rates and natural weathering rates. Studies have consistently reported laboratory rates to be in orders of magnitude faster than the natural weathering rates (White, 2009). These discrepancies have mainly been attributed to (i) changes in fluid composition (ii) changes in primary mineral surfaces (reactive sites) and (iii) the formation of secondary phases; that could slow natural weathering rates. It is indeed difficult to measure the interactive effect of the intrinsic factors (e.g. mineral composition, surface area) and extrinsic factors (e.g. solution composition, climate, bioturbation) occurring at the natural setting, in the laboratory experiments. A modeling approach could be useful in this case. A number of geochemical models (e.g. PHREEQC, EQ3/EQ6) already exist and are capable of estimating mineral dissolution / precipitation rates as a function of time and mineral mass. However most of these approaches assume a constant surface area in a given volume of water (White, 2009). This assumption may become invalid especially at long time scales. One of the widely used weathering models is the PROFILE model (Sverdrup and Warfvinge, 1993). The PROFILE model takes into account the mineral composition, solution composition and surface area in determining dissolution / precipitation rates. However there is less coupling with other processes (e.g. physical weathering, clay migration, bioturbation) which could directly or indirectly influence dissolution / precipitation rates. We propose in this study a coupling between chemical weathering mechanism (defined as a function of reactive area

Rates of mineral dissolution and carbonation in peridotite and basalt

NASA Astrophysics Data System (ADS)

Kelemen, P. B.; Matter, J. M.

2009-12-01

We study natural rates and processes of mineral carbonation in peridotite (olivine-rich rock) in mantle rocks exposed to weathering in northern Oman to learn effective mechanisms from natural processes, and seek ways to accelerate them to achieve significant CO2 capture and storage via mineral carbonation at the lowest possible cost. In our first paper (1), we fit data on mantle olivine carbonation from the DOE Albany Research Center (2,3, ARC). These data, and data from Arizona State University (4, ASU) suggest that a peridotite rock volume heated to 185°C and infused with H2O+CO2 at PCO2 > 75 bars could consume ~ 1 ton CO2 per cubic meter of rock per year. Because it is more abundant than peridotite, other workers focus on carbonation of the most common type of lava on Earth, basalt, whose main mineral constituent is generally labradorite, part of the plagioclase feldspar solid solution series. Our intuition is that labradorite carbonation is much slower than mantle olivine carbonation. To quantify this, we compiled data on dissolution of mantle olivine, labradorite, crystalline basalt, and basaltic glass in aqueous fluids, as well as data on mantle olivine carbonation. The dissolution data are calibrated as a function of surface area (i.e., grain size and shape) and pH, as well as temperature, whereas most of the ARC and ASU experiments were done at a single pH and grain size. Thus, for comparison, we calculated dissolution rates for 70 micron spheres at pH 8, close to the ARC and ASU experimental conditions. At these conditions, olivine carbonation observed by ARC and ASU is 100 to 1000 times faster than labradorite and crystalline basalt, and faster than conventionally measured olivine dissolution rates. The ARC and ASU experiments were different from conventional dissolution experiments in several ways that could lead to an enhancement in olivine reaction rates: (a) they may have lower a(Mg) in fluid due to solid MgCO3 (magnesite) precipitation, (b) they

Reaction rates and prediction of thermal instability during aluminum alloy 6061 dissolution

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

McFarlane, J.; DePaoli, D. W.; Mattus, C. H.

Here, chemical kinetics of dissolution of aluminum alloy 6061 was investigated for the processing of Pu-238 for deep space missions. The rate of dissolution was measured by the heat release and appeared to be controlled by the rate of release of Al(OH) 4 – from the metal surface. Rates of reaction were measured from 273 to 365 K, giving an activation energy of 72 ± 13 kJ•(mol Al) –1 and a pre-exponential factor of 5 ± 3 × 10 9 dm 3mol –1min –1. Minor alloying elements did not appear to affect the reaction kinetics. The average heat of dissolutionmore » was –360 ± 70 kJ•(mol NaAlO 2) –1. When extrapolated to an infinitely dilute solution of aluminum, kJ•(mol NaAlO 2) –1.« less

Reaction rates and prediction of thermal instability during aluminum alloy 6061 dissolution

DOE PAGES

McFarlane, J.; DePaoli, D. W.; Mattus, C. H.

2017-11-10

Here, chemical kinetics of dissolution of aluminum alloy 6061 was investigated for the processing of Pu-238 for deep space missions. The rate of dissolution was measured by the heat release and appeared to be controlled by the rate of release of Al(OH) 4 – from the metal surface. Rates of reaction were measured from 273 to 365 K, giving an activation energy of 72 ± 13 kJ•(mol Al) –1 and a pre-exponential factor of 5 ± 3 × 10 9 dm 3mol –1min –1. Minor alloying elements did not appear to affect the reaction kinetics. The average heat of dissolutionmore » was –360 ± 70 kJ•(mol NaAlO 2) –1. When extrapolated to an infinitely dilute solution of aluminum, kJ•(mol NaAlO 2) –1.« less

Influence of formulation parameters on dissolution rate enhancement of glyburide using liquisolid technique.

PubMed

Singh, Sachin Kumar; Srinivasan, K K; Gowthamarajan, K; Prakash, Dev; Gaikwad, Narayan B; Singare, Dhananjay S

2012-08-01

The aim of this study was to investigate the use of liquisolid technique in improving the dissolution of glyburide in a solid dosage form. This study was designed to evaluate the effects of different formulation variables, i.e. type of non-volatile liquid vehicles and drug concentrations, on drug dissolution rates. The liquisolid tablets were formulated with Propylene glycol, as liquid vehicle. Microcrystalline cellulose was used as a carrier material, silica as a coating material and croscaremellose as a disintegrant. In vitro drug dissolution profiles of the liquisolid formulations were studied and compared with direct compressed non-micronized and micronized tablets of glyburide using USP II, paddle apparatus at 50 rpm for 60 min using 900 ml of 0.05 M Phosphate Buffer, pH 7.5. The stability studies showed that the dissolution profiles of liquisolid tablets prepared with propylene glycol were not affected by ageing significantly, as f2 value found between aged and fresh samples was 51.92. Differential scanning calorimetry revealed that the drug has got solubilized in the liquid vehicle. This was further supported by the powder X-ray diffraction studies of pure drug and the liquisolid powder system. It can be concluded that it is possible to load poorly soluble drug into liquisolid tablets by addition of PVP to the liquid vehicle. This is valuable for the preparation of liquisolid tablets of poorly soluble drugs. The liquisolid tablets prepared with PVP showed a remarkably improved dissolution rate in comparison with DC tablet and other formulations.

Composition, Respirable Fraction and Dissolution Rate of 24 Stone Wool MMVF with their Binder.

PubMed

Wohlleben, Wendel; Waindok, Hubert; Daumann, Björn; Werle, Kai; Drum, Melanie; Egenolf, Heiko

2017-08-07

Man-made vitreous fibres (MMVF) are produced on a large scale for thermal insulation purposes. After extensive studies of fibre effects in the 1980ies and 1990ies, the composition of MMVF was modified to reduce the fibrotic and cancerogenic potential via reduced biopersistence. However, occupational risks by handling, applying, disposing modern MMVF may be underestimated as the conventional regulatory classification -combining composition, in-vivo clearance and effects- seems to be based entirely on MMVF after removal of the binder. Here we report the oxide composition of 23 modern MMVF from Germany, Finland, UK, Denmark, Russia, China (five different producers) and one pre-1995 MMVF. We find that most of the investigated modern MMVF can be classified as "High-alumina, low-silica wool", but several were on or beyond the borderline to "pre-1995 Rock (Stone) wool". We then used well-established flow-through dissolution testing at pH 4.5 and pH 7.4, with and without binder, at various flow rates, to screen the biosolubility of 14 MMVF over 32 days. At the flow rate and acidic pH of reports that found 47 ng/cm 2 /h dissolution rate for reference biopersistent MMVF21 (without binder), we find rates from 17 to 90 ng/cm 2 /h for modern MMVF as customary in trade (with binder). Removing the binder accelerates the dissolution significantly, but not to the level of reference biosoluble MMVF34. We finally simulated handling or disposing of MMVF and measured size fractions in the aerosol. The respirable fraction of modern MMVF is low, but not less than pre-1995 MMVF. The average composition of modern stone wool MMVF is different from historic biopersistent MMVF, but to a lesser extent than expected. The dissolution rates measured by abiotic methods indicate that the binder has a significant influence on dissolution via gel formation. Considering the content of respirable fibres, these findings imply that the risk assessment of modern stone wool may need to be revisited based

Biopharmaceutical classification of drugs using intrinsic dissolution rate (IDR) and rat intestinal permeability.

PubMed

Zakeri-Milani, Parvin; Barzegar-Jalali, Mohammad; Azimi, Mandana; Valizadeh, Hadi

2009-09-01

The solubility and dissolution rate of active ingredients are of major importance in preformulation studies of pharmaceutical dosage forms. In the present study, passively absorbed drugs are classified based on their intrinsic dissolution rate (IDR) and their intestinal permeabilities. IDR was determined by measuring the dissolution of a non-disintegrating disk of drug, and effective intestinal permeability of tested drugs in rat jejunum was determined using single perfusion technique. The obtained intrinsic dissolution rate values were in the range of 0.035-56.8 mg/min/cm(2) for tested drugs. The minimum and maximum intestinal permeabilities in rat intestine were determined to be 1.6 x 10(-5) and 2 x 10(-4)cm/s, respectively. Four classes of drugs were defined: Category I: P(eff,rat)>5 x 10(-5) (cm/s) or P(eff,human)>4.7 x 10(-5) (cm/s), IDR>1(mg/min/cm(2)), Category II: P(eff,rat)>5 x 10(-5) (cm/s) or P(eff,human)>4.7 x 10(-5) (cm/s), IDR<1(mg/min/cm(2)), Category III: P(eff,rat)<5 x 10(-5) (cm/s) or P(eff,human)<4.7 x 10(-5) (cm/s), IDR>1 (mg/min/cm(2)) and Category IV: P(eff,rat)<5 x 10(-5) (cm/s) or P(eff,human)<4.7 x 10(-5) (cm/s), IDR<1(mg/min/cm(2)). According to the results obtained and proposed classification of drugs, it is concluded that drugs could be categorized correctly based on their IDR and intestinal permeability values.

Neogene geomorphic and climatic evolution of the central San Juan Mountains, Colorado: K/Ar age and stable isotope data on supergene alunite and jarosite from the Creede mining district

USGS Publications Warehouse

Rye, Robert O.; Bethke, Philip M.; Lanphere, Marvin A.; Steven, Thomas A.

2000-01-01

K/Ar age determinations or supergene alunite and jarosite, formed during Neogene weathering of the epithermal silver and base-metal ores of the Creede mining district, have been combined with geologic evidence to estimate the timing of regional uplift of the southern Rocky Mountains and related canyon cutting. In addition, oxygen and hydrogen isotopic studies suggest climate changes in the central San Juan Mountains during the past 5 m.y. Alunite [ideally (K,Na)Al3(SO4)2(OH)6] and jarosite [ideally KFe3(SO4)2(OH)6] can be dated by K/Ar or 40Ar/39Ar techniques and both contain OH and SO4 sites that enable four stable isotope analyses (δD, δ18OOH, and δ34S) to be made. This supergene alunite and jarosite formed by weathering of sulfide-rich ore bodies may record the evolution of the chemical and hydrologic processes affecting ancient oxidized acid ground water, as well as details of climate history and geomorphic evolution. Fine-grained (1-10 μm) supergene alunite and jarosite occur in minor fractures in the upper, oxidized parts of the 25 Ma sulfide-bearing veins of the Creede mining district, and jarosite also occurs in adjacent oxidized Ag-bearing clastic sediments. K/Ar ages for alunite range from 4.8 to 3.1 Ma, and for jarosite range from 2.6 to 0.9 Ma. The δD values for alunite and jarosite show opposite correlations with elevation, and values for jarosite correlate with age. Calculated δDH2O values of alunite fluids approach but are larger than those of present-day meteoric water. Calculated δDH2O values for jarosite fluids are more variable; the values of the youngest jarosites are lowest and are similar to those of present-day meteoric water in the district. The narrow δD-δ18OSO4 values of alunites reflects oxidation of sulfide below the water table. The greater range in these values for jarosites reflects oxidation of sulfide under vadose conditions. The ages of alunite mark the position of the paleo-water table at the end of a period of moderate

Dissolution of nontronite in chloride brines and implications for the aqueous history of Mars

NASA Astrophysics Data System (ADS)

Steiner, M. H.; Hausrath, E. M.; Elwood Madden, M. E.; Tschauner, O.; Ehlmann, B. L.; Olsen, A. A.; Gainey, S. R.; Smith, J. S.

2016-12-01

Increasing evidence suggests the presence of recent liquid water, including brines, on Mars. Brines have therefore likely impacted clay minerals such as the Fe-rich mineral nontronite found in martian ancient terrains. To interpret these interactions, we conducted batch experiments to measure the apparent dissolution rate constant of nontronite at 25.0 °C at activities of water (aH2O) of 1.00 (0.01 M CaCl2 or NaCl), 0.75 (saturated NaCl or 3.00 mol kg-1 CaCl2), and 0.50 (5.00 mol kg-1 CaCl2). Experiments at aH2O = 1.00 (0.01 M CaCl2) were also conducted at 4.0 °C, 25.0 °C, and 45.0 °C to measure an apparent activation energy for the dissolution of nontronite. Apparent dissolution rate constants at 25.0 °C in CaCl2-containing solutions decrease with decreasing activity of water as follows: 1.18 × 10-12 ± 9 × 10-14 mol mineral m-2 s-1 (aH2O = 1.00) > 2.36 × 10-13 ± 3.1 × 10-14 mol mineral m-2 s-1 (aH2O = 0.75) > 2.05 × 10-14 ± 2.9 × 10-15 mol mineral m-2 s-1 (aH2O = 0.50). Similar results were observed at 25.0 °C in NaCl-containing solutions: 1.89 × 10-12 ± 1 × 10-13 mol mineral m-2 s-1 (aH2O = 1.00) > 1.98 × 10-13 ± 2.3 × 10-14 mol mineral m-2 s-1 (aH2O = 0.75). This decrease in apparent dissolution rate constants with decreasing activity of water follows a relationship of the form: log kdiss = 3.70 ± 0.20 × aH2O - 15.49, where kdiss is the apparent dissolution rate constant, and aH2O is the activity of water. The slope of this relationship (3.70 ± 0.20) is within uncertainty of that of other minerals where the relationship between dissolution rates and activity of water has been tested, including forsteritic olivine (log R = 3.27 ± 0.91 × aH2O - 11.00) (Olsen et al., 2015) and jarosite (log R = 3.85 ± 0.43 × aH2O - 12.84) (Dixon et al., 2015), where R is the mineral dissolution rate. This result allows prediction of mineral dissolution as a function of activity of water and suggests that with decreasing activity of water, mineral

Improving the dissolution rate of poorly water soluble drug by solid dispersion and solid solution: pros and cons.

PubMed

Chokshi, Rina J; Zia, Hossein; Sandhu, Harpreet K; Shah, Navnit H; Malick, Waseem A

2007-01-01

The solid dispersions with poloxamer 188 (P188) and solid solutions with polyvinylpyrrolidone K30 (PVPK30) were evaluated and compared in an effort to improve aqueous solubility and bioavailability of a model hydrophobic drug. All preparations were characterized by differential scanning calorimetry, powder X-ray diffraction, intrinsic dissolution rates, and contact angle measurements. Accelerated stability studies also were conducted to determine the effects of aging on the stability of various formulations. The selected solid dispersion and solid solution formulations were further evaluated in beagle dogs for in vivo testing. Solid dispersions were characterized to show that the drug retains its crystallinity and forms a two-phase system. Solid solutions were characterized to be an amorphous monophasic system with transition of crystalline drug to amorphous state. The evaluation of the intrinsic dissolution rates of various preparations indicated that the solid solutions have higher initial dissolution rates compared with solid dispersions. However, after storage at accelerated conditions, the dissolution rates of solid solutions were lower due to partial reversion to crystalline form. The drug in solid dispersion showed better bioavailability in comparison to solid solution. Therefore, considering physical stability and in vivo study results, the solid dispersion was the most suitable choice to improve dissolution rates and hence the bioavailability of the poorly water soluble drug.

Effect of chemical composition of man-made vitreous fibers on the rate of dissolution in vitro at different pHs.

PubMed

Christensen, V R; Jensen, S L; Guldberg, M; Kamstrup, O

1994-10-01

Measurements of rates of dissolution of typical insulation wool fibers (glasswool and basalt based stonewool) and an experimental fiber were made using a flow-through equipment. The liquids used were a modified Gamble's solution, adjusted to pH 4.8 and 7.7 +/- 0.2, respectively. The dissolution of SiO2 and CaO was determined over periods of up to three months. The rate of dissolution of stonewool fibers was lower than that of glasswool fibers at pH 7.7, whereas the opposite was true at pH 4.8. The stonewool fibers dissolve congruently, but glasswool fibers tend to dissolve with leaching. The rates of dissolution of fibers of different compositions, including insulation wool (glasswool, basalt-based stonewool, slagwool) and experimental fibers were screened using a stationary set-up. Both the chemical composition and pH influenced the rates of dissolution. At pH 7.7 alumina was a determining component and at pH 4.8 the content of SiO2 and CaO was determinant. One experimental fiber with a high content of alumina was an exception having a fairly high rate of dissolution both at pH 4.8 and 7.7.

Effect of chemical composition of man-made vitreous fibers on the rate of dissolution in vitro at different pHs.

PubMed Central

Christensen, V R; Jensen, S L; Guldberg, M; Kamstrup, O

1994-01-01

Measurements of rates of dissolution of typical insulation wool fibers (glasswool and basalt based stonewool) and an experimental fiber were made using a flow-through equipment. The liquids used were a modified Gamble's solution, adjusted to pH 4.8 and 7.7 +/- 0.2, respectively. The dissolution of SiO2 and CaO was determined over periods of up to three months. The rate of dissolution of stonewool fibers was lower than that of glasswool fibers at pH 7.7, whereas the opposite was true at pH 4.8. The stonewool fibers dissolve congruently, but glasswool fibers tend to dissolve with leaching. The rates of dissolution of fibers of different compositions, including insulation wool (glasswool, basalt-based stonewool, slagwool) and experimental fibers were screened using a stationary set-up. Both the chemical composition and pH influenced the rates of dissolution. At pH 7.7 alumina was a determining component and at pH 4.8 the content of SiO2 and CaO was determinant. One experimental fiber with a high content of alumina was an exception having a fairly high rate of dissolution both at pH 4.8 and 7.7. PMID:7882962

Role of Solvents in Improvement of Dissolution Rate of Drugs: Crystal Habit and Crystal Agglomeration

PubMed Central

Maghsoodi, Maryam

2015-01-01

Crystallization is often used for manufacturing drug substances. Advances of crystallization have achieved control over drug identity and purity, but control over the physical form remains poor. This review discusses the influence of solvents used in crystallization process on crystal habit and agglomeration of crystals with potential implication for dissolution. According to literature it has been known that habit modification of crystals by use of proper solvents may enhance the dissolution properties by changing the size, number and the nature of crystal faces exposed to the dissolution medium. Also, the faster dissolution rate of drug from the agglomerates of crystals compared with the single crystals may be related to porous structure of the agglomerates and consequently their better wettability. It is concluded from this review that in-depth understanding of role of the solvents in crystallization process can be applied to engineering of crystal habit or crystal agglomeration, and predictably dissolution improvement in poorly soluble drugs. PMID:25789214

Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

USGS Publications Warehouse

Brown, J.G.; Glynn, P.D.

2003-01-01

The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

Kinetics of scheelite dissolution in groundwater: defining the release rate of tungsten contamination from a natural source

NASA Astrophysics Data System (ADS)

Montgomery, S. D.; Mckibben, M. A.

2011-12-01

Tungsten, an emerging contaminant, has no EPA standard for its permissible levels in drinking water. At sites in California, Nevada, and Arizona there may be a correlation between elevated levels of tungsten in drinking water and clusters of childhood acute lymphocytic leukemia (ALL). Developing a better understanding of how tungsten is released from rocks into surface and groundwaters is therefore of growing environmental interest. Knowledge of tungstate ore mineral weathering processes, particularly the rates of dissolution of scheelite (CaWO4) in groundwater, could improve models of how tungsten is released and transported in natural waters. Our research is focusing on experimental determination of the rates and products of tungstate mineral dissolution in synthetic groundwater, as a function of temperature, pH and mineral surface area. The initial rate method is being used to develop rate laws. Batch reactor experiments are conducted within constant temperature circulation baths over a pH range of 2-9. Cleaned scheelite powder with grain diameters of 106-150um is placed between two screens in a sample platform and then placed inside a two liter Teflon vessel filled with synthetic groundwater. Ports on the vessel allow sample extraction, temperature and pH measurement, gas inflow, and water circulation. Aliquots of solution are taken periodically for product analysis by ICP -MS. Changes in mineral surface characteristics are monitored using SEM and EDS methods. Results so far reveal that the dissolution of scheelite is incongruent at both neutral and low pH. Solid tungstic acid forms on scheelite mineral surfaces under acidic conditions, implying that this phase controls the dissolution rate in acidic environments. The influence of dissolved CO2 and resultant calcium carbonate precipitation on the dissolution of scheelite at higher pH is also being investigated. The rate law being developed for scheelite dissolution will be useful in reactive-transport computer

Differing disintegration and dissolution rates, pharmacokinetic profiles and gastrointestinal tolerability of over the counter ibuprofen formulations.

PubMed

Bjarnason, Ingvar; Sancak, Ozgur; Crossley, Anne; Penrose, Andrew; Lanas, Angel

2018-02-01

Formulations of over the counter (OTC) NSAIDs differ substantially, but information is lacking on whether this alters their gastrointestinal profiles. To assess disintegration and dissolution rates and pharmacokinetics of four preparations of OTC ibuprofen and relate these with spontaneously reported gastrointestinal adverse events. Disintegration and dissolution rates of ibuprofen tablets as (a) acid, (b) sodium salt, (c) lysine salt, and (d) as a liquid gelatine capsule were assessed. Pharmacokinetic data gastrointestinal and spontaneously reported adverse events arising from global sales were obtained from files from Reckitt Benckiser. Disintegration at low pH was progressively shorter for the preparations from a-to-d with formation of correspondingly smaller ibuprofen crystals, while dissolution was consistently poor. Dissolution at a neutral pH was least rapid for the liquid gelatine capsule. Pharmacokinetic data showed a shorter t max and a higher C max for preparations b-d as compared with ibuprofen acid. Spontaneously reported abdominal symptoms were rare with the liquid gelatine preparation. The formulations of OTC ibuprofen differ in their disintegration and dissolution properties, pharmacokinetic profiles and apparent gastrointestinal tolerability. Spontaneously reported abdominal symptoms were five times lower with the liquid gelatine capsule as compared with ibuprofen acid despite a 30% increase in C max . © 2017 Royal Pharmaceutical Society.

Dissolution of minerals with rough surfaces

NASA Astrophysics Data System (ADS)

de Assis, Thiago A.; Aarão Reis, Fábio D. A.

2018-05-01

We study dissolution of minerals with initial rough surfaces using kinetic Monte Carlo simulations and a scaling approach. We consider a simple cubic lattice structure, a thermally activated rate of detachment of a molecule (site), and rough surface configurations produced by fractional Brownian motion algorithm. First we revisit the problem of dissolution of initial flat surfaces, in which the dissolution rate rF reaches an approximately constant value at short times and is controlled by detachment of step edge sites. For initial rough surfaces, the dissolution rate r at short times is much larger than rF ; after dissolution of some hundreds of molecular layers, r decreases by some orders of magnitude across several time decades. Meanwhile, the surface evolves through configurations of decreasing energy, beginning with dissolution of isolated sites, then formation of terraces with disordered boundaries, their growth, and final smoothing. A crossover time to a smooth configuration is defined when r = 1.5rF ; the surface retreat at the crossover is approximately 3 times the initial roughness and is temperature-independent, while the crossover time is proportional to the initial roughness and is controlled by step-edge site detachment. The initial dissolution process is described by the so-called rough rates, which are measured for fixed ratios between the surface retreat and the initial roughness. The temperature dependence of the rough rates indicates control by kink site detachment; in general, it suggests that rough rates are controlled by the weakest microscopic bonds during the nucleation and formation of the lowest energy configurations of the crystalline surface. Our results are related to recent laboratory studies which show enhanced dissolution in polished calcite surfaces. In the application to calcite dissolution in alkaline environment, the minimal values of recently measured dissolution rate spectra give rF ∼10-9 mol/(m2 s), and the calculated rate

Bulk Dissolution Rates of Cadmium and Bismuth Tellurides As a Function of pH, Temperature and Dissolved Oxygen.

PubMed

Biver, Marc; Filella, Montserrat

2016-05-03

The toxicity of Cd being well established and that of Te suspected, the bulk, surface-normalized steady-state dissolution rates of two industrially important binary tellurides-polycrystalline cadmium and bismuth tellurides- were studied over the pH range 3-11, at various temperatures (25-70 °C) and dissolved oxygen concentrations (0-100% O2 in the gas phase). The behavior of both tellurides is strikingly different. The dissolution rates of CdTe monotonically decreased with increasing pH, the trend becoming more pronounced with increasing temperature. Activation energies were of the order of magnitude associated with surface controlled processes; they decreased with decreasing acidity. At pH 7, the CdTe dissolution rate increased linearly with dissolved oxygen. In anoxic solution, CdTe dissolved at a finite rate. In contrast, the dissolution rate of Bi2Te3 passed through a minimum at pH 5.3. The activation energy had a maximum in the rate minimum at pH 5.3 and fell below the threshold for diffusion control at pH 11. No oxygen dependence was detected. Bi2Te3 dissolves much more slowly than CdTe; from one to more than 3.5 orders of magnitude in the Bi2Te3 rate minimum. Both will readily dissolve under long-term landfill deposition conditions but comparatively slowly.

Magnesite Dissolution Rates Across Scales: Role of Spatial Heterogeneity, Equilibrium Lengths, and Reactive Time Scales

NASA Astrophysics Data System (ADS)

Wen, H.; Li, L.

2017-12-01

This work develops a general rate law for magnesite dissolution in heterogeneous media under variable flow and length conditions, expanding the previous work under one particular flow and length conditions (Wen and Li, 2017). We aim to answer: 1) How does spatial heterogeneity influence the time and length scales to reach equilibrium? 2) How do relative timescales of advection, diffusion/dispersion, and reactions influence dissolution rates under variable flow and length conditions? We carried out 640 Monte-Carlo numerical experiments of magnesite dissolution within quartz matrix with heterogeneity characterized by permeability variance and correlation length under a range of length and flow velocity. A rate law Rhete = kAT(1-exp(τeq,m/τa))(1-exp(- Lβ))^α was developed. The former part is rates in equivalent homogeneous media kAT(1-exp(τeq,m/τa)), depending on rate constant k, magnesite surface area AT, and relative timescales of reactions τeq,m and advection τa. The latter term (1-exp(- Lβ))^α is the heterogeneity factor χ that quantifies the deviation of heterogeneous media from its homogeneous counterpart. The term has a scaling factor, called reactive transport number β=τa/(τad,r+τeq,m), for domain length L, and the geostatistical characteristics of heterogeneity α. The β quantifies the relative timescales of advection at the domain scale τa versus the advective-diffusive-dispersive transport time out of reactive zones τad,r and reaction time τeq,m. The χ is close to 1 and is insignificant under long residence time conditions (low flow velocity and / or long length) where the residence time is longer than the time needed for Mg to dissolve and transport out of reactive zones (τad,r+τeq,m) so that equilibrium is reached and homogenization occurs. In contrast, χ deviates from 1 and is significant only when β is small, which occurs at short length or fast flow where timescales of reactive transport in reactive zones are much longer than

Low temperature dissolution flowsheet for Pu metal

DOE PAGES

Daniel, Jr., William E.; Almond, Philip M.; Rudisill, Tracy S.

2017-06-30

The Savannah River National Laboratory was requested to develop a Pu metal dissolution flowsheet at two reduced temperature ranges for implementation in the Savannah River Site H-Canyon facility. The dissolution and H 2 generation rates during Pu metal dissolution were investigated using a dissolving solution at ambient temperature (20–30°C) and for an intermediate temperature of 50–60°C. The Pu metal dissolution rate measured at 57°C was approximately 20 times slower than at boiling (112–116°C). As a result, the dissolution rate at ambient temperature (24°C) was approximately 80 times slower than the dissolution rate at boiling. Hydrogen concentrations were less than detectablemore » (<0.1 vol%).« less

INFLUENCE OF TYPE AND NEUTRALISATION CAPACITY OF ANTACIDS ON DISSOLUTION RATE OF CIPROFLOXACIN AND MOXIFLOXACIN FROM TABLETS

PubMed Central

Uzunović, Alija; Vranić, Edina

2009-01-01

Dissolution rate of two fluoroquinolone antibiotics (ciprofloxacin and moxifloxacin) was analysed in presence/absence of three antacid formulations. Disintegration time and neutralisation capacity of antacid tablets were also checked. Variation in disintegration time indicated the importance of this parameter, and allowed evaluation of the influence of postponed antacid-fluoroquinolone contact. The results obtained in this study showed decreased dissolution rate of fluoroquinolone antibiotics from tablets in simultaneous presence of antacids, regardless of their type and neutralisation capacity. PMID:19284403

Dolomite dissolution rates and possible Holocene dedolomitization of water-bearing units in the Edwards aquifer, south-central Texas

USGS Publications Warehouse

Deike, R.G.

1990-01-01

Rates of dolomite dissolution can be used to test the concept, based on geomorphologic evidence, that a major part of the Edwards aquifer could have formed within the Holocene, a timeframe of approximately 10,000 years. During formation of the aquifer in the Edwards limestone (Cretaceous, Albian) of the Balcones fault zone, dolomite dissolution and porosity development were synchronous and the result of mixing-zone dedolomitization. Initiation of the mixing zone in the early Holocene (???11,000 years before present) is suggested by the maximum age of formation of major discharge sites that allowed the influx of meteoric water into brine-filled, dolomitic preaquifer units. Dedolomitization, the dissolution of dolomite and net precipitation of calcite, has left aquifer units that are calcitic, and 40 vol.% interconnected pore space. The mass of dolomite missing is obtained by comparison of stratigraphically equivalent altered and unaltered units. One dissolution rate (1.76 ?? 10-4 mmol dolomite kgH2O-1yr-1) is determined from this mass, 104yr reaction time, and a log-linear function describing the increase in mass discharge (three orders of magnitude) during aquifer formation. The second estimated dissolution rate is obtained from the mass transfer of dolomite to solution calculated from the increase in magnesium in pore fluids selected from the modern aquifer to represent a typical flowpath during aquifer formation. A reaction time of 104yr for this mass transfer yields a rate of 0.56 ?? 10-4 mmol dolomite kgH2O-1yr-1. Both of these rates are comparable to modern rates of dolomite dissolution (0.3 to 4.5 ?? 10-4 mmol dolomite kgH2O-1yr-1) calculated from measured reaction times in the Tertiary Floridan aquifer system in Florida and the Madison aquifer in the Mississippian Madison Limestone of the Northern Great Plains. Similarity of these rates to the estimated paleo-rates of dolomite dissolution supports a 104 yr reaction timeframe. The Holocene reaction time also

Liquigroud technique: a new concept for enhancing dissolution rate of glibenclamide by combination of liquisolid and co-grinding technologies.

PubMed

Azharshekoufeh, Leila; Shokri, Javad; Barzegar-Jalali, Mohammad; Javadzadeh, Yousef

2017-01-01

Introduction: The potential of combining liquisolid and co-grinding technologies (liquiground technique) was investigated to improve the dissolution rate of a water-insoluble agent (glibenclamide) with formulation-dependent bioavailability. Methods: To this end, different formulations of liquisolid tablets with a wide variety of non-volatile solvents contained varied ratios of drug: solvent and dissimilar carriers were prepared, and then their release profiles were evaluated. Furthermore, the effect of size reduction by ball milling on the dissolution behavior of glibenclamide from liquisolid tablets was investigated. Any interaction between the drug and the excipient or crystallinity changes during formulation procedure was also examined using X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results: The present study revealed that classic liquisolid technique did not significantly affect the drug dissolution profile as compared to the conventional tablets. Size reduction obtained by co-grinding of liquid medication was more effective than the implementation of liquisolid technique in enhancing the dissolution rate of glibenclamide. The XRD and DSC data displayed no formation of complex or any crystallinity changes in both formulations. Conclusion: An enhanced dissolution rate of glibenclamide is achievable through the combination of liquisolid and co-grinding technologies.

Hot Melt Extrudates Formulated Using Design Space: One Simple Process for Both Palatability and Dissolution Rate Improvement.

PubMed

Malaquias, Lorena F B; Schulte, Heidi L; Chaker, Juliano A; Karan, Kapish; Durig, Thomas; Marreto, Ricardo N; Gratieri, Tais; Gelfuso, Guilherme M; Cunha-Filho, Marcilio

2018-01-01

This work aimed at obtaining an optimized itraconazole (ITZ) solid oral formulation in terms of palatability and dissolution rate by combining different polymers using hot melt extrusion (HME), according to a simplex centroid mixture design. For this, the polymers Plasdone ® (poly(1-vinylpyrrolidone-co-vinyl acetate) [PVP/VA]), Klucel ® ELF (2-hydroxypropyl ether cellulose [HPC]), and Soluplus ® (SOL, polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol) were processed using a laboratory HME equipment operating without recirculation at constant temperature. Samples were characterized by physicochemical assays, as well as dissolution rate and palatability using an e-tongue. All materials became homogeneous and dense after HME processing. Thermal and structural analyses demonstrated drug amorphization, whereas IR spectroscopy evidenced drug stability and drug-excipient interactions in HME systems. Extrudates presented a significant increase in dissolution rate compared to ITZ raw material, mainly with formulations containing PVP/VA and HPC. A pronounced improvement in taste masking was also identified for HME systems, especially in those containing higher amounts of SOL and HPC. Data showed polymers act synergistically favoring formulation functional properties. Predicted best formulation should contain ITZ 25.0%, SOL 33.2%, HPC 28.9%, and PVP/VA 12.9% (w/w). Optimized response considering dissolution rate and palatability reinforces the benefit of polymer combinations. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Dissolution rates of pure methane hydrate and carbon-dioxide hydrate in undersaturated seawater at 1000-m depth

USGS Publications Warehouse

Rehder, G.; Kirby, S.H.; Durham, W.B.; Stern, L.A.; Peltzer, E.T.; Pinkston, J.; Brewer, P.G.

2004-01-01

To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH4 and CO2 hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 ??m/s and between 9.0 and 10.6 ?? 10-2 ??m/s for the CO2 and CH4 hydrates, respectively, corresponding to dissolution rates of 4.15 ?? 0.5 mmol CO2/m2s and 0.37 ?? 0.03 mmol CH4/m2s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH4) or tens of mm (CO2) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO2 hydrates in marine carbon sequestration strategies. ?? 2003 Elsevier Ltd.

Acid decomposition and thiourea leaching of silver from hazardous jarosite residues: Effect of some cations on the stability of the thiourea system.

PubMed

Calla-Choque, D; Nava-Alonso, F; Fuentes-Aceituno, J C

2016-11-05

The recovery of silver from hazardous jarosite residues was studied employing thiourea as leaching agent at acid pH and 90°C. The stability of the thiourea in synthetic solutions was evaluated in the presence of some cations that can be present in this leaching system: cupric and ferric ions as oxidant species, and zinc, lead and iron as divalent ions. Two silver leaching methods were studied: the simultaneous jarosite decomposition-silver leaching, and the jarosite decomposition followed by the silver leaching. The study with synthetic solutions demonstrated that cupric and ferric ions have a negative effect on thiourea stability due to their oxidant properties. The effect of cupric ions is more significant than the effect of ferric ions; other studied cations (Fe(2+), Zn(2+), Pb(2+)) had no effect on the stability of thiourea. When the decomposition of jarosite and the silver leaching are carried out simultaneously, 70% of the silver can be recovered. When the acid decomposition was performed at pH 0.5 followed by the leaching step at pH 1, total silver recovery increased up to 90%. The zinc is completely dissolved with any of these processes while the lead is practically insoluble with these systems producing a lead-rich residue. Copyright © 2016 Elsevier B.V. All rights reserved.

A novel determination of calcite dissolution kinetics in seawater

NASA Astrophysics Data System (ADS)

Subhas, Adam V.; Rollins, Nick E.; Berelson, William M.; Dong, Sijia; Erez, Jonathan; Adkins, Jess F.

2015-12-01

We present a novel determination of the dissolution kinetics of inorganic calcite in seawater. We dissolved 13 C -labeled calcite in unlabeled seawater, and traced the evolving δ13 C composition of the fluid over time to establish dissolution rates. This method provides sensitive determinations of dissolution rate, which we couple with tight constraints on both seawater saturation state and surface area of the dissolving minerals. We have determined dissolution rates for two different abiotic calcite materials and three different grain sizes. Near-equilibrium dissolution rates are highly nonlinear, and are well normalized by geometric surface area, giving an empirical dissolution rate dependence on saturation state (Ω) of: This result substantiates the non-linear response of calcite dissolution to undersaturation. The bulk dissolution rate constant calculated here is in excellent agreement with those determined in far from equilibrium and dilute solution experiments. Plots of dissolution versus undersaturation indicates the presence of at least two dissolution mechanisms, implying a criticality in the calcite-seawater system. Finally, our new rate determination has implications for modeling of pelagic and seafloor dissolution. Nonlinear dissolution kinetics in a simple 1-D lysocline model indicate a possible transition from kinetic to diffusive control with increasing water depth, and also confirm the importance of respiration-driven dissolution in setting the shape of the calcite lysocline.

Bio-dissolution of Ni, V and Mo from spent petroleum catalyst using iron oxidizing bacteria.

PubMed

Pradhan, Debabrata; Kim, Dong J; Roychaudhury, Gautam; Lee, Seoung W

2010-01-01

Bioleaching studies of spent petroleum catalyst containing Ni, V and Mo were carried out using iron oxidizing bacteria. Various leaching parameters such as Fe(II) concentration, pulp density, pH, temperature and particle size were studied to evaluate their effects on the leaching efficiency as well as the kinetics of dissolution. The percentage of leaching of Ni and V were higher than Mo. The leaching process followed a diffusion controlled model and the product layer was observed to be impervious due to formation of ammonium jarosite (NH(4))Fe(3)(SO(4))(2)(OH)(6). Apart from this, the lower leaching efficiency of Mo was due to a hydrophobic coating of elemental sulfur over Mo matrix in the spent catalyst. The diffusivities of the attacking species for Ni, V and Mo were also calculated.

Variable-focus microscopy and UV surface dissolution imaging as complementary techniques in intrinsic dissolution rate determination.

PubMed

Ward, Adam; Walton, Karl; Box, Karl; Østergaard, Jesper; Gillie, Lisa J; Conway, Barbara R; Asare-Addo, Kofi

2017-09-15

This work reports a novel approach to the assessment of the surface properties of compacts used in Surface Dissolution Imaging (SDI). SDI is useful for determining intrinsic dissolution rate (IDR), an important parameter in early stage drug development. Surface topography, post-compaction and post-SDI run, have been measured using a non-contact, optical, three-dimensional microscope based on focus variation, the Alicona Infinite Focus Microscope, with the aim of correlating the IDRs to the surface properties. Ibuprofen (IBU) was used as a model poorly-soluble drug. DSC and XRD were used to monitor possible polymorphic changes that may have occurred post-compaction and post-SDI run. IBUs IDR decreased from 0.033mg/min/cm 2 to 0.022mg/min/cm 2 from 10 to 20min, respectively, during the experiment. XRD and DSC showed no form changes during the SDI run. The surface topography images showed that a distinct imprint was embossed on the surfaces of some compacts which could affect IDRs. Surface parameter values were associated with the SDI experiments which showed strong correlations with the IDR values. The variable-focus microscope can be used as a complimentary tool in the determination of IDR values from the SDI. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico III: Quartz dissolution rates

USGS Publications Warehouse

Schulz, M.S.; White, A.F.

1999-01-01

The paucity of weathering rates for quartz in the natural environment stems both from the slow rate at which quartz dissolves and the difficulty in differentiating solute Si contributed by quartz from that derived from other silicate minerals. This study, a first effort in quantifying natural rates of quartz dissolution, takes advantage of extremely rapid tropical weathering, simple regolith mineralogy, and detailed information on hydrologic and chemical transport. Quartz abundances and grain sizes are relatively constant with depth in a thick saprolite. Limited quartz dissolution is indicated by solution rounding of primary angularity and by the formation of etch pits. A low correlation of surface area (0.14 and 0.42 m2 g-1) with grain size indicates that internal microfractures and pitting are the principal contributors to total surface area. Pore water silica concentration increases linearly with depth. On a molar basis, between one and three quarters of pore water silica is derived from quartz with the remainder contributed from biotite weathering. Average solute Si remains thermodynamically undersaturated with respect to recently revised estimates of quartz solubility (17-81 ??M). Etch pitting is more abundant on grains in the upper saprolite and is associated with pore waters lower in dissolved silica. Rate constants describing quartz dissolution increase with decreasing depth (from 10-14.5-10-15.1 mol m-2 s-1), which correlate with both greater thermodynamic undersaturation and increasing etch pit densities. Unlike for many aluminosilicates, the calculated natural weathering rates of quartz fall slightly below the rate constants previously reported for experimental studies (10-12.4-10-14.2 mol m-2 s-1). This agreement reflects the structural simplicity of quartz, dilute solutes, and near-hydrologic saturation.

Dissolution and Precipitation Behaviour during Continuous Heating of Al–Mg–Si Alloys in a Wide Range of Heating Rates

PubMed Central

Osten, Julia; Milkereit, Benjamin; Schick, Christoph; Kessler, Olaf

2015-01-01

In the present study, the dissolution and precipitation behaviour of four different aluminium alloys (EN AW-6005A, EN AW-6082, EN AW-6016, and EN AW-6181) in four different initial heat treatment conditions (T4, T6, overaged, and soft annealed) was investigated during heating in a wide dynamic range. Differential scanning calorimetry (DSC) was used to record heating curves between 20 and 600 °C. Heating rates were studied from 0.01 K/s to 5 K/s. We paid particular attention to control baseline stability, generating flat baselines and allowing accurate quantitative evaluation of the resulting DSC curves. As the heating rate increases, the individual dissolution and precipitation reactions shift to higher temperatures. The reactions during heating are significantly superimposed and partially run simultaneously. In addition, precipitation and dissolution reactions are increasingly suppressed as the heating rate increases, whereby exothermic precipitation reactions are suppressed earlier than endothermic dissolution reactions. Integrating the heating curves allowed the enthalpy levels of the different initial microstructural conditions to be quantified. Referring to time–temperature–austenitisation diagrams for steels, continuous heating dissolution diagrams for aluminium alloys were constructed to summarise the results in graphical form. These diagrams may support process optimisation in heat treatment shops.

Evaluation of correlation between dissolution rates of loxoprofen tablets and their surface morphology observed by scanning electron microscope and atomic force microscope.

PubMed

Yoshikawa, Shinichi; Murata, Ryo; Shida, Shigenari; Uwai, Koji; Suzuki, Tsuneyoshi; Katsumata, Shunji; Takeshita, Mitsuhiro

2010-01-01

We observed the surface morphological structures of 60 mg tablets of Loxonin, Loxot, and Lobu using scanning electron microscope (SEM) and atomic force microscope (AFM) to evaluate the dissolution rates. We found a significant difference among the initial dissolution rates of the three kinds of loxoprofen sodium tablets. Petal forms of different sizes were commonly observed on the surface of the Loxonin and Loxot tablets in which loxoprofen sodium was confirmed by measuring the energy-dispersible X-ray (EDX) spectrum of NaKalpha using SEM. However, a petal form was not observed on the surface of the Lobu tablet, indicating differences among the drug production processes. Surface area and particle size of the principal ingredient in tablets are important factors for dissolution rate. The mean size of the smallest fine particles constituting each tablet was also determined with AFM. There was a correlation between the initial dissolution rate and the mean size of the smallest particles in each tablet. Visualizing tablet surface morphology using SEM and AFM provides information on the drug production processes and initial dissolution rate, and is associated with the time course of pharmacological activities after tablet administration.

Non-destructive prediction of enteric coating layer thickness and drug dissolution rate by near-infrared spectroscopy and X-ray computed tomography.

PubMed

Ariyasu, Aoi; Hattori, Yusuke; Otsuka, Makoto

2017-06-15

The coating layer thickness of enteric-coated tablets is a key factor that determines the drug dissolution rate from the tablet. Near-infrared spectroscopy (NIRS) enables non-destructive and quick measurement of the coating layer thickness, and thus allows the investigation of the relation between enteric coating layer thickness and drug dissolution rate. Two marketed products of aspirin enteric-coated tablets were used in this study, and the correlation between the predicted coating layer thickness and the obtained drug dissolution rate was investigated. Our results showed correlation for one product; the drug dissolution rate decreased with the increase in enteric coating layer thickness, whereas, there was no correlation for the other product. Additional examination of the distribution of coating layer thickness by X-ray computed tomography (CT) showed homogenous distribution of coating layer thickness for the former product, whereas the latter product exhibited heterogeneous distribution within the tablet, as well as inconsistent trend in the thickness distribution between the tablets. It was suggested that this heterogeneity and inconsistent trend in layer thickness distribution contributed to the absence of correlation between the layer thickness of the face and side regions of the tablets, which resulted in the loss of correlation between the coating layer thickness and drug dissolution rate. Therefore, the predictability of drug dissolution rate from enteric-coated tablets depended on the homogeneity of the coating layer thickness. In addition, the importance of micro analysis, X-ray CT in this study, was suggested even if the macro analysis, NIRS in this study, are finally applied for the measurement. Copyright © 2017 Elsevier B.V. All rights reserved.

On the influence of etch pits in the overall dissolution rate of apatite basal sections

NASA Astrophysics Data System (ADS)

Alencar, Igor; Guedes, Sandro; Palissari, Rosane; Hadler, Julio C.

2015-09-01

Determination of efficiencies for particle detection plays a central role for proper estimation of reaction rates. If chemical etching is employed in the revelation of latent particle tracks in solid-state detectors, dissolution rates and etchable lengths are important factors governing the revelation and observation. In this work, the mask method, where a reference part of the sample is protected during dissolution, was employed to measure step heights in basal sections of apatite etched with a nitric acid, HNO, solution at a concentration of 1.1 M and a temperature of 20 °C. We show a drastic increase in the etching velocity as the number of etch pits in the surface augments, in accordance with the dissolution stepwave model, where the outcrop of each etch pit generates a continuous sequence of stepwaves. The number of etch pits was varied by irradiation with neutrons and perpendicularly incident heavy ions. The size dependence of the etch-pit opening with etching duration for ion (200-300 MeV 152Sm and 238U) tracks was also investigated. There is no distinction for the etch pits between the different ions, and the dissolution seems to be governed by the opening velocity when a high number of etch pits are present in the surface. Measurements of the etchable lengths of these ion tracks show an increase in these lengths when samples are not pre-annealed before irradiation. We discuss the implications of these findings for fission-track modelling.

Morphological evolution of dissolving feldspar particles with anisotropic surface kinetics and implications for dissolution rate normalization and grain size dependence: A kinetic modeling study

NASA Astrophysics Data System (ADS)

Zhang, Li; Lüttge, Andreas

2009-11-01

With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms ( Zhang and Lüttge, 2008, 2009), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si ( ΦSi-O-Si/ kT) and Al-(O)-Si ( ΦAl-O-Si/ kT). When the ratio of ΦSi-O-Si/ kT to ΦAl-O-Si/ kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive

Determining the dissolution rates of actinide glasses: A time and temperature Product Consistency Test study

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

Daniel, W.E.; Best, D.R.

1995-12-01

Vitrification has been identified as one potential option for the e materials such as Americium (Am), Curium (Cm), Neptunium (Np), and Plutonium (Pu). A process is being developed at the Savannah River Site to safely vitrify all of the highly radioactive Am/Cm material and a portion of the fissile (Pu) actinide materials stored on site. Vitrification of the Am/Cm will allow the material to be transported and easily stored at the Oak Ridge National Laboratory. The Am/Cm glass has been specifically designed to be (1) highly durable in aqueous environments and (2) selectively attacked by nitric acid to allow recoverymore » of the valuable Am and Cm isotopes. A similar glass composition will allow for safe storage of surplus plutonium. This paper will address the composition, relative durability, and dissolution rate characteristics of the actinide glass, Loeffler Target, that will be used in the Americium/Curium Vitrification Project at Westinghouse Savannah River Company near Aiken, South Carolina. The first part discusses the tests performed on the Loeffler Target Glass concerning instantaneous dissolution rates. The second part presents information concerning pseudo-activation energy for the one week glass dissolution process.« less

Solid dispersions, part II: new strategies in manufacturing methods for dissolution rate enhancement of poorly water-soluble drugs.

PubMed

Bikiaris, Dimitrios N

2011-12-01

The absorption of poorly water-soluble drugs, when presented in the crystalline state to the gastrointestinal tract, is typically dissolution rate-limited, and according to BCS these drugs belong mainly to class II. Both dissolution kinetics and solubility are particle size dependent. Nowadays, various techniques are available to the pharmaceutical industry for dissolution rate enhancement of such drugs. Among such techniques, nanosuspensions and drug formulation in solid dispersions are those with the highest interest. This review discusses strategies undertaken over the last 10 years, which have been applied for the dissolution enhancement of poorly water-soluble drugs; such processes include melt mixing, electrospinning, microwave irradiation and the use of inorganic nanoparticles. Many problems in this field still need to be solved, mainly the use of toxic solvents, and for this reason the use of innovative new procedures and materials will increase over the coming years. Melt mixing remains extremely promising for the preparation of SDs and will probably become the most used method in the future for the preparation of solid drug dispersions.

Swelling and erosion properties of hydroxypropylmethylcellulose (Hypromellose) matrices--influence of agitation rate and dissolution medium composition.

PubMed

Kavanagh, Nicole; Corrigan, Owen I

2004-07-26

The effect of dissolution medium variables, such as medium composition, ionic strength and agitation rate, on the swelling and erosion of Hypromellose (hydroxypropylmethylcellulose, HPMC) matrices of different molecular weights was examined. Swelling and erosion of HPMC polymers was determined by measuring the wet and subsequent dry weights of matrices. It was possible to describe the rate of dissolution medium uptake in terms of a square root relationship and the erosion of the polymer in terms of the cube root law. The extent of swelling increased with increasing molecular weight, and decreased with increasing agitation rate. The erosion rate was seen to increase with decrease in polymer molecular weight, with a decrease in ionic strength and with increasing agitation rate. The sensitivity of polymer erosion to the degree of agitation may influence the ability of these polymers to give reproducible, agitation-independent release, compared to more rigid non-eroding matrix materials, in the complex hydrodynamic environment of the gastrointestinal tract.

The Kinetics of Dissolution Revisited

NASA Astrophysics Data System (ADS)

Antonel, Paula S.; Hoijemberg, Pablo A.; Maiante, Leandro M.; Lagorio, M. Gabriela

2003-09-01

An experiment analyzing the kinetics of dissolution of a solid with cylindrical geometry in water is presented. The dissolution process is followed by measuring the solid mass and its size parameters (thickness and diameter) as a function of time. It is verified that the dissolution rate follows the Nernst model. Data treatment is compared with the dissolution of a spherical solid previously described. Kinetics, diffusion concepts, and polynomial fitting of experimental data are combined in this simple experiment.

Accurate rates of the complex mechanisms for growth and dissolu-tion of minerals using a combination of rare event theories

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

Stack, Andrew G; Raiten, Paolo; Gale, Julian D.

2012-01-01

Mineral growth and dissolution are often treated as occurring via a single, reversible process that governs the rate of reaction. We show that multiple, distinct intermediate states can occur during both growth and dissolution. Specifically, we have used metadynamics, a method to efficiently explore the free energy landscape of a system, coupled to umbrella sampling and reactive flux calculations, to examine the mechanism and rates of attachment and detachment of a barium ion onto a stepped, barite (BaSO4) surface. The activation energies calculated for the rate limiting reactions, which are different for attachment and detachment, precisely match those measured experimentallymore » during both growth and dissolution. These results can potentially explain anomalous, non-steady state mineral reaction rates observed experimentally, and will enable the design of more efficient growth inhibitors and facilitate an understanding of the effect of impurities.« less

Conflict Resolution in Marriage: Toward a Theory of Spousal Strategies and Marital Dissolution Rates.

ERIC Educational Resources Information Center

Chafetz, Janet Saltzman

1980-01-01

There are four strategies spouses may attempt to employ in cases of conflict: authority, control, influence, and manipulation. Rates of marital dissolution are a function of the relative equality between spouses in terms of the types of conflict-resolution strategies they are able to employ. (Author)

The effect of iron content and dissolved O2 on dissolution rates of clinopyroxene at pH 5.8 and 25°C: Preliminary results

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.; Drever, J.I.

1996-01-01

Dissolution experiments using augite (Mg0.87Ca0.85Fe0.19Na0.09Al0.03Si2O6) and diopside (Mg0.91Ca0.93Fe0.07Na0.03Al0.03Si2O6) were conducted in flow-through reactors (5-ml/h flow rate). A pH of 5.8 was maintained by bubbling pure CO2 through a solution of 0.01 M KHCO3 at 25°C. Two experiments were run for each pyroxene type. In one experiment dissolved O2 concentration in reactors was 0.6 (±0.1) ppm and in the second dissolved O2 was 1.5 (±0.1) ppm. After 60 days, augite dissolution rates (based on Si release) were approximately three times greater in the 1.5 ppm. dissolved O2 experiments than in the sealed experiments. In contrast, diopside dissolution rates were independent of dissolved O2 concentrations. Preliminary results from the augite experiments suggest that dissolution rate is directly related to oxidation of iron. This effect was not observed in experiments performed on iron-poor diopside. Additionally, dissolution rates of diopside were much slower than those of augite, again suggesting a relationship between Fe content, Fe oxidation and dissolution rates.

Disintegration rate and properties of active pharmaceutical ingredient particles as determined from the dissolution time profile of a pharmaceutical formulation: an inverse problem.

PubMed

Horkovics-Kovats, Stefan

2014-02-01

Dissolution profile of a finished dosage form (FDF) contains hidden information regarding the disintegration of the form and the particle properties of the active pharmaceutical ingredient. Here, an extraction of this information from the dissolution profile without limitation to sink conditions is provided. In the article, mathematical relationships between the continuously measured dissolution profile of an FDF containing uniform or heterogeneous particles and its disintegration rate are developed. Further, the determinability of the disintegration kinetics and particle properties released from an FDF using the derived recurrent procedure was analyzed. On the basis of the theoretical data sets, it was demonstrated that the introduced analysis of dissolution profiles correctly identifies the disintegration rate of FDF containing multiple particle types. Furthermore, for known disintegration rates, the intrinsic lifetime of particles (time needed for total particle dissolution in infinite volume) released from the FDF and their relative amount can be determined. The extractable information from FDF dissolution time profiles can be utilized in designing of the formulation process, resulting in improved understanding of FDF properties, contributing thus to the implementation of quality by design in the FDF development. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Adsorption onto Mesoporous Silica Using Supercritical Fluid Technology Improves Dissolution Rate of Carbamazepine-a Poorly Soluble Compound.

PubMed

Gandhi, Aditya V; Thipsay, Priyanka; Kirthivasan, Bharat; Squillante, Emilio

2017-11-01

The purpose of this research was to design and characterize an immediate-release formulation of carbamazepine (CBZ), a poorly soluble anti-epileptic drug, using a porous silica carrier. Carbon dioxide in its supercritical state (2000 psi, 30-35°C) was used as an anti-solvent to precipitate CBZ onto two particle size variants of silica. Adsorption isotherms were used as a pre-formulation strategy to select optimum ratios of silica and CBZ. The obtained drug-silica formulations were characterized by dissolution studies, differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and scanning electron microscopy (SEM). This formulation strategy resulted in a 2.4-fold improvement in dissolution rate when compared to pure drug after 30 min of dissolution testing. PXRD and DSC confirmed the amorphous nature of CBZ in the formulations as well as the differences in polymorphic forms of commercial and supercritical fluid-processed CBZ. Additionally, solid-state NMR spectroscopy showed that the spin-lattice relaxation time for bulk drug (without silica) was ∼7.5 times greater than that for silica-confined CBZ, implying that when CBZ was adsorbed onto mesoporous silica, it is structurally disordered and had higher structural mobility, a characteristic of amorphous solids. The mesoporous silica matrix prevented CBZ crystal growth by imposing spatial constraint on CBZ nuclei and hence resulted in faster dissolution compared to bulk solid drug. Adsorption onto mesoporous silica using supercritical fluid technology may be used as a novel formulation strategy for amorphization of poorly soluble compounds, in turn improving their dissolution rate.

Dissolution enhancement of tadalafil by liquisolid technique.

PubMed

Lu, Mei; Xing, Haonan; Yang, Tianzhi; Yu, Jiankun; Yang, Zhen; Sun, Yanping; Ding, Pingtian

2017-02-01

This study aimed to enhance the dissolution of tadalafil, a poorly water-soluble drug by applying liquisolid technique. The effects of two critical formulation variables, namely drug concentration (17.5% and 35%, w/w) and excipients ratio (10, 15 and 20) on dissolution rates were investigated. Pre-compression tests, including particle size distribution, flowability determination, Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray diffractometry (XRD) and scanning electron microscopy (SEM), were carried out to investigate the mechanism of dissolution enhancement. Tadalafil liquisolid tablets were prepared and their quality control tests, dissolution study, contact angle measurement, Raman mapping, and storage stability test were performed. The results suggested that all the liquisolid tablets exhibited significantly higher dissolution rates than the conventional tablets and pure tadalafil. FT-IR spectrum reflected no drug-excipient interactions. DSC and XRD studies indicated reduction in crystallinity of tadalafil, which was further confirmed by SEM and Raman mapping outcomes. The contact angle measurement demonstrated obvious increase in wetting property. Taken together, the reduction of particle size and crystallinity, and the improvement of wettability were the main mechanisms for the enhanced dissolution rate. No significant changes were observed in drug crystallinity and dissolution behavior after storage based on XRD, SEM and dissolution results.

Silicon Isotopes doping experiments to measure quartz dissolution and precipitation rates at equilibrium and test the principle of detailed balance

NASA Astrophysics Data System (ADS)

Zhu, C.; Rimstidt, J. D.; Liu, Z.; Yuan, H.

2016-12-01

The principle of detailed balance (PDB) has been a cornerstone for irreversible thermodynamics and chemical kinetics for a long time, and its wide application in geochemistry has mostly been implicit and without experimental testing of its applicability. Nevertheless, many extrapolations based on PDB without experimental validation have far reaching impacts on society's mega environmental enterprises. Here we report an isotope doping method that independently measures simultaneous dissolution and precipitation rates and can test this principle. The technique reacts a solution enriched in a rare isotope of an element with a solid having natural isotopic abundances (Beck et al., 1992; Gaillardet, 2008; Gruber et al., 2013). Dissolution and precipitation rates are found from the changing isotopic ratios. Our quartz experiment doped with 29Si showed that the equilibrium dissolution rate remains unchanged at all degrees of undersaturation. We recommend this approach to test the validity of using the detailed balance relationship in rate equations for other substances.

Constraints on the magnitude and rate of CO2 dissolution at Bravo Dome natural gas field

PubMed Central

Sathaye, Kiran J.; Hesse, Marc A.; Cassidy, Martin; Stockli, Daniel F.

2014-01-01

The injection of carbon dioxide (CO2) captured at large point sources into deep saline aquifers can significantly reduce anthropogenic CO2 emissions from fossil fuels. Dissolution of the injected CO2 into the formation brine is a trapping mechanism that helps to ensure the long-term security of geological CO2 storage. We use thermochronology to estimate the timing of CO2 emplacement at Bravo Dome, a large natural CO2 field at a depth of 700 m in New Mexico. Together with estimates of the total mass loss from the field we present, to our knowledge, the first constraints on the magnitude, mechanisms, and rates of CO2 dissolution on millennial timescales. Apatite (U-Th)/He thermochronology records heating of the Bravo Dome reservoir due to the emplacement of hot volcanic gases 1.2–1.5 Ma. The CO2 accumulation is therefore significantly older than previous estimates of 10 ka, which demonstrates that safe long-term geological CO2 storage is possible. Integrating geophysical and geochemical data, we estimate that 1.3 Gt CO2 are currently stored at Bravo Dome, but that only 22% of the emplaced CO2 has dissolved into the brine over 1.2 My. Roughly 40% of the dissolution occurred during the emplacement. The CO2 dissolved after emplacement exceeds the amount expected from diffusion and provides field evidence for convective dissolution with a rate of 0.1 g/(m2y). The similarity between Bravo Dome and major US saline aquifers suggests that significant amounts of CO2 are likely to dissolve during injection at US storage sites, but that convective dissolution is unlikely to trap all injected CO2 on the 10-ky timescale typically considered for storage projects. PMID:25313084

Constraints on the magnitude and rate of CO 2 dissolution at Bravo Dome natural gas field

DOE PAGES

Sathaye, Kiran J.; Hesse, Marc A.; Cassidy, M.; ...

2014-10-13

The injection of carbon dioxide (CO 2) captured at large point sources into deep saline aquifers can significantly reduce anthropogenic CO 2 emissions from fossil fuels. Dissolution of the injected CO 2 into the formation brine is a trapping mechanism that helps to ensure the long-term security of geological CO 2 storage. We use thermochronology to estimate the timing of CO 2 emplacement at Bravo Dome, a large natural CO 2 field at a depth of 700 m in New Mexico. Together with estimates of the total mass loss from the field we present, to our knowledge, the first constraintsmore » on the magnitude, mechanisms, and rates of CO 2 dissolution on millennial timescales. Apatite (U-Th)/He thermochronology records heating of the Bravo Dome reservoir due to the emplacement of hot volcanic gases 1.2–1.5 Ma. The CO 2 accumulation is therefore significantly older than previous estimates of 10 ka, which demonstrates that safe long-term geological CO 2 storage is possible. Here, integrating geophysical and geochemical data, we estimate that 1.3 Gt CO 2 are currently stored at Bravo Dome, but that only 22% of the emplaced CO 2 has dissolved into the brine over 1.2 My. Roughly 40% of the dissolution occurred during the emplacement. The CO 2 dissolved after emplacement exceeds the amount expected from diffusion and provides field evidence for convective dissolution with a rate of 0.1 g/(m 2y). Finally, the similarity between Bravo Dome and major US saline aquifers suggests that significant amounts of CO 2 are likely to dissolve during injection at US storage sites, but that convective dissolution is unlikely to trap all injected CO 2 on the 10-ky timescale typically considered for storage projects.« less

Ego-Dissolution and Psychedelics: Validation of the Ego-Dissolution Inventory (EDI).

PubMed

Nour, Matthew M; Evans, Lisa; Nutt, David; Carhart-Harris, Robin L

2016-01-01

The experience of a compromised sense of "self", termed ego-dissolution, is a key feature of the psychedelic experience. This study aimed to validate the Ego-Dissolution Inventory (EDI), a new 8-item self-report scale designed to measure ego-dissolution. Additionally, we aimed to investigate the specificity of the relationship between psychedelics and ego-dissolution. Sixteen items relating to altered ego-consciousness were included in an internet questionnaire; eight relating to the experience of ego-dissolution (comprising the EDI), and eight relating to the antithetical experience of increased self-assuredness, termed ego-inflation. Items were rated using a visual analog scale. Participants answered the questionnaire for experiences with classical psychedelic drugs, cocaine and/or alcohol. They also answered the seven questions from the Mystical Experiences Questionnaire (MEQ) relating to the experience of unity with one's surroundings. Six hundred and ninety-one participants completed the questionnaire, providing data for 1828 drug experiences (1043 psychedelics, 377 cocaine, 408 alcohol). Exploratory factor analysis demonstrated that the eight EDI items loaded exclusively onto a single common factor, which was orthogonal to a second factor comprised of the items relating to ego-inflation (rho = -0.110), demonstrating discriminant validity. The EDI correlated strongly with the MEQ-derived measure of unitive experience (rho = 0.735), demonstrating convergent validity. EDI internal consistency was excellent (Cronbach's alpha 0.93). Three analyses confirmed the specificity of ego-dissolution for experiences occasioned by psychedelic drugs. Firstly, EDI score correlated with drug-dose for psychedelic drugs (rho = 0.371), but not for cocaine (rho = 0.115) or alcohol (rho = -0.055). Secondly, the linear regression line relating the subjective intensity of the experience to ego-dissolution was significantly steeper for psychedelics (unstandardized regression

Ego-Dissolution and Psychedelics: Validation of the Ego-Dissolution Inventory (EDI)

PubMed Central

Nour, Matthew M.; Evans, Lisa; Nutt, David; Carhart-Harris, Robin L.

2016-01-01

Aims: The experience of a compromised sense of “self”, termed ego-dissolution, is a key feature of the psychedelic experience. This study aimed to validate the Ego-Dissolution Inventory (EDI), a new 8-item self-report scale designed to measure ego-dissolution. Additionally, we aimed to investigate the specificity of the relationship between psychedelics and ego-dissolution. Method: Sixteen items relating to altered ego-consciousness were included in an internet questionnaire; eight relating to the experience of ego-dissolution (comprising the EDI), and eight relating to the antithetical experience of increased self-assuredness, termed ego-inflation. Items were rated using a visual analog scale. Participants answered the questionnaire for experiences with classical psychedelic drugs, cocaine and/or alcohol. They also answered the seven questions from the Mystical Experiences Questionnaire (MEQ) relating to the experience of unity with one’s surroundings. Results: Six hundred and ninety-one participants completed the questionnaire, providing data for 1828 drug experiences (1043 psychedelics, 377 cocaine, 408 alcohol). Exploratory factor analysis demonstrated that the eight EDI items loaded exclusively onto a single common factor, which was orthogonal to a second factor comprised of the items relating to ego-inflation (rho = −0.110), demonstrating discriminant validity. The EDI correlated strongly with the MEQ-derived measure of unitive experience (rho = 0.735), demonstrating convergent validity. EDI internal consistency was excellent (Cronbach’s alpha 0.93). Three analyses confirmed the specificity of ego-dissolution for experiences occasioned by psychedelic drugs. Firstly, EDI score correlated with drug-dose for psychedelic drugs (rho = 0.371), but not for cocaine (rho = 0.115) or alcohol (rho = −0.055). Secondly, the linear regression line relating the subjective intensity of the experience to ego-dissolution was significantly steeper for psychedelics

Microbial reduction of Fe(III) in the Fifthian and Muloorina illites: Contrasting extents and rates of bioreduction

USGS Publications Warehouse

Seabaugh, Jennifer L.; Dong, Hailiang; Kukkadapu, Ravi K.; Eberl, Dennis D.; Morton, John P.; Kim, J.

2006-01-01

Shewanella putrefaciens CN32 reduces Fe(III) within two illites which have different properties: the Fithian bulk fraction and the <0.2 m fraction of Muloorina. The Fithian illite contained 4.6% (w/w) total Fe, 81% of which was Fe(III). It was dominated by illite with some jarosite (∼32% of the total Fe(III)) and goethite (11% of the total Fe(III)). The Muloorina illite was pure and contained 9.2% Fe, 93% of which was Fe(III). Illite suspensions were buffered at pH 7 and were inoculated with CN32 cells with lactate as the electron donor. Select treatments included anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle. Bioproduction of Fe(II) was determined by ferrozine analysis. The unreduced and bioreduced solids were characterized by Mössbauer spectroscopy, X-ray diffraction and transmission electron microscopy. The extent of Fe(III) reduction in the bulk Fithian illite was enhanced by the presence of AQDS (73%) with complete reduction of jarosite and goethite and partial reduction of illite. Mössbauer spectroscopy and chemical extraction determined that 21–25% of illite-associated Fe(III) was bioreduced. The extent of bioreduction was less in the absence of AQDS (63%) and only jarosite was completely reduced with partial reduction of goethite and illite. The XRD and TEM data revealed no significant illite dissolution or biogenic minerals, suggesting that illite was reduced in the solid state and biogenic Fe(II) from jarosite and goethite was either released to aqueous solution or adsorbed onto residual solid surfaces. In contrast, only 1% of the structural Fe(III) in Muloorina illite was bioreduced. The difference in the extent and rate of bioreduction between the two illites was probably due to the difference in layer charge and the total structural Fe content between the Fithian illite (0.56 per formula) and Muloorina illite (0.87). There may be other factors contributing to the observed differences, such as expandability, surface area and the

Optimization of Dissolution Compartments in a Biorelevant Dissolution Apparatus Golem v2, Supported by Multivariate Analysis.

PubMed

Stupák, Ivan; Pavloková, Sylvie; Vysloužil, Jakub; Dohnal, Jiří; Čulen, Martin

2017-11-23

Biorelevant dissolution instruments represent an important tool for pharmaceutical research and development. These instruments are designed to simulate the dissolution of drug formulations in conditions most closely mimicking the gastrointestinal tract. In this work, we focused on the optimization of dissolution compartments/vessels for an updated version of the biorelevant dissolution apparatus-Golem v2. We designed eight compartments of uniform size but different inner geometry. The dissolution performance of the compartments was tested using immediate release caffeine tablets and evaluated by standard statistical methods and principal component analysis. Based on two phases of dissolution testing (using 250 and 100 mL of dissolution medium), we selected two compartment types yielding the highest measurement reproducibility. We also confirmed a statistically ssignificant effect of agitation rate and dissolution volume on the extent of drug dissolved and measurement reproducibility.

Preparation of Chloramphenicol/Amino Acid Combinations Exhibiting Enhanced Dissolution Rates and Reduced Drug-Induced Oxidative Stress.

PubMed

Sterren, Vanesa B; Aiassa, Virginia; Garnero, Claudia; Linck, Yamila Garro; Chattah, Ana K; Monti, Gustavo A; Longhi, Marcela R; Zoppi, Ariana

2017-11-01

Chloramphenicol is an old antibiotic agent that is re-emerging as a valuable alternative for the treatment of multidrug-resistant pathogens. However, it exhibits suboptimal biopharmaceutical properties and toxicity profiles. In this work, chloramphenicol was combined with essential amino acids (arginine, cysteine, glycine, and leucine) with the aim of improving its dissolution rate and reduce its toxicity towards leukocytes. The chloramphenicol/amino acid solid samples were prepared by freeze-drying method and characterized in the solid state by using Fourier transform infrared spectroscopy, powder X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and solid-state nuclear magnetic resonance. The dissolution properties, antimicrobial activity, reactive oxygen species production, and stability of the different samples were studied. The dissolution rate of all combinations was significantly increased in comparison to that of the pure active pharmaceutical ingredient. Additionally, oxidative stress production in human leukocytes caused by chloramphenicol was decreased in the chloramphenicol/amino acid combinations, while the antimicrobial activity of the antibiotic was maintained. The CAP:Leu binary combination resulted in the most outstanding solid system makes it suitable candidate for the development of pharmaceutical formulations of this antimicrobial agent with an improved safety profile.

Xylitol as a potential co-crystal co-former for enhancing dissolution rate of felodipine: preparation and evaluation of sublingual tablets.

PubMed

Arafa, Mona F; El-Gizawy, Sanaa A; Osman, Mohamed A; El Maghraby, Gamal M

2018-06-01

Dissolution enhancement is a promising strategy for improving drug bioavailability. Co-crystallization of drugs with inert material can help in this direction. The benefit will become even greater if the inert material can form co-crystal while maintaining its main function as excipient. Accordingly, the objective of the current study was to investigate xylitol as a potential co-crystal co-former for felodipine with the goal of preparing felodipine sublingual tablets. Co-crystallization was achieved by wet co-grinding of the crystals deposited from methanolic solutions containing felodipine with increasing molar ratios of xylitol (1:1, 1:2 and 1:3). The developed co-crystals were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) before monitoring drug dissolution. These results reflected the development of new crystalline species depending on the relative proportions of felodipine and xylitol with complete co-crystallization of felodipine being achieved in the presence of double its molar concentration of xylitol. This co-crystal formulation was compressed into sublingual tablet with ultrashort disintegration time with subsequent fast dissolution. Co-crystal formation was associated with enhanced dissolution with the optimum formulation producing the fastest dissolution rate. In conclusion, xylitol can be considered as a co-crystal co-former for enhanced dissolution rate of drugs.

Olivine dissolution from Indian dunite in saline water.

PubMed

Agrawal, Amit Kumar; Mehra, Anurag

2016-11-01

The rate and mechanism of olivine dissolution was studied using naturally weathered dunite FO 98.21 (Mg 1.884 Fe 0.391 SiO 4 ) from an Indian source, that also contains serpentine mineral lizardite. A series of batch dissolution experiments were carried out to check the influence of temperature (30-75 ∘ C), initial dunite concentration (0.5 and 20 g/L), and salinity (0-35 g/L NaCl) under fixed head space CO 2 pressure (P[Formula: see text] = 1 barg) on dunite dissolution. Dissolved Mg, Si, and Fe concentrations were determined by inductive coupled plasma atomic emission spectroscopy. End-product solids were characterized by scanning electron microscopy and X-ray diffraction. Initially, rates of dissolution of Si and Mg were observed to be in stoichiometric proportion. After 8 h, the dissolution rate was observed to decline. At the end of the experiment (504 h), an amorphous silica-rich layer was observed over the dunite surface. This results in decay of the dissolution rate. The operating conditions (i.e., salinity, temperature, and mineral loading) affect the dissolution kinetics in a very complex manner because of which the observed experimental trends do not exhibit a direct trend.

Dissolution of Uranium Oxides Under Alkaline Oxidizing Conditions

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

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-11-01

Bench scale experiments were conducted to determine the dissolution characteristics of uranium oxide powders (UO2, U3O8, and UO3) in aqueous peroxide-carbonate solutions. Experimental parameters included H2O2 concentration, carbonate counter cation (NH4+, Na+, K+, and Rb+), and pH. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M. The three uranium oxide powders exhibited different dissolution patterns however, UO3 exhibited prompt complete dissolution. Carbonate counter cation affected the dissolution kinetics. There is minimal impact of solution pH, over the range 8.8 to 10.6, on initial dissolution rate.

An analysis of variable dissolution rates of sacrificial zinc anodes: a case study of the Hamble estuary, UK.

PubMed

Rees, Aldous B; Gallagher, Anthony; Comber, Sean; Wright, Laurence A

2017-09-01

Sacrificial anodes are intrinsic to the protection of boats and marine structures by preventing the corrosion of metals higher up the galvanic scale through their preferential breakdown. The dissolution of anodes directly inputs component metals into local receiving waters, with variable rates of dissolution evident in coastal and estuarine environments. With recent changes to the Environmental Quality Standard (EQS), the load for zinc in estuaries such as the Hamble, UK, which has a large amount of recreational craft, now exceeds the zinc standard of 7.9 μg/l. A survey of boat owners determined corrosion rates and estimated zinc loading at between 6.95 and 7.11 t/year. The research confirms the variable anode corrosion within the Hamble and highlighted a lack of awareness of anode technology among boat owners. Monitoring and investigation discounted metal structures and subterranean power cables as being responsible for these variations but instead linked accelerated dissolution to marina power supplies and estuarine salinity variations.

Enhancement of dissolution rate of poorly-soluble active ingredients by supercritical fluid processes. Part I: Micronization of neat particles.

PubMed

Perrut, M; Jung, J; Leboeuf, F

2005-01-06

In this first of two articles, we discuss some issues surrounding the dissolution rate enhancement of poorly-soluble active ingredients micronized into nano-particles using several supercritical fluid particle design processes including rapid expansion of supercritical solutions (RESS), supercritical anti-solvent (SAS) and particles from gas-saturated solutions/suspensions (PGSS). Experimental results confirm that dissolution rates do not only depend on the surface area and particle size of the processed powder, but are greatly affected by other physico-chemical characteristics such as crystal morphology and wettability that may reduce the benefit of micronization.

A kinetic rate model for crystalline basalt dissolution at temperature and pressure conditions relevant for geologic CO2 sequestration

NASA Astrophysics Data System (ADS)

Pollyea, R.; Rimstidt, J. D.

2016-12-01

Geologic carbon sequestration in terrestrial basalt reservoirs is predicated on permanent CO2 trapping through CO2-water-rock dissolution reactions followed by carbonate precipitation. Bench-scale experiments have shown these reaction paths to be rapid, occurring on a timescale 100 - 102 years. Moreover, recent results from the CarbFix basalt sequestration pilot project in Iceland demonstrate >95% CO2 isolation two years after a small-scale injection. In order to assess the viability of basalt sequestration worldwide (e.g., Deccan Traps, Columbia Plateau, etc.), flexible simulation tools are required that distill the dissolution reactions into a user-friendly format that is readily transmissible to existing reactive transport numerical simulators. In the present research, we combine experimental results extant in the literature for Icelandic basalt to develop kinetic rate models describing the pH-dependent dissolution of (1) basaltic glass and (2) an aggregate mineral assemblage for crystalline basalt comprising olivine, pyroxene, and plagioclase phases. In order to utilize these kinetic rate models with numerical simulation, a thermodynamic solubility model for each phase is developed for use with the reactive transport simulation code, TOUGHREACT. We use reactive transport simulation in a simple 1-D reactor to compare dissolution of the aggregate crystalline basalt phase with the traditional formulation comprising individual mineral phases for the crystalline basalt. Simulation results are in general agreement, illustrating the efficacy of this simplified approach for modeling basalt dissolution at temperature and pressure conditions typical of geologic CO2 reservoirs. Moreover, this approach may be of value to investigators seeking dissolution models for crystalline basalt in other mafic provinces.

A three step supercritical process to improve the dissolution rate of eflucimibe.

PubMed

Rodier, Elisabeth; Lochard, Hubert; Sauceau, Martial; Letourneau, Jean-Jacques; Freiss, Bernard; Fages, Jacques

2005-10-01

The aim of this study is to improve the dissolution properties of a poorly-soluble active substance, Eflucimibe by associating it with gamma-cyclodextrin. To achieve this objective, a new three-step process based on supercritical fluid technology has been proposed. First, Eflucimibe and cyclodextrin are co-crystallized using an anti-solvent process, dimethylsulfoxide being the solvent and supercritical carbon dioxide being the anti-solvent. Second, the co-crystallized powder is held in a static mode under supercritical conditions for several hours. This is the maturing step. Third, in a final stripping step, supercritical CO(2) is flowed through the matured powder to extract the residual solvent. The coupling of the first two steps brings about a significant synergistic effect to improve the dissolution rate of the drug. The nature of the entity obtained at the end of each step is discussed and some suggestions are made as to what happens in these operations. It is shown the co-crystallization ensures a good dispersion of both compounds and is rather insensitive to the operating parameters tested. The maturing step allows some dissolution-recrystallization to occur thus intensifying the intimate contact between the two compounds. Addition of water is necessary to make maturing effective as this is governed by the transfer properties of the medium. The stripping step allows extraction of the residual solvent but also removes some of the Eflucimibe which is the main drawback of this final stage.

Chemical and Mineralogical Characterization of Acid-Sulfate Alteration of Basaltic Material on Mauna Kea Volcano, Hawaii: Jarosite and Hydrated Halloysite

NASA Technical Reports Server (NTRS)

Graff, Trevor G.; Morris, R. V.; Archilles C. N.; Agresti, D. G.; Ming, D. W.; Hamilton, J. C.; Mertzman, S. A.; Smith, J.

2012-01-01

Sulfates have been identified on the martian surface during robotic surface exploration and by orbital remote sensing. Measurements at Meridiani Planum (MP) by the Alpha-Particle X-ray Spectrometer (APXS) and Mossbauer (MB) instruments on the Mars Exploration Rover Opportunity document the presence of a ubiquitous sulfate-rich outcrop (20-40% SO3) that has jarosite as an anhydrous Fe3+-sulfate [1- 3]. The presence of jarosite implies a highly acidic (pH <3) formation environment [4]. Jarosite and other sulfate minerals, including kieserite, gypsum, and alunite have also been identified in several locations in orbital remote sensing data from the MEx OMEGA and MRO CRISM instruments [e.g. 5-8]. Acid sulfate weathering of basaltic materials is an obvious pathway for formation of sulfate-bearing phases on Mars [e.g. 4, 9, 10]. In order to constrain acid-sulfate pathways on Mars, we are studying the mineralogical and chemical manifestations of acid-sulfate alteration of basaltic compositions in terrestrial environments. We have previously shown that acidsulfate alteration of tephra under hydrothermal conditions on the Puu Poliahu cone (summit region of Mauna Kea volcano, Hawaii) resulted in jarosite and alunite as sulfate-bearing alteration products [11-14]. Other, more soluble, sulfates may have formed, but were leached away by rain and melting snow. Acidsulfate processes on Puu Poliahu also formed hematite spherules similar (except in size) to the hematite spherules observed at MP as an alteration product [14]. Phyllosilicates, usually smectite }minor kaolinite are also present as alteration products [13]. We discuss here an occurrence of acid-sulfate alteration on Mauna Kea Volcano (Hawaii). We report VNIR spectra (0.35-2.5 microns ASD spectrometer), Mossbauer spectra (MER-like ESPI backscatter spectrometer), powder XRD (PANalytical), and major element chemical compositions (XRF with LOI and Fe redox) for comparison to similar data acquired or to be acquired by MRO

The effect of fuel chemistry on UO2 dissolution

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

Casella, Amanda; Hanson, Brady; Miller, William

2016-08-01

The dissolution rate of both unirradiated UO2 and used nuclear fuel has been studied by numerous countries as part of the performance assessment of proposed geologic repositories. In the scenario of waste package failure and groundwater infiltration into the fuel, the effects of variables such as temperature, dissolved oxygen, and water and fuel chemistry on the dissolution rates of the fuel are necessary to provide a quantitative estimate of the potential release over geologic time frames. The primary objective of this research was to determine the influence these parameters have on the dissolution rate of unirradiated UO2 under repository conditionsmore » and compare them to the rates predicted by current dissolution models. Both unirradiated UO2 and UO2 doped with varying concentrations of Gd2O3, to simulate used fuel composition after long time periods where radiolysis has minor contributions to dissolution, were examined. In general, a rise in temperature increased the dissolution rate of UO2 and had a larger effect on pure UO2 than on those doped with Gd2O3. Oxygen dependence was observed in the UO2 samples with no dopant and increased as the temperature rose; in the doped fuels less dependence was observed. The addition of gadolinia into the UO2 matrix showed a significant decrease in the dissolution rate. The matrix stabilization effect resulting from the dopant proved even more beneficial in lowering the dissolution rate at higher temperatures and dissolved O2 concentrations in the leachate where the rates would typically be elevated.« less

First-order dissolution rate law and the role of surface layers in glass performance assessment

NASA Astrophysics Data System (ADS)

Grambow, B.; Müller, R.

2001-09-01

The first-order dissolution rate law is used for nuclear waste glass performance predictions since 1984. A first discussion of the role of saturation effects was initiated at the MRS conference that year. In paper (1) it was stated that "For glass dissolution A* (the reaction affinity) cannot become zero since saturation only involves the reacting surface while soluble elements still might be extracted from the glass" [B. Grambow, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 15]. Saturation of silica at the surface and condensation of surface silanol groups was considered as being responsible for the slow down of reaction rates by as much as a factor of 1000. Precipitation of Si containing secondary phases such as quartz was invoked as a mechanism for keeping final dissolution affinities higher than zero. Another (2) paper [A.B. Barkatt, P.B. Macedo, B.C. Gibson, C.J. Montrose, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 3] stated that "… under repository conditions the extent of glass dissolution will be moderate due to saturation with respect to certain major elements (in particular, Si, Al and Ca). Consequently, the concentration levels of the more soluble glass constituents in the aqueous medium are expected to fall appreciable below their solubility limit." The formation of dense surface layers was considered responsible for explaining the saturation effect. The mathematical model assumed stop of reaction in closed systems, once solubility limits were achieved. For more than 15 years the question of the correctness of one or the other concept has seldom been posed and has not yet been resolved. The need of repository performance assessment for validated rate laws demands a solution, particularly since the consequences of the two concepts and research requirements for the long-term glass behavior are quite different. In concept (1) the stability of the `equilibrium surface region' is not relevant because, by definition, this region is stable chemically and after a

In-vitro dissolution rate and molecular docking studies of cabergoline drug with β-cyclodextrin

NASA Astrophysics Data System (ADS)

Shanmuga priya, Arumugam; Balakrishnan, Suganya bharathi; Veerakanellore, Giri Babu; Stalin, Thambusamy

2018-05-01

The physicochemical properties and dissolution profile of cabergoline drug (CAB) with β-cyclodextrin (β-CD) inclusion complex were investigated by the UV spectroscopy. The inclusion complex has used to calculate the stability constant and gives the stoichiometry molar ratio is 1:1 between CAB and β-CD. The phase solubility diagram and the aqueous solubility of CAB (60%) was found to be enhanced by β-CD. In addition, the phase solubility profile of CAB with β-CD was classified as AL-type. Binary systems of CAB with β-CD were prepared by Physical mixture, Kneading and solvent evaporation methods. The solid-state properties of the inclusion complex were characterized by Fourier transformation-infrared spectroscopy, Differential scanning calorimetry, Powder X-ray diffractometric patterns and Scanning electron microscopic techniques. Theoretically, β-CD and CAB inclusion complex obtained by molecular docking studies, it is in good correlation with the results obtained through experimental methods using the Schrödinger software program. In-vitro dissolution profiles of the inclusion complexes were carried out and obvious increase in dissolution rate was observed when compared with pure CAB drug and the complexes.

Does the stepwave model predict mica dissolution kinetics?

NASA Astrophysics Data System (ADS)

Kurganskaya, Inna; Arvidson, Rolf S.; Fischer, Cornelius; Luttge, Andreas

2012-11-01

The micas are a unique class of minerals because of their layered structure. A frequent question arising in mica dissolution studies is whether this layered structure radically changes the dissolution mechanism. We address this question here, using data from VSI and AFM experiments involving muscovite to evaluate crystallographic controls on mica dissolution. These data provide insight into the dissolution process, and reveal important links to patterns of dissolution observed in framework minerals. Under our experimental conditions (pH 9.4, 155 °C), the minimal global rate of normal surface retreat observed in VSI data was 1.42 × 10-10 mol/m2/s (σ = 27%) while the local rate observed at deep etch pits reached 416 × 10-10 mol/m2/s (σ = 49%). Complementary AFM data clearly show crystallographic control of mica dissolution, both in terms of step advance and the geometric influence of interlayer rotation (stacking periodicity). These observations indicate that basal/edge surface area ratios are highly variable and change continuously over the course of reaction, thus obviating their utility as characteristic parameters defining mica reactivity. Instead, these observations of overall dissolution rate and the influence of screw dislocations illustrate the link between atomic step movement and overall dissolution rate defined by surface retreat normal to the mica surface. Considered in light of similar observations available elsewhere in the literature, these relationships provide support for application of the stepwave model to mica dissolution kinetics. This approach provides a basic mechanistic link between the dissolution kinetics of phyllosilicates, framework silicates, and related minerals, and suggests a resolution to the general problem of mica reactivity.

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

Mathematical modeling of drug dissolution.

PubMed

Siepmann, J; Siepmann, F

2013-08-30

The dissolution of a drug administered in the solid state is a pre-requisite for efficient subsequent transport within the human body. This is because only dissolved drug molecules/ions/atoms are able to diffuse, e.g. through living tissue. Thus, generally major barriers, including the mucosa of the gastro intestinal tract, can only be crossed after dissolution. Consequently, the process of dissolution is of fundamental importance for the bioavailability and, hence, therapeutic efficacy of various pharmaco-treatments. Poor aqueous solubility and/or very low dissolution rates potentially lead to insufficient availability at the site of action and, hence, failure of the treatment in vivo, despite a potentially ideal chemical structure of the drug to interact with its target site. Different physical phenomena are involved in the process of drug dissolution in an aqueous body fluid, namely the wetting of the particle's surface, breakdown of solid state bonds, solvation, diffusion through the liquid unstirred boundary layer surrounding the particle as well as convection in the surrounding bulk fluid. Appropriate mathematical equations can be used to quantify these mass transport steps, and more or less complex theories can be developed to describe the resulting drug dissolution kinetics. This article gives an overview on the current state of the art of modeling drug dissolution and points out the assumptions the different theories are based on. Various practical examples are given in order to illustrate the benefits of such models. This review is not restricted to mathematical theories considering drugs exhibiting poor aqueous solubility and/or low dissolution rates, but also addresses models quantifying drug release from controlled release dosage forms, in which the process of drug dissolution plays a major role. Copyright © 2013 Elsevier B.V. All rights reserved.

Low temperature dissolution flowsheet for plutonium metal

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

Daniel, W. E.; Almond, P. M.; Rudisill, T. S.

2016-05-01

The H-Canyon flowsheet used to dissolve Pu metal for PuO 2 production utilizes boiling HNO 3. SRNL was requested to develop a complementary dissolution flowsheet at two reduced temperature ranges. The dissolution and H 2 generation rates of Pu metal were investigated using a dissolving solution at ambient temperature (20-30 °C) and for an intermediate temperature of 50-60 °C. Additionally, the testing included an investigation of the dissolution rates and characterization of the off-gas generated from the ambient temperature dissolution of carbon steel cans and the nylon bags that contain the Pu metal when charged to the dissolver.

Montmorillonite dissolution kinetics: Experimental and reactive transport modeling interpretation

NASA Astrophysics Data System (ADS)

Cappelli, Chiara; Yokoyama, Shingo; Cama, Jordi; Huertas, F. Javier

2018-04-01

The dissolution kinetics of K-montmorillonite was studied at 25 °C, acidic pH (2-4) and 0.01 M ionic strength by means of well-mixed flow-through experiments. The variations of Si, Al and Mg over time resulted in high releases of Si and Mg and Al deficit, which yielded long periods of incongruent dissolution before reaching stoichiometric steady state. This behavior was caused by simultaneous dissolution of nanoparticles and cation exchange between the interlayer K and released Ca, Mg and Al and H. Since Si was only involved in the dissolution reaction, it was used to calculate steady-state dissolution rates, RSi, over a wide solution saturation state (ΔGr ranged from -5 to -40 kcal mol-1). The effects of pH and the degree of undersaturation (ΔGr) on the K-montmorillonite dissolution rate were determined using RSi. Employing dissolution rates farthest from equilibrium, the catalytic pH effect on the K-montmorillonite dissolution rate was expressed as Rdiss = k·aH0.56±0.05 whereas using all dissolution rates, the ΔGr effect was expressed as a non-linear f(ΔGr) function Rdiss = k · [1 - exp(-3.8 × 10-4 · (|ΔGr|/RT)2.13)] The functionality of this expression is similar to the equations reported for dissolution of Na-montmorillonite at pH 3 and 50 °C (Metz, 2001) and Na-K-Ca-montmorillonite at pH 9 and 80 °C (Cama et al., 2000; Marty et al., 2011), which lends support to the use of a single f(ΔGr) term to calculate the rate over the pH range 0-14. Thus, we propose a rate law that also accounts for the effect of pOH and temperature by using the pOH-rate dependence and the apparent activation energy proposed by Rozalén et al. (2008) and Amram and Ganor (2005), respectively, and normalizing the dissolution rate constant with the edge surface area of the K-montmorillonite. 1D reactive transport simulations of the experimental data were performed using the Crunchflow code (Steefel et al., 2015) to quantitatively interpret the evolution of the released cations

Development of a novel myconanomining approach for the recovery of agriculturally important elements from jarosite waste.

PubMed

Bedi, Ankita; Singh, Braj Raj; Deshmukh, Sunil K; Aggarwal, Nisha; Barrow, Colin J; Adholeya, Alok

2018-05-01

In this study, an ecofriendly and economically viable waste management approach have been attempted towards the biosynthesis of agriculturally important nanoparticles from jarosite waste. Aspergillus terreus strain J4 isolated from jarosite (waste from Debari Zinc Smelter, Udaipur, India), showed good leaching efficiency along with nanoparticles (NPs) formation under ambient conditions. Fourier-transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) confirmed the formation of NPs. Energy dispersive X-ray spectroscopy (EDX analysis) showed strong signals for zinc, iron, calcium and magnesium, with these materials being leached out. TEM analysis and high resolution transmission electron microscopy (HRTEM) showed semi-quasi spherical particles having average size of 10-50nm. Thus, a novel biomethodology was developed using fungal cell-free extract for bioleaching and subsequently nanoconversion of the waste materials into nanostructured form. These biosynthesized nanoparticles were tested for their efficacy on seed emergence activity of wheat (Triticum aestivum) seeds and showed enhanced growth at concentration of 20ppm. These nanomaterials are expected to enhance plant growth properties and being targeted as additives in soil fertility and crop productivity enhancement. Copyright © 2017. Published by Elsevier B.V.

Oxidative Dissolution of Arsenopyrite by Mesophilic and Moderately Thermophilic Acidophiles †

PubMed Central

Tuovinen, Olli H.; Bhatti, Tariq M.; Bigham, Jerry M.; Hallberg, Kevin B.; Garcia, Oswaldo; Lindström, E. Börje

1994-01-01

The purpose of this work was to determine solution- and solid-phase changes associated with the oxidative leaching of arsenopyrite (FeAsS) by Thiobacillus ferrooxidans and a moderately thermoacidophilic mixed culture. Jarosite [KFe3(SO4)2(OH)6], elemental sulfur (S0), and amorphous ferric arsenate were detected by X-ray diffraction as solid-phase products. The oxidation was not a strongly acid-producing reaction and was accompanied by a relatively low redox level. The X-ray diffraction lines of jarosite increased considerably when ferrous sulfate was used as an additional substrate for T. ferroxidans. A moderately thermoacidophilic mixed culture oxidized arsenopyrite faster at 45°C than did T. ferroxidans at 22°C, and the oxidation was accompanied by a nearly stoichiometric release of Fe and As. The redox potential was initially low but subsequently increased during arsenopyrite oxidation by the thermoacidophiles. Jarosite, S0, and amorphous ferric arsenate were also formed under these conditions. PMID:16349379

Mechanism of Urea Crystal Dissolution in Water from Molecular Dynamics Simulation.

PubMed

Anand, Abhinav; Patey, G N

2018-01-25

Molecular dynamics simulations are used to determine the mechanism of urea crystal dissolution in water under sink conditions. Crystals of cubic and tablet shapes are considered, and results are reported for four commonly used water models. The dissolution rates for different water models can differ considerably, but the overall dissolution mechanism remains the same. Urea dissolution occurs in three stages: a relatively fast initial stage, a slower intermediate stage, and a final stage. We show that the long intermediate stage is well described by classical rate laws, which assume that the dissolution rate is proportional to the active surface area. By carrying out simulations at different temperatures, we show that urea dissolution is an activated process, with an activation energy of ∼32 kJ mol -1 . Our simulations give no indication of a significant diffusion layer, and we conclude that the detachment of molecules from the crystal is the rate-determining step for dissolution. The results we report for urea are consistent with earlier observations for the dissolution of NaCl crystals. This suggests that the three-stage mechanism and classical rate laws might apply to the dissolution of other ionic and molecular crystals.

Mineralogical, chemical, and crystallographic properties of supergene jarosite-group minerals from the Xitieshan Pb-Zn sulfide deposit, northern Tibetan Plateau, China

USGS Publications Warehouse

Chen, Lei; Li, Jian-Wei; Rye, Robert O.; Benzel, William H.; Lowers, H.A.; He, Ming-Zhong

2013-01-01

Supergene jarosite-group minerals are widespread in weathering profiles overlying Pb-Zn sulfide ores at Xitieshan, northern Tibetan Plateau, China. They consist predominantly of K-deficient natrojarosite, with lesser amounts of K-rich natrojarosite and plumbojarosite. Electron microprobe (EMP) analyses, scanning electron microcopy (SEM) investigation, and X-ray mapping reveal that the jarosite-group minerals are characterized by spectacular oscillatory zoning composed of alternating growth bands of K-deficient and K-bearing natrojarosite (K2O >1 wt.%). Plumbojarosite, whenever present, occurs as an overgrowth in the outermost bands, and its composition can be best represented by K0.29Na0.19Pb0.31Fe2.66Al0.22(SO4)1.65(PO4)0.31(AsO4)0.04(OH)7.37. The substitution of monovalent for divalent cations at the A site of plumbojarosite is charge balanced by the substitution of five-valent for six-valent anions in XO,4/sub> at the X site. Thermogravimetric analysis (TGA) of representative samples reveal mass losses of 11.46 wt.% at 446.6 °C and 21.42 wt.% at 683.4 °C due to dehydroxylation and desulfidation, respectively. TGA data also indicate that the natrojarosite structure collapses at 446.6 °C, resulting in the formation of NaFe(SO4)2 and minor hematite. The decomposition products of NaFe(SO4) are hematite and Na,2SO4. Powder X-ray diffraction (XRD) analyses show that the jarosite-group minerals have mean unit-cell parameters of a=7.315 ä and c=016.598 ä. XRD and EMP data support the view that substitutions of Na for K in the A site and full Fe occupancy in the B site can considerably decrease the unit-cell parameter c, but only slightly increase a. The results from this study suggest that the observed oscillatory zoning of jarosite-group minerals at Xitieshan resulted mainly from substitutions of K for Na at the A site and P for S at the X site.

Does the dose-solubility ratio affect the mean dissolution time of drugs?

PubMed

Lánský, P; Weiss, M

1999-09-01

To present a new model for describing drug dissolution. On the basis of the new model to characterize the dissolution profile by the distribution function of the random dissolution time of a drug molecule, which generalizes the classical first order model. Instead of assuming a constant fractional dissolution rate, as in the classical model, it is considered that the fractional dissolution rate is a decreasing function of the dissolved amount controlled by the dose-solubility ratio. The differential equation derived from this assumption is solved and the distribution measures (half-dissolution time, mean dissolution time, relative dispersion of the dissolution time, dissolution time density, and fractional dissolution rate) are calculated. Finally, instead of monotonically decreasing the fractional dissolution rate, a generalization resulting in zero dissolution rate at time origin is introduced. The behavior of the model is divided into two regions defined by q, the ratio of the dose to the solubility level: q < 1 (complete dissolution of the dose, dissolution time) and q > 1 (saturation of the solution, saturation time). The singular case q = 1 is also treated and in this situation the mean as well as the relative dispersion of the dissolution time increase to infinity. The model was successfully fitted to data (1). This empirical model is descriptive without detailed physical reasoning behind its derivation. According to the model, the mean dissolution time is affected by the dose-solubility ratio. Although this prediction appears to be in accordance with preliminary application, further validation based on more suitable experimental data is required.

A silica-supported solid dispersion of bifendate using supercritical carbon dioxide method with enhanced dissolution rate and oral bioavailability.

PubMed

Cai, Cuifang; Liu, Muhua; Li, Yun; Guo, Bei; Chang, Hui; Zhang, Xiangrong; Yang, Xiaoxu; Zhang, Tianhong

2016-01-01

In this study, to enhance the dissolution rate and oral bioavailability of bifendate, a silica-supported solid dispersion (SD) of bifendate was prepared using supercritical carbon dioxide (ScCO2) technology. The properties of bifendate-silica SD were characterized by differential scanning calorimetry (DSC), X-ray diffraction (X-RD) and scanning electron microscopy. The pharmacokinetic study was carried out in beagle dogs using commercial bifendate dropping pills as a reference which is a conventional SD formulation of bifendate and PEG6000. A novel method of Ultra Performance Convergence Chromatography-tandem mass spectrometry (UPC(2)™-MS/MS) method was applied to determine bifendate concentration in plasma. The amorphous state of bifendate in bifendate-silica SD was revealed in X-RD and DSC when the ratios of bifendate and silica were 1:15 and 1:19, respectively. In vitro dissolution rate was significantly improved with cumulative release of 67% within 20 min relative to 8% for the physical mixture of bifendate and silica, and which was also higher than the commercial dropping pill of 52%. After storage at 75% relative humidity (RH) for 10 d, no recrystallization was found and reduced dissolution rate was obtained due to the absorption of moisture. In pharmacokinetic study, Cmax and AUC0-t for bifendate-silica SD were 153.1 ng/ml and 979.8 ng h/ml, respectively. AUC0-t of bifendate-silica SDs was ∼1.6-fold higher than that of the commercial dropping pills. These results suggest that adsorbing bifendate onto porous silica via ScCO2 technique could be a feasible method to enhance oral bioavailability together with a higher dissolution rate.

High temperature dissolution of oxides in complexing media

NASA Astrophysics Data System (ADS)

Sathyaseelan, Valil S.; Rufus, Appadurai L.; Subramanian, Hariharan; Bhaskarapillai, Anupkumar; Wilson, Shiny; Narasimhan, Sevilimedu V.; Velmurugan, Sankaralingam

2011-12-01

Dissolution of transition metal oxides such as magnetite (Fe 3O 4), mixed ferrites (NiFe 2O 4, ZnFe 2O 4, MgFe 2O 4), bonaccordite (Ni 2FeBO 5) and chromium oxide (Cr 2O 3) in organic complexing media was attempted at higher temperatures (80-180 °C). On increasing the temperature from 80 to 180 °C, the dissolution rate of magnetite in nitrilo triacetic acid (NTA) medium increased six folds. The trend obtained for the dissolution of other oxides was ZnFe 2O 4 > NiFe 2O 4 > MgFe 2O 4 > Cr 2O 3, which followed the same trend as the lability of their metal-oxo bonds. Other complexing agents such as ethylene diamine tetra acetic acid (EDTA), pyridine dicarboxylic acid (PDCA), citric acid and reducing agents viz., oxalic acid and ascorbic acid were also evaluated for their oxide dissolution efficiency at 160 °C. EDTA showed maximum dissolution rate of 21.4 μm/h for magnetite. Addition of oxalic acid/ascorbic acid to complexing media (NTA/EDTA) showed identical effect on the dissolution of magnetite. Addition of hydrazine, another reducing agent, to NTA decreased the rate of dissolution of magnetite by 50%.

Convective dissolution of carbon dioxide in saline aquifers

NASA Astrophysics Data System (ADS)

Neufeld, Jerome A.; Hesse, Marc A.; Riaz, Amir; Hallworth, Mark A.; Tchelepi, Hamdi A.; Huppert, Herbert E.

2010-11-01

Geological carbon dioxide (CO2) storage is a means of reducing anthropogenic emissions. Dissolution of CO2 into the brine, resulting in stable stratification, increases storage security. The dissolution rate is determined by convection in the brine driven by the increase of brine density with CO2 saturation. We present a new analogue fluid system that reproduces the convective behaviour of CO2-enriched brine. Laboratory experiments and high-resolution numerical simulations show that the convective flux scales with the Rayleigh number to the 4/5 power, in contrast with a classical linear relationship. A scaling argument for the convective flux incorporating lateral diffusion from downwelling plumes explains this nonlinear relationship for the convective flux, provides a physical picture of high Rayleigh number convection in a porous medium, and predicts the CO2 dissolution rates in CO2 accumulations. These estimates of the dissolution rate show that convective dissolution can play an important role in enhancing storage security.

Glass fiber dissolution in simulated lung fluid and measures needed to improve consistency and correspondence to in vivo dissolution.

PubMed Central

Mattson, S M

1994-01-01

The dissolution of a range of glass fibers including commercial glass and mineral wools has been studied using a modification of Gamble's solution in a flow system at pH 7.4 and 37 degrees C. Dissolution has been followed by weight loss, effluent analysis, and morphology change of fibers and bulk glass. Flow per glass surface area can strongly affect both dissolution rate and morphology due to the effect of the dissolution process on the fluid. Effluent pH is shown to be a guide for choice of optimum flow/area conditions. These conditions provide measurable concentrations of dissolved glass in the effluent while maintaining their concentrations below the point at which they significantly affect the dissolution process. SiO2 and Al2O3 vary widely in the extent to which they are involved in the leaching process, which removes alkalis, alkaline earths, and B2O3. This makes analysis of a single component in the effluent unsuitable as a means of comparing the dissolution rates of a wide range of compositions. PMID:7882963

Acoustic activation of water-in-oil microemulsions for controlled salt dissolution.

PubMed

Baxamusa, Salmaan; Ehrmann, Paul; Ong, Jemi

2018-06-18

The dynamic nature of the oil-water interface allows for sequestration of material within the dispersed domains of a microemulsion. Microstructural changes should therefore change the dissolution rate of a solid surface in a microemulsion. We hypothesize that microstructural changes due to formulation and cavitation in an acoustic field will enable control over solid dissolution rates. Water-in-oil microemulsions were formulated using cyclohexane, water, Triton X-100, and hexanol. The microstructure and solvation properties of Winsor Type IV formulations were characterized. Dissolution rates of KH 2 PO 4 (KDP), were measured. A kinetic analysis isolated the effect of the microstructure, and rate enhancements due to cavitation effects on the microstructure were characterized by measuring dissolution rates in an ultrasonic field. Dispersed aqueous domains of 2-6 nm radius dissolve a solid block of KDP at 0-10 nm/min. Dissolution rate is governed not by the domain-surface collision frequency but rather by a dissolution probability per domain-surface encounter. Higher probabilities are correlated with larger domains. Rapid and reversible dissolution rate increases of up to 270× were observed under ultrasonic conditions, with <20% of the increase due to bulk heating effects. The rest is attributed to cavitation-induced changes to the domain microstructure, providing a simple method for remotely activating and de-activating dissolution. Copyright © 2018 Elsevier Inc. All rights reserved.

Catalysis and chemical mechanisms of calcite dissolution in seawater.

PubMed

Subhas, Adam V; Adkins, Jess F; Rollins, Nick E; Naviaux, John; Erez, Jonathan; Berelson, William M

2017-07-18

Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric [Formula: see text] on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13 C-labeled calcites in natural seawater. We show that the time-evolving enrichment of [Formula: see text] in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13 C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution-precipitation shifts significantly toward a dissolution-dominated mechanism below about [Formula: see text] Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of [Formula: see text] is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid-solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at [Formula: see text], which we interpret as the onset of homogeneous etch pit nucleation.

Synergistic effect of reductive and ligand-promoted dissolution of goethite.

PubMed

Wang, Zimeng; Schenkeveld, Walter D C; Kraemer, Stephan M; Giammar, Daniel E

2015-06-16

Ligand-promoted dissolution and reductive dissolution of iron (hydr)oxide minerals control the bioavailability of iron in many environmental systems and have been recognized as biological iron acquisition strategies. This study investigated the potential synergism between ligands (desferrioxamine B (DFOB) or N,N'-Di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED)) and a reductant (ascorbate) in goethite dissolution. Batch experiments were performed at pH 6 with ligand or reductant alone and in combination, and under both oxic and anoxic conditions. Goethite dissolution in the presence of reductant or ligand alone followed classic surface-controlled dissolution kinetics. Ascorbate alone does not promote goethite dissolution under oxic conditions due to rapid reoxidation of Fe(II). The rate coefficients for goethite dissolution by ligands are closely correlated with the stability constants of the aqueous Fe(III)-ligand complexes. A synergistic effect of DFOB and ascorbate on the rate of goethite dissolution was observed (total rates greater than the sum of the individual rates), and this effect was most pronounced under oxic conditions. For HBED, macroscopically the synergistic effect was hidden due to the inhibitory effect of ascorbate on HBED adsorption. After accounting for the concentrations of adsorbed ascorbate and HBED, a synergistic effect could still be identified. The potential synergism between ligand and reductant for iron (hydr)oxide dissolution may have important implications for iron bioavailability in soil environments.

Dissolution of cinnabar (HgS) in the presence of natural organic matter

USGS Publications Warehouse

Waples, J.S.; Nagy, K.L.; Aiken, G.R.; Ryan, J.N.

2005-01-01

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 ?? 10-13 to 7.16 ?? 10-12 mol Hg (mg C)-1 m-2 s-1. Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R2 = 0.88), aromaticity (R2 = 0.80), and molecular weight (R2 = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface. Copyright ?? 2005 Elsevier Ltd.

Kinetics of Inorganic Calcite Dissolution in Seawater under Pressure

NASA Astrophysics Data System (ADS)

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

2016-02-01

While understanding calcium carbonate dissolution is vital in constructing global carbon cycles and predicting the effect of seawater acidification as a result of increasing atmospheric CO2, there is still a major debate over the basic formulation of a dissolution rate law. The kinetics of calcium carbonate dissolution are typically described by the equation: Rate=k(1-Ω)n, while Ω=[Ca2+][CO32-]/Ksp. In this study, 13C-labeled calcite is dissolved in unlabeled seawater and the evolving d13C composition of the fluid is traced over time to establish dissolution rate. Instead of changing ion concentration to obtain varying Ω (as in our previous study; Subhas et al. 2015), we changed Ksp by conducting experiments under different pressures (described in theory as ∂lnKsp/∂P=-ΔV/RT, where ΔV is partial molal volume). This involved the construction of a pressure vessel that could hold our sample bag and provide aliquots while remaining pressurized. Pressure experiments were conducted between 0-2000PSI. Results support the conclusion in our previous study that near-equilibrium dissolution rates are highly nonlinear, but give a disparate relationship between undersaturation and dissolution rate if Ω is calculated assuming the specific ΔV embedded in CO2SYS. A revised ΔV from -37cm3 to -65cm3 would make the dissolution formulation equation agree, but clearly appears unreasonable. Our results are explained by a pressure effect on carbonate dissolution kinetics over and above the influence of pressure on Ω. If this is a phenomenon that occurs in nature, then we would predict that dissolution should be occurring shallower in the water column (as sometimes observed) than indicated by standard Ω calculations.

Dissolution of solid dosage form. II. Equations for the dissolution of nondisintegrating tablet under the sink condition.

PubMed

Yonezawa, Y; Shirakura, K; Otsuka, A; Sunada, H

1991-03-01

An equation for dissolution from the whole surface of a nondisintegrating single component tablet under the sink condition was derived. Also, equations for several dissolution manners of the tablet under the sink condition were derived in the postulation of the dominant dissolution rate constant which determines the dissolution manner. The applicability or validity of these equations were examined by the dissolution measurements with nondisintegrating single component tablets. About one-tenth the amount of the amount needed to saturate the solution was used to prepare a tablet, and dissolution measurements were carried out with the tablet whose flat or side surface was masked with an adhesive tape in accordance with the conditions for derivation of equations. Among the derived equations, dissolution from the whole surface of a tablet was expressed by a form similar to the cube root law equation for particles. Hence, a single component tablet compressed by the use of a suitable amount was thought to behave like a single crystal. Also, equations derived for several dissolution manners were thought to be applicable for the dissolution of a nonspherical particle and crystal concerning the crystal's habit and its dissolution property, and the extended applicability was examined by converting the crystal into a simplified or idealized form, i.e., rectangle or plate.

Combinatorial localized dissolution analysis: Application to acid-induced dissolution of dental enamel and the effect of surface treatments.

PubMed

Parker, Alexander S; Al Botros, Rehab; Kinnear, Sophie L; Snowden, Michael E; McKelvey, Kim; Ashcroft, Alexander T; Carvell, Mel; Joiner, Andrew; Peruffo, Massimo; Philpotts, Carol; Unwin, Patrick R

2016-08-15

A combination of scanning electrochemical cell microscopy (SECCM) and atomic force microscopy (AFM) is used to quantitatively study the acid-induced dissolution of dental enamel. A micron-scale liquid meniscus formed at the end of a dual barrelled pipette, which constitutes the SECCM probe, is brought into contact with the enamel surface for a defined period. Dissolution occurs at the interface of the meniscus and the enamel surface, under conditions of well-defined mass transport, creating etch pits that are then analysed via AFM. This technique is applied to bovine dental enamel, and the effect of various treatments of the enamel surface on acid dissolution (1mM HNO3) is studied. The treatments investigated are zinc ions, fluoride ions and the two combined. A finite element method (FEM) simulation of SECCM mass transport and interfacial reactivity, allows the intrinsic rate constant for acid-induced dissolution to be quantitatively determined. The dissolution of enamel, in terms of Ca(2+) flux ( [Formula: see text] ), is first order with respect to the interfacial proton concentration and given by the following rate law: [Formula: see text] , with k0=0.099±0.008cms(-1). Treating the enamel with either fluoride or zinc ions slows the dissolution rate, although in this model system the partly protective barrier only extends around 10-20nm into the enamel surface, so that after a period of a few seconds dissolution of modified surfaces tends towards that of native enamel. A combination of both treatments exhibits the greatest protection to the enamel surface, but the effect is again transient. Copyright © 2016 Elsevier Inc. All rights reserved.

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

NASA Astrophysics Data System (ADS)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

Chlorite Dissolution Rates From 25 to 275 degrees and pH 3 to 10

DOE Data Explorer

Carroll, Susan

2013-09-27

We have calculated a chlorite dissolution rate equation at far from equilibrium conditions by combining new data (20 experiments at high temperature) with previously published data Smith et al. 2013 and Lowson et al. 2007. All rate data (from the 127 experiments) are tabulated in this data submission. More information on the calculation of the rate data can be found in our FY13 Annual support (Carroll LLNL, 2013) which has been submitted to the GDR. The rate equation fills a data gap in geothemal kinetic data base and can be used directly to estimate the impact of chemical alteration on all geothermal processes. It is especially important for understanding the role of chemical alteration in the weakening for shear zones in EGS systems.

Lung Biopersistence and in Vitro Dissolution Rate Predict the Pathogenic Potential of Synthetic Vitreous Fibers.

PubMed

Hesterberg, T W; Hart, G A

2000-01-01

Here we review the past decade of research on inorganic fiber toxicology, which demonstrates that fiber biopersistence and in vitro dissolution rate correlate well with fiber pathogenicity. Test fibers for these studies included eight synthetic vitreous fibers (SVFs)-refractory ceramic fiber (RCF1), four fiber glasses (FCs), rock wool, slag wool, HT stone wool-and two asbestos types (crocidolite and amosite). Fiber toxicology and biopersistence were investigated using rodents exposed by inhalation. To evaluate chronic inhalation toxicity, rodents were exposed nose-only to ∼ 100 fibers >20 µm in length (F > 20 µm)/cm(3), 6 h/day, 5 days/wk, for 2 yr (rats) or 1½ yr (hamsters). To evaluate lung biopersistence, rats were exposed nose-only for 5 days to fiber aerosol; lung burdens were then analyzed during 1 yr postexposure. In vitro dissolution rate was evaluated in a flow-through system using physiological solutions that mimic the inorganic components of extra- and intracellular lung fluids. The 10 test fibers encompassed a range of respiratory toxicities, from transient inflammation only to carcinogenesis. Lung clearance weighted half-times (WT½) for F > 20 µm were 6-15 days for stonewool, building insulation FCs, and slag wool; 50-80 days for rock wool, 2 special-application FCs, and RCFI; and >400 days for asbestos. WT½ correlated with pathogenicity: The rapidly clearing fibers were innocuous (insulation FCs, slag wool, and stonewool), but the more biopersistent fibers were fibrogenic (rock wool) or fibrogenic and carcinogenic (special-application FCs, RCFI, amosite and crocidolite asbestos). In vitro dissolution rates (k dis= ng/cm(2)/h) of the 10 fibers at pH 7.4 or 4.5 ranged from < 1 to >600. Fibers that dissolved rapidly in vitro also cleared quickly from the lung and induced only transient inflammation in the chronic studies. In contrast, fibers that dissolved slowly in vitro were biopersistent in the lung and tended to induce permanent pathogenicity

The influence of amorphization methods on the apparent solubility and dissolution rate of tadalafil.

PubMed

Wlodarski, K; Sawicki, W; Paluch, K J; Tajber, L; Grembecka, M; Hawelek, L; Wojnarowska, Z; Grzybowska, K; Talik, E; Paluch, M

2014-10-01

This study for the first time investigates the solubility and dissolution rate of amorphous tadalafil (Td)--a poorly water soluble chemical compound which is commonly used for treating the erectile dysfunction. To convert the crystalline form of Td drug to its amorphous counterpart we have employed most of the commercially available amorphization techniques i.e. vitrification, cryogenic grinding, ball milling, spray drying, freeze drying and antisolvent precipitation. Among the mentioned methods only quenched cooling of the molten sample was found to be an inappropriate method of Td amorphization. This is due to the thermal decomposition of Td above 200°C, as proved by the thermogravimetric analysis (TGA). Disordered character of all examined samples was confirmed using differential scanning calorimetry (DSC) and X-ray powder diffraction (PXRD). In the case of most amorphous powders, the largest 3-fold increase of apparent solubility was observed after 5 min, indicating their fast recrystallization in water. On the other hand, the partially amorphous precipitate of Td and hypromellose enhanced the solubility of Td approximately 14 times, as compared with a crystalline substance, which remained constant for half an hour. Finally, disk intrinsic dissolution rate (DIDR) of amorphous forms of Td was also examined. Copyright © 2014 Elsevier B.V. All rights reserved.

High temperature dissolution of chromium substituted nickel ferrite in nitrilotriacetic acid medium

NASA Astrophysics Data System (ADS)

Sathyaseelan, V. S.; Chandramohan, P.; Velmurugan, S.

2016-12-01

High temperature (HT) dissolution of chromium substituted nickel ferrite was carried out with relevance to the decontamination of nuclear reactors by way of chemical dissolution of contaminated corrosion product oxides present on stainless steel coolant circuit surfaces. Chromium substituted nickel ferrites of composition, NiFe(2-x)CrxO4 (x ≤ 1), was synthetically prepared and characterized. HT dissolution of these oxides was carried out in nitrilotriacetic acid medium at 160 °C. Dissolution was remarkably increased at 160 °C when compared to at 85 °C in a reducing decontamination formulation. Complete dissolution could be achieved for the oxides with chromium content 0 and 0.2. Increasing the chromium content brought about a marked reduction in the dissolution rate. About 40 fold decrease in rate of dissolution was observed when chromium was increased from 0 to 1. The rate of dissolution was not very significantly reduced in the presence of N2H4. Dissolution of oxide was found to be stoichiometric.

Dissolution enhancement of chlorzoxazone using cogrinding technique

PubMed Central

Raval, Mihir K.; Patel, Jaydeep M.; Parikh, Rajesh K.; Sheth, Navin R.

2015-01-01

Purpose: The aim of the present work was to improve rate of dissolution and processing parameters of BCS class II drug, chlorzoxazone using cogrinding technique in the presence of different excipients as a carrier. Materials and Methods: The drug was coground with various carriers like polyethylene glycol (PEG 4000), hydroxypropyl methylcellulose (HPMC) E50LV, polyvinylpyrrolidone (PVP)K30, Kaolin and Neusilin US2 using ball mill, where only PEG 4000 improved dissolution rate of drug by bringing amorphization in 1:3 ratio. The coground mixture after 3 and 6 h was evaluated for various analytical, physicochemical and mechanical parameters. Results: The analysis showed conversion of Chlorzoxazone from its crystalline to amorphization form upon grinding with PEG 4000. Coground mixture as well as its directly compressed tablet showed 2.5-fold increment in the dissolution rate compared with pure drug. Directly compressible tablets prepared from pure drug required a large quantity of microcrystalline cellulose (MCC) during compression. The coground mixture and formulation was found stable in nature even after storage (40°C/75% relative humidity). Conclusions: Cogrinding can be successfully utilized to improve the rate of dissolution of poorly water soluble drugs and hence bioavailability. PMID:26682195

Dissolution of covalent adaptable network polymers in organic solvent

NASA Astrophysics Data System (ADS)

Yu, Kai; Yang, Hua; Dao, Binh H.; Shi, Qian; Yakacki, Christopher M.

2017-12-01

It was recently reported that thermosetting polymers can be fully dissolved in a proper organic solvent utilizing a bond-exchange reaction (BER), where small molecules diffuse into the polymer, break the long polymer chains into short segments, and eventually dissolve the network when sufficient solvent is provided. The solvent-assisted dissolution approach was applied to fully recycle thermosets and their fiber composites. This paper presents the first multi-scale modeling framework to predict the dissolution kinetics and mechanics of thermosets in organic solvent. The model connects the micro-scale network dynamics with macro-scale material properties: in the micro-scale, a model is developed based on the kinetics of BERs to describe the cleavage rate of polymer chains and evolution of chain segment length during the dissolution. The micro-scale model is then fed into a continuum-level model with considerations of the transportation of solvent molecules and chain segments in the system. The model shows good prediction on conversion rate of functional groups, degradation of network mechanical properties, and dissolution rate of thermosets during the dissolution. It identifies the underlying kinetic factors governing the dissolution process, and reveals the influence of different material and processing variables on the dissolution process, such as time, temperature, catalyst concentration, and chain length between cross-links.

Catalysis and chemical mechanisms of calcite dissolution in seawater

PubMed Central

Adkins, Jess F.; Rollins, Nick E.; Naviaux, John; Erez, Jonathan; Berelson, William M.

2017-01-01

Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric CO2 on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13C-labeled calcites in natural seawater. We show that the time-evolving enrichment of 𝜹13C in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution–precipitation shifts significantly toward a dissolution-dominated mechanism below about Ω= 0.7. Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of CO2 is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid–solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at Ω= 0.7, which we interpret as the onset of homogeneous etch pit nucleation. PMID:28720698

Setting accelerated dissolution test for PLGA microspheres containing peptide, investigation of critical parameters affecting drug release rate and mechanism.

PubMed

Tomic, I; Vidis-Millward, A; Mueller-Zsigmondy, M; Cardot, J-M

2016-05-30

The objective of this study was development of accelerated in vitro release method for peptide loaded PLGA microspheres using flow-through apparatus and assessment of the effect of dissolution parameters (pH, temperature, medium composition) on drug release rate and mechanism. Accelerated release conditions were set as pH 2 and 45°C, in phosphate buffer saline (PBS) 0.02M. When the pH was changed from 2 to 4, diffusion controlled phases (burst and lag) were not affected, while release rate during erosion phase decreased two-fold due to slower ester bonds hydrolyses. Decreasing temperature from 45°C to 40°C, release rate showed three-fold deceleration without significant change in release mechanism. Effect of medium composition on drug release was tested in PBS 0.01M (200 mOsm/kg) and PBS 0.01M with glucose (380 mOsm/kg). Buffer concentration significantly affected drug release rate and mechanism due to the change in osmotic pressure, while ionic strength did not have any effect on peptide release. Furthermore, dialysis sac and sample-and-separate techniques were used, in order to evaluate significance of dissolution technique choice on the release process. After fitting obtained data to different mathematical models, flow-through method was confirmed as the most appropriate for accelerated in vitro dissolution testing for a given formulation. Copyright © 2016 Elsevier B.V. All rights reserved.

General solution for diffusion-controlled dissolution of spherical particles. 1. Theory.

PubMed

Wang, J; Flanagan, D R

1999-07-01

Three classical particle dissolution rate expressions are commonly used to interpret particle dissolution rate phenomena. Our analysis shows that an assumption used in the derivation of the traditional cube-root law may not be accurate under all conditions for diffusion-controlled particle dissolution. Mathematical analysis shows that the three classical particle dissolution rate expressions are approximate solutions to a general diffusion layer model. The cube-root law is most appropriate when particle size is much larger than the diffusion layer thickness, the two-thirds-root expression applies when the particle size is much smaller than the diffusion layer thickness. The square-root expression is intermediate between these two models. A general solution to the diffusion layer model for monodispersed spherical particles dissolution was derived for sink and nonsink conditions. Constant diffusion layer thickness was assumed in the derivation. Simulated dissolution data showed that the ratio between particle size and diffusion layer thickness (a0/h) is an important factor in controlling the shape of particle dissolution profiles. A new semiempirical general particle dissolution equation is also discussed which encompasses the three classical particle dissolution expressions. The success of the general equation in explaining limitations of traditional particle dissolution expressions demonstrates the usefulness of the general diffusion layer model.

Does the presence of bacteria effect basaltic glass dissolution rates? 1: Dead Pseudomonas reactants

NASA Astrophysics Data System (ADS)

Stockmann, Gabrielle J.; Shirokova, Liudmila S.; Pokrovsky, Oleg S.; Oelkers, Eric H.; Benezeth, Pascale

2010-05-01

Basaltic glass and crystalline basalt formations in Iceland have been suggested for industrial CO2 storage due to their porous and permeable properties and high reactivity. Acid CO2-saturated waters in contact with basaltic glass will lead to rapid dissolution of the glass and release of divalent cations, (Ca2+, Mg2+, Fe2+) that can react to form stable carbonates and thereby trap the CO2. However, the basalt formations in Iceland not only contains glass and mineral assemblages, but also host microbiological communities that either by their presence or by active involvement in chemical reactions could affect the amount of basaltic glass being dissolved and CO2 being trapped. Samples of natural bacteria communities from the CO2 storage grounds in Iceland were collected, separated, and purified using agar plate technique and cultured under laboratory conditions in nutrient broth-rich media. Heterotrophic aerobic Gram-negative strain of Pseudomonas reactants was selected for a series of flow-through experiments aimed at evaluation of basaltic glass dissolution rate in the presense of increasing amounts of dead bacteria and their lysis products. The experiments were carried out using mixed-flow reactors at pH 4, 6, 8 and 10 at 25 °C. Each of the four reactors contained 1 gram of basaltic glass of the size fraction 45-125 μm. This glass was dissolved in ~ 0.01 M buffer solutions (acetate, MES, bicarbonate and carbonate+bicarbonate mixture) of the desired pH. All experiments ran 2 months, keeping the flowrate and temperature stable and only changing the concentration of dead bacteria in the inlet solutions (from 0 to 430 mg/L). Experiments were performed in sterile conditions, and bacterial growth was prevented by adding NaN3 to the inlet solutions. Routine culturing of bacteria on the agar plates confirmed the sterility of experiments. Samples of outlet solutions were analyzed for major cations and trace elements by ICP-MS. Results demonstrate a slight decrease in the

Insight into Flufenamic Acid Cocrystal Dissolution in the Presence of a Polymer in Solution: from Single Crystal to Powder Dissolution.

PubMed

Guo, Minshan; Wang, Ke; Qiao, Ning; Fábián, László; Sadiq, Ghazala; Li, Mingzhong

2017-12-04

Effects of three polymers, polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and copolymer of vinylpyrrolidone/vinyl acetate (PVP-VA), on the dissolution behavior of the cocrystals of flufenamic acid with theophylline (FFA-TP CO) and nicotinamide (FFA-NIC CO) were investigated at multiple length scales. At the molecular level, the interactions of crystal surfaces with a polymer were analyzed by observing etching pattern changes using atomic force microscopy. At the macroscopic scale, dissolution rates of particular faces of a single crystal were determined by measurement of the physical retreat velocities of the faces using optical light microscopy. In the bulk experiments, the FFA concentration in a dissolution medium in the absence or presence of a polymer was measured under both sink and nonsink conditions. It has been found that the dissolution mechanisms of FFA-TP CO are controlled by the defect sites of the crystal surface and by precipitation of the parent drug FFA as individual crystals in the bulk fluid. In contrast, the dissolution mechanisms of FFA-NIC CO are controlled by surface layer removal and by a surface precipitation mechanism, where the parent drug FFA precipitates directly onto the surface of the dissolving cocrystals. Through controlling the dissolution environment by predissolving a polymer, PVP or PVP-VA, which can interact with the crystal surface to alter its dissolution properties, improved solubility, and dissolution rates of FFA-TP CO and FFA-NIC CO have been demonstrated.

Chemical Dissolution of Simulant FCA Cladding and Plates

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

Daniel, G.; Pierce, R.; O'Rourke, P.

The Savannah River Site (SRS) has received some fast critical assembly (FCA) fuel from the Japan Atomic Energy Agency (JAEA) for disposition. Among the JAEA FCA fuel are approximately 7090 rectangular Stainless Steel clad fuel elements. Each element has an internal Pu-10.6Al alloy metal wafer. The thickness of each element is either 1/16 inch or 1/32 inch. The dimensions of each element ranges from 2 inches x 1 inch to 2 inches x 4 inches. This report discusses the potential chemical dissolution of the FCA clad material or stainless steel. This technology uses nitric acid-potassium fluoride (HNO 3-KF) flowsheets ofmore » H-Canyon to dissolve the FCA elements from a rack of materials. Historically, dissolution flowsheets have aimed to maximize Pu dissolution rates while minimizing stainless steel dissolution (corrosion) rates. Because the FCA cladding is made of stainless steel, this work sought to accelerate stainless steel dissolution.« less

How does natural groundwater flow affect CO2 dissolution in saline aquifers?

NASA Astrophysics Data System (ADS)

Rosenzweig, R.; Michel-Meyer, I.; Tsinober, A.; Shavit, U.

2017-12-01

The dissolution of supercritical CO2 in aquifer brine is one of the most important trapping mechanisms in CO2 geological storage. Diffusion-limited dissolution is a very slow process. However, since the CO2-rich water is slightly denser than the CO2-free water, when CO2-free water is overlaid by heavier CO2-rich water, convective instability results in fingers of dense CO2-rich water that propagate downwards, causing CO2-unsaturated water to move upwards. This convection process significantly accelerates the dissolution rate of CO2 into the aquifer water.Most previous works have neglected the effect of natural groundwater flow and assumed it has no effect on the dissolution dynamics. However, it was found that in some of the saline aquifers groundwater flow rate, although small, is not zero. In this research, we study the effect of groundwater flow on dissolution by performing laboratory experiments in a bead pack cell using a mixture of methanol and ethylene-glycol as a CO2 analog while varying the water horizontal flow rate. We find that water horizontal flow decreases the number of fingers, their wavelength and their propagation velocity. When testing high water flow rates, no fingers were developed and the dissolution process was entirely diffusive. The effect of water flow on the dissolution rate did not show a clear picture. When increasing the horizontal flow rate the convective dissolution flux slightly decreased and then increased again. It seems that the combination of density-driven flow, water horizontal flow, mechanical dispersion and molecular diffusion affect the dissolution rate in a complex and non-monotonic manner. These intriguing dynamics should be further studied to understand their effect on dissolution trapping.

Solid dispersions, part I: recent evolutions and future opportunities in manufacturing methods for dissolution rate enhancement of poorly water-soluble drugs.

PubMed

Bikiaris, Dimitrios N

2011-11-01

In recent years, the number of active pharmaceutical ingredients with high therapeutic impact, but very low water solubility, has increased significantly. Thus, a great challenge for pharmaceutical technology is to create new formulations and efficient drug-delivery systems to overcome these dissolution problems. Drug formulation in solid dispersions (SDs) is one of the most commonly used techniques for the dissolution rate enhancement of poorly water-soluble drugs. Generally, SDs can be defined as a dispersion of active ingredients in molecular, amorphous and/or microcrystalline forms into an inert carrier. This review covers literature which states that the dissolution enhancement of SDs is based on the fact that drugs in the nanoscale range, or in amorphous phase, dissolve faster and to a greater extent than micronized drug particles. This is in accordance to the Noyes-Whitney equation, while the wetting properties of the used polymer may also play an important role. The main factors why SD-based pharmaceutical products on the market are steadily increasing over the last few years are: the recent progress in various methods used for the preparation of SDs, the effect of evolved interactions in physical state of the drug and formulation stability during storage, the characterization of the physical state of the drug and the mechanism of dissolution rate enhancement.

Secondary calcification and dissolution respond differently to future ocean conditions

NASA Astrophysics Data System (ADS)

Silbiger, N. J.; Donahue, M. J.

2014-09-01

Climate change threatens both the accretion and erosion processes that sustain coral reefs. Secondary calcification, bioerosion, and reef dissolution are integral to the structural complexity and long-term persistence of coral reefs, yet these processes have received less research attention than reef accretion by corals. In this study, we use climate scenarios from RCP8.5 to examine the combined effects of rising ocean acidity and SST on both secondary calcification and dissolution rates of a natural coral rubble community using a flow-through aquarium system. We found that secondary reef calcification and dissolution responded differently to the combined effect of pCO2 and temperature. Calcification had a non-linear response to the combined effect of pCO2-temperature: the highest calcification rate occurred slightly above ambient conditions and the lowest calcification rate was in the highest pCO2-temperature condition. In contrast, dissolution increased linearly with pCO2-temperature. The rubble community switched from net calcification to net dissolution at +272 μatm pCO2 and 0.84 °C above ambient conditions, suggesting that rubble reefs may shift from net calcification to net dissolution before the end of the century. Our results indicate that dissolution may be more sensitive to climate change than calcification, and that calcification and dissolution have different functional responses to climate stressors, highlighting the need to study the effects of climate stressors on both calcification and dissolution to predict future changes in coral reefs.

Automated potentiometric procedure for studying dissolution kinetics acidic drugs under sink conditions.

PubMed

Underwood, F L; Cadwallader, D E

1978-08-01

An automated potentiometric procedure was used for studying in vitro dissolution kinetics of acidic drugs. Theoretical considerations indicated that the pH-stat method could be used to establish approximate sink conditions or, possibly, a perfect sink. Data obtained from dissolution studies using the pH-stat method were compared with data obtained from known sink and nonsink conditions. These comparisons indicated that the pH-stat method can be used to establish a sink condition for dissolution studies. The effective diffusion layer thicknesses for benzoic and salicylic acids dissolving in water were determined, and a theoretical dissolution rate was calculated utilizing these values. The close agreement between the experimental dissolution rates obtained under pH-stat conditions and theoretical dissolution rates indicated that perfect sink conditions were established under the experimental conditions used.

Accelerated dissolution testing for controlled release microspheres using the flow-through dissolution apparatus.

PubMed

Collier, Jarrod W; Thakare, Mohan; Garner, Solomon T; Israel, Bridg'ette; Ahmed, Hisham; Granade, Saundra; Strong, Deborah L; Price, James C; Capomacchia, A C

2009-01-01

Theophylline controlled release capsules (THEO-24 CR) were used as a model system to evaluate accelerated dissolution tests for process and quality control and formulation development of controlled release formulations. Dissolution test acceleration was provided by increasing temperature, pH, flow rate, or adding surfactant. Electron microscope studies on the theophylline microspheres subsequent to each experiment showed that at pH values of 6.6 and 7.6 the microspheres remained intact, but at pH 8.6 they showed deterioration. As temperature was increased from 37-57 degrees C, no change in microsphere integrity was noted. Increased flow rate also showed no detrimental effect on integrity. The effect of increased temperature was determined to be the statistically significant variable.

In situ nanoscale observations of gypsum dissolution by digital holographic microscopy.

PubMed

Feng, Pan; Brand, Alexander S; Chen, Lei; Bullard, Jeffrey W

2017-06-01

Recent topography measurements of gypsum dissolution have not reported the absolute dissolution rates, but instead focus on the rates of formation and growth of etch pits. In this study, the in situ absolute retreat rates of gypsum (010) cleavage surfaces at etch pits, at cleavage steps, and at apparently defect-free portions of the surface are measured in flowing water by reflection digital holographic microscopy. Observations made on randomly sampled fields of view on seven different cleavage surfaces reveal a range of local dissolution rates, the local rate being determined by the topographical features at which material is removed. Four characteristic types of topographical activity are observed: 1) smooth regions, free of etch pits or other noticeable defects, where dissolution rates are relatively low; 2) shallow, wide etch pits bounded by faceted walls which grow gradually at rates somewhat greater than in smooth regions; 3) narrow, deep etch pits which form and grow throughout the observation period at rates that exceed those at the shallow etch pits; and 4) relatively few, submicrometer cleavage steps which move in a wave-like manner and yield local dissolution fluxes that are about five times greater than at etch pits. Molar dissolution rates at all topographical features except submicrometer steps can be aggregated into a continuous, mildly bimodal distribution with a mean of 3.0 µmolm -2 s -1 and a standard deviation of 0.7 µmolm -2 s -1 .

Kinetics of gibbsite dissolution under low ionic strength conditions

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

Ganor, J.; Mogollon, J.L.; Lasaga, A.C.

1999-06-01

Experiments measuring synthetic gibbsite dissolution rates were carried out using both a stirred-flow-through reactor and a column reactor at 25 C, and pH range of 2.5--4.1. All experiments were conducted under far from equilibrium conditions ({Delta}G < {minus}1.1 kcal/mole). The experiments were performed with perchloric acid under relatively low (and variable) ionic strength conditions. An excellent agreement was found between the results of the well-mixed flow-through experiments and those of the (nonmixed) column experiments. This agreement shows that the gibbsite dissolution rate is independent of the stirring rate and therefore supports the conclusion of Bloom and Erich (1987) that gibbsitemore » dissolution reaction is surface controlled and not diffusion controlled. The Brunauer-Emmett-Teller (BET) surface area of the gibbsite increased during the flow-through experiments, while in the column experiments no significant change in surface area was observed. The significant differences in the BET surface area between the column experiments and the flow-through experiments, and the excellent agreement between the rates obtained by both methods, enable the authors to justify the substitution of the BET surface area for the reactive surface area. The dissolution rate of gibbsite varied as a function of the perchloric acid concentration. The authors interpret the gibbsite dissolution rate as a result of a combined effect of proton catalysis and perchlorate inhibition. Following the theoretical study of Ganor and Lasaga (1998) they propose specific reaction mechanisms for the gibbsite dissolution in the presence of perchloric acid. The mathematical predictions of two of these reaction mechanisms adequately describe the experimental data.« less

Clinopyroxene dissolution in basaltic melt

NASA Astrophysics Data System (ADS)

Chen, Yang; Zhang, Youxue

2009-10-01

The history of magmatic systems may be inferred from reactions between mantle xenoliths and host basalt if the thermodynamics and kinetics of the reactions are quantified. To study diffusive and convective clinopyroxene dissolution in silicate melts, diffusive clinopyroxene dissolution experiments were conducted at 0.47-1.90 GPa and 1509-1790 K in a piston-cylinder apparatus. Clinopyroxene saturation is found to be roughly determined by MgO and CaO content. The effective binary diffusivities, DMgO and DCaO, and the interface melt saturation condition, C0MgO×C0CaO, are extracted from the experiments. DMgO and DCaO show Arrhenian dependence on temperature. The pressure dependence is small and not resolved within 0.47-1.90 GPa. C0MgO×C0CaO in the interface melt increases with increasing temperature, but decreases with increasing pressure. Convective clinopyroxene dissolution, where the convection is driven by the density difference between the crystal and melt, is modeled using the diffusivities and interface melt saturation condition. Previous studies showed that the convective dissolution rate depends on the thermodynamics, kinetics and fluid dynamics of the system. Comparing our results for clinopyroxene dissolution to results from a previous study on convective olivine dissolution shows that the kinetic and fluid dynamic aspects of the two minerals are quite similar. However, the thermodynamics of clinopyroxene dissolution depends more strongly on the degree of superheating and composition of the host melt than that of olivine dissolution. The models for clinopyroxene and olivine dissolution are tested against literature experiments on mineral-melt interaction. They are then applied to previously proposed reactions between Hawaii basalts and mantle minerals, mid-ocean ridge basalts and mantle minerals, and xenoliths digestion in a basalt at Kuandian, Northeast China.

Dissolution Flowsheet for High Flux Isotope Reactor Fuel

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

Daniel, W. E.; Rudisill, T. S.; O'Rourke, P. E.

2016-09-27

As part of the Spent Nuclear Fuel (SNF) processing campaign, H-Canyon is planning to begin dissolving High Flux Isotope Reactor (HFIR) fuel in late FY17 or early FY18. Each HFIR fuel core contains inner and outer fuel elements which were fabricated from uranium oxide (U 3O 8) dispersed in a continuous Al phase using traditional powder metallurgy techniques. Fuels fabricated in this manner, like other SNF’s processed in H-Canyon, dissolve by the same general mechanisms with similar gas generation rates and the production of H 2. The HFIR fuel cores will be dissolved and the recovered U will be down-blendedmore » into low-enriched U. HFIR fuel was previously processed in H-Canyon using a unique insert in both the 6.1D and 6.4D dissolvers. Multiple cores will be charged to the same dissolver solution maximizing the concentration of dissolved Al. The objective of this study was to identify flowsheet conditions through literature review and laboratory experimentation to safely and efficiently dissolve the HFIR fuel in H-Canyon. Laboratory-scale experiments were performed to evaluate the dissolution of HFIR fuel using both Al 1100 and Al 6061 T6 alloy coupons. The Al 1100 alloy was considered a representative surrogate which provided an upper bound on the generation of flammable (i.e., H 2) gas during the dissolution process. The dissolution of the Al 6061 T6 alloy proceeded at a slower rate than the Al 1100 alloy, and was used to verify that the target Al concentration in solution could be achieved for the selected Hg concentration. Mass spectrometry and Raman spectroscopy were used to provide continuous monitoring of the concentration of H 2 and other permanent gases in the dissolution offgas, allowing the development of H 2 generation rate profiles. The H 2 generation rates were subsequently used to evaluate if a full HFIR core could be dissolved in an H-Canyon dissolver without exceeding 60% of the calculated lower flammability limit (LFL) for H 2 at a given Hg

Factors Affecting the Dissolution of Indomethacin Solid Dispersions.

PubMed

Zhang, Wei; Zhang, Chen-Ning; He, Yue; Duan, Ban-Yan; Yang, Guang-Yi; Ma, Wei-Dong; Zhang, Yong-Hong

2017-11-01

The aim of this study was to investigate the influence of factors such as carrier type, drug/carrier ratio, binary carriers, and preparation method on the dissolution of an insoluble drug, indomethacin (IM), under supersaturation conditions. Using a solvent evaporation (SE) method, poloxamer 188 and PVP K30 showed better dissolution among the selected carriers. Furthermore, as the ratio of carriers increased (drug/carrier ratio from 1:0.5 to 1:2), the dissolution rate increased especially in almost two times poloxamer 188 solid dispersions (SDs), while the reverse results were observed for PVP K30 SDs. For the binary carrier SD, a lower dissolution was found. Under hot melt extrusion (HME), the dissolution of poloxamer 188 SD and PVP K30 SD was 0.83- and 0.94-folds lower than that using SE, respectively, while the binary carrier SD showed the best dissolution. For poloxamer 188 SDs, the drug's crystal form changed when using SE, while no crystal form change was observed using HME. IM was amorphous in PVP K30 SDs prepared by both methods. For binary carrier systems, amorphous and crystalline drugs coexisted in SD using SE, and negligible amorphous IM was in SD using HME. This study indicated that a higher amorphous proportion in SD did not correlate with higher dissolution rate, and other factors, such as carrier type, particle size, and density, were also critical.

DISSOLUTION OF PLUTONIUM METAL IN 8-10 M NITRIC ACID

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

Rudisill, T. S.; Pierce, R. A.

2012-07-02

The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO{sub 2}) using Phase II of HB-Line. To support the new mission, the development of a Pu metal dissolution flowsheet which utilizes concentrated (8-10 M) nitric acid (HNO{sub 3}) solutions containing potassium fluoride (KF) is required. Dissolution of Pu metal in concentrated HNO{sub 3} is desired to eliminate the need to adjust the solution acidity prior to purification by anion exchange. The preferred flowsheet would use 8-10 M HNO{sub 3}, 0.015-0.07 M KF, and 0.5-1.0 g/L Gd to dissolve the Pu upmore » to 6.75 g/L. An alternate flowsheet would use 8-10 M HNO{sub 3}, 0.05-0.2 M KF, and 1-2 g/L B to dissolve the Pu. The targeted average Pu metal dissolution rate is 20 mg/min-cm{sup 2}, which is sufficient to dissolve a “standard” 2250-g Pu metal button in 24 h. Plutonium metal dissolution rate measurements showed that if Gd is used as the nuclear poison, the optimum dissolution conditions occur in 10 M HNO{sub 3}, 0.04-0.05 M KF, and 0.5-1.0 g/L Gd at 112 to 116 °C (boiling). These conditions will result in an estimated Pu metal dissolution rate of ~11-15 mg/min-cm{sup 2} and will result in dissolution times of 36-48 h for standard buttons. The recommended minimum and maximum KF concentrations are 0.03 M and 0.07 M, respectively. The data also indicate that lower KF concentrations would yield dissolution rates for B comparable to those observed with Gd at the same HNO{sub 3} concentration and dissolution temperature. To confirm that the optimal conditions identified by the dissolution rate measurements can be used to dissolve Pu metal up to 6.75 g/L in the presence of representative concentrations of Fe and Gd or B, a series of experiments was performed to demonstrate the flowsheets. In three of the five experiments, the offgas generation rate during the dissolution was measured and samples were analyzed for hydrogen gas (H{sub 2}). The

Comparison of Dissolution Similarity Assessment Methods for Products with Large Variations: f2 Statistics and Model-Independent Multivariate Confidence Region Procedure for Dissolution Profiles of Multiple Oral Products.

PubMed

Yoshida, Hiroyuki; Shibata, Hiroko; Izutsu, Ken-Ichi; Goda, Yukihiro

2017-01-01

The current Japanese Ministry of Health Labour and Welfare (MHLW)'s Guideline for Bioequivalence Studies of Generic Products uses averaged dissolution rates for the assessment of dissolution similarity between test and reference formulations. This study clarifies how the application of model-independent multivariate confidence region procedure (Method B), described in the European Medical Agency and U.S. Food and Drug Administration guidelines, affects similarity outcomes obtained empirically from dissolution profiles with large variations in individual dissolution rates. Sixty-one datasets of dissolution profiles for immediate release, oral generic, and corresponding innovator products that showed large variation in individual dissolution rates in generic products were assessed on their similarity by using the f 2 statistics defined in the MHLW guidelines (MHLW f 2 method) and two different Method B procedures, including a bootstrap method applied with f 2 statistics (BS method) and a multivariate analysis method using the Mahalanobis distance (MV method). The MHLW f 2 and BS methods provided similar dissolution similarities between reference and generic products. Although a small difference in the similarity assessment may be due to the decrease in the lower confidence interval for expected f 2 values derived from the large variation in individual dissolution rates, the MV method provided results different from those obtained through MHLW f 2 and BS methods. Analysis of actual dissolution data for products with large individual variations would provide valuable information towards an enhanced understanding of these methods and their possible incorporation in the MHLW guidelines.

Secondary calcification and dissolution respond differently to future ocean conditions

NASA Astrophysics Data System (ADS)

Silbiger, N. J.; Donahue, M. J.

2015-01-01

Climate change threatens both the accretion and erosion processes that sustain coral reefs. Secondary calcification, bioerosion, and reef dissolution are integral to the structural complexity and long-term persistence of coral reefs, yet these processes have received less research attention than reef accretion by corals. In this study, we use climate scenarios from RCP 8.5 to examine the combined effects of rising ocean acidity and sea surface temperature (SST) on both secondary calcification and dissolution rates of a natural coral rubble community using a flow-through aquarium system. We found that secondary reef calcification and dissolution responded differently to the combined effect of pCO2 and temperature. Calcification had a non-linear response to the combined effect of pCO2 and temperature: the highest calcification rate occurred slightly above ambient conditions and the lowest calcification rate was in the highest temperature-pCO2 condition. In contrast, dissolution increased linearly with temperature-pCO2 . The rubble community switched from net calcification to net dissolution at +271 μatm pCO2 and 0.75 °C above ambient conditions, suggesting that rubble reefs may shift from net calcification to net dissolution before the end of the century. Our results indicate that (i) dissolution may be more sensitive to climate change than calcification and (ii) that calcification and dissolution have different functional responses to climate stressors; this highlights the need to study the effects of climate stressors on both calcification and dissolution to predict future changes in coral reefs.

Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

NASA Astrophysics Data System (ADS)

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

2008-01-01

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

The dissolution behavior of borosilicate glasses in far-from equilibrium conditions

NASA Astrophysics Data System (ADS)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin P.; Ryan, Joseph V.; Asmussen, R. Matthew

2018-04-01

An area of agreement in the waste glass corrosion community is that, at far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this work is to study the effects of temperature and pH on the dissolution rate of three model nuclear waste glasses (SON68, ISG, AFCI). The dissolution rate data are then used to parameterize a kinetic rate model based on Transition State Theory that has been developed to model glass corrosion behavior in dilute conditions. To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH (22 °C) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies though quantifiable differences exist. The glass dissolution rates were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), with which a robust uncertainty analysis is performed. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, a mathematical description of the effect of glass composition on the rate parameter values should be possible. This would allow for the possibility of calculating the forward dissolution rate of glass based solely on composition. In addition, the method of determination of parameter uncertainty and correlation provides a framework for other rate models that describe the dissolution rates of other amorphous and crystalline materials in a wide range of chemical conditions. The higher level of uncertainty analysis would provide

DISSOLUTION OF PLUTONIUM METAL IN 8-10 M NITRIC ACID

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

Rudisill, T.; Pierce, R.

2012-02-21

The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO{sub 2}) using Phase II of HB-Line. To support the new mission, the development of a Pu metal dissolution flowsheet which utilizes concentrated (8-10 M) nitric acid (HNO{sub 3}) solutions containing potassium fluoride (KF) is required. Dissolution of Pu metal in concentrated HNO{sub 3} is desired to eliminate the need to adjust the solution acidity prior to purification by anion exchange. The preferred flowsheet would use 8-10 M HNO{sub 3}, 0.015-0.07 M KF, and 0.5-1.0 g/L Gd to dissolve the Pu upmore » to 6.75 g/L. An alternate flowsheet would use 8-10 M HNO{sub 3}, 0.1-0.2 M KF, and 1-2 g/L B to dissolve the Pu. The targeted average Pu metal dissolution rate is 20 mg/min-cm{sup 2}, which is sufficient to dissolve a 'standard' 2250-g Pu metal button in 24 h. Plutonium metal dissolution rate measurements showed that if Gd is used as the nuclear poison, the optimum dissolution conditions occur in 10 M HNO{sub 3}, 0.04-0.05 M KF, and 0.5-1.0 g/L Gd at 112 to 116 C (boiling). These conditions will result in an estimated Pu metal dissolution rate of {approx}11-15 mg/min-cm{sup 2} and will result in dissolution times of 36-48 h for standard buttons. The recommended minimum and maximum KF concentrations are 0.03 M and 0.07 M, respectively. The maximum KF concentration is dictated by a potential room-temperature Pu-Gd-F precipitation issue at low Pu concentrations. The purpose of the experimental work described in this report was two-fold. Initially a series of screening experiments was performed to measure the dissolution rate of Pu metal as functions of the HNO{sub 3}, KF, and Gd or B concentrations. The objective of the screening tests was to propose optimized conditions for subsequent flowsheet demonstration tests. Based on the rate measurements, this study found that optimal dissolution conditions in solutions containing 0.5-1.0 g/L Gd

Montmorillonite Dissolution in Simulated Lung Fluids

NASA Astrophysics Data System (ADS)

Schmidt, M.; Wendlandt, R. F.

2008-12-01

Because lung fluids" first interaction is with the surface of inhaled grains, the surface properties of inhaled mineral dusts may have a generally mitigating effect on cytotoxicity and carcinogenicity. Wendlandt et al. (Appl. Geochem. 22, 2007) investigated the surface properties of respirable-sized quartz grains in bentonites and recognized pervasive montmorillonite surface coatings on silica grains. The purpose of this study was to determine the dissolution rate and biodurability of montmorillonite in simulated lung fluids and to assess its potential to mitigate silica cytotoxicity. Modified batch reaction experiments were conducted on purified and size fractionated calcic (SAz-2; 0.4-5 μm) and sodic (DC-2; 0.4-2 μm) montmorillonites for 120 to 160 days of reaction time at 37°C in both simulated extracellular lung fluid (Lu) and simulated lysosomal fluid (Ly). Modified batch experiments simulated a flow-through setup and minimized sample handling difficulties. Reacted Lu and Ly fluid was analyzed for Mg, Al, and Si on an ICP-OE spectrometer. Steady state dissolution was reached 90-100 days after the start of the experiment and maintained for 40-60 days. Measured montmorillonite dissolution rates based on BET surface areas and Si steady state release range from 4.1x10-15 mol/m2/s at the slowest to 1.0x10-14 mol/m2/s at the fastest with relative uncertainties of less than 10%. Samples reacting in Ly (pH = 4.55) dissolved faster than those in Lu (pH = 7.40), and DC-2 dissolved faster than SAz-2. The measured range of biodurabilities was 1,300 to 3,400 years for a 1 μm grain assuming a spherical volume and a molar volume equal to that of illite. The difference in salinities of the two fluids was too slight to draw conclusions about the relationship of ionic strength to dissolution rate. Results indicate that montmorillonite dissolution is incongruent and edge controlled. Dissolution rates for DC- 2 and SAz-2 clays were comparable to those reported in the

Effect of CO2 Solubility on Dissolution Rates of Minerals in Porous Media Imbibed with Brine: Actual Efficiency of CO2 Sequestration

NASA Astrophysics Data System (ADS)

Alizadeh Nomeli, M.; Riaz, A.

2016-12-01

A new model is developed for geochemical reactions to access dissolution rate of minerals in saline aquifers with respect to saturated concentration of dissolved CO2 as a function of parameters that are dynamically available during computer program execution such as pressure, temperature, and salinity. A general Arrhenius-type equation, with an explicit dependence on the pH of brine, is employed to determine the rates of mineral dissolution. The amount of dissolved CO2 is determined with the help of an accurate PVTx model for the temperature range of 50-100C and pressures up to 600 bar relevant to the geologic sequestration of CO2. We show how activity coefficients for a given salinity condition alters solubility, pH, and reaction rates. We further evaluate the significance of the pre-exponential factor and the reaction order associated with the modified Arrhenius equation to determine the sensitivity of the reaction rates as a function to the pH of the system. It is found that the model can reasonably reproduce experimental data with new parameters that we obtain from sensitivity studies. Using the new rate equation, we investigate geochemically induced alterations of fracture geometry due to mineral dissolution. Finally, we use our model to evaluate the effects of temperature, pressure, and salinity on the actual efficiency of CO2 storage.

Interactions between a poorly soluble cationic drug and sodium dodecyl sulfate in dissolution medium and their impact on in vitro dissolution behavior.

PubMed

Huang, Zongyun; Parikh, Shuchi; Fish, William P

2018-01-15

In the pharmaceutical industry, in vitro dissolution testing ofsolid oral dosage forms is a very important tool for drug development and quality control. However, ion-pairing interaction between the ionic drugand surfactants in dissolution medium often occurs, resulting in inconsistent and incomplete drug release. The aim of this study is toevaluate the effects ofsodium dodecyl sulfate (SDS) mediated medium onthe dissolution behaviors of a poorly soluble cationic drug (Drug B). The study was carried out by measuring solubility of Drug B substance and dissolution rate of Drug B product in media containing SDS.Desolubilization of Drug B substance was observed at pH 4.5 in the presence of SDS at concentrations below critical micelle concentration (CMC) which is attributed to the formation of an insoluble di-dodecyl sulfate salt between SDS and Drug B. This ion-pairing effect is less significant with increasing medium pH where Drug B is less ionized and CMC of SDS is lower. In medium at pH 4.5, dissolution of Drug B product was found incomplete with SDS concentration below CMC due to the desolubilization of Drug B substance. In media with SDS level above CMC, the dissolution rate is rather slower with higher inter-vessel variations compared to that obtained in pH 4.5 medium without SDS. The dissolution results demonstrate that the presence of SDS in medium generates unexpected irregular dissolution profiles for Drug B which are attributed to incompatible dissolution medium for this particular drug. Therefore, non-ionic surfactant was selected for Drug B product dissolution method and ion-pairing effect in SDS mediated medium should be evaluated when developing a dissolution method for any poorly soluble cationic drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparison and analysis of theoretical models for diffusion-controlled dissolution.

PubMed

Wang, Yanxing; Abrahamsson, Bertil; Lindfors, Lennart; Brasseur, James G

2012-05-07

Dissolution models require, at their core, an accurate diffusion model. The accuracy of the model for diffusion-dominated dissolution is particularly important with the trend toward micro- and nanoscale drug particles. Often such models are based on the concept of a "diffusion layer." Here a framework is developed for diffusion-dominated dissolution models, and we discuss the inadequacy of classical models that are based on an unphysical constant diffusion layer thickness assumption, or do not correctly modify dissolution rate due to "confinement effects": (1) the increase in bulk concentration from confinement of the dissolution process, (2) the modification of the flux model (the Sherwood number) by confinement. We derive the exact mathematical solution for a spherical particle in a confined fluid with impermeable boundaries. Using this solution, we analyze the accuracy of a time-dependent "infinite domain model" (IDM) and "quasi steady-state model" (QSM), both formally derived for infinite domains but which can be applied in approximate fashion to confined dissolution with proper adjustment of a concentration parameter. We show that dissolution rate is sensitive to the degree of confinement or, equivalently, to the total concentration C(tot). The most practical model, the QSM, is shown to be very accurate for most applications and, consequently, can be used with confidence in design-level dissolution models so long as confinement is accurately treated. The QSM predicts the ratio of diffusion layer thickness to particle radius (the Sherwood number) as a constant plus a correction that depends on the degree of confinement. The QSM also predicts that the time required for complete saturation or dissolution in diffusion-controlled dissolution experiments is singular (i.e., infinite) when total concentration equals the solubility. Using the QSM, we show that measured differences in dissolution rate in a diffusion-controlled dissolution experiment are a result of

(W7860)Monte Carlo Simulations of the Dissolution of Borosilicate and Aluminoborosilicate

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

Kerisit, Sebastien; Pierce, Eric M

2011-01-01

The aim of this study was to provide atomic-level insights into the dissolution behavior of borosilicate and aluminoborosilicate glasses in dilute aqueous solutions. In the first part of this work, the effects of different structural features, such as the presence of non-bridging oxygens (NBO) or the formation of boroxol rings, on glass dissolution were evaluated separately and led to the following conclusions. (1) The dependence of the dissolution rate on the amount of NBO was found to be linear at all Si/B ratios and the accelerating effect of NBO was shown to increase with increasing Si/B ratio. (2) The formationmore » of boroxol rings and of clusters of boroxol rings resulted in an increase of the dissolution rate at all Si/B ratios and, again, the extent of the rate increase was strongly dependent on the Si/B ratio. (3) For aluminosilicate glasses, the implementation of the aluminum avoidance rule was found to increase the rate of dissolution relative to that obtained for a random distribution. In the second part of this work, the dissolution of the NeB glasses studied by Pierce et al. [Pierce E. M., Reed L. R., Shaw W. J., McGrail B. P., Icenhower J. P., Windisch C. F., Cordova E. A. and Broady J. (2010) Experimental determination of the effect of the ratio of B/Al on glass dissolution along the nepheline (NaAlSiO4) - Malinkoite (NaBSiO4) join. Geochim. Cosmochim. Acta 74, 2634-2654] was modeled in dilute aqueous solutions. Pierce et al. concluded from their study that either the rupture of the Al-O bonds or that of the Si O bonds was the rate-limiting step controlling the dissolution of the NeB glasses. The simulations refined this conclusion and showed that, at low B/Al ratios, the rupture of both Al O Si and Si O Si linkages contributed to the dissolution rate whereas, at high B/Al ratios, the dissolution rate was independent of the rupture of Al-O-Si linkages and was controlled by S1 sites (silicon sites at the glass-water interface with one connection

Sources of acid and metals from the weathering of the Dinero waste pile, Lake Fork watershed, Leadville, Colorado

USGS Publications Warehouse

Diehl, S.F.; Hageman, Phil L.; Smith, Kathleen S.; Herron, J.T.; Desborough, G.A.

2005-01-01

Two trenches were dug into the south Dinero mine-waste pile near Leadville, Colorado, to study the weathering of rock fragments and the mineralogic sources of metal contaminants in the surrounding wetland and Lake Fork Watershed. Water seeping from the base of the south Dinero waste-rock pile was pH 2.9, whereas leachate from a composite sample of the rock waste was pH 3.3. The waste pile was mostly devoid of vegetation, open to infiltration of precipitation, and saturated at the base because of placement in the wetland. The south mine-waste pile is composed of poorly sorted material, ranging from boulder-size to fine-grained rock fragments. The trenches showed both matrix-supported and clast-supported zones, with faint horizontal color banding, suggesting zonation of Fe oxides. Secondary minerals such as jarosite and gypsum occurred throughout the depth of the trenches. Infiltration of water and transport of dissolved material through the pile is evidenced by optically continuous secondary mineral deposits that fill or line voids. Iron-sulfate material exhibits microlaminations with shrinkage cracking and preferential dissolution of microlayers that evidence drying and wetting events. In addition to fluids, submicron-sized to very fine-grained particles such as jarosite are transported through channel ways in the pile. Rock fragments are coated with a mixture of clay, jarosite, and manganese oxides. Dissolution of minerals is a primary source of metals. Skeletal remnants of grains, outlined by Fe-oxide minerals, are common. Potassium jarosite is the most abundant jarosite phase, but Pb-and Ag-bearing jarosite are common. Grain-sized clusters of jarosite suggest that entire sulfide grains were replaced by very fine-grained jarosite crystals. The waste piles were removed from the wetland and reclaimed upslope in 2003. This was an opportunity to test methods to identify sources of acid and metals and metal transport processes within a waste pile. A series of

Estimating the time for dissolution of spent fuel exposed to unlimited water

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

Leider, H.R.; Nguyen, S.N.; Stout, R.B.

1991-12-01

The release of radionuclides from spent fuel cannot be precisely predicted at this point because a satisfactory dissolution model based on specific chemical processes is not yet available. However, preliminary results on the dissolution rate of UO{sub 2} and spent fuel as a function of temperature and water composition have recently been reported. This information, together with data on fragment size distribution of spent fuel, are used to estimate the dissolution response of spent fuel in excess flowing water within the framework of a simple model. In this model, the reaction/dissolution front advances linearly with time and geometry is preserved.more » This also estimates the dissolution rate of the bulk of the fission products and higher actinides, which are uniformly distributed in the UO{sub 2} matrix and are presumed to dissolve congruently. We have used a fuel fragment distribution actually observed to calculate the time for total dissolution of spent fuel. A worst-case estimate was also made using the initial (maximum) rate of dissolution to predict the total dissolution time. The time for total dissolution of centimeter size particles is estimated to be 5.5 {times} 10{sup 4} years at 25{degrees}C.« less

Enhancement of dissolution rate through eutectic mixture and solid solution of posaconazole and benznidazole.

PubMed

Figueirêdo, Camila Bezerra Melo; Nadvorny, Daniela; de Medeiros Vieira, Amanda Carla Quintas; Soares Sobrinho, José Lamartine; Rolim Neto, Pedro José; Lee, Ping I; de La Roca Soares, Monica Felts

2017-06-15

Benznidazole (BNZ), the only commercialized antichagasic drug, and the antifungal compound posaconazole (PCZ) have shown synergistic action in the therapy of Chagas disease, however both active pharmaceutical ingredients (APIs) exhibit low aqueous solubility potentially limiting their bioavailability and therapeutic efficacy. In this paper, we report for the first time the formation of a eutectic mixture as well as an amorphous solid solution of PCZ and BNZ (at the same characteristic ratio of 80:20wt%), which provided enhanced solubility and dissolution rate for both APIs. This eutectic system was characterized by DSC and the melting points obtained were used for the construction of a phase diagram. The preservation of the characteristic PXRD patterns and the IR spectra of the parent APIs, and the visualization of a characteristic eutectic lamellar crystalline microstructure using Confocal Raman Microscopy confirm this system as a true eutectic mixture. The PXRD result also confirms the amorphous nature of the prepared solid solution. Theoretical chemical analyses indicate the predominance of π-stacking interactions in the amorphous solid solution, whereas an electrostatic interaction between the APIs is responsible for maintaining the alternating lamellar crystalline microstructure in the eutectic mixture. Both the eutectic mixture and the amorphous solid solution happen to have a characteristic PCZ to BNZ ratio similar to that of their pharmacological doses for treating Chagas disease, thus providing a unique therapeutic combination dose with enhanced apparent solubility and dissolution rate. Copyright © 2017 Elsevier B.V. All rights reserved.

A Model for Dissolution of Lime in Steelmaking Slags

NASA Astrophysics Data System (ADS)

Sarkar, Rahul; Roy, Ushasi; Ghosh, Dinabandhu

2016-08-01

In a previous study by Sarkar et al. (Metall. Mater. Trans. B 46B:961 2015), a dynamic model of the LD steelmaking was developed. The prediction of the previous model (Sarkar et al. in Metall. Mater. Trans. B 46B:961 2015) for the bath (metal) composition matched well with the plant data (Cicutti et al. in Proceedings of 6th International Conference on Molten Slags, Fluxes and Salts, Stockholm City, 2000). However, with respect to the slag composition, the prediction was not satisfactory. The current study aims to improve upon the previous model Sarkar et al. (Metall. Mater. Trans. B 46B:961 2015) by incorporating a lime dissolution submodel into the earlier one. From the industrial point of view, the understanding of the lime dissolution kinetics is important to meet the ever-increasing demand of producing low-P steel at a low basicity. In the current study, three-step kinetics for the lime dissolution is hypothesized on the assumption that a solid layer of 2CaO·SiO2 should form around the unreacted core of the lime. From the available experimental data, it seems improbable that the observed kinetics should be controlled singly by any one kinetic step. Accordingly, a general, mixed control model has been proposed to calculate the dissolution rate of the lime under varying slag compositions and temperatures. First, the rate equation for each of the three rate-controlling steps has been derived, for three different lime geometries. Next, the rate equation for the mixed control kinetics has been derived and solved to find the dissolution rate. The model predictions have been validated by means of the experimental data available in the literature. In addition, the effects of the process conditions on the dissolution rate have been studied, and compared with the experimental results wherever possible. Incorporation of this submodel into the earlier global model (Sarkar et al. in Metall. Mater. Trans. B 46B:961 2015) enables the prediction of the lime dissolution rate

In Situ Observation of Dissolution of Oxide Inclusions in Steelmaking Slags

NASA Astrophysics Data System (ADS)

Sharma, Mukesh; Mu, Wangzhong; Dogan, Neslihan

2018-05-01

Better understanding of removal of non-metallic inclusions is of importance in the steelmaking process to control the cleanliness of steel. In this study, the dissolution rate of Al2O3 and Al2TiO5 inclusions in a liquid CaO-SiO2-Al2O3 slag was measured using high-temperature confocal scanning laser microscopy (HT-CSLM) at 1550°C. The dissolution rate of inclusions is expressed as a function of the rate of decrease of the radius of solid particles with time. It is found that Al2O3 inclusions have a slower dissolution rate than that of Al2TiO5 inclusions at 1550°C. The rate-limiting steps are investigated in terms of a shrinking core model. It is shown that the rate-limiting step for dissolution of both inclusion types is mass transfer in the slag at 1550°C.

Coherent anti-Stokes Raman Scattering (CARS) Microscopy Visualizes Pharmaceutical Tablets During Dissolution

PubMed Central

Fussell, Andrew L.; Kleinebudde, Peter; Herek, Jennifer; Strachan, Clare J.; Offerhaus, Herman L.

2014-01-01

Traditional pharmaceutical dissolution tests determine the amount of drug dissolved over time by measuring drug content in the dissolution medium. This method provides little direct information about what is happening on the surface of the dissolving tablet. As the tablet surface composition and structure can change during dissolution, it is essential to monitor it during dissolution testing. In this work coherent anti-Stokes Raman scattering microscopy is used to image the surface of tablets during dissolution while UV absorption spectroscopy is simultaneously providing inline analysis of dissolved drug concentration for tablets containing a 50% mixture of theophylline anhydrate and ethyl cellulose. The measurements showed that in situ CARS microscopy is capable of imaging selectively theophylline in the presence of ethyl cellulose. Additionally, the theophylline anhydrate converted to theophylline monohydrate during dissolution, with needle-shaped crystals growing on the tablet surface during dissolution. The conversion of theophylline anhydrate to monohydrate, combined with reduced exposure of the drug to the flowing dissolution medium resulted in decreased dissolution rates. Our results show that in situ CARS microscopy combined with inline UV absorption spectroscopy is capable of monitoring pharmaceutical tablet dissolution and correlating surface changes with changes in dissolution rate. PMID:25045833

Interface dissolution control of the 14C profile in marine sediment

USGS Publications Warehouse

Keir, R.S.; Michel, R.L.

1993-01-01

The process of carbonate dissolution at the sediment-water interface has two possible endmember boundary conditions. Either the carbonate particles dissolve mostly before they are incorporated into the sediment by bioturbation (interface dissolution), or the vertical mixing is rapid relative to their extermination rate (homogeneous dissolution). In this study, a detailed radiocarbon profile was determined in deep equatorial Pacific sediment that receives a high rate of carbonate supply. In addition, a box model of sediment mixing was used to simulate radiocarbon, carbonate content and excess thorium profiles that result from either boundary process following a dissolution increase. Results from homogeneous dissolution imply a strong, very recent erosional event, while interface dissolution suggests that moderately increased dissolution began about 10,000 years ago. In order to achieve the observed mixed layer radiocarbon age, increased homogeneous dissolution would concentrate a greater amount of clay and 230Th than is observed, while for interface dissolution the predicted concentrations are too small. These results together with small discontinuities beneath the mixed layer in 230Th profiles suggest a two-stage increase in interface dissolution in the deep Pacific, the first occurring near the beginning of the Holocene and the second more recently, roughly 5000 years ago. ?? 1993.

42 CFR 412.331 - Determining hospital-specific rates in cases of hospital merger, consolidation, or dissolution.

Code of Federal Regulations, 2012 CFR

2012-10-01

... hospital merger, consolidation, or dissolution. 412.331 Section 412.331 Public Health CENTERS FOR MEDICARE... cases of hospital merger, consolidation, or dissolution. (a) New hospital merger or consolidation. If... dissolution. If a hospital separates into two or more hospitals that are subject to capital payments under...

42 CFR 412.331 - Determining hospital-specific rates in cases of hospital merger, consolidation, or dissolution.

Code of Federal Regulations, 2014 CFR

2014-10-01

... hospital merger, consolidation, or dissolution. 412.331 Section 412.331 Public Health CENTERS FOR MEDICARE... cases of hospital merger, consolidation, or dissolution. (a) New hospital merger or consolidation. If... dissolution. If a hospital separates into two or more hospitals that are subject to capital payments under...

42 CFR 412.331 - Determining hospital-specific rates in cases of hospital merger, consolidation, or dissolution.

Code of Federal Regulations, 2011 CFR

2011-10-01

... hospital merger, consolidation, or dissolution. 412.331 Section 412.331 Public Health CENTERS FOR MEDICARE... cases of hospital merger, consolidation, or dissolution. (a) New hospital merger or consolidation. If... dissolution. If a hospital separates into two or more hospitals that are subject to capital payments under...

42 CFR 412.331 - Determining hospital-specific rates in cases of hospital merger, consolidation, or dissolution.

Code of Federal Regulations, 2013 CFR

2013-10-01

... hospital merger, consolidation, or dissolution. 412.331 Section 412.331 Public Health CENTERS FOR MEDICARE... cases of hospital merger, consolidation, or dissolution. (a) New hospital merger or consolidation. If... dissolution. If a hospital separates into two or more hospitals that are subject to capital payments under...

Contact Angle Measurements: an Alternative Approach Towards Understanding the Mechanism of Increased Drug Dissolution from Ethylcellulose Tablets Containing Surfactant and Exploring the Relationship Between Their Contact Angles and Dissolution Behaviors.

PubMed

Liu, Tiaotiao; Hao, Jingqiang; Yang, Baixue; Hu, Beibei; Cui, Zhixiang; Li, Sanming

2018-05-01

The addition of surfactant in tablet was a well-defined approach to improve drug dissolution rate. While the selected surfactant played a vital role in improving the wettability of tablet by medium, it was equally important to improve the dissolution rate by permeation effect due to production of pores or the reduced inter-particle adhesion. Furthermore, understanding the mechanism of dissolution rate increased was significant. In this work, contact angle measurement was taken up as an alternative approach for understanding the dissolution rate enhancement for tablet containing surfactant. Ethylcellulose, as a substrate, was used to prepare tablet. Four surfactants, sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), dodecyltrimethylammonium bromide (DTAB), and sodium lauryl sulfonate (SLS), were used. Berberine hydrochloride, metformin hydrochloride, and rutin were selected as model drugs. The contact angle of tablet in the absence and presence of surfactant was measured to explore the mechanism. The dissolution test was investigated to verify the mechanism and to establish a correlation with the contact angle. The result showed that the mechanism was the penetration effect rather than the wetting effect. The dissolution increased with a reduction in the contact angle. DTAB was found to obtain the highest level of dissolution enhancement and the lowest contact angle, while SDS, SDBS, and SLS were found to be the less effective in both dissolution enhancement and contact angle decrease. Therefore, contact angle was a good indicator for dissolution behavior besides exploring the mechanism of increased dissolution, which shows great potential in formula screening.

The Dissolution Behavior of Borosilicate Glasses in Far-From Equilibrium Conditions

DOE PAGES

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin P.; ...

2018-02-10

An area of agreement in the waste glass corrosion community is that, at far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this work is to study the effects of temperature and pH on the dissolution rate of three model nuclear waste glasses (SON68, ISG, AFCI). The dissolution rate data are then used to parameterize a kinetic rate model based on Transition State Theory that has been developed to model glass corrosion behavior in dilute conditions. To do this, experiments were conducted atmore » temperatures of 23, 40, 70, and 90 °C and pH(22 °C) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies though quantifiable differences exist. The glass dissolution rates were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), with which a robust uncertainty analysis is performed. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, a mathematical description of the effect of glass composition on the rate parameter values should be possible. This would allow for the possibility of calculating the forward dissolution rate of glass based solely on composition. In addition, the method of determination of parameter uncertainty and correlation provides a framework for other rate models that describe the dissolution rates of other amorphous and crystalline materials in a wide range of chemical conditions. As a result, the higher level of uncertainty

The Dissolution Behavior of Borosilicate Glasses in Far-From Equilibrium Conditions

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

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin P.

An area of agreement in the waste glass corrosion community is that, at far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this work is to study the effects of temperature and pH on the dissolution rate of three model nuclear waste glasses (SON68, ISG, AFCI). The dissolution rate data are then used to parameterize a kinetic rate model based on Transition State Theory that has been developed to model glass corrosion behavior in dilute conditions. To do this, experiments were conducted atmore » temperatures of 23, 40, 70, and 90 °C and pH(22 °C) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies though quantifiable differences exist. The glass dissolution rates were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), with which a robust uncertainty analysis is performed. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, a mathematical description of the effect of glass composition on the rate parameter values should be possible. This would allow for the possibility of calculating the forward dissolution rate of glass based solely on composition. In addition, the method of determination of parameter uncertainty and correlation provides a framework for other rate models that describe the dissolution rates of other amorphous and crystalline materials in a wide range of chemical conditions. As a result, the higher level of uncertainty

Artificial weathering as a function of CO2 injection in Pahang Sandstone Malaysia: investigation of dissolution rate in surficial condition.

PubMed

Jalilavi, Madjid; Zoveidavianpoor, Mansoor; Attarhamed, Farshid; Junin, Radzuan; Mohsin, Rahmat

2014-01-13

Formation of carbonate minerals by CO2 sequestration is a potential means to reduce atmospheric CO2 emissions. Vast amount of alkaline and alkali earth metals exist in silicate minerals that may be carbonated. Laboratory experiments carried out to study the dissolution rate in Pahang Sandstone, Malaysia, by CO2 injection at different flow rate in surficial condition. X-ray Powder Diffraction (XRD), Scanning Electron Microscope (SEM) with Energy Dispersive X-ray Spectroscopy (EDX), Atomic Absorption Spectroscopy (AAS) and weight losses measurement were performed to analyze the solid and liquid phase before and after the reaction process. The weight changes and mineral dissolution caused by CO2 injection for two hours CO2 bubbling and one week' aging were 0.28% and 18.74%, respectively. The average variation of concentrations of alkaline earth metals in solution varied from 22.62% for Ca(2+) to 17.42% for Mg(2+), with in between 16.18% observed for the alkali earth metal, potassium. Analysis of variance (ANOVA) test is performed to determine significant differences of the element concentration, including Ca, Mg, and K, before and after the reaction experiment. Such changes show that the deposition of alkali and alkaline earth metals and the dissolution of required elements in sandstone samples are enhanced by CO2 injection.

Artificial Weathering as a Function of CO2 Injection in Pahang Sandstone Malaysia: Investigation of Dissolution Rate in Surficial Condition

NASA Astrophysics Data System (ADS)

Jalilavi, Madjid; Zoveidavianpoor, Mansoor; Attarhamed, Farshid; Junin, Radzuan; Mohsin, Rahmat

2014-01-01

Formation of carbonate minerals by CO2 sequestration is a potential means to reduce atmospheric CO2 emissions. Vast amount of alkaline and alkali earth metals exist in silicate minerals that may be carbonated. Laboratory experiments carried out to study the dissolution rate in Pahang Sandstone, Malaysia, by CO2 injection at different flow rate in surficial condition. X-ray Powder Diffraction (XRD), Scanning Electron Microscope (SEM) with Energy Dispersive X-ray Spectroscopy (EDX), Atomic Absorption Spectroscopy (AAS) and weight losses measurement were performed to analyze the solid and liquid phase before and after the reaction process. The weight changes and mineral dissolution caused by CO2 injection for two hours CO2 bubbling and one week' aging were 0.28% and 18.74%, respectively. The average variation of concentrations of alkaline earth metals in solution varied from 22.62% for Ca2+ to 17.42% for Mg2+, with in between 16.18% observed for the alkali earth metal, potassium. Analysis of variance (ANOVA) test is performed to determine significant differences of the element concentration, including Ca, Mg, and K, before and after the reaction experiment. Such changes show that the deposition of alkali and alkaline earth metals and the dissolution of required elements in sandstone samples are enhanced by CO2 injection.

In vitro dissolution of uranium oxide by baboon alveolar macrophages.

PubMed Central

Poncy, J L; Metivier, H; Dhilly, M; Verry, M; Masse, R

1992-01-01

In vitro cellular dissolution tests for insoluble forms of uranium oxide are technically difficult with conventional methodology using adherent alveolar macrophages. The limited number of cells per flask and the slow dissolution rate in a large volume of nutritive medium are obvious restricting factors. Macrophages in suspension cannot be substituted because they represent different and poorly reproducible functional subtypes with regard to activation and enzyme secretion. Preliminary results on the dissolution of uranium oxide using immobilized alveolar macrophages are promising because large numbers of highly functional macrophages can be cultured in a limited volume. Cells were obtained by bronchoalveolar lavages performed on baboons (Papio papio) and then immobilized after the phagocytosis of uranium octoxide (U3O8) particles in alginate beads linked with Ca2+. The dissolution rate expressed as percentage of initial uranium content in cells was 0.039 +/- 0.016%/day for particles with a count median geometric diameter of 3.84 microns(sigma g = 1.84). A 2-fold increase in the dissolution rate was observed when the same number of particles was immobilized without macrophages. These results, obtained in vitro, suggest that the U3O8 preparation investigated should be assigned to inhalation class Y as recommended by the International Commission on Radiological Protection. Future experiments are intended to clarify this preliminary work and to examine the dissolution characteristics of other particles such as uranium dioxide. It is recommended that the dissolution rate should be measured over an interval of 3 weeks, which is compatible with the survival time of immobilized cells in culture and may reveal transformation states occurring with aging of the particles. PMID:1396447

On the influence of carbonate in mineral dissolution: I. The thermodynamics and kinetics of hematite dissolution in bicarbonate solutions at T = 25° C

NASA Astrophysics Data System (ADS)

Bruno, Jordi; Stumm, Werner; Wersin, Paul; Brandberg, Frederick

1992-03-01

We have studied the thermodynamics and kinetics of hematite dissolution in bicarbonate solutions under constant pCO 2. The solubility of hematite is increased in the presence of bicarbonate. We have established that the complexes responsible for this increase are FeOHCO 3 (aq) and Fe(CO 3) 2-. The stability constants of these complexes at the infinite dilution standard state are log β 11 = -3.83 ± 0.21 and log β 2 = 7.40 ± 0.11 , respectively (all errors are given at 2σ confidence level through this work). The rate of dissolution of hematite is enhanced in bicarbonate solutions. This rate of dissolution can be expressed as R diss = k 1[HCO 3-] 0.23 (mol m -2h -1), with k 1 = 1.42 10 -7h -1. The combination of the study of the surface complexation and kinetics of dissolution of hematite in bicarbonate solutions indicate that the dissolution of hematite is surface controlled and bicarbonate promoted. The rate of dissolution follows the expression R diss = k HCO 3-FeOH - HCO 3-}, where k HCO 3- = 1.1 10 -3 h -1. The implications of these findings in the oxic cycle of iron in natural waters are discussed, most importantly in order to explain the high-Fe(III) concentrations measured in groundwaters from the Poços de Caldas complex in Brazil.

Carbonate mineral dissolution kinetics in high pressure experiments

NASA Astrophysics Data System (ADS)

Dethlefsen, F.; Dörr, C.; Schäfer, D.; Ebert, M.

2012-04-01

The potential CO2 reservoirs in the North German Basin are overlain by a series of Mesozoic barrier rocks and aquifers and finally mostly by Tertiary and Quaternary close-to-surface aquifers. The unexpected rise of stored CO2 from its reservoir into close-to-surface aquifer systems, perhaps through a broken well casing, may pose a threat to groundwater quality because of the acidifying effect of CO2 dissolution in water. The consequences may be further worsening of the groundwater quality due to the mobilization of heavy metals. Buffer mechanisms counteracting the acidification are for instance the dissolution of carbonates. Carbonate dissolution kinetics is comparably fast and carbonates can be abundant in close-to-surface aquifers. The disadvantages of batch experiments compared to column experiments in order to determine rate constants are well known and have for instance been described by v. GRINSVEN and RIEMSDIJK (1992). Therefore, we have designed, developed, tested, and used a high-pressure laboratory column system to simulate aquifer conditions in a flow through setup within the CO2-MoPa project. The calcite dissolution kinetics was determined for CO2-pressures of 6, 10, and 50 bars. The results were evaluated by using the PHREEQC code with a 1-D reactive transport model, applying a LASAGA (1984) -type kinetic dissolution equation (PALANDRI and KHARAKA, 2004; eq. 7). While PALANDRI and KHARAKA (2004) gave calcite dissolution rate constants originating from batch experiments of log kacid = -0.3 and log kneutral = -5.81, the data of the column experiment were best fitted using log kacid = -2.3 and log kneutral = -7.81, so that the rate constants fitted using the lab experiment applying 50 bars pCO2 were approximately 100 times lower than according to the literature data. Rate constants of experiments performed at less CO2 pressure (pCO2 = 6 bars: log kacid = -1.78; log kneutral = -7.29) were only 30 times lower than literature data. These discrepancies in the

Microbially mediated barite dissolution in anoxic brines

USGS Publications Warehouse

Ouyang, Bingjie; Akob, Denise M.; Dunlap, Darren S.; Renock, Devon

2017-01-01

Fluids injected into shale formations during hydraulic fracturing of black shale return with extraordinarily high total-dissolved-solids (TDS) and high concentrations of barium (Ba) and radium (Ra). Barite, BaSO4, has been implicated as a possible source of Ba as well as a problematic mineral scale that forms on internal well surfaces, often in close association with radiobarite, (Ba,Ra)SO4. The dissolution of barite by abiotic processes is well quantified. However, the identification of microbial communities in flowback and produced water necessitates the need to understand barite dissolution in the presence of bacteria. Therefore, we evaluated the rates and mechanisms of abiotic and microbially-mediated barite dissolution under anoxic and hypersaline conditions in the laboratory. Barite dissolution experiments were conducted with bacterial enrichment cultures established from produced water from Marcellus Shale wells located in northcentral Pennsylvania. These cultures were dominated by anaerobic halophilic bacteria from the genus Halanaerobium. Dissolved Ba was determined by ICP-OES and barite surfaces were investigated by SEM and AFM. Our results reveal that: 1) higher amounts of barium (up to ∼5 × ) are released from barite in the presence of Halanaerobium cultures compared to brine controls after 30 days of reaction, 2) etch pits that develop on the barite (001) surface in the presence of Halanaerobium exhibit a morphology that is distinct from those that form during control experiments without bacteria, 3) etch pits that develop in the presence of Halanaerobium exhibit a morphology that is similar to the morphology of etch pits formed in the presence of strong organic chelators, EDTA and DTPA, and 4) experiments using dialysis membranes to separate barite from bacteria suggest that direct contact between the two is not required in order to promote dissolution. These results suggest that Halanaerobium increase the rate of barite dissolution in anoxic and

Oxidative dissolution of silver nanoparticles: A new theoretical approach.

PubMed

Adamczyk, Zbigniew; Oćwieja, Magdalena; Mrowiec, Halina; Walas, Stanisław; Lupa, Dawid

2016-05-01

A general model of an oxidative dissolution of silver particle suspensions was developed that rigorously considers the bulk and surface solute transport. A two-step surface reaction scheme was proposed that comprises the formation of the silver oxide phase by direct oxidation and the acidic dissolution of this phase leading to silver ion release. By considering this, a complete set of equations is formulated describing oxygen and silver ion transport to and from particles' surfaces. These equations are solved in some limiting cases of nanoparticle dissolution in dilute suspensions. The obtained kinetic equations were used for the interpretation of experimental data pertinent to the dissolution kinetics of citrate-stabilized silver nanoparticles. In these kinetic measurements the role of pH and bulk suspension concentration was quantitatively evaluated by using the atomic absorption spectrometry (AAS). It was shown that the theoretical model adequately reflects the main features of the experimental results, especially the significant increase in the dissolution rate for lower pH. Also the presence of two kinetic regimes was quantitatively explained in terms of the decrease in the coverage of the fast dissolving oxide layer. The overall silver dissolution rate constants characterizing these two regimes were determined. Copyright © 2015 Elsevier Inc. All rights reserved.

Tissue dissolution by a novel multisonic ultracleaning system and sodium hypochlorite.

PubMed

Haapasalo, Markus; Wang, Zhejun; Shen, Ya; Curtis, Allison; Patel, Payal; Khakpour, Mehrzad

2014-08-01

This study aimed to evaluate the effectiveness of a novel Multisonic Ultracleaning System (Sonendo Inc, Laguna Hills, CA) in tissue dissolution in comparison with conventional irrigation devices. Pieces of bovine muscle tissue (68 ± 2 mg) were placed in 0.7-mL test tubes (height: 23.60 mm, inner diameter: 6.00 mm, outer diameter: 7.75 mm) and exposed to 5 minutes of irrigation by different devices. Endodontic devices included the Multisonic Ultracleaning System, the Piezon Master 700 (EMS, Dallas, TX) ultrasonic system with agitation, the EndoVac negative-pressure irrigation system (SybronEndo, Orange, CA), and a conventional positive-pressure 27-G irrigation needle at a flow rate of 10 mL/min. The systems were tested with 0.5%, 3%, and 6% sodium hypochlorite (NaOCl) at room temperature (21°C) as well as 40°C. Irrigation with sterile water was used as a control. The mass of tissue specimens was measured and recorded before and after the use of each device, and if the specimen was completely dissolved visually within 5 minutes, the dissolution time was recorded. The rate of tissue dissolution (%/s) was then calculated. The Multisonic Ultracleaning System had the fastest rate of tissue dissolution (P < .05), at 1.0% ± 0.1% per second using 0.5% NaOCl, 2.3% ± 0.9% per second using 3% NaOCl, and 2.9% ± 0.7% per second using 6% NaOCl. This tissue dissolution rate was more than 8 times greater than the second fastest device tested (P < .01), the Piezon Master 700 ultrasonic system, which resulted in a tissue dissolution rate of 0.328% ± 0.002% per second using 6% NaOCl at 40°C. For all irrigation devices tested, the rate of tissue dissolution increased with a higher concentration and temperature of the NaOCl solution. The novel Multisonic Ultracleaning System achieved a significantly faster tissue dissolution rate when compared with the other systems examined in vitro. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights

Initial dissolution kinetics of cocrystal of carbamazepine with nicotinamide.

PubMed

Hattori, Yusuke; Sato, Maiko; Otsuka, Makoto

2015-11-01

Objectives of this study are investigating the initial dissolution kinetics of the cocrystal of carbamazepine (CBZ) with nicotinamide (NIC) and understanding its initial dissolution process. Cocrystal solids of CBZ with NIC were prepared by co-milling and solvent evaporation methods. The formation of cocrystal solid was verified via X-ray diffraction measurement. Dissolution tests of the solids were performed using an original flow cell and ultraviolet-visible spectroscopic detector. The spectra monitored in situ were analyzed to determine the dissolved compounds separately using the classical least squares regression method. The initial dissolution profiles were interpreted using simultaneous model of dissolution and phase changes. In the initial dissolution, CBZ in the cocrystal structure dissolved in water and it was suggested that CBZ reached a metastable intermediate state simultaneously with dissolution. The cocrystal solid prepared by solvent evaporation provided a higher rate constant of the phase change than that prepared by co-milling. Our results thus support the use of evaporation as the method of choice to produce ordered cocrystal structures. We suggest that CBZ forms dihydrate during the dissolution process; however, during the initial phase of dissolution, CBZ changes to a metastable intermediate phase. © 2015 Royal Pharmaceutical Society.

Dissolution Kinetics of Spheroidal-Shaped Precipitates in Age-Hardenable Aluminum Alloys

NASA Astrophysics Data System (ADS)

Anjabin, Nozar; Salehi, Majid Seyed

2018-05-01

As a first attempt, a mathematical model is proposed to predict the dissolution kinetics of non-spherical secondary phase precipitates during solution heat treatment of age-hardenable aluminum alloys. The model uses general spheroidal geometry to describe the dissolution process of the alloys containing needle/disc-shaped particles with different size distributions in a finite matrix. It is found that as the aspect ratio deviates from unity, the dissolution rate is accelerated. Also, the dissolution rate of the particles in the alloy containing the particle size distribution is lower than that of mono-sized particles system. The modeling results for dissolution of θ' precipitates in an Al-Cu alloy are compared with experiments, and a good agreement was found between the modeling and the experimental results. The proposed model can be applied to different isothermal and non-isothermal annealing conditions.

Initial Drug Dissolution from Amorphous Solid Dispersions Controlled by Polymer Dissolution and Drug-Polymer Interaction.

PubMed

Chen, Yuejie; Wang, Shujing; Wang, Shan; Liu, Chengyu; Su, Ching; Hageman, Michael; Hussain, Munir; Haskell, Roy; Stefanski, Kevin; Qian, Feng

2016-10-01

To identify the key formulation factors controlling the initial drug and polymer dissolution rates from an amorphous solid dispersion (ASD). Ketoconazole (KTZ) ASDs using PVP, PVP-VA, HMPC, or HPMC-AS as polymeric matrix were prepared. For each drug-polymer system, two types of formulations with the same composition were prepared: 1. Spray dried dispersion (SDD) that is homogenous at molecular level, 2. Physical blend of SDD (80% drug loading) and pure polymer (SDD-PB) that is homogenous only at powder level. Flory-Huggins interaction parameters (χ) between KTZ and the four polymers were obtained by Flory-Huggins model fitting. Solution (13)C NMR and FT-IR were conducted to investigate the specific drug-polymer interaction in the solution and solid state, respectively. Intrinsic dissolution of both the drug and the polymer from ASDs were studied using a Higuchi style intrinsic dissolution apparatus. PXRD and confocal Raman microscopy were used to confirm the absence of drug crystallinity on the tablet surface before and after dissolution study. In solid state, KTZ is completely miscible with PVP, PVP-VA, or HPMC-AS, demonstrated by the negative χ values of -0.36, -0.46, -1.68, respectively; while is poorly miscible with HPMC shown by a positive χ value of 0.23. According to solution (13)C NMR and FT-IR studies, KTZ interacts with HPMC-AS strongly through H-bonding and dipole induced interaction; with PVPs and PVP-VA moderately through dipole-induced interactions; and with HPMC weakly without detectable attractive interaction. Furthermore, the "apparent" strength of drug-polymer interaction, measured by the extent of peak shift on NMR or FT-IR spectra, increases with the increasing number of interacting drug-polymer pairs. For ASDs with the presence of considerable drug-polymer interactions, such as KTZ/PVPs, KTZ/PVP-VA, or KTZ /HPMC-AS systems, drug released at the same rate as the polymer when intimate drug-polymer mixing was ensured (i.e., the SDD systems

Microfluidics experiments of dissolution in a fracture. Influence of Damköhler and Péclet numbers, and of the geometry on the dissolution pattern

NASA Astrophysics Data System (ADS)

Osselin, Florian; Budek, Agnieszka; Cybulski, Olgierd; Szymczak, Piotr

2015-04-01

Dissolution of natural rocks is an ever present phenomenon in nature. The shaping of natural landscapes by the dissolution of limestone gives for example birth to exceptional features like karsts. Currently dissolution is also at the heart of key research topics as Carbon Capture and Storage or Enhanced Oil Recovery. The basics principles of dissolution are well-known, however, the sheer amount of different patterns arising from these mechanisms and the strong dependency on parameters such as pore network, chemical composition and flow rate, make it particularly difficult to study theoretically and experimentally. In this study we present a microfluidic experiment simulating the behavior of a dissolving fluid in a fracture. The experiments consist of a chip of gyspum inserted between two polycarbonate plates and subjected to a constant flow rate of pure water. The point in using microfluidics is that it allows a complete control on the experimental parameters such as geometry and chemical composition of the porous medium, flow rate, fracture aperture, roughness of the fracture walls, and an in situ observation of the geometry evolution which is impossible with 3D natural rocks. Thanks to our experiments we have been able to cover the whole range of dissolution patterns, from wormholing or DLA fingering to homogeneous dissolution, by changing Péclet and Damköhler numbers. Moreover, we have been able to tweak the geometry of our artificial fracture, inserting finger seeds or non-dissolvable obstacles. The comparison of the experimental patterns with the numerical dissolution code dissol (Szymczak and Ladd 2011) has then shown a very good correlation of the patterns, giving confidence in both experiments and modeling.

Effect of Microenvironmental pH Modulation on the Dissolution Rate and Oral Absorption of the Salt of a Weak Acid - Case Study of GDC-0810.

PubMed

Hou, Hao Helen; Jia, Wei; Liu, Lichuan; Cheeti, Sravanthi; Li, Jane; Nauka, Ewa; Nagapudi, Karthik

2018-01-29

The purpose of this work is to investigate the effect of microenvironmental pH modulation on the in vitro dissolution rate and oral absorption of GDC-0810, an oral anti-cancer drug, in human. The pH-solubility profile of GDC-0810 free acid and pH max of its N-Methyl-D-glucamine (NMG) salt were determined. Precipitation studies were conducted for GDC-0810 NMG salt at different pH values. GDC-0810 200-mg dose NMG salt tablet formulations containing different levels of sodium bicarbonate as the pH modifier were tested for dissolution under the dual pH-dilution scheme. Three tablet formulations were evaluated in human as a part of a relative bioavailability study. A 200-mg dose of GDC-0810 was administered QD with low fat food. Intrinsic solubility of GDC-0810 free acid was found to be extremely low. The pH max of the NMG salt suggested a strong tendency for form conversion to the free acid under GI conditions. In vitro dissolution profiles showed that the dissolution rate and extent of GDC-0810 increased with increasing the level of sodium bicarbonate in the formulation. The human PK data showed a similar trend for the geometric mean of C max and AUC 0-t for formulations containing 5%, 10%, and 15% sodium bicarbonate, but the difference is not statistically significant. Incorporation of a basic pH modifier, sodium bicarbonate, in GDC-0810 NMG salt tablet formulations enhanced in vitro dissolution rate of GDC-0810 via microenvironmental pH modulation. The human PK data showed no statistically significant difference in drug exposure from tablets containing 5%, 10%, and 15% sodium bicarbonate.

Dissolution of steel slags in aqueous media.

PubMed

Yadav, Shashikant; Mehra, Anurag

2017-07-01

Steel slag is a major industrial waste in steel industries, and its dissolution behavior in water needs to be characterized in the larger context of its potential use as an agent for sequestering CO 2 . For this purpose, a small closed system batch reactor was used to conduct the dissolution of steel slags in an aqueous medium under various dissolution conditions. In this study, two different types of steel slags were procured from steel plants in India, having diverse structural features, mineralogical compositions, and particle sizes. The experiment was performed at different temperatures for 240 h of dissolution at atmospheric pressure. The dissolution rates of major and minor slag elements were quantified through liquid-phase elemental analysis using an inductively coupled plasma atomic emission spectroscopy at different time intervals. Advanced analytical techniques such as field emission gun-scanning electron microscope, energy-dispersive X-ray, BET, and XRD were also used to analyze mineralogical and structural changes in the slag particles. High dissolution of slags was observed irrespective of the particle size distribution, which suggests high carbonation potential. Concentrations of toxic heavy metals in the leachate were far below maximum acceptable limits. Thus, the present study investigates the dissolution behavior of different mineral ions of steel slag in aqueous media in light of its potential application in CO 2 sequestration.

Artificial Weathering as a Function of CO2 Injection in Pahang Sandstone Malaysia: Investigation of Dissolution Rate in Surficial Condition

PubMed Central

Jalilavi, Madjid; Zoveidavianpoor, Mansoor; Attarhamed, Farshid; Junin, Radzuan; Mohsin, Rahmat

2014-01-01

Formation of carbonate minerals by CO2 sequestration is a potential means to reduce atmospheric CO2 emissions. Vast amount of alkaline and alkali earth metals exist in silicate minerals that may be carbonated. Laboratory experiments carried out to study the dissolution rate in Pahang Sandstone, Malaysia, by CO2 injection at different flow rate in surficial condition. X-ray Powder Diffraction (XRD), Scanning Electron Microscope (SEM) with Energy Dispersive X-ray Spectroscopy (EDX), Atomic Absorption Spectroscopy (AAS) and weight losses measurement were performed to analyze the solid and liquid phase before and after the reaction process. The weight changes and mineral dissolution caused by CO2 injection for two hours CO2 bubbling and one week' aging were 0.28% and 18.74%, respectively. The average variation of concentrations of alkaline earth metals in solution varied from 22.62% for Ca2+ to 17.42% for Mg2+, with in between 16.18% observed for the alkali earth metal, potassium. Analysis of variance (ANOVA) test is performed to determine significant differences of the element concentration, including Ca, Mg, and K, before and after the reaction experiment. Such changes show that the deposition of alkali and alkaline earth metals and the dissolution of required elements in sandstone samples are enhanced by CO2 injection. PMID:24413195

Increase of apatite dissolution rate by Scots pine roots associated or not with Burkholderia glathei PML1(12)Rp in open-system flow microcosms

NASA Astrophysics Data System (ADS)

Calvaruso, Christophe; Turpault, Marie-Pierre; Frey-Klett, Pascale; Uroz, Stéphane; Pierret, Marie-Claire; Tosheva, Zornitza; Kies, Antoine

2013-04-01

The release of nutritive elements through apatite dissolution represents the main source of phosphorus, calcium, and several micronutrients (e.g., Zn, Cu) for organisms in non-fertilized forest ecosystems. The aim of this study was to quantify, for the first time, the dissolution rate of apatite grains by tree roots that were or were not associated with a mineral weathering bacterial strain, and by various acids known to be produced by tree roots and soil bacterial strains in open-system flow microcosms. In addition, we explored whether the mobilization of trace elements (including rare earth elements) upon apatite dissolution was affected by the presence of trees and associated microorganisms. The dissolution rate of apatite by Scots pine plants that were or were not inoculated with the strain Burkholderia glathei PML1(12)Rp, and by inorganic (nitric) and organic (citric, oxalic and gluconic) acids at pH 5.5, 4.8, 3.8, 3.5, 3.0, and 2.0 was monitored in two controlled experiments: "plant-bacteria interaction" and "inorganic and organic acids". Analyses of the outlet solutions in the "plant-bacteria interaction" experiment showed that Scots pine roots and B. glathei PML1(12)Rp produced protons and organic acids such as gluconate, oxalate, acetate, and lactate. The weathering budget calculation revealed that Scots pines (with or without PML1(12)Rp) significantly increased (factor > 10) the release of Ca, P, As, Sr, Zn, U, Y, and rare earth elements such as Ce, La, Nd from apatite, compared to control abiotic treatment. Scanning electron microscopy observation confirmed traces of apatite dissolution in contact of roots. Most dissolved elements were taken up by Scots pine roots, i.e., approximately 50% of Ca, 70% of P, 30% of As, 70% of Sr, 90% of Zn, and 100% of U, Y, and rare earth elements. Interestingly, no significant additional effect due to the bacterial strain PML1(12)Rp on apatite dissolution and Scots pine nutrition and growth was observed. The "inorganic

A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

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

Chen Zhu

2006-08-31

Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory measuredmore » and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between laboratory and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO2 injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the second year of the project, we completed CO{sub 2}-Navajo sandstone interaction batch and flow-through experiments and a Navajo sandstone dissolution experiment without the presence of CO{sub 2} at 200 C and 250-300 bars, and initiated dawsonite dissolution and solubility experiments. We also performed additional 5-day experiments at

Ferrihydrite dissolution by pyridine-2,6-bis(monothiocarboxylic acid) and hydrolysis products

NASA Astrophysics Data System (ADS)

Dhungana, Suraj; Anthony, Charles R.; Hersman, Larry E.

2007-12-01

Pyridine-2,6-bis(monothiocarboxylate) (pdtc), a metabolic product of microorganisms, including Pseudomonas putida and Pseudomonas stutzeri was investigated for its ability of dissolve Fe(III)(hydr)oxides at pH 7.5. Concentration dependent dissolution of ferrihydrite under anaerobic environment showed saturation of the dissolution rate at the higher concentration of pdtc. The surface controlled ferrihydrite dissolution rate was determined to be 1.2 × 10 -6 mol m -2 h -1. Anaerobic dissolution of ferrihydrite by pyridine-2,6-dicarboxylic acid or dipicolinic acid (dpa), a hydrolysis product of pdtc, was investigated to study the mechanism(s) involved in the pdtc facilitated ferrihydrite dissolution. These studies suggest that pdtc dissolved ferrihydrite using a reduction step, where dpa chelates the Fe reduced by a second hydrolysis product, H 2S. Dpa facilitated dissolution of ferrihydrite showed very small increase in the Fe dissolution when the concentration of external reductant, ascorbate, was doubled, suggesting the surface dynamics being dominated by the interactions between dpa and ferrihydrite. Greater than stoichiometric amounts of Fe were mobilized during dpa dissolution of ferrihydrite assisted by ascorbate and cysteine. This is attributed to the catalytic dissolution of Fe(III)(hydr)oxides by the in situ generated Fe(II) in the presence of a complex former, dpa.

Dissolution enhancement of Deflazacort using hollow crystals prepared by antisolvent crystallization process.

PubMed

Paulino, A S; Rauber, G; Campos, C E M; Maurício, M H P; de Avillez, R R; Capobianco, G; Cardoso, S G; Cuffini, S L

2013-05-13

Deflazacort (DFZ), a derivate of prednisolone, is a poorly soluble drug which has been proposed to have major advantages over other corticosteroids. Poorly soluble drugs present limited bioavailability due to their low solubility and dissolution rate and several strategies have been developed in order to find ways to improve them. In general, pharmaceutical laboratories use a micronized process to reduce the particle size in order to increase the dissolution of the drugs. However, this process causes changes such as polymorphic transitions, particle agglomeration and a reduction in fluidity and wettability. These solid-state properties affect the dissolution behavior and stability performance of drugs. Crystallization techniques are widely used in the pharmaceutical industry and antisolvent crystallization has been used to obtain ultrafine particles. In this study, DFZ was investigated in terms of its antisolvent crystallization in different solvents and under various preparation conditions (methanol/water ratio, stirring and evaporation rate, etc.), in order to compare the physicochemical properties between crystallized samples and raw materials available on the Brazilian market with and without micronization. Crystalline structure, morphology, and particle size, and their correlation with the Intrinsic Dissolution Rate (IDR) and dissolution profile as relevant biopharmaceutical properties were studied. Crystallization conditions were achieved which provided crystalline samples of hollow-shaped crystals with internal channels, which increased the dissolution rate of DFZ. The antisolvent crystallization process allowed the formation of hollow crystals, which demonstrated a better dissolution profile than the raw material (crystalline and micronized), making this a promising technique as a crystallization strategy for improving the dissolution and thus the bioavailability of poorly soluble drugs. Copyright © 2013 Elsevier B.V. All rights reserved.

The Use of Artificial Neural Network for Prediction of Dissolution Kinetics

PubMed Central

Elçiçek, H.; Akdoğan, E.; Karagöz, S.

2014-01-01

Colemanite is a preferred boron mineral in industry, such as boric acid production, fabrication of heat resistant glass, and cleaning agents. Dissolution of the mineral is one of the most important processes for these industries. In this study, dissolution of colemanite was examined in water saturated with carbon dioxide solutions. Also, prediction of dissolution rate was determined using artificial neural networks (ANNs) which are based on the multilayered perceptron. Reaction temperature, total pressure, stirring speed, solid/liquid ratio, particle size, and reaction time were selected as input parameters to predict the dissolution rate. Experimental dataset was used to train multilayer perceptron (MLP) networks to allow for prediction of dissolution kinetics. Developing ANNs has provided highly accurate predictions in comparison with an obtained mathematical model used through regression method. We conclude that ANNs may be a preferred alternative approach instead of conventional statistical methods for prediction of boron minerals. PMID:25028674

Dissolution of Biogenic and Synthetic UO2 under Varied Reducing Conditions

PubMed Central

ULRICH, KAI – UWE; SINGH, ABHAS; SCHOFIELD, ELEANOR J.; BARGAR, JOHN R.; VEERAMANI, HARISH; SHARP, JONATHAN O.; LATMANI, RIZLAN BERNIER -; GIAMMAR, DANIEL E.

2008-01-01

The chemical stability of biogenic UO2, a nanoparticulate product of environmental bioremediation, may be impacted by the particles’ surface free energy, structural defects, and compositional variability in analogy to abiotic UO2+x (0 ≤ x ≤ 0.25). This study quantifies and compares intrinsic solubility and dissolution rate constants of biogenic nano-UO2 and synthetic bulk UO2.00, taking molecular-scale structure into account. Rates were determined under anoxic conditions as a function of pH and dissolved inorganic carbon in continuous-flow experiments. The dissolution rates of biogenic and synthetic UO2 solids were lowest at near neutral pH and increased with decreasing pH. Similar surface area-normalized rates of biogenic and synthetic UO2 suggest comparable reactive surface site densities. This finding is consistent with the identified structural homology of biogenic UO2 and stoichiometric UO2.00. Compared to carbonate-free anoxic conditions, dissolved inorganic carbon accelerated the dissolution rate of biogenic UO2 by 3 orders of magnitude. This phenomenon suggests continuous surface oxidation of U(IV) to U(VI), with detachment of U(VI) as the rate-determining step in dissolution. Although reducing conditions were maintained throughout the experiments, the UO2 surface can be oxidized by water and radiogenic oxidants. Even in anoxic aquifers, UO2 dissolution may be controlled by surface U(VI) rather than U(IV) phases. PMID:18754482

Selection of effective cocrystals former for dissolution rate improvement of active pharmaceutical ingredients based on lipoaffinity index.

PubMed

Cysewski, Piotr; Przybyłek, Maciej

2017-09-30

New theoretical screening procedure was proposed for appropriate selection of potential cocrystal formers possessing the ability of enhancing dissolution rates of drugs. The procedure relies on the training set comprising 102 positive and 17 negative cases of cocrystals found in the literature. Despite the fact that the only available data were of qualitative character, performed statistical analysis using binary classification allowed to formulate quantitative criterions. Among considered 3679 molecular descriptors the relative value of lipoaffinity index, expressed as the difference between values calculated for active compound and excipient, has been found as the most appropriate measure suited for discrimination of positive and negative cases. Assuming 5% precision, the applied classification criterion led to inclusion of 70% positive cases in the final prediction. Since lipoaffinity index is a molecular descriptor computed using only 2D information about a chemical structure, its estimation is straightforward and computationally inexpensive. The inclusion of an additional criterion quantifying the cocrystallization probability leads to the following conjunction criterions H mix <-0.18 and ΔLA>3.61, allowing for identification of dissolution rate enhancers. The screening procedure was applied for finding the most promising coformers of such drugs as Iloperidone, Ritonavir, Carbamazepine and Enthenzamide. Copyright © 2017 Elsevier B.V. All rights reserved.

Size effects in MgO cube dissolution.

PubMed

Baumann, Stefan O; Schneider, Johannes; Sternig, Andreas; Thomele, Daniel; Stankic, Slavica; Berger, Thomas; Grönbeck, Henrik; Diwald, Oliver

2015-03-10

Stability parameters and dissolution behavior of engineered nanomaterials in aqueous systems are critical to assess their functionality and fate under environmental conditions. Using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, we investigated the stability of cubic MgO particles in water. MgO dissolution proceeding via water dissociation at the oxide surface, disintegration of Mg(2+)-O(2-) surface elements, and their subsequent solvation ultimately leads to precipitation of Mg(OH)2 nanosheets. At a pH ≥ 10, MgO nanocubes with a size distribution below 10 nm quantitatively dissolve within few minutes and convert into Mg(OH)2 nanosheets. This effect is different from MgO cubes originating from magnesium combustion in air. With a size distribution in the range 10 nm ≤ d ≤ 1000 nm they dissolve with a significantly smaller dissolution rate in water. On these particles water induced etching generates (110) faces which, above a certain face area, dissolve at a rate equal to that of (100) planes.1 The delayed solubility of microcrystalline MgO is attributed to surface hydroxide induced self-inhibition effects occurring at the (100) and (110) microplanes. The present work underlines the importance of morphology evolution and surface faceting of engineered nanomaterials particles during their dissolution.

Dissolution of fludrocortisone from phospholipid coprecipitates.

PubMed

Vudathala, G K; Rogers, J A

1992-03-01

The physical properties and dissolution behavior of phospholipid coprecipitates of fludrocortisone acetate (FA) prepared from ethyl acetate, as well as the effect of added polymer, have been determined. The fraction dissolved after 90 min and the initial dissolution rate (IDR) of coprecipitates containing dimyristoyl phosphatidylcholine (DMPC) (4:1, w/w; FA:DMPC) were 77% and 3.5-fold greater than for FA at pH 2.0 and 37 degrees C. The mechanisms of dissolution were similar to those previously established for griseofulvin, but no aging occurred over 4 months at room temperature in a desiccator. The addition of 0.01 mol% of dextran (MW = 2 million) or 0.1 mol% of poly(lactic acid) reduced the fraction of FA dissolved in 90 min by 15% and reduced the IDR by 35%. The addition of poly(vinylpyrrolidone) (PVP) resulted in a minimum of dissolution efficiency at 1 mol% of PVP 10 (MW = 10,000) or PVP 24 (MW = 24,000) and at 0.1 mol% PVP 40 (MW = 40,000). Only PVP 24 influenced the melting point and heat of fusion of the coprecipitates (determined by differential thermal analysis). Coprecipitate dissolution was reasonably described by either second-order or Weibull distribution kinetic models. These results support the application of high drug-containing solid dispersions using phospholipids to increase the dissolution behavior of poorly water-soluble drug solvates and the possibility of modifying drug release by the incorporation of small amounts of polymers.

Volume to dissolve applied dose (VDAD) and apparent dissolution rate (ADR): tools to predict in vivo bioavailability from orally applied drug suspensions.

PubMed

Muenster, Uwe; Pelzetter, Christian; Backensfeld, Thomas; Ohm, Andreas; Kuhlmann, Thomas; Mueller, Hartwig; Lustig, Klemens; Keldenich, Jörg; Greschat, Susanne; Göller, Andreas H; Gnoth, Mark Jean

2011-08-01

Low solubility of drug candidates generated in research contributes to their elimination during subsequent development due to insufficient oral bioavailability (BA) of crystalline compound. Therefore, the purpose of the study was to identify critical in vitro solubility and dissolution parameter that would predict critical in vivo dissolution by means of in vitro-in vivo correlation. Thermodynamic solubility and apparent dissolution rate (ADR) were determined using the shake-flask method and mini-flow-through-cell, respectively. Oral BA studies in rats and humans were conducted from drug solution and suspension/tablets. Relative BA was calculated using F(rel) [%]=AUC(suspension)/AUC(solution)*100, representing a measure of in vivo dissolution. Roughly, F(rel) rat >50% translates into F(rel) human of >90%. Both, ADR and log volume to dissolve applied dose (VDAD), when plotted against F(rel) rat, revealed certain threshold levels, (ADR, ∼150-200 μg of compound dissolved under respective assay conditions; VDAD, ∼100-500 ml/kg) which translate into F(rel) in rats of >50%. Thus, assuming that F(rel)>50% in rats is indicative of sufficient in vivo dissolution in humans after oral application, drugs should exhibit a VDAD of ∼100-500 ml/kg or less in aqueous media to avoid insufficient or varying drug absorption. Copyright © 2011 Elsevier B.V. All rights reserved.

Effects of natural organic matter properties on the dissolution kinetics of zinc oxide nanoparticles

USGS Publications Warehouse

Jiang, Chuanjia; Aiken, George R.; Hsu-Kim, Heileen

2015-01-01

The dissolution of zinc oxide (ZnO) nanoparticles (NPs) is a key step of controlling their environmental fate, bioavailability, and toxicity. Rates of dissolution often depend upon factors such as interactions of NPs with natural organic matter (NOM). We examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution using anodic stripping voltammetry to directly measure dissolved zinc concentrations. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg C L–1) for Suwannee River humic and fulvic acids and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. The findings of this study facilitate a better understanding of the fate of ZnO NPs in organic-rich aquatic environments and highlight SUVA as a facile and useful indicator of NOM interactions with metal-based nanoparticles.

[Evaluation of Dissolution Profiles of Famotidine from Over-the-counter Drugs].

PubMed

Saito, Yuji; Adachi, Naoki; Kato, Miki; Nadai, Masayuki

2018-03-27

  In recent years, self-medication has started to receive more attention in Japan owing to increasing medical costs and health awareness among people. One of the main roles of pharmacists in self-medication is to provide appropriate information regarding over-the-counter (OTC) drugs. However, pharmacists promoting the proper use of OTC drugs have little information on their formulation properties. In this study, we performed dissolution tests on both OTC drugs and ethical drug (ED) containing famotidine, and evaluated the differences in their dissolution profiles. Marked differences in dissolution profiles of OTC drugs were observed in test solutions at pH 1.2, 4.0, and 6.8 and in water. To evaluate the differences quantitatively, we calculated the lag time and dissolution rate constant from the dissolution profiles. Significant differences in lag times and dissolution rate constants between some OTC drugs and ED were observed. We also used similarity factor (f2), to quantify the similarity between dissolution profiles of OTC drugs and ED. f2 values less than 42 were observed in some OTC drugs, suggesting that these differences might influence absorption in vivo resulting in differences in their onset time and efficacy. The findings of this study will provide useful information for the promotion of proper use of OTC drugs.

Influence of the oral dissolution time on the absorption rate of locally administered solid formulations for oromucosal use: the flurbiprofen lozenges paradigm.

PubMed

Imberti, Roberto; De Gregori, Simona; Lisi, Lucia; Navarra, Pierluigi

2014-01-01

Flurbiprofen is a nonsteroidal anti-inflammatory agent preferentially used for local oromucosal treatment of painful and/or inflammatory conditions of the oropharynx such as gingivitis, stomatitis, periodontitis, pharyngitis and laryngitis. In this study, we have investigated the bioavailability of a new generic formulation of flurbiprofen lozenges developed by Epifarma Srl, compared to the originator Benactiv Gola® taken as reference. Within the framework of a formal bioequivalence study, we investigated in particular the putative influence of oral dissolution time (i.e. the time spent suckling the lozenge from its intake to complete dissolution) on the absorption rate, and the contribution of this factor to the total variability of plasma flurbiprofen during absorption. We found that the amount of flurbiprofen absorbed into the systemic circulation is not significantly higher for the test drug compared to that of the reference product. We observed that the length of oral dissolution time is inversely correlated to 10-min flurbiprofen plasma levels in the test but not in the reference formulation. We estimated that oral dissolution time accounts for about 14% of overall variability in flurbiprofen plasma 10 min after test drug administration. © 2014 S. Karger AG, Basel.

Dissolution of Uranium(IV) Oxide in Solutions of Ammonium Carbonate and Hydrogen Peroxide

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

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-09-12

Understanding the dissolution characteristics of uranium oxides is of fundamental scientific interest. Bench scale experiments were conducted to determine the optimal dissolution parameters of uranium(IV) oxide (UO2) powder in solutions of ammonium carbonate [(NH4)2CO3] and hydrogen peroxide (H2O2). Experimental parameters included variable peroxide and carbonate concentrations, and temperature. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M (1:1 to 40:1 mol ratio H2O2:U), with no apparent maximum rate reached under the limited conditions used in our study. Temperature ranging studies show the dissolution rate of UO2 inmore » 1 M (NH4)2CO3 and 0.1 M H2O2 (2:1 mol ratio H2O2:U) increases linearly from 15 °C to 60 °C, again with no apparent maximum rate reached. Dissolution of UO2 in solutions with constant [H2O2] and [(NH4)2CO3] ranging from 0.5 to 2 M showed no difference in rate; however dissolution was significantly reduced in 0.05 M (NH4)2CO3 solution. The results of this study demonstrate the influence of [H2O2], [(NH4)2CO3], and temperature on the dissolution of UO2 in peroxide-containing (NH4)2CO3 solutions. Future studies are planned to elucidate the solution and solid state complexes in these systems.« less

Pore-scale supercritical CO2 dissolution and mass transfer under imbibition conditions

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

Chang, Chun; Zhou, Quanlin; Kneafsey, Timothy J.

2016-06-01

In modeling of geological carbon storage, dissolution of supercritical CO2 (scCO2) is often assumed to be instantaneous with equilibrium phase partitioning. In contrast, recent core-scale imbibition experiments have shown a prolonged depletion of residual scCO2 by dissolution, implying a non-equilibrium mechanism. In this study, eight pore-scale scCO2 dissolution experiments in a 2D heterogeneous, sandstone-analogue micromodel were conducted at supercritical conditions (9 MPa and 40 °C). The micromodel was first saturated with deionized (DI) water and drained by injecting scCO2 to establish a stable scCO2 saturation. DI water was then injected at constant flow rates after scCO2 drainage was completed. Highmore » resolution time-lapse images of scCO2 and water distributions were obtained during imbibition and dissolution, aided by a scCO2-soluble fluorescent dye introduced with scCO2 during drainage. These images were used to estimate scCO2 saturations and scCO2 depletion rates. Experimental results show that (1) a time-independent, varying number of water-flow channels are created during imbibition and later dominant dissolution by the random nature of water flow at the micromodel inlet, and (2) a time-dependent number of water-flow channels are created by coupled imbibition and dissolution following completion of dominant imbibition. The number of water-flow paths, constant or transient in nature, greatly affects the overall depletion rate of scCO2 by dissolution. The average mass fraction of dissolved CO2 (dsCO2) in water effluent varies from 0.38% to 2.72% of CO2 solubility, indicating non-equilibrium scCO2 dissolution in the millimeter-scale pore network. In general, the transient depletion rate decreases as trapped, discontinuous scCO2 bubbles and clusters within water-flow paths dissolve, then remains low with dissolution of large bypassed scCO2 clusters at their interfaces with longitudinal water flow, and finally increases with coupled transverse water

HIV status awareness, partnership dissolution and HIV transmission in generalized epidemics.

PubMed

Reniers, Georges; Armbruster, Benjamin

2012-01-01

HIV status aware couples with at least one HIV positive partner are characterized by high separation and divorce rates. This phenomenon is often described as a corollary of couples HIV Testing and Counseling (HTC) that ought to be minimized. In this contribution, we demonstrate the implications of partnership dissolution in serodiscordant couples for the propagation of HIV. We develop a compartmental model to study epidemic outcomes of elevated partnership dissolution rates in serodiscordant couples and parameterize it with estimates from population-based data (Rakai, Uganda). Via its effect on partnership dissolution, every percentage point increase in HIV status awareness reduces HIV incidence in monogamous populations by 0.27 percent for women and 0.63 percent for men. These effects are even larger when the assumption of monogamy can be relaxed, but are moderated by other behavior changes (e.g., increased condom use) in HIV status aware serodiscordant partnerships. When these behavior changes are taken into account, each percentage point increase in HIV status awareness reduces HIV incidence by 0.13 and 0.32 percent for women and men, respectively (assuming monogamy). The partnership dissolution effect exists because it decreases the fraction of serodiscordant couples in the population and prolongs the time that individuals spend outside partnerships. Our model predicts that elevated partnership dissolution rates in HIV status aware serodiscordant couples reduce the spread of HIV. As a consequence, the full impact of couples HTC for HIV prevention is probably larger than recognized to date. Particularly high partnership dissolution rates in female positive serodiscordant couples contribute to the gender imbalance in HIV infections.

Dissolution Kinetics of Meta-Torbernite under Circum-neutral to Alkaline Conditions

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

Wellman, Dawn M.; McNamara, Bruce K.; Bacon, Diana H.

2009-12-21

Autunite group minerals have been identified in contaminated sediments as the long-term controlling phase of uranium. Meta-torbernite, has been identified in subsurface environments which were subjected to co-contaminant disposal practices from past nuclear weapons and fuel operations. Under these conditions the mobility of uranium in subsurface pore waters is limited by the rate of meta-torbernite dissolution; however, there are no known investigations which report the dissolution behavior of meta-torbernite. The purpose of this investigation was to conduct a series of single-pass flow-through (SPFT) tests to 1) quantify the effect of temperature (23 - 90oC) and pH (6 -10) on meta-torbernitemore » dissolution, 2) compare the dissolution of meta-torbernite to other autunite-group minerals, and 3) evaluate the effect of aqueous phosphate on the dissolution kinetics of meta-torbernite. Results presented here illustrate meta-torbernite dissolution rates increase by ~100X over the pH interval of 6 to 10 (eta = 0.59 ± 0.07), irrespective of temperature. The power law coefficient for meta-torbernite, eta = 0.59 ± 0.07, is greater than that quantified for Ca-meta-autunite, eta = 0.42 ± 0.12. This suggests the stability of meta-torbernite is greater than that of meta-autunite, which is reflected in the predicted stability constants. The rate equation for the dissolution of meta-torbernite as a function of aqueous phosphate concentration is log rdissol (mol m-2 sec-1) = -4.7 x 10-13 + 4.1 x 10-10 [PO43-].« less

Predicting the dissolution kinetics of silicate glasses using machine learning

NASA Astrophysics Data System (ADS)

Anoop Krishnan, N. M.; Mangalathu, Sujith; Smedskjaer, Morten M.; Tandia, Adama; Burton, Henry; Bauchy, Mathieu

2018-05-01

Predicting the dissolution rates of silicate glasses in aqueous conditions is a complex task as the underlying mechanism(s) remain poorly understood and the dissolution kinetics can depend on a large number of intrinsic and extrinsic factors. Here, we assess the potential of data-driven models based on machine learning to predict the dissolution rates of various aluminosilicate glasses exposed to a wide range of solution pH values, from acidic to caustic conditions. Four classes of machine learning methods are investigated, namely, linear regression, support vector machine regression, random forest, and artificial neural network. We observe that, although linear methods all fail to describe the dissolution kinetics, the artificial neural network approach offers excellent predictions, thanks to its inherent ability to handle non-linear data. Overall, we suggest that a more extensive use of machine learning approaches could significantly accelerate the design of novel glasses with tailored properties.

Dissolution of quartz in aqueous basic solution, 106-236 C - Surface kinetics of 'perfect' crystallographic faces

NASA Technical Reports Server (NTRS)

Gratz, Andrew J.; Bird, Peter; Quiro, Glenn B.

1990-01-01

A highly accurate method, called the negative crystal method, for determining the rate of dissolution on specific crystallographic faces of crystals was developed, in which the dissolution rates of nominally perfect crystal faces are obtained by measuring the size of individual negative crystals during a sequence of dissolution steps. The method was applied to determine the apparent activation energy and rate constants for the dissolution of quartz in 0.01 M KOH solutions at temperatures from 106 to 236 C. Also investigated were the effects of hydroxyl activity and ionic strength. The apparent activation energies for the dissolution of the prism and of the rhomb were determined.

Dissolution patterns of biocompatible glasses in 2-amino-2-hydroxymethyl-propane-1,3-diol (Tris) buffer.

PubMed

Fagerlund, S; Hupa, L; Hupa, M

2013-02-01

A continuous flow measurement system with sensitive on-line ion analysis has been applied to study the initial dissolution behaviour of biocompatible glasses in Tris. Altogether 16 glasses with widely varying compositions were studied. The measurement system allowed for quantitative determination of the time-dependent rates of dissolution of sodium, potassium, calcium, magnesium, silicon and phosphorus during the first 10-15 min in contact with Tris solution. The dissolution rates of the different ions showed significant glass to glass variations, but all glasses studied showed one of four distinct dissolution patterns. The ion dissolution rates after an exposure of 1000 s, expressed as the normalized surface-specific mass loss rates, were compared with the in vitro and in vivo reactivity of the glasses as predicted by models in the literature. The results showed a clear correlation between the dissolution rates of the glasses in Tris and their reactivity as measured by other different methods. Consequently, the measured short-term dissolution patterns could be used to determine which glasses are suitable as bioactive, biodegradable, or inert biomaterials for medical devices. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Correlation of dissolution and disintegration results for an immediate-release tablet.

PubMed

Nickerson, Beverly; Kong, Angela; Gerst, Paul; Kao, Shangming

2018-02-20

The drug release rate of a rapidly dissolving immediate-release tablet formulation with a highly soluble drug is proposed to be controlled by the disintegration rate of the tablet. Disintegration and dissolution test methods used to evaluate the tablets were shown to discriminate manufacturing process differences and compositionally variant tablets. In addition, a correlation was established between disintegration and dissolution. In accordance with ICH Q6A, this work demonstrates that disintegration in lieu of dissolution is suitable as the drug product quality control method for evaluating this drug product. Copyright © 2017 Elsevier B.V. All rights reserved.

Dissolution and Separation of Aluminum and Aluminosilicates

DOE PAGES

McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; ...

2015-12-19

The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as amore » function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

Controlled evaluation of silver nanoparticle dissolution using atomic force microscopy.

PubMed

Kent, Ronald D; Vikesland, Peter J

2012-07-03

Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7.0, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, the in-plane radius decreased by 5-11 nm, and the height increased by 6-12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10-550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of unaggregated AgNP dissolution.

Surface properties, solubility and dissolution kinetics of bamboo phytoliths

NASA Astrophysics Data System (ADS)

Fraysse, Fabrice; Pokrovsky, Oleg S.; Schott, Jacques; Meunier, Jean-Dominique

2006-04-01

Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of "soil" phytoliths ( pKsp0=2.74 at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction (ΔHr25-80°C=10.85kJ/mol) is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for "soil" (native) and "heated" (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-p K surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ⩽ pH ⩽ 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation: R=k1·{>SiOH2+}n+k2·{>SiOH0}+k3·{>SiO-}m, where {> i} stands for the concentration of the surface species present at the SiO 2-H 2O interface, ki are the rate constants of the three parallel reactions and n and m represent the order of the proton- and hydroxy-promoted reactions, respectively. It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ˜ 3. This can explain their good preservation in the acidic soil horizons of Réunion Island. In terms of silicon biogeochemical cycle, phytoliths represent a large buffering reservoir

The differences between the branded and generic medicines using solid dosage forms: In-vitro dissolution testing

PubMed Central

Al Ameri, Mubarak Nasser; Nayuni, Nanda; Anil Kumar, K.G.; Perrett, David; Tucker, Arthur; Johnston, Atholl

2011-01-01

Introduction Dissolution is the amount of substance that goes into solution per unit time under standardised conditions of liquid/solid interface, solvent composition and temperature. Dissolution is one of the most important tools to predict the in-vivo bioavailability and in some cases to determine bioequivalence and assure interchangeability. Aim To compare the differences in dissolution behaviour of solid dosage forms between innovators (reference products) and their generic counterparts (tested products). Methods Four replicates for each batch of 37 tested medicines was carried out using A PT-DT70 dissolution tester from Pharma Test. A total of 13 branded medicines and 24 generic counterparts were obtained locally and internationally to detect any differences in their dissolution behaviour. They were tested according to the British Pharmacopeia, European Pharmacopeia and the US Pharmacopeia with the rate of dissolution determined by ultra-violet Spectrophotometery. Results Most tested medicines complied with the pharmacopoeial specifications and achieved 85% dissolution in 60 min. However, some generic medicines showed significant differences in dissolution rate at 60 and 120 min. Many generic medicines showed a slower dissolution rate than their branded counterparts such as the generic forms of omeprazole 20 mg. Some showed an incomplete dissolution such as the generic form of nifedipine 10 mg. Other generics showed faster dissolution rate than their branded counterpart such as the generic forms of meloxicam 15 mg. Moreover, some generics from different batches of the same manufacturer showed significant differences in their dissolution rate such as the generic forms of meloxicam 7.5 mg. Nevertheless, some generic medicines violated the EMA and the FDA guidelines for industry when they failed to achieve 85% dissolution at 60 min, such as the generic form of diclofenac sodium 50 mg. Conclusion Most medicines in this study complied with the pharmacopeial

Miniaturized INtrinsic DISsolution Screening (MINDISS) assay for preformulation.

PubMed

Alsenz, Jochem; Haenel, Elisabeth; Anedda, Aline; Du Castel, Pauline; Cirelli, Giorgio

2016-05-25

This study describes a novel Miniaturized INtrinsic DISsolution Screening (MINDISS) assay for measuring disk intrinsic dissolution rates (DIDR). In MINDISS, compacted mini disks of drugs (2-5mg/disk) are prepared in custom made holders with a surface area of 3mm(2). Disks are immersed, pellet side down, into 0.35ml of appropriate dissolution media per well in 96-well microtiter plates, media are stirred and disk-holders are transferred to new wells after defined periods of time. After filtration, drug concentration in dissolution media is quantified by Ultra Performance Liquid Chromatography (UPLC) and solid state property of the disk is characterized by Raman spectroscopy. MINDISS was identified as an easy-to-use tool for rapid, parallel determination of DIDR of compounds that requires only small amounts of compound and of dissolution medium. Results obtained with marketed drugs in MINDISS correlate well with large scale DIDR methods and indicate that MINDISS can be used for (1) rank-ordering of compounds by intrinsic dissolution in late phase discovery and early development, (2) comparison of polymorphic forms and salts, (3) screening and selection of appropriate dissolution media, and (4) characterization of the intestinal release behavior of compounds along the gastro intestinal tract by changing biorelevant media during experiments. Copyright © 2015 Elsevier B.V. All rights reserved.

Spatial zonation limits magnesite dissolution in porous media

NASA Astrophysics Data System (ADS)

Li, Li; Salehikhoo, Fatemeh; Brantley, Susan L.; Heidari, Peyman

2014-02-01

We investigate how mineral spatial distribution in porous media affects their dissolution rates. Specifically, we measure the dissolution rate of magnesite interspersed in different patterns in packed columns of quartz sand where the magnesite concentration (v/v) was held constant. The largest difference was observed between a “Mixed column” containing uniformly distributed magnesite and a “One-zone column” containing magnesite packed into one cylindrical center zone aligned parallel to the main flow of acidic inlet fluid (flow-parallel One-zone column). The columns were flushed with acid water at a pH of 4.0 at flow velocities of 3.6 or 0.36 m/d. Breakthrough data show that the rate of magnesite dissolution is 1.6-2 times slower in the One-zone column compared to the Mixed column. This extent of rate limitation is much larger than what was observed in our previous work (14%) for a similar One-zone column where the magnesite was packed in a layer aligned perpendicular to flow (flow-transverse One-zone column). Two-dimensional reactive transport modeling with CrunchFlow revealed that ion activity product (IAP) and local dissolution rates at the grid block scale (0.1 cm) vary by orders of magnitude. Much of the central magnesite zone in the One-zone flow-parallel column is characterized by close or equal to equilibrium conditions with IAP/Keq > 0.1. Two important surface areas are defined to understand the observed rates: the effective surface area (Ae) reflects the magnesite that effectively dissolves under far from equilibrium conditions (IAP/Keq < 0.1), while the interface surface area (AI) reflects the effective magnesite surface that lies along the quartz-magnesite interface. Modeling results reveal that the transverse dispersivity at the interface of the quartz and magnesite zones controls mass transport and therefore the values of Ae and AI. Under the conditions examined in this work, the value of Ae varies from 2% to 67% of the total magnesite BET

Dissolution process analysis using model-free Noyes-Whitney integral equation.

PubMed

Hattori, Yusuke; Haruna, Yoshimasa; Otsuka, Makoto

2013-02-01

Drug dissolution process of solid dosages is theoretically described by Noyes-Whitney-Nernst equation. However, the analysis of the process is demonstrated assuming some models. Normally, the model-dependent methods are idealized and require some limitations. In this study, Noyes-Whitney integral equation was proposed and applied to represent the drug dissolution profiles of a solid formulation via the non-linear least squares (NLLS) method. The integral equation is a model-free formula involving the dissolution rate constant as a parameter. In the present study, several solid formulations were prepared via changing the blending time of magnesium stearate (MgSt) with theophylline monohydrate, α-lactose monohydrate, and crystalline cellulose. The formula could excellently represent the dissolution profile, and thereby the rate constant and specific surface area could be obtained by NLLS method. Since the long time blending coated the particle surface with MgSt, it was found that the water permeation was disturbed by its layer dissociating into disintegrant particles. In the end, the solid formulations were not disintegrated; however, the specific surface area gradually increased during the process of dissolution. The X-ray CT observation supported this result and demonstrated that the rough surface was dominant as compared to dissolution, and thus, specific surface area of the solid formulation gradually increased. Copyright © 2012 Elsevier B.V. All rights reserved.

Dissolution behavior of MgO based inert matrix fuel for the transmutation of minor actinides

NASA Astrophysics Data System (ADS)

Mühr-Ebert, E. L.; Lichte, E.; Bukaemskiy, A.; Finkeldei, S.; Klinkenberg, M.; Brandt, F.; Bosbach, D.; Modolo, G.

2018-07-01

This study explores the dissolution properties of magnesia-based inert matrix nuclear fuel (IMF) containing transuranium elements (TRU). Pure MgO pellets as well as MgO pellets containing CeO2, as surrogate for TRU oxides, and are considered as model systems for genuine magnesia based inert matrix fuel were fabricated. The aim of this study is to identify conditions at which the matrix material can be selectively dissolved during the head-end reprocessing step, allowing a separation of MgO from the actinides, whereas the actinides remain undissolved. The dissolution behavior was studied in macroscopic batch experiments as a function of nitric acid concentration, dissolution medium volume, temperature, stirring velocity, and pellet density (85, 90, 96, and 99%TD). To mimic pellets with various burn-ups the density of the here fabricated pellets was varied. MgO is soluble even under mild conditions (RT, 2.5 mol/L HNO3). The dissolution rates of MgO at different acid concentrations are rather similar, whereas the dissolution rate is strongly dependent on the temperature. Via a microscopic approach, a model was developed to describe the evolution of the pellet surface area during dissolution and determine a surface normalized dissolution rate. Moreover, dissolution rates of the inert matrix fuel containing CeO2 were determined as a function of the acid concentration and temperature. During the dissolution of MgO/CeO2 pellets the MgO dissolves completely, while CeO2 (>99%) remains undissolved. This study intends to provide a profound understanding of the chemical performance of magnesia based IMF containing fissile material. The feasibility of the dissolution of magnesia based IMF with nitric acid is discussed.

Microscopic modeling of confined crystal growth and dissolution.

PubMed

Høgberget, Jørgen; Røyne, Anja; Dysthe, Dag K; Jettestuen, Espen

2016-08-01

We extend the (1+1)-dimensional fluid solid-on-solid (SOS) model to include a confining flat surface opposite to the SOS surface subject to a constant load. This load is balanced by a repulsive surface-surface interaction given by an ansatz which agrees with known analytical solutions in the limit of two separated flat surfaces. Mechanical equilibrium is imposed at all times by repositioning the confining surface. By the use of kinetic Monte Carlo (KMC) we calculate how the equilibrium concentration (deposition rate) depends on the applied load, and find it to reproduce analytical thermodynamics independent of the parameters of the interaction ansatz. We also study the dependency between the surface roughness and the saturation level as we vary the surface tension, and expand on previous analyses of the asymmetry between growth and dissolution by parametrizing the linear growth rate constant for growth and dissolution separately. We find the presence of a confining surface to affect the speed of growth and dissolution equally.

Microscopic modeling of confined crystal growth and dissolution

NASA Astrophysics Data System (ADS)

Høgberget, Jørgen; Røyne, Anja; Dysthe, Dag K.; Jettestuen, Espen

2016-08-01

We extend the (1+1)-dimensional fluid solid-on-solid (SOS) model to include a confining flat surface opposite to the SOS surface subject to a constant load. This load is balanced by a repulsive surface-surface interaction given by an ansatz which agrees with known analytical solutions in the limit of two separated flat surfaces. Mechanical equilibrium is imposed at all times by repositioning the confining surface. By the use of kinetic Monte Carlo (KMC) we calculate how the equilibrium concentration (deposition rate) depends on the applied load, and find it to reproduce analytical thermodynamics independent of the parameters of the interaction ansatz. We also study the dependency between the surface roughness and the saturation level as we vary the surface tension, and expand on previous analyses of the asymmetry between growth and dissolution by parametrizing the linear growth rate constant for growth and dissolution separately. We find the presence of a confining surface to affect the speed of growth and dissolution equally.

Improved Dissolution and Oral Bioavailability of Celecoxib by a Dry Elixir System.

PubMed

Cho, Kwan Hyung; Jee, Jun-Pil; Yang, Da A; Kim, Sung Tae; Kang, Dongjin; Kim, Dae-Young; Sim, Taeyong; Park, Sang Yeob; Kim, Kyeongsoon; Jang, Dong-Jin

2018-02-01

The purpose of this study was to develop and evaluate a dry elixir (DE) system for enhancing the dissolution rate and oral bioavailability of celecoxib. DE system has been used for improving solubility, oral bioavailability of poorly water-soluble drugs. The encapsulated drugs or solubilized drugs in the matrix are rapidly dissolved due to the co-solvent effect, resting in both an enhanced dissolution and bioavailability. DEs containing celecoxib were prepared by spray-drying method and characterized by morphology, drug/ethanol content, drug crystallinity, dissolution rate and oral bioavailability. The ethanol content and drug content in DE system could be easily altered by controlling the spraydrying conditions. The dissolution profile of celecoxib from DE proved to be much higher than that of celecoxib powder due to the nano-structured matrix, amorphous state and encapsulated ethanol. The bioavailability of celecoxib from DEs was compared with celecoxib powder alone and commercial product (Celebrex®) in rats. In particular, blood concentrations of celecoxib form DE formulation were much greater than those of native celecoxib and market product. The data demonstrate that the DE system could provide an useful solid dosage form to enhance the solubility, dissolution rate and oral bioavailability of celecoxib.

Nonaqueous Phase Liquid Dissolution in Porous Media: Multi-Scale Effects of Multi-Component Dissolution Kinetics on Cleanup Time

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

McNab, W; Ezzedine, S; Detwiler, R

2007-02-26

Industrial organic solvents such as trichloroethylene (TCE) and tetrachloroethylene (PCE) constitute a principal class of groundwater contaminants. Cleanup of groundwater plume source areas associated with these compounds is problematic, in part, because the compounds often exist in the subsurface as dense nonaqueous phase liquids (DNAPLs). Ganglia (or 'blobs') of DNAPL serve as persistent sources of contaminants that are difficult to locate and remediate (e.g. Fenwick and Blunt, 1998). Current understanding of the physical and chemical processes associated with dissolution of DNAPLs in the subsurface is incomplete and yet is critical for evaluating long-term behavior of contaminant migration, groundwater cleanup, andmore » the efficacy of source area cleanup technologies. As such, a goal of this project has been to contribute to this critical understanding by investigating the multi-phase, multi-component physics of DNAPL dissolution using state-of-the-art experimental and computational techniques. Through this research, we have explored efficient and accurate conceptual and numerical models for source area contaminant transport that can be used to better inform the modeling of source area contaminants, including those at the LLNL Superfund sites, to re-evaluate existing remediation technologies, and to inspire or develop new remediation strategies. The problem of DNAPL dissolution in natural porous media must be viewed in the context of several scales (Khachikian and Harmon, 2000), including the microscopic level at which capillary forces, viscous forces, and gravity/buoyancy forces are manifested at the scale of individual pores (Wilson and Conrad, 1984; Chatzis et al., 1988), the mesoscale where dissolution rates are strongly influenced by the local hydrodynamics, and the field-scale. Historically, the physico-chemical processes associated with DNAPL dissolution have been addressed through the use of lumped mass transfer coefficients which attempt to quantify

Dissolution Dominating Calcification Process in Polar Pteropods Close to the Point of Aragonite Undersaturation

PubMed Central

Bednaršek, Nina; Tarling, Geraint A.; Bakker, Dorothee C. E.; Fielding, Sophie; Feely, Richard A.

2014-01-01

Thecosome pteropods are abundant upper-ocean zooplankton that build aragonite shells. Ocean acidification results in the lowering of aragonite saturation levels in the surface layers, and several incubation studies have shown that rates of calcification in these organisms decrease as a result. This study provides a weight-specific net calcification rate function for thecosome pteropods that includes both rates of dissolution and calcification over a range of plausible future aragonite saturation states (Ωar). We measured gross dissolution in the pteropod Limacina helicina antarctica in the Scotia Sea (Southern Ocean) by incubating living specimens across a range of aragonite saturation states for a maximum of 14 days. Specimens started dissolving almost immediately upon exposure to undersaturated conditions (Ωar∼0.8), losing 1.4% of shell mass per day. The observed rate of gross dissolution was different from that predicted by rate law kinetics of aragonite dissolution, in being higher at Ωar levels slightly above 1 and lower at Ωar levels of between 1 and 0.8. This indicates that shell mass is affected by even transitional levels of saturation, but there is, nevertheless, some partial means of protection for shells when in undersaturated conditions. A function for gross dissolution against Ωar derived from the present observations was compared to a function for gross calcification derived by a different study, and showed that dissolution became the dominating process even at Ωar levels close to 1, with net shell growth ceasing at an Ωar of 1.03. Gross dissolution increasingly dominated net change in shell mass as saturation levels decreased below 1. As well as influencing their viability, such dissolution of pteropod shells in the surface layers will result in slower sinking velocities and decreased carbon and carbonate fluxes to the deep ocean. PMID:25285916

Dissolution dominating calcification process in polar pteropods close to the point of aragonite undersaturation.

PubMed

Bednaršek, Nina; Tarling, Geraint A; Bakker, Dorothee C E; Fielding, Sophie; Feely, Richard A

2014-01-01

Thecosome pteropods are abundant upper-ocean zooplankton that build aragonite shells. Ocean acidification results in the lowering of aragonite saturation levels in the surface layers, and several incubation studies have shown that rates of calcification in these organisms decrease as a result. This study provides a weight-specific net calcification rate function for thecosome pteropods that includes both rates of dissolution and calcification over a range of plausible future aragonite saturation states (Ω(ar)). We measured gross dissolution in the pteropod Limacina helicina antarctica in the Scotia Sea (Southern Ocean) by incubating living specimens across a range of aragonite saturation states for a maximum of 14 days. Specimens started dissolving almost immediately upon exposure to undersaturated conditions (Ω(ar) ∼ 0.8), losing 1.4% of shell mass per day. The observed rate of gross dissolution was different from that predicted by rate law kinetics of aragonite dissolution, in being higher at Ω(ar) levels slightly above 1 and lower at Ω(ar) levels of between 1 and 0.8. This indicates that shell mass is affected by even transitional levels of saturation, but there is, nevertheless, some partial means of protection for shells when in undersaturated conditions. A function for gross dissolution against Ω(ar) derived from the present observations was compared to a function for gross calcification derived by a different study, and showed that dissolution became the dominating process even at Ω(ar) levels close to 1, with net shell growth ceasing at an Ω(ar) of 1.03. Gross dissolution increasingly dominated net change in shell mass as saturation levels decreased below 1. As well as influencing their viability, such dissolution of pteropod shells in the surface layers will result in slower sinking velocities and decreased carbon and carbonate fluxes to the deep ocean.

Role of fiber dissolution in biological activity in rats.

PubMed

Eastes, W; Hadley, J G

1994-12-01

This report deals with the role of dissolution in removing long fibers from the lung and with a mathematical model that predicts chronic effects in rats following inhalation or intraperitoneal (i.p.) injection of fibers. Results of intratracheal instillation studies and inhalation studies in rats demonstrate clearly that long vitreous fibers dissolve in vivo at about the same rate measured in vitro in fluid designed to stimulate the extracellular lung fluid. For the glass, rock, and slag wool fibers tested, dissolution removed most of the fibers longer than 20 microns inhaled into the rats' lungs within 6 months after both short-term (5 days) and long-term (1 to 2 years) exposures. A mathematical model was developed that is based on fiber dissolution and allows one to predict the development of chronic lung diseases in rats. The model predicted the incidence of fibrosis and lung tumors in a series of recent inhalation studies and tumors following ip injection to within about the error of the experiments. The model suggests that all fibers, regardless of their dissolution rate in lung fluid, can produce tumors after ip injection because the dose can be unlimited by this route. After inhalation, in contrast, dissolution of many types of long vitreous fibers occurs rapidly, and disease does not ensue for these fibers.

Haste Makes Waste: The Interplay Between Dissolution and Precipitation of Supersaturating Formulations.

PubMed

Sun, Dajun D; Lee, Ping I

2015-11-01

Contrary to the early philosophy of supersaturating formulation design for oral solid dosage forms, current evidence shows that an exceedingly high rate of supersaturation generation could result in a suboptimal in vitro dissolution profile and subsequently could reduce the in vivo oral bioavailability of amorphous solid dispersions. In this commentary, we outline recent research efforts on the specific effects of the rate and extent of supersaturation generation on the overall kinetic solubility profiles of supersaturating formulations. Additional insights into an appropriate definition of sink versus nonsink dissolution conditions and the solubility advantage of amorphous pharmaceuticals are also highlighted. The interplay between dissolution and precipitation kinetics should be carefully considered in designing a suitable supersaturating formulation to best improve the dissolution behavior and oral bioavailability of poorly water-soluble drugs.

Calorimetric Studies of Precipitation and Dissolution Kinetics in Aluminum Alloys 2219 and 7075

NASA Astrophysics Data System (ADS)

Papazian, John M.

1982-05-01

Differential scanning calorimetry (DSC) was used to study the kinetics of precipitation and dissolution of metastable and stable phases in aluminum alloys 2219 and 7075. A comparison of DSC scans obtained at heating rates of 1, 5, 10, and 20 K per minute showed that, during a DSC scan, the rates of precipitation of θ' and θ in 2219 and η' and η in 7075 were limited by their reaction kinetics. Likewise, the rates of dissolution of GP zones, θ' and η', were found to be dominated by kinetics. In contrast, the dissolution of θ and η was dominated by the thermodynamic equilibrium between these phases and the matrix. Analysis of the kinetically dominated reaction peaks and their dependence on heating rate and particle size showed that the GP zone dissolution reaction could best be described by a three-dimensional volume diffusion limited rate expression with an activation energy equal to that for diffusion. The rate of formation of θ' was best described by an Avrami expression with n = 1.1, indicating that nucleation was not the rate controlling step. A pronounced dependence of the θ' formation rate on prior plastic deformation was observed and ascribed to the influence of the matrix dislocation density on diffusivity.

Synergistic bioleaching of chalcopyrite and bornite in the presence of Acidithiobacillus ferrooxidans.

PubMed

Zhao, Hongbo; Wang, Jun; Hu, Minghao; Qin, Wenqing; Zhang, Yansheng; Qiu, Guanzhou

2013-12-01

Bioleaching of chalcopyrite and bornite in the presence of Acidithiobacillus ferrooxidans was carried out to investigate the influences between each other during bioleaching. Bioleaching results indicated that bornite accelerated the dissolution of chalcopyrite, and chalcopyrite also accelerated the dissolution of bornite, it could be described as a synergistic effect during bioleaching, this synergistic effect might be attributed to the galvanic effect between chalcopyrite and bornite, and to the relatively low solution potential as the addition of bornite. Significantly amount of elemental sulfur and jarosite formed on the minerals surface might be the main passivation film inhibiting the further dissolution, and the amount of elemental sulfur significantly increased with the addition of bornite. Results of electrochemical measurements indicated that the oxidation and reduction mechanisms of chalcopyrite and bornite were similar, the addition of bornite or chalcopyrite did not change the oxidative and reductive mechanisms, but increased the oxidation rate. Copyright © 2013 Elsevier Ltd. All rights reserved.

Piroxicam cocrystals with phenolic coformers: preparation, characterization, and dissolution properties.

PubMed

Emami, Shahram; Adibkia, Khosro; Barzegar-Jalali, Mohammad; Siahi-Shadbad, Mohammadreza

2018-04-04

This study explores the preparation and investigation of dissolution properties of piroxicam cocrystals. Differential scanning calorimetry (DSC) was used to determine the capability of resorcinol (RES), methylparaben (MPB), and vanillin (VAN) to form cocrystals with piroxicam (PRX). Generation of cocrystals was attempted by liquid assisted grinding and slurry methods. Cocrystals were characterized by thermal methods, powder X-ray diffraction, and Fourier-transform infrared spectroscopy. Apparent solubility, intrinsic dissolution rate (IDR), and powder dissolution profile of cocrystals were compared with anhydrous piroxicam, piroxicam monohydrate (PRXMH), and previously reported piroxicam-succinic acid cocrystal. Contact angles and particle sizes of the studied solids were also measured. Based on the DSC screening results, we prepared and characterized PRX-RES and PRX-MPB cocrystals. Interestingly, the cocrystals not only failed to improve apparent solubility and IDR of PRX but also showed lower values than PRX that were attributed to induction of phase transformation of PRX to PRXMH. In contrary, cocrystals performed better than PRX in powder dissolution studies. The higher dissolution rates of cocrystals were explained by improved wettability and reduced sizes. This study has highlighted the complexity of solid state properties of cocrystals and has provided new evidence for the in-solution stability issues of cocrystals.

Phase Behavior of Ritonavir Amorphous Solid Dispersions during Hydration and Dissolution.

PubMed

Purohit, Hitesh S; Taylor, Lynne S

2017-12-01

The aim of this research was to study the interplay of solid and solution state phase transformations during the dissolution of ritonavir (RTV) amorphous solid dispersions (ASDs). RTV ASDs with polyvinylpyrrolidone (PVP), polyvinylpyrrolidone vinyl acetate (PVPVA) and hydroxypropyl methylcellulose acetate succinate (HPMCAS) were prepared at 10-50% drug loading by solvent evaporation. The miscibility of RTV ASDs was studied before and after exposure to 97% relative humidity (RH). Non-sink dissolution studies were performed on fresh and moisture-exposed ASDs. RTV and polymer release were monitored using ultraviolet-visible spectroscopy. Techniques including fluorescence spectroscopy, confocal imaging, scanning electron microscopy (SEM), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and nanoparticle tracking analysis (NTA) were utilized to monitor solid and the solution state phase transformations. All RTV-PVP and RTV-PVPVA ASDs underwent moisture-induced amorphous-amorphous phase separation (AAPS) on high RH storage whereas RTV-HPMCAS ASDs remained miscible. Non-sink dissolution of PVP- and PVPVA-based ASDs at low drug loadings led to rapid RTV and polymer release resulting in concentrations in excess of amorphous solubility, liquid-liquid phase separation (LLPS) and amorphous nanodroplet formation. High drug loading PVP- and PVPVA-based ASDs did not exhibit LLPS upon dissolution as a consequence of extensive AAPS in the hydrated ASD matrix. All RTV-HPMCAS ASDs led to LLPS upon dissolution. RTV ASD dissolution is governed by a competition between the dissolution rate and the rate of phase separation in the hydrated ASD matrix. LLPS was observed for ASDs where the drug release was polymer controlled and only ASDs that remained miscible during the initial phase of dissolution led to LLPS. Techniques such as fluorescence spectroscopy, confocal imaging and SEM were useful in understanding the phase behavior of ASDs upon hydration and dissolution

Phosphorous availability influences the dissolution of apatite by soil fungi

NASA Astrophysics Data System (ADS)

Rosling, A.; Suttle, K. B.; Johansson, E.; van Hees, P. W.; Banfield, J. F.

2007-12-01

We conducted mineral dissolution experiments using fungi isolated from a grassland soil in northern California to determine the response of fungi to different levels of phosphorus availability and to identify pathways of apatite dissolution by fungal exudates. Fluorapatite dissolution experiments were performed either with fungi present or under abiotic conditions using cell-free liquid media conditioned by fungal growth at different phosphorus and calcium availabilities. Among biogeochemically active soil fungal isolates apatite dissolution was either active in response to phosphorus limiting growth conditions or passive as a result of mycelial growth. Zygomycete isolates in the order of Mucorales acidify their growth media substrate in the presence of phosphorus, mainly through production of oxalic acid. Cell-free exudates induced fluorapatite dissolution at a rate of 10 -0.9 ± 0.14 and 10 -1.2 ± 0.22 mmol P/m2/s. The Ascomycete isolate, in the family Trichocomaceae, induced fluorapatite dissolution at a rate of 10 - 1.1 ± 0.05 mmol P/m2/s by lowering the pH of the media under phosphorus-limited conditions, without producing significant amounts of low molecular weight organic acids (LMWOAs). Oxalate strongly etches fluorapatite along channels parallel to [001], forming needle like features, while exudates from Trichocomaceae induced surface rounding. We conclude that while LMWOAs are well-studied weathering agents these does not appear to be produced by fungi in response to phosphorus limiting growth conditions.

Evaluation and selection of bio-relevant dissolution media for a poorly water-soluble new chemical entity.

PubMed

Tang, L; Khan, S U; Muhammad, N A

2001-11-01

The purpose of this work is to develop a bio-relevant dissolution method for formulation screening in order to select an enhanced bioavailable formulation for a poorly water-soluble drug. The methods used included a modified rotating disk apparatus for measuring intrinsic dissolution rate of the new chemical entity (NCE) and the USP dissolution method II for evaluating dissolution profiles of the drug in three different dosage forms. The in vitro dissolution results were compared with the in vivo bioavailability for selecting a bio-relevant medium. The results showed that the solubility of the NCE was proportional to the concentration of sodium lauryl sulfate (SLS) in the media. The apparent intrinsic dissolution rate of the NCE was linear to the rotational speed of the disk, which indicated that the dissolution of the drug is a diffusion-controlled mechanism. The apparent intrinsic dissolution rate was also linear to the surfactant concentration in the media, which was interpreted using the Noyes and Whitney Empirical Theory. Three formulations were studied in three different SLS media using the bulk drug as a reference. The dissolution results were compared with the corresponding bioavailability results in dogs. In the 1% SLS--sink conditions--the drug release from all the formulations was complete and the dissolution results were discriminative for the difference in particle size of the drug in the formulations. However, the data showed poor IVIV correlation. In the 0.5% SLS medium--non-sink conditions--the dissolution results showed the same rank order among the tested formulations as the bioavailability. The best IVIV correlation was obtained from the dissolution in 0.25% SLS medium, an over-saturated condition. The conclusions are: a surfactant medium increases the apparent intrinsic dissolution rate of the NCE linearly due to an increase in solubility. A low concentration of surfactant in the medium (0.25%) is more bio-relevant than higher concentrations of

Attenuation of Glass Dissolution in the Presence of Natural Additives

NASA Technical Reports Server (NTRS)

Sang, Jing C.; Barkatt, Aaron; OKeefe, John A.

1993-01-01

The study described here explored the dissolution kinetics of glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase. The results demonstrated the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. The study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses as well as to better understanding of the environmental degradation of natural and ancient glasses.

An empirical model for dissolution profile and its application to floating dosage forms.

PubMed

Weiss, Michael; Kriangkrai, Worawut; Sungthongjeen, Srisagul

2014-06-02

A sum of two inverse Gaussian functions is proposed as a highly flexible empirical model for fitting of in vitro dissolution profiles. The model was applied to quantitatively describe theophylline release from effervescent multi-layer coated floating tablets containing different amounts of the anti-tacking agents talc or glyceryl monostearate. Model parameters were estimated by nonlinear regression (mixed-effects modeling). The estimated parameters were used to determine the mean dissolution time, as well as to reconstruct the time course of release rate for each formulation, whereby the fractional release rate can serve as a diagnostic tool for classification of dissolution processes. The approach allows quantification of dissolution behavior and could provide additional insights into the underlying processes. Copyright © 2014 Elsevier B.V. All rights reserved.

Computational hydrodynamic comparison of a mini vessel and a USP 2 dissolution testing system to predict the dynamic operating conditions for similarity of dissolution performance.

PubMed

Wang, Bing; Bredael, Gerard; Armenante, Piero M

2018-03-25

The hydrodynamic characteristics of a mini vessel and a USP 2 dissolution testing system were obtained and compared to predict the tablet-liquid mass transfer coefficient from velocity distributions near the tablet and establish the dynamic operating conditions under which dissolution in mini vessels could be conducted to generate concentration profiles similar to those in the USP 2. Velocity profiles were obtained experimentally using Particle Image Velocimetry (PIV). Computational Fluid Dynamics (CFD) was used to predict the velocity distribution and strain rate around a model tablet. A CFD-based mass transfer model was also developed. When plotted against strain rate, the predicted tablet-liquid mass transfer coefficient was found to be independent of the system where it was obtained, implying that a tablet would dissolve at the same rate in both systems provided that the concentration gradient between the tablet surface and the bulk is the same, the tablet surface area per unit liquid volume is identical, and the two systems are operated at the appropriate agitation speeds specified in this work. The results of this work will help dissolution scientists operate mini vessels so as to predict the dissolution profiles in the USP 2, especially during the early stages of drug development. Copyright © 2018 Elsevier B.V. All rights reserved.

Carboxylate-containing chelating agent interactions with amorphous chromium hydroxide: Adsorption and dissolution

NASA Astrophysics Data System (ADS)

Carbonaro, Richard F.; Gray, Benjamin N.; Whitehead, Charles F.; Stone, Alan T.

2008-07-01

Anthropogenic chelating agents and biological chelating agents produced by indigenous organisms may dissolve Cr III (hydr)oxides in soils and sediments. The resulting dissolved Cr III-chelating agent complexes are more readily transported through porous media, thereby spreading contamination. With this work, we examine chelating agent-assisted dissolution of amorphous chromium hydroxide (ACH) by the (amino)carboxylate chelating agents iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), tricarballylic acid (TCA), citric acid (CIT), ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediaminetetraacetic acid (CDTA), and trimethylenediaminetetraacetic acid (TMDTA). The extent of chelating agent adsorption onto ACH increased quickly over the first few hours, and then increased more gradually until a constant extent was attained. The extent of chelating agent adsorption versus pH followed "ligand-like" behavior. All chelating agents with the exception of TCA and IDA effectively dissolved significant amounts of ACH within 10 days from pH 4.0 to 9.4. IDA dissolved ACH below pH 6.5 and above pH 7.5. Rates of ACH dissolution normalized to the extent of chelating agent adsorption were pH dependent. IDA, NTA, CIT, and CDTA exhibited an increase in normalized dissolution rate with decreasing pH. EDTA and TMDTA exhibited a maximum in normalized dissolution rate near pH 8.5. Use of acetic acid as a pH buffer in experiments decreased the extent of chelating agent adsorption for IDA, NTA, and CIT but increased normalized rates of chelating agent-assisted dissolution for all chelating agents except EDTA. The results from this study provide the necessary information to calculate the extents and time scales of ACH dissolution in the presence of (amino)carboxylate chelating agents.

In Situ Observation of Calcium Aluminate Inclusions Dissolution into Steelmaking Slag

NASA Astrophysics Data System (ADS)

Miao, Keyan; Haas, Alyssa; Sharma, Mukesh; Mu, Wangzhong; Dogan, Neslihan

2018-06-01

The dissolution rate of calcium aluminate inclusions in CaO-SiO2-Al2O3 slags has been studied using confocal scanning laser microscopy (CSLM) at elevated temperatures: 1773 K, 1823 K, and 1873 K (1500 °C, 1550 °C, and 1600 °C). The inclusion particles used in this experimental work were produced in our laboratory and their production technique is explained in detail. Even though the particles had irregular shapes, there was no rotation observed. Further, the total dissolution time decreased with increasing temperature and decreasing SiO2 content in the slag. The rate limiting steps are discussed in terms of shrinking core models and diffusion into a stagnant fluid model. It is shown that the rate limiting step for dissolution is mass transfer in the slag at 1823 K and 1873 K (1550 °C and 1600 °C). Further investigations are required to determine the dissolution mechanism at 1773 K (1500 °C). The calculated diffusion coefficients were inversely proportional to the slag viscosity and the obtained values for the systems studied ranged between 5.64 × 10-12 and 5.8 × 10-10 m2/s.

Mineralogy maketh mountains: Granitic landscapes shaped by dissolution

NASA Astrophysics Data System (ADS)

Eggleton, Richard A.

2017-05-01

In tectonically quiet regions, the shape of the landscape is controlled by the erosion resistance of the rocks. Erosion largely depends on the release of particles from the weathering rock, which in turn requires a degree of dissolution of the more soluble grains. The rate of dissolution of the common rock forming minerals allows the construction of a numerical Rock Weatherability Scale (RWS) based on the rock's modal mineralogical analysis. Applied regionally to three granitic landscape regions of the Bega Valley of southern New South Wales, the Tate Batholith and Featherbed Volcanics of north Queensland, and granitoids in the Beaufort region of Victoria, the mean elevation of the larger plutons in each region correlates highly (r = 0.83-0.93) with their RWS. Variation in composition within a pluton also shows there is a clear connection between changes in RWS and relief within the pluton. From these results it is apparent that the landscape of such granitic terrains is determined very largely by mineral dissolution rates, with plagioclase composition and content being a major factor.

Effect of particle size on solubility, dissolution rate, and oral bioavailability: evaluation using coenzyme Q10 as naked nanocrystals

PubMed Central

Sun, Jiao; Wang, Fan; Sui, Yue; She, Zhennan; Zhai, Wenjun; Wang, Chunling; Deng, Yihui

2012-01-01

In this paper work, four naked nanocrystals (size range 80–700 nm) were prepared without any surfactant or polymer using the solvent/nonsolvent method. The effects of particle size on their solubility, dissolution, and oral bioavailability were investigated. Solubility and dissolution testing were performed in three types of dissolution medium, and the studies demonstrated that the equilibrium solubilities of coenzyme Q10 nanocrystals and bulk drugs were not affected by the dissolution media but the kinetic solubilities were. Kinetic solubility curves and changes in particle size distribution were determined and well explained by the proposed solubilization model for the nanocrystals and bulk drugs. The particle size effect on dissolution was clearly influenced by the diffusion coefficients of the various dissolution media, and the dissolution velocity of coenzyme Q10 increased as particle size decreased. The bioavailability of coenzyme Q10 after oral administration in beagle dogs was improved by reducing the particle size. For 700 nm nanocrystals, the AUC0–48 was 4.4-fold greater than that for the coarse suspensions, but a further decrease in particle size from 700 nm to 120 nm did not contribute to improvement in bioavailability until the particle size was reduced to 80 nm, when bioavailability was increased by 7.3-fold. PMID:23166438

Ocean acidification: Towards a better understanding of calcite dissolution

NASA Astrophysics Data System (ADS)

Wilhelmus, Monica M.; Adkins, Jess; Menemenlis, Dimitris

2016-11-01

The drastic increase of anthropogenic CO2 emissions over the past two centuries has altered the chemical structure of the ocean, acidifying upper ocean waters. The net impact of this pH decrease on marine ecosystems is still unclear, given the unprecedented rate at which CO2 is being released into the atmosphere. As part of the carbon cycle, calcium carbonate dissolution in sediments neutralizes CO2: phytoplankton at the surface produce carbonate minerals, which sink and reach the seafloor after the organisms die. On time scales of thousands of years, the calcium carbonate in these shells ultimately reacts with CO2 in seawater. Research in this field has been extensive; nevertheless, the dissolution rate law, the impact of boundary layer transport, and the feedback with the global ocean carbon cycle remain controversial. Here, we (i) develop a comprehensive numerical framework via 1D modeling of carbonate dissolution in sediments, (ii) approximate its impact on water column properties by implementing a polynomial approximation to the system's response into a global ocean biogeochemistry general circulation model (OBGCM), and (iii) examine the OBGCM sensitivity response to different formulations of sediment boundary layer properties. We find that, even though the burial equilibration time scales of calcium carbonate are in the order of thousands of years, the formulation of a bottom sediment model along with an improved description of the dissolution rate law can have consequences on multi-year to decadal time scales.

Glass composition and solution speciation effects on stage III dissolution

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

Trivelpiece, Cory L.; Rice, Jarret A.; Pantano, Carlo G.

To understand and mitigate the onset of Stage III corrosion of multicomponent oxides waste glasses. Stage III refers to a resumption of the high initial rate of glass dissolution in some glass samples that have otherwise exhibited dissolution at the much lower residual rate for a long time (Stage II). Although the onset of Stage III is known to occur concurrently with the precipitation of particular alteration products, the root cause of the transition is still unknown. Certain glass compositions (notably AFCI) and high pH environmental conditions are also associated with this observed transition.

Defining level A IVIVC dissolution specifications based on individual in vitro dissolution profiles of a controlled release formulation.

PubMed

González-García, I; García-Arieta, A; Merino-Sanjuan, M; Mangas-Sanjuan, V; Bermejo, M

2018-07-01

Regulatory guidelines recommend that, when a level A IVIVC is established, dissolution specification should be established using averaged data and the maximum difference between AUC and C max between the reference and test formulations cannot be greater than 20%. However, averaging data assumes a loss of information and may reflect a bias in the results. The objective of the current work is to present a new approach to establish dissolution specifications using a new methodology (individual approach) instead of average data (classical approach). Different scenarios were established based on the relationship between in vitro-in vivo dissolution rate coefficient using a level A IVIVC of a controlled release formulation. Then, in order to compare this new approach with the classical one, six additional batches were simulated. For each batch, 1000 simulations of a dissolution assay were run. C max ratios between the reference formulation and each batch were calculated showing that the individual approach was more sensitive and able to detect differences between the reference and the batch formulation compared to the classical approach. Additionally, the new methodology displays wider dissolution specification limits than the classical approach, ensuring that any tablet from the new batch would generate in vivo profiles which its AUC or C max ratio will be out of the 0.8-1.25 range, taking into account the in vitro and in vivo variability of the new batches developed. Copyright © 2018 Elsevier B.V. All rights reserved.

Kinetics and mechanism of hydroxyapatite crystal dissolution in weak acid buffers using the rotating disk method.

PubMed

Wu, M S; Higuchi, W I; Fox, J L; Friedman, M

1976-01-01

The model given in this report and the rotating disk method provide a useful combination in the study of dental enamel and hydroxyapatite dissolution kinetics. The present approach is a significant improvement over earlier studies, and both the ionic activity product that governs the dissolution reaction and the apparent surface dissolution reaction rate constant may be simultaneously obtained. Thus, these investigations have established the baseline for the dissolution rate studies under sink conditions. Concurrent studies, under conditions where the acidic buffer mediums are partially saturated with respect to hydroxyapatite have shown another dissolution site for hydroxyapatite that operates at a higher ionic activity product but has a much smaller apparent surface reaction rate constant. This has raised the question of whether the presence of this second site may interfere with the proper theoretical analysis of the experimental results obtained under sink conditions. A preliminary analysis of the two-site model has shown that the dissolution kinetics of hydroxyapatite under sink conditions is almost completely governed by the sink condition site (KHAP = 10(-124.5), k' = 174) established in this report. The difference between the predicted dissolution rate for the one-site model and the two-site model are generally of the order of 4 to 5% where the experiments are conducted under sink conditions and over the range of variables covered in the present study.

Aluminum Target Dissolution in Support of the Pu-238 Program

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

McFarlane, Joanna; Benker, Dennis; DePaoli, David W

2014-09-01

Selection of an aluminum alloy for target cladding affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the caustic dissolution step, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. We present a study to maximize dissolution of aluminum metal alloy, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. These datamore » have been compared with published calculations of aluminum phase diagrams. Temperature logging during the transients has been investigated as a means to generate kinetic and mass transport data on the dissolution process. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

In-life pteropod shell dissolution as an indicator of past ocean carbonate saturation

NASA Astrophysics Data System (ADS)

Wall-Palmer, Deborah; Smart, Christopher W.; Hart, Malcolm B.

2013-12-01

Recent concern over the effects of ocean acidification upon calcifying organisms has highlighted the aragonitic shelled thecosomatous pteropods as being at a high risk. Both in-situ and laboratory studies have shown that an increased dissolved CO2 concentration, leading to decreased water pH and low carbonate concentration, causes reduced calcification rates and enhanced dissolution in the shells of living pteropods. In fossil records unaffected by post-depositional dissolution, this in-life shell dissolution can be detected. Here we present the first evidence of variations of in-life pteropod shell dissolution due to variations in surface water carbonate concentration during the Late Pleistocene by analysing the surface layer of pteropod shells in marine sediment cores from the Caribbean Sea and Indian Ocean. In-life shell dissolution was determined by applying the Limacina Dissolution Index (LDX) to the sub-tropical pteropod Limacina inflata. Average shell size information shows that high in-life dissolution is accompanied by smaller shell sizes in L. inflata, which may indicate a reduction in calcification rate. Comparison of the LDX profile to Late Pleistocene Vostok atmospheric CO2 concentrations, shows that in-life pteropod dissolution is closely associated to variations in past ocean carbonate saturation. This study confirms the findings of laboratory studies, showing enhanced shell dissolution and reduced calcification in living pteropods when surface ocean carbonate concentrations were lower. Results also demonstrate that oceanic pH levels that were less acidic and changing less rapidly than those predicted for the 21st Century, negatively affected pteropods during the Late Pleistocene.

Addition of Sodium Bicarbonate to Irrigation Solution May Assist in Dissolution of Uric Acid Fragments During Ureteroscopy.

PubMed

Paonessa, Jessica E; Williams, James C; Lingeman, James E

2018-04-01

We hypothesized that adding sodium bicarbonate (bicarb) to normal saline (NS) irrigation during ureteroscopy in patients with uric acid (UA) nephrolithiasis may assist in dissolving small stone fragments produced during laser lithotripsy. In vitro testing was performed to determine whether dissolution of UA fragments could be accomplished within 1 hour. In total 100% UA renal calculi were fragmented, filtered, and separated by size. Fragment sizes were <0.5 mm and 0.5 to 1 mm. Similar amounts of stone material were agitated in solution at room temperature. Four solutions were tested (NS, NS +1 ampule bicarb/L, NS +2, NS +3). Both groups were filtered to remove solutions after fixed periods. Filtered specimens were dried and weighed. Fragment dissolution rates were calculated as percent removed per hour. Additional testing was performed to determine whether increasing the temperature of solution affected dissolution rates. For fragments <0.5 mm, adding 2 or 3 bicarb ampules/L NS produced a dissolution rate averaging 91% ± 29% per hour. This rate averaged 226% faster than NS alone. With fragments 0.5 to 1 mm, addition of 2 or 3 bicarb ampules/L NS yielded a dissolution rate averaging 22% ± 7% per hour, which was nearly five times higher than NS alone. There was a trend for an increase in mean dissolution rate with higher temperature but this increase was not significant (p = 0.30). The addition of bicarbonate to NS more than doubles the dissolution rate of UA stone fragments and fragments less than 0.5 mm can be completely dissolved within 1 hour. Addition of bicarb to NS irrigation is a simple and inexpensive approach that may assist in the dissolution of UA fragments produced during ureteroscopic laser lithotripsy. Further studies are needed to determine whether a clinical benefit exists.

5 CFR 2634.410 - Dissolution.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 5 Administrative Personnel 3 2014-01-01 2014-01-01 false Dissolution. 2634.410 Section 2634.410..., QUALIFIED TRUSTS, AND CERTIFICATES OF DIVESTITURE Qualified Trusts § 2634.410 Dissolution. Within thirty days of dissolution of a qualified trust, the interested party shall file a report of the dissolution...

5 CFR 2634.410 - Dissolution.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 5 Administrative Personnel 3 2013-01-01 2013-01-01 false Dissolution. 2634.410 Section 2634.410..., QUALIFIED TRUSTS, AND CERTIFICATES OF DIVESTITURE Qualified Trusts § 2634.410 Dissolution. Within thirty days of dissolution of a qualified trust, the interested party shall file a report of the dissolution...

In vitro acellular dissolution of mineral fibres: A comparative study.

PubMed

Gualtieri, Alessandro F; Pollastri, Simone; Bursi Gandolfi, Nicola; Gualtieri, Magdalena Lassinantti

2018-05-04

The study of the mechanisms by which mineral fibres promote adverse effects in both animals and humans is a hot topic of multidisciplinary research with many aspects that still need to be elucidated. Besides length and diameter, a key parameter that determines the toxicity/pathogenicity of a fibre is biopersistence, one component of which is biodurability. In this paper, biodurability of mineral fibres of social and economic importance (chrysotile, amphibole asbestos and fibrous erionite) has been determined for the first time in a systematic comparative way from in vitro acellular dissolution experiments. Dissolution was possible using the Gamble solution as simulated lung fluid (pH = 4 and at body temperature) so to reproduce the macrophage phagolysosome environment. The investigated mineral fibres display very different dissolution rates. For a 0.25 μm thick fibre, the calculated dissolution time of chrysotile is in the range 94-177 days, very short if compared to that of amphibole fibres (49-245 years), and fibrous erionite (181 years). Diffraction and SEM data on the dissolution products evidence that chrysotile rapidly undergoes amorphization with the formation of a nanophasic silica-rich fibrous metastable pseudomorph as first dissolution step whereas amphibole asbestos and fibrous erionite show minor signs of dissolution even after 9-12 months.

Dissolution of Si in Molten Al with Gas Injection

NASA Astrophysics Data System (ADS)

Seyed Ahmadi, Mehran

Silicon is an essential component of many aluminum alloys, as it imparts a range of desirable characteristics. However, there are considerable practical difficulties in dissolving solid Si in molten Al, because the dissolution process is slow, resulting in material and energy losses. It is thus essential to examine Si dissolution in molten Al, to identify means of accelerating the process. This thesis presents an experimental study of the effect of Si purity, bath temperature, fluid flow conditions, and gas stirring on the dissolution of Si in molten Al, plus the results of physical and numerical modeling of the flow to corroborate the experimental results. The dissolution experiments were conducted in a revolving liquid metal tank to generate a bulk velocity, and gas was introduced into the melt using top lance injection. Cylindrical Si specimens were immersed into molten Al for fixed durations, and upon removal the dissolved Si was measured. The shape and trajectory of injected bubbles were examined by means of auxiliary water experiments and video recordings of the molten Al free surface. The gas-agitated liquid was simulated using the commercial software FLOW-3D. The simulation results provide insights into bubble dynamics and offer estimates of the fluctuating velocities within the Al bath. The experimental results indicate that the dissolution rate of Si increases in tandem with the melt temperature and bulk velocity. A higher bath temperature increases the solubility of Si at the solid/liquid interface, resulting in a greater driving force for mass transfer, and a higher liquid velocity decreases the resistance to mass transfer via a thinner mass boundary layer. Impurities (with lower diffusion coefficients) in the form of inclusions obstruct the dissolution of the Si main matrix. Finally, dissolution rate enhancement was observed by gas agitation. It is postulated that the bubble-induced fluctuating velocities disturb the mass boundary layer, which

Effect of taste masking technology on fast dissolving oral film: dissolution rate and bioavailability

NASA Astrophysics Data System (ADS)

Zhu, Ying; You, Xinru; Huang, Keqing; Raza, Faisal; Lu, Xin; Chen, Yuejian; Dhinakar, Arvind; Zhang, Yuan; Kang, Yang; Wu, Jun; Ge, Liang

2018-07-01

Fast dissolving oral film is a stamp-style, drug-loaded polymer film with rapid disintegration and dissolution. This new kind of drug delivery system requires effective taste masking technology. Suspension intermediate and liposome intermediate were prepared, respectively, for the formulation of two kinds of fast dissolving oral films with the aim of studying the effect of taste masking technology on the bioavailability of oral films. Loratadine was selected as the model drug. The surface pH of the films was close to neutral, avoiding oral mucosal irritation or side effects. The thickness of a 2 cm × 2 cm suspension oral film containing 10 mg of loratadine was 100 μm. Electron microscope analysis showed that liposomes were spherical before and after re-dissolution, and drugs with obvious bitterness could be masked by the encapsulation of liposomes. Dissolution of the two films was superior to that of the commercial tablets. Rat pharmacokinetic experiments showed that the oral bioavailability of the suspension film was significantly higher than that of the commercial tablets, and the relative bioavailability of the suspension film was 175%. Liposomal film produced a certain amount of improvement in bioavailability, but lower than that of the suspension film.

Dissolution of solid lipid extrudates in biorelevant media.

PubMed

Witzleb, R; Müllertz, A; Kanikanti, V-R; Hamann, H-J; Kleinebudde, P

2012-01-17

Solid lipid extrudates with the model drug praziquantel were produced with chemically diverse lipids and investigated regarding their dissolution behaviour in different media. The lipids used in this study were glyceryl tripalmitate, glyceryl dibehenate, glyceryl monostearate, cetyl palmitate and solid paraffin. Thermoanalytical and dissolution behaviour was investigated directly after extrusion and after 3 and 6 months open storage at 40°C/75% RH. Dissolution studies were conducted in hydrochloric acid (HCl) pH 1.2 with different levels of polysorbate 20 and with a biorelevant medium containing pancreatic lipase, bile salts and phospholipids. Furthermore, the impact of lipid digestion on drug release was studied using in vitro lipolysis. The release of praziquantel from cetyl palmitate and glyceryl monostearate in the biorelevant medium was much faster than in HCl, whereas there was hardly any difference for the other lipids. It was shown that drug release from glyceryl monostearate matrices is driven by both solubilisation and enzymatic degradation of the lipid, whereas dissolution from cetyl palmitate extrudates is dependent only on solubilisation by surfactants in the medium. Moreover, storage influenced the appearance of the extrudate surface and the dissolution rate for all lipids except solid paraffin. Copyright © 2011 Elsevier B.V. All rights reserved.

What controls silicon isotope fractionation during dissolution of diatom opal?

NASA Astrophysics Data System (ADS)

Wetzel, F.; de Souza, G. F.; Reynolds, B. C.

2014-04-01

The silicon isotope composition of opal frustules from photosynthesising diatoms is a promising tool for studying past changes in the marine silicon cycle, and indirectly that of carbon. Dissolution of this opal may be accompanied by silicon isotope fractionation that could disturb the pristine silicon isotope composition of diatom opal acquired in the surface ocean. It has previously been shown that dissolution of fresh and sediment trap diatom opal in seawater does fractionate silicon isotopes. However, as the mechanism of silicon isotope fractionation remained elusive, it is uncertain whether opal dissolution in general is associated with silicon isotope fractionation considering that opal chemistry and surface properties are spatially and temporally (i.e. opal of different age) diverse. In this study we dissolved sediment core diatom opal in 5 mM NaOH and found that this process is not associated with significant silicon isotope fractionation. Since no variability of the isotope effect was observed over a wide range of dissolution rates, we can rule out the suggestion that back-reactions had a significant influence on the net isotope effect. Similarly, we did not observe an impact of temperature, specific surface area, or degree of undersaturation on silicon isotope partitioning during dissolution, such that these can most likely also be ruled out as controlling factors. We discuss the potential impacts of the chemical composition of the dissolution medium and age of diatom opal on silicon isotope fractionation during dissolution. It appears most likely that the controlling mechanism of silicon isotope fractionation during dissolution is related to the reactivity, or potentially, aluminium content of the opal. Such a dependency would imply that silicon isotope fractionation during dissolution of diatom opal is spatially and temporally variable. However, since the isotope effects during dissolution are small, the silicon isotope composition of diatom opal

Thin film modeling of crystal dissolution and growth in confinement.

PubMed

Gagliardi, Luca; Pierre-Louis, Olivier

2018-01-01

We present a continuum model describing dissolution and growth of a crystal contact confined against a substrate. Diffusion and hydrodynamics in the liquid film separating the crystal and the substrate are modeled within the lubrication approximation. The model also accounts for the disjoining pressure and surface tension. Within this framework, we obtain evolution equations which govern the nonequilibrium dynamics of the crystal interface. Based on this model, we explore the problem of dissolution under an external load, known as pressure solution. We find that in steady state, diverging (power-law) crystal-surface repulsions lead to flat contacts with a monotonic increase of the dissolution rate as a function of the load. Forces induced by viscous dissipation then surpass those due to disjoining pressure at large enough loads. In contrast, finite repulsions (exponential) lead to sharp pointy contacts with a dissolution rate independent of the load and the liquid viscosity. Ultimately, in steady state, the crystal never touches the substrate when pressed against it. This result is independent from the nature of the crystal-surface interaction due to the combined effects of viscosity and surface tension.

Thin film modeling of crystal dissolution and growth in confinement

NASA Astrophysics Data System (ADS)

Gagliardi, Luca; Pierre-Louis, Olivier

2018-01-01

We present a continuum model describing dissolution and growth of a crystal contact confined against a substrate. Diffusion and hydrodynamics in the liquid film separating the crystal and the substrate are modeled within the lubrication approximation. The model also accounts for the disjoining pressure and surface tension. Within this framework, we obtain evolution equations which govern the nonequilibrium dynamics of the crystal interface. Based on this model, we explore the problem of dissolution under an external load, known as pressure solution. We find that in steady state, diverging (power-law) crystal-surface repulsions lead to flat contacts with a monotonic increase of the dissolution rate as a function of the load. Forces induced by viscous dissipation then surpass those due to disjoining pressure at large enough loads. In contrast, finite repulsions (exponential) lead to sharp pointy contacts with a dissolution rate independent of the load and the liquid viscosity. Ultimately, in steady state, the crystal never touches the substrate when pressed against it. This result is independent from the nature of the crystal-surface interaction due to the combined effects of viscosity and surface tension.

In Vitro Dissolution Tests of Plutonium and Americium Containing Contamination Originating From ZPPR Fuel Plates

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

William F. Bauer; Brian K. Schuetz; Gary M. Huestis

2012-09-01

Assessing the extent of internal dose is of concern whenever workers are exposed to airborne radionuclides or other contaminants. Internal dose determinations depend upon a reasonable estimate of the expected biological half-life of the contaminants in the respiratory tract. One issue with refractory elements is determining the dissolution rate of the element. Actinides such as plutonium (Pu) and Americium (Am) tend to be very refractory and can have biological half-lives of tens of years. In the event of an exposure, the dissolution rates of the radionuclides of interest needs to be assessed in order to assign the proper internal dosemore » estimates. During the November 2011 incident at the Idaho National Laboratory (INL) involving a ZPPR fuel plate, air filters in a constant air monitor (CAM) and a giraffe filter apparatus captured airborne particulate matter. These filters were used in dissolution rate experiments to determine the apparent dissolution half-life of Pu and Am in simulated biological fluids. This report describes these experiments and the results. The dissolution rates were found to follow a three term exponential decay equation. Differences were noted depending upon the nature of the biological fluid simulant. Overall, greater than 95% of the Pu and 93% of the Am were in a very slow dissolving component with dissolution half-lives of over 10 years.« less

Dissolution assessment of allopurinol immediate release tablets by near infrared spectroscopy.

PubMed

Smetiško, Jelena; Miljanić, Snežana

2017-10-25

The purpose of this study was to develop a NIR spectroscopic method for assessment of drug dissolution from allopurinol immediate release tablets. Thirty three different batches of allopurinol immediate release tablets containing constant amount of the active ingredient, but varying in excipients content and physical properties were introduced in a PLS calibration model. Correlating allopurinol dissolution reference values measured by the routinely used UV/Vis method, with the data extracted from the NIR spectra, values of correlation coefficient, bias, slope, residual prediction determination and root mean square error of prediction (0.9632, 0.328%, 1.001, 3.58, 3.75%) were evaluated. The obtained values implied that the NIR diffuse reflectance spectroscopy could serve as a faster and simpler alternative to the conventional dissolution procedure, even for the tablets with a very fast dissolution rate (>85% in 15minutes). Apart from the possibility of prediction of the allopurinol dissolution rate, the other multivariate technique, PCA, provided additional data on the non-chemical characteristics of the product, which could not be obtained from the reference dissolution values. Analysis on an independent set of samples confirmed that a difference between the UV/Vis reference method and the proposed NIR method was not significant. According to the presented results, the proposed NIR method may be suitable for practical application in routine analysis and for continuously monitoring the product's chemical and physical properties responsible for expected quality. Copyright © 2017 Elsevier B.V. All rights reserved.

In Vivo Predictive Dissolution: Comparing the Effect of Bicarbonate and Phosphate Buffer on the Dissolution of Weak Acids and Weak Bases.

PubMed

Krieg, Brian J; Taghavi, Seyed Mohammad; Amidon, Gordon L; Amidon, Gregory E

2015-09-01

Bicarbonate is the main buffer in the small intestine and it is well known that buffer properties such as pKa can affect the dissolution rate of ionizable drugs. However, bicarbonate buffer is complicated to work with experimentally. Finding a suitable substitute for bicarbonate buffer may provide a way to perform more physiologically relevant dissolution tests. The dissolution of weak acid and weak base drugs was conducted in bicarbonate and phosphate buffer using rotating disk dissolution methodology. Experimental results were compared with the predicted results using the film model approach of (Mooney K, Mintun M, Himmelstein K, Stella V. 1981. J Pharm Sci 70(1):22-32) based on equilibrium assumptions as well as a model accounting for the slow hydration reaction, CO2 + H2 O → H2 CO3 . Assuming carbonic acid is irreversible in the dehydration direction: CO2 + H2 O ← H2 CO3 , the transport analysis can accurately predict rotating disk dissolution of weak acid and weak base drugs in bicarbonate buffer. The predictions show that matching the dissolution of weak acid and weak base drugs in phosphate and bicarbonate buffer is possible. The phosphate buffer concentration necessary to match physiologically relevant bicarbonate buffer [e.g., 10.5 mM (HCO3 (-) ), pH = 6.5] is typically in the range of 1-25 mM and is very dependent upon drug solubility and pKa . © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Effect of the size of nanoparticles on their dissolution within metal-glass nanocomposites under sustained irradiation

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

Vu, T. H. Y., E-mail: thi-hai-yen.vu@polytechnique.edu; Ramjauny, Y.; Rizza, G.

2016-01-21

We investigate the dissolution law of metallic nanoparticles (NPs) under sustained irradiation. The system is composed of isolated spherical gold NPs (4–100 nm) embedded in an amorphous silica host matrix. Samples are irradiated at room temperature in the nuclear stopping power regime with 4 MeV Au ions for fluences up to 8 × 10{sup 16 }cm{sup −2}. Experimentally, the dependence of the dissolution kinetics on the irradiation fluence is linear for large NPs (45–100 nm) and exponential for small NPs (4–25 nm). A lattice-based kinetic Monte Carlo (KMC) code, which includes atomic diffusion and ballistic displacement events, is used to simulate the dynamical competition between irradiation effectsmore » and thermal healing. The KMC simulations allow for a qualitative description of the NP dissolution in two main stages, in good agreement with the experiment. Moreover, the perfect correlation obtained between the evolution of the simulated flux of ejected atoms and the dissolution rate in two stages implies that there exists an effect of the size of NPs on their dissolution and a critical size for the transition between the two stages. The Frost-Russell model providing an analytical solution for the dissolution rate, accounts well for the first dissolution stage but fails in reproducing the data for the second stage. An improved model obtained by including a size-dependent recoil generation rate permits fully describing the dissolution for any NP size. This proves, in particular, that the size effect on the generation rate is the principal reason for the existence of two regimes. Finally, our results also demonstrate that it is justified to use a unidirectional approximation to describe the dissolution of the NP under irradiation, because the solute concentration is particularly low in metal-glass nanocomposites.« less

Effect of the size of nanoparticles on their dissolution within metal-glass nanocomposites under sustained irradiation

NASA Astrophysics Data System (ADS)

Vu, T. H. Y.; Ramjauny, Y.; Rizza, G.; Hayoun, M.

2016-01-01

We investigate the dissolution law of metallic nanoparticles (NPs) under sustained irradiation. The system is composed of isolated spherical gold NPs (4-100 nm) embedded in an amorphous silica host matrix. Samples are irradiated at room temperature in the nuclear stopping power regime with 4 MeV Au ions for fluences up to 8 × 1016 cm-2. Experimentally, the dependence of the dissolution kinetics on the irradiation fluence is linear for large NPs (45-100 nm) and exponential for small NPs (4-25 nm). A lattice-based kinetic Monte Carlo (KMC) code, which includes atomic diffusion and ballistic displacement events, is used to simulate the dynamical competition between irradiation effects and thermal healing. The KMC simulations allow for a qualitative description of the NP dissolution in two main stages, in good agreement with the experiment. Moreover, the perfect correlation obtained between the evolution of the simulated flux of ejected atoms and the dissolution rate in two stages implies that there exists an effect of the size of NPs on their dissolution and a critical size for the transition between the two stages. The Frost-Russell model providing an analytical solution for the dissolution rate, accounts well for the first dissolution stage but fails in reproducing the data for the second stage. An improved model obtained by including a size-dependent recoil generation rate permits fully describing the dissolution for any NP size. This proves, in particular, that the size effect on the generation rate is the principal reason for the existence of two regimes. Finally, our results also demonstrate that it is justified to use a unidirectional approximation to describe the dissolution of the NP under irradiation, because the solute concentration is particularly low in metal-glass nanocomposites.

Two-phase convective CO 2 dissolution in saline aquifers

DOE PAGES

Martinez, Mario J.; Hesse, Marc A.

2016-01-30

Geologic carbon storage in deep saline aquifers is a promising technology for reducing anthropogenic emissions into the atmosphere. Dissolution of injected CO 2 into resident brines is one of the primary trapping mechanisms generally considered necessary to provide long-term storage security. Given that diffusion of CO 2 in brine is woefully slow, convective dissolution, driven by a small increase in brine density with CO 2 saturation, is considered to be the primary mechanism of dissolution trapping. Previous studies of convective dissolution have typically only considered the convective process in the single-phase region below the capillary transition zone and have eithermore » ignored the overlying two-phase region where dissolution actually takes place or replaced it with a virtual region with reduced or enhanced constant permeability. Our objective is to improve estimates of the long-term dissolution flux of CO 2 into brine by including the capillary transition zone in two-phase model simulations. In the fully two-phase model, there is a capillary transition zone above the brine-saturated region over which the brine saturation decreases with increasing elevation. Our two-phase simulations show that the dissolution flux obtained by assuming a brine-saturated, single-phase porous region with a closed upper boundary is recovered in the limit of vanishing entry pressure and capillary transition zone. For typical finite entry pressures and capillary transition zone, however, convection currents penetrate into the two-phase region. As a result, this removes the mass transfer limitation of the diffusive boundary layer and enhances the convective dissolution flux of CO 2 more than 3 times above the rate assuming single-phase conditions.« less

Kinetics of cellular dissolution in a Cu-Cd alloy

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

Nakkalil, R.; Gupta, S.P.

1989-07-01

Dissolution of the cellular precipitate by cell boundary migration has been studied in a Cu-2 at.% Cd alloy in the temperature range 777--878 K. Microstructural observations have revealed that the process of dissolution begins at the original position of the grain boundary as well as the cell boundary. The steady state rate of cell boundary migration decreased with decreasing temperature of dissolution and became zero at approximately 770 K, which is about 30 K below the equilibrium solves temperature. The boundary diffusivities were determined at a number of temperatures by using the theory of Petermann and Hornbogen modified for dissolution.more » The diffusivity values calculated from the experimental data are seven orders of magnitude higher than the corresponding volume diffusivities. From the temperature dependence of the diffusivity, an activation energy of 157 kJ mol{sup {minus} 1} is obtained, which is bout three-quarters of the activation energy for the bulk diffusion of Cd into Cu. From the diffusivity and activation energy values, it is concluded that the diffusion of Cd along the migrating grain boundaries control the dissolution of the cellular precipitate in this alloy.« less

Working Late: Do Workplace Sex Ratios Affect Partnership Formation and Dissolution?

ERIC Educational Resources Information Center

Svarer, Michael

2007-01-01

In this paper, I analyze the association between workplace sex ratios and partnership formation and dissolution. I find that the risk of dissolution increases with the fraction of coworkers of the opposite sex at both the female and male workplace. On the other hand, workplace sex ratios are not important for the overall transition rate from…

A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

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

Chen Zhu; William E. Seyfried

2005-01-01

Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory-measured andmore » field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between lab and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO{sub 2} injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the first year of the project, we have successfully developed a sample preparation method and completed three batch feldspar dissolution experiments at 200 C and 300 bars. The changes of solution chemistry as dissolution experiments progressed were monitored with on-line sampling of the aqueous phase at the constant temperature and

Biogenic hydroxyapatite (Apatite II™) dissolution kinetics and metal removal from acid mine drainage.

PubMed

Oliva, J; Cama, J; Cortina, J L; Ayora, C; De Pablo, J

2012-04-30

Apatite II™ is a biogenic hydroxyapatite (expressed as Ca(5)(PO(4))OH) derived from fish bone. Using grains of Apatite II™ with a fraction size between 250 and 500 μm, batch and flow-through experiments were carried out to (1) determine the solubility constant for the dissolution reaction Ca(5)(PO(4))(3)(OH) ⇔ 5Ca(2+) + 3PO(4)(3-) + OH(-), (2) obtain steady-state dissolution rates over the pH range between 2.22 and 7.14, and (3) study the Apatite II™'s mechanisms to remove Pb(2+), Zn(2+), Mn(2+), and Cu(2+) from metal polluted water as it dissolves. The logK(S) value obtained was -50.8±0.82 at 25 °C. Far-from-equilibrium fish-bone hydroxyapatite dissolution rates decrease by increasing pH. Assuming that the dissolution reaction is controlled by fast adsorption of a proton on a specific surface site that dominates through the pH range studied, probably ≡PO(-), followed by a slow hydrolysis step, the dissolution rate dependence is expressed in mol m(-2) s(-1) as where Rate(25 °C) = -8.9 × 10(-10) × [9.96 × 10(5) × a(H+)]/[1 + 9.96 × 10(5) × a(H+)] where a(H+) is the proton activity in solution. Removal of Pb(2+), Zn(2+), Mn(2+) and Cu(2+) was by formation of phosphate-metal compounds on the Apatite II™ substrate, whereas removal of Cd(2+) was by surface adsorption. Increase in pH enhanced the removal of aqueous heavy metals. Using the kinetic parameters obtained (e.g., dissolution rate and pH-rate dependence law), reactive transport simulations reproduced the experimental variation of pH and concentrations of Ca, P and toxic divalent metal in a column experiment filled with Apatite II™ that was designed to simulate the Apatite II™-metal polluted water interaction. Copyright © 2012 Elsevier B.V. All rights reserved.

Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

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

Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

2016-07-22

Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruentmore » dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). In conclusion, our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.« less

Inverse modeling of BTEX dissolution and biodegradation at the Bemidji, MN crude-oil spill site

USGS Publications Warehouse

Essaid, H.I.; Cozzarelli, I.M.; Eganhouse, R.P.; Herkelrath, W.N.; Bekins, B.A.; Delin, G.N.

2003-01-01

The U.S. Geological Survey (USGS) solute transport and biodegradation code BIOMOC was used in conjunction with the USGS universal inverse modeling code UCODE to quantify field-scale hydrocarbon dissolution and biodegradation at the USGS Toxic Substances Hydrology Program crude-oil spill research site located near Bemidji, MN. This inverse modeling effort used the extensive historical data compiled at the Bemidji site from 1986 to 1997 and incorporated a multicomponent transport and biodegradation model. Inverse modeling was successful when coupled transport and degradation processes were incorporated into the model and a single dissolution rate coefficient was used for all BTEX components. Assuming a stationary oil body, we simulated benzene, toluene, ethylbenzene, m,p-xylene, and o-xylene (BTEX) concentrations in the oil and ground water, respectively, as well as dissolved oxygen. Dissolution from the oil phase and aerobic and anaerobic degradation processes were represented. The parameters estimated were the recharge rate, hydraulic conductivity, dissolution rate coefficient, individual first-order BTEX anaerobic degradation rates, and transverse dispersivity. Results were similar for simulations obtained using several alternative conceptual models of the hydrologic system and biodegradation processes. The dissolved BTEX concentration data were not sufficient to discriminate between these conceptual models. The calibrated simulations reproduced the general large-scale evolution of the plume, but did not reproduce the observed small-scale spatial and temporal variability in concentrations. The estimated anaerobic biodegradation rates for toluene and o-xylene were greater than the dissolution rate coefficient. However, the estimated anaerobic biodegradation rates for benzene, ethylbenzene, and m,p-xylene were less than the dissolution rate coefficient. The calibrated model was used to determine the BTEX mass balance in the oil body and groundwater plume

Justification of Drug Product Dissolution Rate and Drug Substance Particle Size Specifications Based on Absorption PBPK Modeling for Lesinurad Immediate Release Tablets.

PubMed

Pepin, Xavier J H; Flanagan, Talia R; Holt, David J; Eidelman, Anna; Treacy, Don; Rowlings, Colin E

2016-09-06

In silico absorption modeling has been performed, to assess the impact of in vitro dissolution on in vivo performance for ZURAMPIC (lesinurad) tablets. The dissolution profiles of lesinurad tablets generated using the quality control method were used as an input to a GastroPlus model to estimate in vivo dissolution in the various parts of the GI tract and predict human exposure. A model was set up, which accounts for differences of dosage form transit, dissolution, local pH in the GI tract, and fluid volumes available for dissolution. The predictive ability of the model was demonstrated by confirming that it can reproduce the Cmax observed for independent clinical trial. The model also indicated that drug product batches that pass the proposed dissolution specification of Q = 80% in 30 min are anticipated to be bioequivalent to the clinical reference batch. To further explore the dissolution space, additional simulations were performed using a theoretical dissolution profile below the proposed specification. The GastroPlus modeling indicates that such a batch will also be bioequivalent to standard clinical batches despite having a dissolution profile, which would fail the proposed dissolution specification of Q = 80% in 30 min. This demonstrates that the proposed dissolution specification sits comfortably within a region of dissolution performance where bioequivalence is anticipated and is not near an edge of failure for dissolution, providing additional confidence to the proposed specifications. Finally, simulations were performed using a virtual drug substance batch with a particle size distribution at the limit of the proposed specification for particle size. Based on these simulations, such a batch is also anticipated to be bioequivalent to clinical reference, demonstrating that the proposed specification limits for particle size distribution would give products bioequivalent to the pivotal clinical batches.

Computational fluid dynamics (CFD) studies of a miniaturized dissolution system.

PubMed

Frenning, G; Ahnfelt, E; Sjögren, E; Lennernäs, H

2017-04-15

Dissolution testing is an important tool that has applications ranging from fundamental studies of drug-release mechanisms to quality control of the final product. The rate of release of the drug from the delivery system is known to be affected by hydrodynamics. In this study we used computational fluid dynamics to simulate and investigate the hydrodynamics in a novel miniaturized dissolution method for parenteral formulations. The dissolution method is based on a rotating disc system and uses a rotating sample reservoir which is separated from the remaining dissolution medium by a nylon screen. Sample reservoirs of two sizes were investigated (SR6 and SR8) and the hydrodynamic studies were performed at rotation rates of 100, 200 and 400rpm. The overall fluid flow was similar for all investigated cases, with a lateral upward spiraling motion and central downward motion in the form of a vortex to and through the screen. The simulations indicated that the exchange of dissolution medium between the sample reservoir and the remaining release medium was rapid for typical screens, for which almost complete mixing would be expected to occur within less than one minute at 400rpm. The local hydrodynamic conditions in the sample reservoirs depended on their size; SR8 appeared to be relatively more affected than SR6 by the resistance to liquid flow resulting from the screen. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-inhibition can limit biologically enhanced TCE dissolution from a TCE DNAPL.

PubMed

Haest, P J; Springael, D; Seuntjens, P; Smolders, E

2012-11-01

Biodegradation of trichloroethene (TCE) near a Dense Non Aqueous Phase Liquid (DNAPL) can enhance the dissolution rate of the DNAPL by increasing the concentration gradient at the DNAPL-water interface. Two-dimensional flow-through sand boxes containing a TCE DNAPL and inoculated with a TCE dechlorinating consortium were set up to measure this bio-enhanced dissolution under anaerobic conditions. The total mass of TCE and daughter products in the effluent of the biotic boxes was 3-6 fold larger than in the effluent of the abiotic box. However, the mass of daughter products only accounted for 19-55% of the total mass of chlorinated compounds in the effluent, suggesting that bio-enhanced dissolution factors were maximally 1.3-2.2. The enhanced dissolution most likely primarily resulted from variable DNAPL distribution rather than biodegradation. Specific dechlorination rates previously determined in a stirred liquid medium were used in a reactive transport model to identify the rate limiting factors. The model adequately simulated the overall TCE degradation when predicted resident microbial numbers approached observed values and indicated an enhancement factor for TCE dissolution of 1.01. The model shows that dechlorination of TCE in the 2D box was limited due to the short residence time and the self-inhibition of the TCE degradation. A parameter sensitivity analysis predicts that the bio-enhanced dissolution factor for this TCE source zone can only exceed a value of 2 if the TCE self-inhibition is drastically reduced (when a TCE tolerant dehalogenating community is present) or if the DNAPL is located in a low-permeable layer with a small Darcy velocity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Kinetics and mechanism of natural fluorapatite dissolution at 25 °C and pH from 3 to 12

NASA Astrophysics Data System (ADS)

Chaïrat, Claire; Schott, Jacques; Oelkers, Eric H.; Lartigue, Jean-Eric; Harouiya, Najatte

2007-12-01

The dissolution rates of natural fluorapatite (FAP), Ca 10(PO 4) 6F 2, were measured at 25 °C in mixed-flow reactors as a function of pH from 3.0 to 11.7, and aqueous calcium, phosphorus, and fluoride concentration. After an initial preferential Ca and/or F release, stoichiometric Ca, P, and F release was observed. Measured FAP dissolution rates decrease with increasing pH at 3 ⩽ pH ⩽ 7, FAP dissolution rates are pH independent at 7 ⩽ pH ⩽ 10, and FAP dissolution rates again decrease with increasing pH at pH ⩾ 10. Measured FAP dissolution rates are independent of aqueous Ca, P, and F concentration at pH ≈ 3 and pH ≈ 10. Apatite dissolution appears to be initiated by the relatively rapid removal from the near surface of F and the Ca located in the M1 sites, via proton for Ca exchange reactions. Dissolution rates are controlled by the destruction of this F and Ca depleted surface layer. The destruction of this layer is facilitated by the adsorption/penetration of protons into the surface at acidic conditions, and by surface hydration at neutral and basic conditions. Taking into account these two parallel mechanisms, measured fluorapatite forward dissolution rates can be accurately described using r+(molms)=6.61×10-6{aK}/{1+aK+aCa4aF1.4aOH0.6aH6K}+3.69×10-8[tbnd CaOH2+] where ai refers to the activity of the ith aqueous species, [tbnd CaOH2+] denotes the concentration of hydrated calcium sites at the surface of the leached layer (mol m -2), and Kex and Kads stand for the apparent stability constants of the Ca 2+/H + exchange and adsorption/penetration reactions, respectively.

Oxidative dissolution of biogenic uraninite in groundwater at Old Rifle, CO

USGS Publications Warehouse

Campbell, Kate M.; Veeramani, Harish; Ulrich, Kai-Uwe; Blue, Lisa Y.; Giammar, Dianiel E.; Bernier-Latmani, Rizlan; Stubbs, Joanne E.; Suvorova, Elena; Yabusaki, Steve; Lezama-Pacheco, Juan S.; Mehta, Apurva; Long, Philip E.; Bargar, John R.

2011-01-01

Reductive bioremediation is currently being explored as a possible strategy for uranium-contaminated aquifers such as the Old Rifle site (Colorado). The stability of U(IV) phases under oxidizing conditions is key to the performance of this procedure. An in situ method was developed to study oxidative dissolution of biogenic uraninite (UO2), a desirable U(VI) bioreduction product, in the Old Rifle, CO, aquifer under different variable oxygen conditions. Overall uranium loss rates were 50–100 times slower than laboratory rates. After accounting for molecular diffusion through the sample holders, a reactive transport model using laboratory dissolution rates was able to predict overall uranium loss. The presence of biomass further retarded diffusion and oxidation rates. These results confirm the importance of diffusion in controlling in-aquifer U(IV) oxidation rates. Upon retrieval, uraninite was found to be free of U(VI), indicating dissolution occurred via oxidation and removal of surface atoms. Interaction of groundwater solutes such as Ca2+ or silicate with uraninite surfaces also may retard in-aquifer U loss rates. These results indicate that the prolonged stability of U(IV) species in aquifers is strongly influenced by permeability, the presence of bacterial cells and cell exudates, and groundwater geochemistry.

Evaluation of melt granulation and ultrasonic spray congealing as techniques to enhance the dissolution of praziquantel.

PubMed

Passerini, Nadia; Albertini, Beatrice; Perissutti, Beatrice; Rodriguez, Lorenzo

2006-08-02

Praziquantel (PZQ), an anthelminthic drug widely used in developing countries, is classified in Class II in the Biopharmaceutics Classification Systems; this means that PZQ has very low water solubility and high permeability, thus the dissolution is the absorption rate-limiting factor. The aim of this work was to evaluate the suitability of melt granulation and ultrasonic spray congealing as techniques for enhancing the dissolution rate of PZQ. Granules in high shear mixer were prepared by melt granulation, using polyethylene glycol 4000 or poloxamer 188 as meltable binders and alpha-lactose monohydrate as a filler. Quite regularly shaped granules having main size fraction in the range 200-500 microm were obtained using both formulations; however, only poloxamer 188 granules demonstrated a significant (P=0.05) increase of the PZQ dissolution rate compared to pure drug. To evaluate the potential of ultrasonic spray congealing, Gelucire 50/13 microparticles having different drug to carrier ratios (5, 10, 20 and 30%, w/w) were then prepared. The results showed that all the microparticles had a significant higher dissolution rate (P=0.05) respect to pure PZQ. The increase of the PZQ content considerably decreased the dissolution rate of the drug: 5 and 10% PZQ loaded systems evidenced dissolution significantly enhanced compared to 20 and 30% PZQ microparticles. The microparticle's characterisation, performed by Differential Scanning Calorimetry, Hot Stage Microscopy, X-ray powder diffraction and FT-Infrared analysis, evidenced the absence of both modifications of the solid state of PZQ and of significant interactions between the drug and the carrier. In conclusion, melt granulation and ultrasonic spray congealing could be proposed as solvent free, rapid and low expensive manufacturing methods to increase the in vitro dissolution rate of PZQ.

Sodium alginate as a potential carrier in solid dispersion formulations to enhance dissolution rate and apparent water solubility of BCS II drugs.

PubMed

Borba, Paola Aline Amarante; Pinotti, Marihá; de Campos, Carlos Eduardo Maduro; Pezzini, Bianca Ramos; Stulzer, Hellen Karine

2016-02-10

The solid dispersion technique is the most effective method for improving the dissolution rate of poorly water-soluble drugs, however it depends on a suitable carrier selection. The work explored the use of the biopolymer sodium alginate (SA) as a potential carrier in solid dispersions (SD). The data demonstrated that SA was able to improve the biopharmaceutical properties of the BCS II drug telmisartan (TEL) of low solubility even using relative small drug:polymer ratio. A solid state grinding process was used to prepare the solid dispersions (SD) during 45 min. The SD were prepared in different proportions of drug and carrier of 1:1, 1:3, 1:5, 1:7 and 1:9 (mass/mass). DSC, XRPD, FTIR and Raman confirmed the presence of molecular interactions between TEL and the carrier. FTIR supports the presence of hydrogen bonds between TEL and the carrier. SD_1:5, SD_1:7 and SD_1:9 enhanced the dissolution rate of the drug releasing more than 80% of the drug in just 30 min (83%, 84% and 87%). The the t-test results demonstrated equal dissolution efficiency values for SD_1:7 and Micardis(®), however the similarity (f2) and difference (f1) fit factors showed that the SD and Micardis(®) are statistically different. The physical stability studies demonstrated that SD using sodium alginate as a carrier remained unchanged during the period of 90 days at room temperature, showing that the sodium alginate acts as a good anti plasticizer agent, preventing the drug recrystallization. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enhanced dissolution of sildenafil citrate as dry foam tablets.

PubMed

Sawatdee, Somchai; Atipairin, Apichart; Sae Yoon, Attawadee; Srichana, Teerapol; Changsan, Narumon

2017-01-30

Dry foam formulation technology is alternative approach to enhance dissolution of the drug. Sildenafil citrate was suspended in sodium dodecyl sulfate solution and adding a mixture of maltodextrin and mannitol as diluent to form a paste. Sildenafil citrate paste was passed through a nozzle spray bottle to obtain smooth foam. The homogeneous foam was dried in a vacuum oven and sieved to obtain dry foam granules. The granules were mixed with croscarmellose sodium, magnesium stearate and compressed into tablet. All formulations were evaluated for their physicochemical properties and dissolution profiles. All the tested excipients were compatible with sildenafil citrate by both differential scanning calorimetry (DSC) and infrared (IR) analysis. There are no X-ray diffraction (XRD) peaks representing crystals of sildenafil citrate observed form dry foam formulations. The hardness of tablets was about 5 kg, friability test <1% with a disintegration time <5 min. The sildenafil citrate dry foam tablet had higher dissolution rate in 0.1 N HCl in comparison with commercial sildenafil citrate tablet, sildenafil citrate prepared by direct compression and wet granulation method. Sildenafil citrate dry foam tablet with the high-level composition of surfactant, water and diluent showed enhanced dissolution rate than that of the lower-level composition of these excipients. This formulation was stable under accelerated conditions for at least 6 months.

Effect of taste masking technology on fast dissolving oral film: dissolution rate and bioavailability.

PubMed

Zhu, Ying; You, Xinru; Huang, Keqing; Raza, Faisal; Lu, Xin; Chen, Yuejian; Dhinakar, Arvind; Zhang, Yuan; Kang, Yang; Wu, Jun; Ge, Liang

2018-07-27

Fast dissolving oral film is a stamp-style, drug-loaded polymer film with rapid disintegration and dissolution. This new kind of drug delivery system requires effective taste masking technology. Suspension intermediate and liposome intermediate were prepared, respectively, for the formulation of two kinds of fast dissolving oral films with the aim of studying the effect of taste masking technology on the bioavailability of oral films. Loratadine was selected as the model drug. The surface pH of the films was close to neutral, avoiding oral mucosal irritation or side effects. The thickness of a 2 cm × 2 cm suspension oral film containing 10 mg of loratadine was 100 μm. Electron microscope analysis showed that liposomes were spherical before and after re-dissolution, and drugs with obvious bitterness could be masked by the encapsulation of liposomes. Dissolution of the two films was superior to that of the commercial tablets. Rat pharmacokinetic experiments showed that the oral bioavailability of the suspension film was significantly higher than that of the commercial tablets, and the relative bioavailability of the suspension film was 175%. Liposomal film produced a certain amount of improvement in bioavailability, but lower than that of the suspension film.

Fe-Containing Allophane and Hisingerite Dissolution and Implications for Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Ralston, S. J.; Hausrath, E. M.; Tschauner, O.; Rampe, E. B.; Clark-Hogancamp, J. V.; Christoffersen, R.

2017-01-01

The mass-normalized dissolution rates measured in this study demonstrate that hisingerite and Fe-substituted allophane dissolve rapidly, much faster than crystalline phyllosilicates such as nontronite and kaolinite that have similar compositions. In addition, hisingerite dissolves more rapidly than allophane. Future work will focus on measuring dissolution rates at other pH values, so that dissolution rate laws for allophane and hisingerite can be derived. Results will be used to interpret data from Gale Crater. These initial experiments suggest that, if the liquid water present in Gale Crater was highly acidic, it was likely present for only a short time, allowing some amorphous soil-material similar to allophane to persist. Further experiments will enable us to constrain the timescales over which liquid water was present in Gale Crater and provide insight into its pH. This information is essential to assessing the potential habitability of ancient Mars.

Kinetics of carbonate mineral dissolution in CO2-acidified brines at storage reservoir conditions.

PubMed

Peng, Cheng; Anabaraonye, Benaiah U; Crawshaw, John P; Maitland, Geoffrey C; Trusler, J P Martin

2016-10-20

We report experimental measurements of the dissolution rate of several carbonate minerals in CO 2 -saturated water or brine at temperatures between 323 K and 373 K and at pressures up to 15 MPa. The dissolution kinetics of pure calcite were studied in CO 2 -saturated NaCl brines with molalities of up to 5 mol kg -1 . The results of these experiments were found to depend only weakly on the brine molality and to conform reasonably well with a kinetic model involving two parallel first-order reactions: one involving reactions with protons and the other involving reaction with carbonic acid. The dissolution rates of dolomite and magnesite were studied in both aqueous HCl solution and in CO 2 -saturated water. For these minerals, the dissolution rates could be explained by a simpler kinetic model involving only direct reaction between protons and the mineral surface. Finally, the rates of dissolution of two carbonate-reservoir analogue minerals (Ketton limestone and North-Sea chalk) in CO 2 -saturated water were found to follow the same kinetics as found for pure calcite. Vertical scanning interferometry was used to study the surface morphology of unreacted and reacted samples. The results of the present study may find application in reactive-flow simulations of CO 2 -injection into carbonate-mineral saline aquifers.

Characterization of Thin Film Dissolution in Water with in Situ Monitoring of Film Thickness Using Reflectometry.

PubMed

Yersak, Alexander S; Lewis, Ryan J; Tran, Jenny; Lee, Yung C

2016-07-13

Reflectometry was implemented as an in situ thickness measurement technique for rapid characterization of the dissolution dynamics of thin film protective barriers in elevated water temperatures above 100 °C. Using this technique, multiple types of coatings were simultaneously evaluated in days rather than years. This technique enabled the uninterrupted characterization of dissolution rates for different coating deposition temperatures, postdeposition annealing conditions, and locations on the coating surfaces. Atomic layer deposition (ALD) SiO2 and wet thermally grown SiO2 (wtg-SiO2) thin films were demonstrated to be dissolution-predictable barriers for the protection of metals such as copper. A ∼49% reduction in dissolution rate was achieved for ALD SiO2 films by increasing the deposition temperatures from 150 to 300 °C. ALD SiO2 deposited at 300 °C and followed by annealing in an inert N2 environment at 1065 °C resulted in a further ∼51% reduction in dissolution rate compared with the nonannealed sample. ALD SiO2 dissolution rates were thus lowered to values of wtg-SiO2 in water by the combination of increasing the deposition temperature and postdeposition annealing. Thin metal films, such as copper, without a SiO2 barrier corroded at an expected ∼1-2 nm/day rate when immersed in room temperature water. This measurement technique can be applied to any optically transparent coating.

Toward an In Vivo Dissolution Methodology: A Comparison of Phosphate and Bicarbonate Buffers

PubMed Central

Sheng, Jennifer J.; McNamara, Daniel P.; Amidon, Gordon L.

2011-01-01

Purpose To evaluate the difference between the pharmaceutical phosphate buffers and the gastrointestinal bicarbonates in dissolution of ketoprofen and indomethacin, to illustrate the dependence of buffer differential on biopharmaceutical properties of BCS II weak acids, and to recommend phosphate buffers equivalent to bicarbonates. Methods The intrinsic dissolution rates of, ketoprofen and indomethacin, were experimentally measured using rotating disk method at 37°C in USP SIF/FaSSIF and various concentrations of bicarbonates. Theoretical models including an improved reaction plane model and a film model were applied to estimate the surrogate phosphate buffers equivalent to the bicarbonates. Results Experimental results show that the intrinsic dissolution rates of ketoprofen and indomethacin, in USP and FaSSIF phosphate buffers are 1.5–3.0 times of that in the 15 mM bicarbonates. Theoretical analysis demonstrates that the buffer differential is largely dependent on the drug pKa and secondly on solubility, and weakly dependent on the drug diffusivity. Further, in accordance with the drug pKa, solubility and diffusivity, simple phosphate surrogate was proposed to match an average bicarbonate value (15 mM) of the upper gastrointestinal region. Specifically, phosphate buffers of 13–15 mM and 3–4 mM were recommended for ketoprofen and indomethacin, respectively. For both ketoprofen and indomethacin, the intrinsic dissolution using the phosphate surrogate buffers closely approximated the 15 mM bicarbonate buffer. Conclusions This work demonstrates the substantial difference between pharmaceutical phosphates and physiological bicarbonates in determining the drug intrinsic dissolution rates of BCS II weak acids, such as ketoprofen and indomethacin. Surrogate phosphates were recommended in order to closely reflect the in vivo dissolution of ketoprofen and indomethacin in gastrointestinal bicarbonates, which has significant implications for defining buffer systems for

Coral reef sediment dissolution: Insights from chamber incubations around the globe

NASA Astrophysics Data System (ADS)

Cyronak, T.; Andersson, A. J.; Eyre, B.

2016-02-01

Ocean acidification (OA) is expected to negatively affect the calcium carbonate (CaCO3) budget of coral reefs by decreasing calcification and increasing CaCO3 dissolution rates. Sediments represent the largest reservoir of CaCO3 in coral reefs and form important habitats above and below the hide tide mark. Results from in situ benthic incubations at different coral reef locations around the world (Australia, Tahiti, Bermuda, Cook Islands, and Hawaii) reveal that there is a general trend between bulk seawater aragonite saturation state (Ωar) and net CaCO3 sediment dissolution rates. Experimental incubations also indicate that the ratio of production to respiration (P/R) in the sediments plays a significant role in CaCO3 dissolution, with high P/R ratios potentially offsetting the effects of human induced OA. This is most likely due to benthic microalgae photosynthesizing and consuming CO2, which produces conditions more favourable for CaCO3 precipitation in sediment pore waters. Despite any interactions with benthic organic metabolism, sediment dissolution could be an order of magnitude more sensitive to OA compared to the process of biogenic calcification. Increases in CaCO3 sediment dissolution under predicted CO2 emissions could shift the net ecosystem calcification (NEC) of coral reefs from net CaCO3 precipitating to net dissolving by the end of this century.

Monte Carlo Simulations of the Dissolution of Borosilicate and Aluminoborosilicate Glasses in Dilute Aqueous Solutions

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

Kerisit, Sebastien N.; Pierce, Eric M.

The aim of this study was to provide atomic-level insights into the dissolution behavior of borosilicate and aluminoborosilicate glasses to complement and help interpret previous experimental work on the NeB glass series studied by Pierce et al. [Pierce E. M., Reed L. R., Shaw W. J., McGrail B. P., Icenhower J. P., Windisch C. F., Cordova E. A. and Broady J. (2010) Experimental determination of the effect of the ratio of B/Al on glass dissolution along the nepheline (NaAlSiO4) - Malinkoite (NaBSiO4) join. Geochim. Cosmochim. Acta 74, 2634-2654]. The composition of these glasses was 50 mol% SiO2 - 25 mol%more » Na2O - (25-x) mol% Al2O3 - x mol% B2O3, with x varying from 0 to 20 mol%. In the first part of this work, the different structural features of these glasses (e.g., presence of non-bridging oxygens, partition of boron between trigonal and tetrahedral bonding environments, and formation of boroxol rings), identified in the study of Pierce et al., were implemented in the Monte Carlo program. Their effects on the dissolution of borosilicate and aluminosilicate glasses were then evaluated individually and led to the following conclusions. (1) The dependence of the dissolution rate on the amount of non-bridging oxygens was found to be linear at all Si/B ratios and the accelerating effect of non-bridging oxygens was shown to increase with increasing Si/B ratio. (2) The formation of boroxol rings and of clusters of boroxol rings resulted in an increase of the dissolution rate at all Si/B ratios and, again, the extent of the rate increase was strongly dependent on the Si/B ratio. (3) For aluminosilicate glasses, the implementation of the aluminum avoidance rule was found to increase the rate of dissolution relative to that obtained for a random distribution. In the second part of this work, Monte Carlo simulations were performed to model the dissolution of the NeB glasses in dilute conditions. One of the conclusions that emerged from the study of Pierce et al. was

Parental Education and Family Dissolution: A Cross‐National and Cohort Comparison

PubMed Central

Härkönen, Juho

2018-01-01

This is the first study to systematically analyze whether the association between parental education and family dissolution varies cross‐nationally and over time. The authors use meta‐analytic tools to study cross‐national variation between 17 countries with data from the Generations and Gender Study and Harmonized Histories. The association shows considerable cross‐national variation, but is positive in most countries. The association between parental education and family dissolution has become less positive or even negative in six countries. The findings show that the association between parental education and family dissolution is generally positive or nil, even if the association between own education and family dissolution is in many countries increasingly negative. The authors find suggestive evidence that the association is related to the crude divorce rate, but not to the generosity of the welfare state in these countries. The implications of these findings for understanding the stratification in family dissolution are discussed. PMID:29657335

Hydrogeomorphic and ecological control on carbonate dissolution in a patterned landscape in South Florida

NASA Astrophysics Data System (ADS)

Dong, X.; Heffernan, J. B.; Murray, A. B.; Cohen, M. J.; Martin, J. B.

2016-12-01

The evolution of the critical zone both shapes and reflects hydrologic, geochemical, and ecological processes. These interactions are poorly understood in karst landscapes with highly soluble bedrock. In this study, we used the regular-dispersed wetland basins of Big Cypress National Preserve in Florida as a focal case to model the hydrologic, geochemical, and biological mechanisms that affect soil development in karst landscapes. We addressed two questions: (1) What is the minimum timescale for wetland basin development, and (2) do changes in soil depth feed back on dissolution processes and if so by what mechanism? We developed an atmosphere-water-soil model with coupled water-solute transport, incorporating major ion equilibria and kinetic non-equilibrium chemistry, and biogenic acid production via roots distributed through the soil horizon. Under current Florida climate, weathering to a depth of 2 m (a typical depth of wetland basins) would take 4000 6000 yrs, suggesting that landscape pattern could have origins as recent as the most recent stabilization of sea level. Our model further illustrates that interactions between ecological and hydrologic processes influence the rate and depth-dependence of weathering. Absent inundation, dissolution rate decreased exponentially with distance from the bedrock to groundwater table. Inundation generally increased bedrock dissolution, but surface water chemistry and residence time produced complex and non-linear effects on dissolution rate. Biogenic acidity accelerated the dissolution rate by 50 and 1,000 times in inundated and exposed soils. Phase portrait analysis indicated that exponential decreases in bedrock dissolution rate with soil depth could produce stable basin depths. Negative feedback between hydro-period and total basin volume could stabilize the basin radius, but the lesser strength of this mechanism may explain the coalescence of wetland basins observed in some parts of the Big Cypress Landscape.

Biomimetic Dissolution: A Tool to Predict Amorphous Solid Dispersion Performance.

PubMed

Puppolo, Michael M; Hughey, Justin R; Dillon, Traciann; Storey, David; Jansen-Varnum, Susan

2017-11-01

The presented study describes the development of a membrane permeation non-sink dissolution method that can provide analysis of complete drug speciation and emulate the in vivo performance of poorly water-soluble Biopharmaceutical Classification System class II compounds. The designed membrane permeation methodology permits evaluation of free/dissolved/unbound drug from amorphous solid dispersion formulations with the use of a two-cell apparatus, biorelevant dissolution media, and a biomimetic polymer membrane. It offers insight into oral drug dissolution, permeation, and absorption. Amorphous solid dispersions of felodipine were prepared by hot melt extrusion and spray drying techniques and evaluated for in vitro performance. Prior to ranking performance of extruded and spray-dried felodipine solid dispersions, optimization of the dissolution methodology was performed for parameters such as agitation rate, membrane type, and membrane pore size. The particle size and zeta potential were analyzed during dissolution experiments to understand drug/polymer speciation and supersaturation sustainment of felodipine solid dispersions. Bland-Altman analysis was performed to measure the agreement or equivalence between dissolution profiles acquired using polymer membranes and porcine intestines and to establish the biomimetic nature of the treated polymer membranes. The utility of the membrane permeation dissolution methodology is seen during the evaluation of felodipine solid dispersions produced by spray drying and hot melt extrusion. The membrane permeation dissolution methodology can suggest formulation performance and be employed as a screening tool for selection of candidates to move forward to pharmacokinetic studies. Furthermore, the presented model is a cost-effective technique.

Modeling spray/puddle dissolution processes for deep-ultraviolet acid-hardened resists

NASA Astrophysics Data System (ADS)

Hutchinson, John M.; Das, Siddhartha; Qian, Qi-De; Gaw, Henry T.

1993-10-01

A study of the dissolution behavior of acid-hardened resists (AHR) was undertaken for spray and spray/puddle development processes. The Site Services DSM-100 end-point detection system is used to measure both spray and puddle dissolution data for a commercially available deep-ultraviolet AHR resist, Shipley SNR-248. The DSM allows in situ measurement of dissolution rate on the wafer chuck and hence allows parameter extraction for modeling spray and puddle processes. The dissolution data for spray and puddle processes was collected across a range of exposure dose and postexposure bake temperature. The development recipe was varied to decouple the contribution of the spray and puddle modes to the overall dissolution characteristics. The mechanisms involved in spray versus puddle dissolution and the impact of spray versus puddle dissolution on process performance metrics has been investigated. We used the effective-dose-modeling approach and the measurement capability of the DSM-100 and developed a lumped parameter model for acid-hardened resists that incorporates the effects of exposure, postexposure bake temperature and time, and development condition. The PARMEX photoresist-modeling program is used to determine parameters for the spray and for the puddle process. The lumped parameter AHR model developed showed good agreement with experimental data.

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2004-01-01

Dissolution and precipitation rates of brucite (Mg(OH) 2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10 -4 to 3 M), saturation index (-12 < log Ω < 0.4) and aqueous magnesium concentrations (10 -6 to 5·10 -4 M). Brucite surface charge and isoelectric point (pH IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m 2) and lack of dependence on ionic strength predicts the dominance of >MgOH 2+ species at pH < 8 and their progressive replacement by >MgOH° and >MgO - as pH increases to 10-12. Rates are proportional to the square of >MgOH 2+ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH 2+ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity: R=k Mg+ · {>MgOH 2+} 2 · (1-Ω 2) where kMg+ is the dissolution rate constant, {> i} is surface species concentration (mol/m 2), and Ω is the solution saturation index with respect to brucite. Measurements of nonsteady state brucite dissolution rates, in response to cycling the pH from 12 to 2 (pH-jump experiments), indicate the important role of surface hydroxylation — that leads to the formation of Mg oxo or -hydroxo complexes — in the formation of dissolution-active sites. Replacement of water molecules by these oxygen donor complexes in the Mg coordination sphere

Spousal Dissimilarity, Race, and Marital Dissolution

ERIC Educational Resources Information Center

Clarkwest, Andrew

2007-01-01

I test the claims that spousal differences in ideational, behavioral, and other traits contribute to elevated rates of marital dissolution among African Americans. Using data from 3 waves of the National Survey of Families and Households (N = 5,424), I find that African American spouses experience high levels of dissimilarity in traits that may…

Increasing dissolution of trospium chloride by co-crystallization with urea

NASA Astrophysics Data System (ADS)

Skořepová, Eliška; Hušák, Michal; Čejka, Jan; Zámostný, Petr; Kratochvíl, Bohumil

2014-08-01

The search for various solid forms of an active pharmaceutical ingredient (API) is an important step in drug development. Our aim was to prepare co-crystals of trospium chloride, an anticholinergic drug used for the treatment of incontinence, and to investigate if they have advantageous properties for drug formulation. Phase identification was done by powder X-ray diffraction and single-crystal X-ray diffraction. The chemical composition was verified by solution NMR and the dissolution rate of the prepared phases was studied by IDR (intrinsic dissolution rate). For further analysis of phase stability and transitions, combined thermal analysis and temperature-resolved X-ray powder diffraction were used. Urea was selected as a co-crystallization partner. Trospium chloride urea (1:1) co-crystal was prepared by a solvent evaporation. From single-crystal data, the co-crystal structure was solved in a space group P21/c and compared to previously published structures of trospium chloride. Intrinsic dissolution rate revealed that the co-crystal dissolves 32% faster than pure API. However, its low thermal and pressure stability makes it a challenging choice for the final drug formulation.

Experimental investigation of the dissolution of fractures. From early stage instability to phase diagram

NASA Astrophysics Data System (ADS)

Osselin, Florian; Budek, Agnieszka; Cybulski, Olgierd; Kondratiuk, Pawel; Garstecki, Piotr; Szymczak, Piotr

2016-04-01

Dissolution of natural rocks is a fundamental geological process and a key part of landscape formation and weathering processes. Moreover, in current hot topics like Carbon Capture and Storage or Enhanced Oil Recovery, mastering dissolution of the host rock is fundamental for the efficiency and the security of the operation. The basic principles of dissolution are well-known and the theory of the reactive infiltration instability has been extensively studied. However, the experimental aspect has proved very challenging because of the strong dependence of the outcome with pore network, chemical composition, flow rate... In this study we are trying to tackle this issue by using a very simple and efficient device consisting of a chip of pure gypsum inserted between two polycarbonate plates and subjected to a constant flow rate of pure water. Thanks to this device, we are able to control all parameters such as flow rate, fracture aperture, roughness of the walls... but also to observe in situ the progression of the dissolution thanks to the transparency of the polycarbonate which is impossible with 3D rocks. We have been using this experimental set-up to explore and investigate all aspects of the dissolution in a fracture, such as initial instability and phase diagram of different dissolution patterns, and to compare it with theory and simulations, yielding very good agreement and interesting feedbacks on the coupling between flow and chemistry in geological media

Solid-state characterization and dissolution properties of meloxicam-moringa coagulant-PVP ternary solid dispersions.

PubMed

Noolkar, Suhail B; Jadhav, Namdeo R; Bhende, Santosh A; Killedar, Suresh G

2013-06-01

The effect of ternary solid dispersions of poor water-soluble NSAID meloxicam with moringa coagulant (obtained by salt extraction of moringa seeds) and polyvinylpyrrolidone on the in vitro dissolution properties has been investigated. Binary (meloxicam-moringa and meloxicam-polyvinylpyrrolidone (PVP)) and ternary (meloxicam-moringa-PVP) systems were prepared by physical kneading and ball milling and characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and X-ray diffractometry. The in vitro dissolution behavior of meloxicam from the different products was evaluated by means of United States Pharmacopeia type II dissolution apparatus. The results of solid-state studies indicated the presence of strong interactions between meloxicam, moringa, and PVP which were of totally amorphous nature. All ternary combinations were significantly more effective than the corresponding binary systems in improving the dissolution rate of meloxicam. The best performance in this respect was given by the ternary combination employing meloxicam-moringa-PVP ratio of [1:(3:1)] prepared by ball milling, with about six times increase in percent dissolution rate, whereas meloxicam-moringa (1:3) and meloxicam-PVP (1:4) prepared by ball milling improved dissolution of meloxicam by almost 3- and 2.5-folds, respectively. The achieved excellent dissolution enhancement of meloxicam in the ternary systems was attributed to the combined effects of impartation of hydrophilic characteristic by PVP, as well as to the synergistic interaction between moringa and PVP.

Electrochemical Dissolution of Tungsten Carbide in NaCl-KCl-Na2WO4 Molten Salt

NASA Astrophysics Data System (ADS)

Zhang, Liwen; Nie, Zuoren; Xi, Xiaoli; Ma, Liwen; Xiao, Xiangjun; Li, Ming

2018-02-01

Tungsten carbide was utilized as anode to extract tungsten in a NaCl-KCl-Na2WO4 molten salt, and the electrochemical dissolution was investigated. Although the molten salt electrochemical method is a short process method of tungsten extraction from tungsten carbide in one step, the dissolution efficiency and current efficiency are quite low. In order to improve the dissolution rate and current efficiency, the sodium tungstate was added as the active substance. The dissolution rate, the anode current efficiency, and the cathode current efficiency were calculated with different contents of sodium tungstate addition. The anodes prior to and following the reaction, as well as the product, were analyzed through X-ray diffraction, scanning electron microscopy, and energy dispersive spectrometry. The results demonstrated that the sodium tungstate could improve the dissolution rate and the current efficiency, due to the addition of sodium tungstate decreasing the charge transfer resistance in the electrolysis system. Due to the fact that the addition of sodium tungstate could remove the carbon during electrolysis, pure tungsten powders with 100 nm diameter were obtained when the content of sodium tungstate was 1.0 pct.

In situ dissolution analysis of pharmaceutical dosage forms using coherent anti-Stokes Raman scattering (CARS) microscopy

NASA Astrophysics Data System (ADS)

Fussell, A. L.; Garbacik, E. T.; Löbmann, K.; Offerhaus, H. L.; Kleinebudde, P.; Strachan, C. J.

2014-02-01

A custom-built intrinsic flow-through dissolution setup was developed and incorporated into a home-built CARS microscope consisting of a synchronously pumped optical parametric oscillator (OPO) and an inverted microscope with a 20X/0.5NA objective. CARS dissolution images (512×512 pixels) were collected every 1.12s for the duration of the dissolution experiment. Hyperspectral CARS images were obtained pre- and postdissolution by rapidly imaging while sweeping the wavelength of the OPO in discrete steps so that each frame in the data stack corresponds to a vibrational frequency. An image-processing routine projects this hyperspectral data into a single image wherein each compound appears with a unique color. Dissolution was conducted using theophylline and cimetidine-naproxen co-amorphous mixture. After 15 minutes of theophylline dissolution, hyperspectral imaging showed a conversion of theophylline anhydrate to the monohydrate, confirmed by a peak shift in the CARS spectra. CARS dissolution images showed that monohydrate crystal growth began immediately and reached a maximum with complete surface coverage at about 300s. This result correlated with the UV dissolution data where surface crystal growth on theophylline compacts resulted in a rapidly reducing dissolution rate during the first 300s. Co-amorphous cimetidinenaproxen didn't appear to crystallize during dissolution. We observed solid-state conversions on the compact's surface in situ during dissolution. Hyperspectral CARS imaging allowed visual discrimination between the solid-state forms on the compact's surface. In the case of theophylline we were able to correlate the solid-state change with a change in dissolution rate.

Coupled alkali feldspar dissolution and secondary mineral precipitation in batch systems: 4. Numerical modeling of kinetic reaction paths

NASA Astrophysics Data System (ADS)

Zhu, Chen; Lu, Peng; Zheng, Zuoping; Ganor, Jiwchar

2010-07-01

This paper explores how dissolution and precipitation reactions are coupled in batch reactor experimental systems at elevated temperatures. This is the fourth paper in our series of "Coupled Alkali Feldspar Dissolution and Secondary Mineral Precipitation in Batch Systems". In our third paper, we demonstrated via speciation-solubility modeling that partial equilibrium between secondary minerals and aqueous solutions was not attained in feldspar hydrolysis batch reactors at 90-300 °C and that a strong coupling between dissolution and precipitation reactions follows as a consequence of the slower precipitation of secondary minerals ( Zhu and Lu, 2009). Here, we develop this concept further by using numerical reaction path models to elucidate how the dissolution and precipitation reactions are coupled. Modeling results show that a quasi-steady state was reached. At the quasi-steady state, dissolution reactions proceeded at rates that are orders of magnitude slower than the rates measured at far from equilibrium. The quasi-steady state is determined by the relative rate constants, and strongly influenced by the function of Gibbs free energy of reaction ( ΔG) in the rate laws. To explore the potential effects of fluid flow rates on the coupling of reactions, we extrapolate a batch system ( Ganor et al., 2007) to open systems and simulated one-dimensional reactive mass transport for oligoclase dissolution and kaolinite precipitation in homogeneous porous media. Different steady states were achieved at different locations along the one-dimensional domain. The time-space distribution and saturation indices (SI) at the steady states were a function of flow rates for a given kinetic model. Regardless of the differences in SI, the ratio between oligoclase dissolution rates and kaolinite precipitation rates remained 1.626, as in the batch system case ( Ganor et al., 2007). Therefore, our simulation results demonstrated coupling among dissolution, precipitation, and flow rates

Dissolution enhancement of gliclazide using pH change approach in presence of twelve stabilizers with various physico-chemical properties.

PubMed

Talari, Roya; Varshosaz, Jaleh; Mostafavi, Seyed Abolfazl; Nokhodchi, Ali

2009-01-01

The micronization using milling process to enhance dissolution rate is extremely inefficient due to a high energy input, and disruptions in the crystal lattice which can cause physical or chemical instability. Therefore, the aim of the present study is to use in situ micronization process through pH change method to produce micron-size gliclazide particles for fast dissolution hence better bioavailability. Gliclazide was recrystallized in presence of 12 different stabilizers and the effects of each stabilizer on micromeritic behaviors, morphology of microcrystals, dissolution rate and solid state of recrystallized drug particles were investigated. The results showed that recrystallized samples showed faster dissolution rate than untreated gliclazide particles and the fastest dissolution rate was observed for the samples recrystallized in presence of PEG 1500. Some of the recrystallized drug samples in presence of stabilizers dissolved 100% within the first 5 min showing at least 10 times greater dissolution rate than the dissolution rate of untreated gliclazide powders. Micromeritic studies showed that in situ micronization technique via pH change method is able to produce smaller particle size with a high surface area. The results also showed that the type of stabilizer had significant impact on morphology of recrystallized drug particles. The untreated gliclazide is rod or rectangular shape, whereas the crystals produced in presence of stabilizers, depending on the type of stabilizer, were very fine particles with irregular, cubic, rectangular, granular and spherical/modular shape. The results showed that crystallization of gliclazide in presence of stabilizers reduced the crystallinity of the samples as confirmed by XRPD and DSC results. In situ micronization of gliclazide through pH change method can successfully be used to produce micron-sized drug particles to enhance dissolution rate.

Kinetics of dissolution of UO2 in nitric acid solutions: A multiparametric study of the non-catalysed reaction

NASA Astrophysics Data System (ADS)

Cordara, T.; Szenknect, S.; Claparede, L.; Podor, R.; Mesbah, A.; Lavalette, C.; Dacheux, N.

2017-12-01

UO2 pellets were prepared by densification of oxides obtained from the conversion of the oxalate precursor. Then characterized in order to perform a multiparametric study of the dissolution in nitric acid medium. In this frame, for each sample, the densification rate, the grain size and the specific surface area of the prepared pellets were determined prior to the final dissolution experiments. By varying the concentration of the nitric acid solution and temperature, three different and successive steps were identified during the dissolution. Under the less aggressive conditions considered, a first transient step corresponding to the dissolution of the most reactive phases was observed at the solid/solution interface. Then, for all the tested conditions, a steady state step was established during which the normalised dissolution rate was found to be constant. It was followed by a third step characterized by a strong and continuous increase of the normalised dissolution rate. The duration of the steady state, also called "induction period", was found to vary drastically as a function of the HNO3 concentration and temperature. However, independently of the conditions, this steady state step stopped at almost similar dissolved material weight loss and dissolved uranium concentration. During the induction period, no important evolution of the topology of the solid/liquid interface was evidenced authorizing the use of the starting reactive specific surface area to evaluate the normalised dissolution rates thus the chemical durability of the sintered pellets. From the multiparametric study of UO2 dissolution proposed, oxidation of U(IV) to U(VI) by nitrate ions at the solid/liquid interface constitutes the limiting step in the overall dissolution mechanism associated to this induction period.

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

USGS Publications Warehouse

Tuttle, M.L.W.; Breit, G.N.

2009-01-01

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C

12 CFR 546.4 - Voluntary dissolution.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 12 Banks and Banking 6 2014-01-01 2012-01-01 true Voluntary dissolution. 546.4 Section 546.4 Banks... ASSOCIATIONS-MERGER, DISSOLUTION, REORGANIZATION, AND CONVERSION § 546.4 Voluntary dissolution. A Federal savings association's board of directors may propose a plan for dissolution of the association. The plan...

12 CFR 546.4 - Voluntary dissolution.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 12 Banks and Banking 6 2013-01-01 2012-01-01 true Voluntary dissolution. 546.4 Section 546.4 Banks... ASSOCIATIONS-MERGER, DISSOLUTION, REORGANIZATION, AND CONVERSION § 546.4 Voluntary dissolution. A Federal savings association's board of directors may propose a plan for dissolution of the association. The plan...

12 CFR 546.4 - Voluntary dissolution.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 12 Banks and Banking 5 2010-01-01 2010-01-01 false Voluntary dissolution. 546.4 Section 546.4... ASSOCIATIONS-MERGER, DISSOLUTION, REORGANIZATION, AND CONVERSION § 546.4 Voluntary dissolution. A Federal savings association's board of directors may propose a plan for dissolution of the association. The plan...

12 CFR 146.4 - Voluntary dissolution.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 12 Banks and Banking 1 2014-01-01 2014-01-01 false Voluntary dissolution. 146.4 Section 146.4... ASSOCIATIONS-MERGER, DISSOLUTION, REORGANIZATION, AND CONVERSION § 146.4 Voluntary dissolution. (a) A Federal savings association's board of directors may propose a plan for dissolution of the association. The plan...

12 CFR 146.4 - Voluntary dissolution.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 12 Banks and Banking 1 2013-01-01 2013-01-01 false Voluntary dissolution. 146.4 Section 146.4... ASSOCIATIONS-MERGER, DISSOLUTION, REORGANIZATION, AND CONVERSION § 146.4 Voluntary dissolution. (a) A Federal savings association's board of directors may propose a plan for dissolution of the association. The plan...

12 CFR 546.4 - Voluntary dissolution.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 12 Banks and Banking 5 2011-01-01 2011-01-01 false Voluntary dissolution. 546.4 Section 546.4... ASSOCIATIONS-MERGER, DISSOLUTION, REORGANIZATION, AND CONVERSION § 546.4 Voluntary dissolution. A Federal savings association's board of directors may propose a plan for dissolution of the association. The plan...

12 CFR 546.4 - Voluntary dissolution.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 12 Banks and Banking 6 2012-01-01 2012-01-01 false Voluntary dissolution. 546.4 Section 546.4... ASSOCIATIONS-MERGER, DISSOLUTION, REORGANIZATION, AND CONVERSION § 546.4 Voluntary dissolution. A Federal savings association's board of directors may propose a plan for dissolution of the association. The plan...

12 CFR 146.4 - Voluntary dissolution.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 12 Banks and Banking 1 2012-01-01 2012-01-01 false Voluntary dissolution. 146.4 Section 146.4... ASSOCIATIONS-MERGER, DISSOLUTION, REORGANIZATION, AND CONVERSION § 146.4 Voluntary dissolution. (a) A Federal savings association's board of directors may propose a plan for dissolution of the association. The plan...

Laboratory studies of 2H evaporator scale dissolution in dilute nitric acid

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

Oji, L.

The rate of 2H evaporator scale solids dissolution in dilute nitric acid has been experimentally evaluated under laboratory conditions in the SRNL shielded cells. The 2H scale sample used for the dissolution study came from the bottom of the evaporator cone section and the wall section of the evaporator cone. The accumulation rate of aluminum and silicon, assumed to be the two principal elemental constituents of the 2H evaporator scale aluminosilicate mineral, were monitored in solution. Aluminum and silicon concentration changes, with heating time at a constant oven temperature of 90 deg C, were used to ascertain the extent ofmore » dissolution of the 2H evaporator scale mineral. The 2H evaporator scale solids, assumed to be composed of mostly aluminosilicate mineral, readily dissolves in 1.5 and 1.25 M dilute nitric acid solutions yielding principal elemental components of aluminum and silicon in solution. The 2H scale dissolution rate constant, based on aluminum accumulation in 1.5 and 1.25 M dilute nitric acid solution are, respectively, 9.21E-04 ± 6.39E-04 min{sup -1} and 1.07E-03 ± 7.51E-05 min{sup -1}. Silicon accumulation rate in solution does track the aluminum accumulation profile during the first few minutes of scale dissolution. It however diverges towards the end of the scale dissolution. This divergence therefore means the aluminum-to-silicon ratio in the first phase of the scale dissolution (non-steady state conditions) is different from the ratio towards the end of the scale dissolution. Possible causes of this change in silicon accumulation in solution as the scale dissolution progresses may include silicon precipitation from solution or the 2H evaporator scale is a heterogeneous mixture of aluminosilicate minerals with several impurities. The average half-life for the decomposition of the 2H evaporator scale mineral in 1.5 M nitric acid is 12.5 hours, while the half-life for the decomposition of the 2H evaporator scale in 1.25 M nitric acid is

Modelling and shadowgraph imaging of cocrystal dissolution and assessment of in vitro antimicrobial activity for sulfadimidine/4-aminosalicylic acid cocrystals.

PubMed

Serrano, Dolores R; Persoons, Tim; D'Arcy, Deirdre M; Galiana, Carolina; Dea-Ayuela, Maria Auxiliadora; Healy, Anne Marie

2016-06-30

The aim of this work was to evaluate the influence of crystal habit on the dissolution and in vitro antibacterial and anitiprotozoal activity of sulfadimidine:4-aminosalicylic acid cocrystals. Cocrystals were produced via milling or solvent mediated processes. In vitro dissolution was carried out in the flow-through apparatus, with shadowgraph imaging and mechanistic mathematical models used to observe and simulate particle dissolution. In vitro activity was tested using agar diffusion assays. Cocrystallisation via milling produced small polyhedral crystals with antimicrobial activity significantly higher than sulfadimidine alone, consistent with a fast dissolution rate which was matched only by cocrystals which were milled following solvent evaporation. Cocrystallisation by solvent evaporation (ethanol, acetone) or spray drying produced flattened, plate-like or quasi-spherical cocrystals, respectively, with more hydrophobic surfaces and greater tendency to form aggregates in aqueous media, limiting both the dissolution rate and in vitro activity. Deviation from predicted dissolution profiles was attributable to aggregation behaviour, supported by observations from shadowgraph imaging. Aggregation behaviour during dissolution of cocrystals with different habits affected the dissolution rate, consistent with in vitro activity. Combining mechanistic models with shadowgraph imaging is a valuable approach for dissolution process analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of sodium lauryl sulfate in dissolution media on dissolution of hard gelatin capsule shells.

PubMed

Zhao, Fang; Malayev, Vyacheslav; Rao, Venkatramana; Hussain, Munir

2004-01-01

Sodium lauryl sulfate (SLS) is a commonly used surfactant in dissolution media for poorly water soluble drugs. However, it has occasionally been observed that SLS negatively impacts the dissolution of drug products formulated in gelatin capsules. This study investigated the effect of SLS on the dissolution of hard gelatin capsule shells. The USP paddle method was used with online UV monitoring at 214 nm (peptide bond). Empty size #0 capsule shells were held to the bottom of the dissolution vessel by magnetic three-prong sinkers. SLS significantly slowed down the dissolution of gelatin shells at pH < 5. Visually, the gelatin shells transformed into some less-soluble precipitate under these conditions. This precipitate was found to contain a higher sulfur content than the gelatin control sample by elemental analysis, indicating that SLS is part of the precipitate. Additionally, the slowdown of capsule shell dissolution was shown to be dependent on the SLS concentration and the ionic strength of the media. SLS interacts with gelatin to form a less-soluble precipitate at pH < 5. The use of SLS in dissolution media at acidic pH should be carefully evaluated for gelatin capsule products.

Effect of Food Thickener on Dissolution and Laxative Activity of Magnesium Oxide Tablets in Mice.

PubMed

Tomita, Takashi; Goto, Hidekazu; Yoshimura, Yuya; Kato, Kazushige; Yoshida, Tadashi; Tanaka, Katsuya; Sumiya, Kenji; Kohda, Yukinao

2016-01-01

The present study examined the dissolution of magnesium oxide (MgO) from MgO tablets placed in a food thickening agent (food thickener) and its effects on laxative activity. We prepared mixtures of MgO tablets suspended in an aqueous suspension and food thickeners in order to evaluate the dissolution of MgO. The results of the dissolution tests revealed that agar-based food thickeners did not affect the MgO dissolution. In contrast, some xanthan gum-based food-thickener products show dissolution rates with certain mixtures containing disintegrated MgO tablets suspended in a food thickener that decrease over time. However, other xanthan gum-based food-thickener products show dissolution rates that decrease immediately after mixing, regardless of the time they were allowed to stand. In order to investigate the laxative activity of MgO, we orally administered a mixture of MgO suspension and food thickener to mice and observed their bowel movements. The animal experiments showed that when agar-based food thickeners were used, the laxative activity of MgO was not affected, but it decreased when xanthan gum-based food thickeners were used.

Aggregation, sedimentation, dissolution and bioavailability of ...

EPA Pesticide Factsheets

To understand their fate and transport in estuarine systems, the aggregation, sedimentation, and dissolution of CdSe quantum dots (QDs) in seawater were investigated. Hydrodynamic size increased from 40 to 60 nm to >1 mm within 1 h in seawater, and the aggregates were highly polydispersed. Their sedimentation rates in seawater were measured to be 4–10 mm/day. Humic acid (HA), further increased their size and polydispersity, and slowed sedimentation. Light increased their dissolution and release of dissolved Cd. The ZnS shell also slowed release of Cd ions. With sufficient light, HA increased the dissolution of QDs, while with low light, HA alone did not change their dissolution. The benthic zone in estuarine systems is the most probable long-term destination of QDs due to aggregation and sedimentation. The bioavailability of was evaluated using the mysid Americamysis bahia. The 7-day LC50s of particulate and dissolved QDs were 290 and 23 μg (total Cd)/L, respectively. For mysids, the acute toxicity appears to be from Cd ions; however, research on the effects of QDs should be conducted with other organisms where QDs may be lodged in critical tissues such as gills or filtering apparatus and Cd ions may be released and delivered directly to those tissues. Because of their increasing use and value to society, cadmium-based quantum dots (QDs) will inevitably find their way into marine systems. In an effort to understand the fate and transport of CdSe QDs in estuar

Dissolution of first unions in Colombia, Panama, and Peru.

PubMed

Goldman, N

1981-11-01

An analysis of marital histories from World Fertility Survey data in Colombia, Panama, and Peru indicates a high level of union dissolution: the probabilities of a first union ending by separation within twenty years of the onset of union equal .27, .40, and .18 in the three countries respectively. Dissolution probabilities are especially high among women with young ages at first union and among women residing in urban areas. For all subgroups studied, consensual unions are characterized by several times the risk of separation of legal marriages. Consensual unions are especially frequent among women in rural areas, women with little education and women who enter unions at young ages. The different prevalence of consensual unions among the different subgroups affects the associations between union stability and various correlates so that it becomes essential to investigate the factors affecting union stability for both consensual unions and legal marriages. In spite of high dissolution rates, remarriage rates in all three countries are also high, as are the percentages of time spent in a union. Hence, the potential effects of voluntary disruption of unions on fertility appear to be modest.

Generation and Performance of Automated Jarosite Mineral Detectors for Vis/NIR Spectrometers at Mars

NASA Technical Reports Server (NTRS)

Gilmore, M. S.; Bornstein, B.; Merrill, M. D.; Castano, R.; Greenwood, J. P.

2005-01-01

Sulfate salt discoveries at the Eagle and Endurance craters in Meridiani Planum by the Mars Exploration Rover Opportunity have proven mineralogically the existence and involvement of water in Mars past. Visible and near infrared spectrometers like the Mars Express OMEGA, the Mars Reconnaissance Orbiter CRISM and the 2009 Mars Science Laboratory Rover cameras are powerful tools for the identification of water-bearing salts and other high priority minerals at Mars. The increasing spectral resolution and rover mission lifetimes represented by these missions currently necessitate data compression in order to ease downlink restrictions. On board data processing techniques can be used to guide the selection, measurement and return of scientifically important data from relevant targets, thus easing bandwidth stress and increasing scientific return. We have developed an automated support vector machine (SVM) detector operating in the visible/near-infrared (VisNIR, 300-2500 nm) spectral range trained to recognize the mineral jarosite (typically KFe3(SO4)2(OH)6), positively identified by the Mossbauer spectrometer at Meridiani Planum. Additional information is included in the original extended abstract.

Modeling NAPL dissolution from pendular rings in idealized porous media

NASA Astrophysics Data System (ADS)

Huang, Junqi; Christ, John A.; Goltz, Mark N.; Demond, Avery H.

2015-10-01

The dissolution rate of nonaqueous phase liquid (NAPL) often governs the remediation time frame at subsurface hazardous waste sites. Most formulations for estimating this rate are empirical and assume that the NAPL is the nonwetting fluid. However, field evidence suggests that some waste sites might be organic wet. Thus, formulations that assume the NAPL is nonwetting may be inappropriate for estimating the rates of NAPL dissolution. An exact solution to the Young-Laplace equation, assuming NAPL resides as pendular rings around the contact points of porous media idealized as spherical particles in a hexagonal close packing arrangement, is presented in this work to provide a theoretical prediction for NAPL-water interfacial area. This analytic expression for interfacial area is then coupled with an exact solution to the advection-diffusion equation in a capillary tube assuming Hagen-Poiseuille flow to provide a theoretical means of calculating the mass transfer rate coefficient for dissolution at the NAPL-water interface in an organic-wet system. A comparison of the predictions from this theoretical model with predictions from empirically derived formulations from the literature for water-wet systems showed a consistent range of values for the mass transfer rate coefficient, despite the significant differences in model foundations (water wetting versus NAPL wetting, theoretical versus empirical). This finding implies that, under these system conditions, the important parameter is interfacial area, with a lesser role played by NAPL configuration.

The effect of electrolytes on dolomite dissolution: nanoscale observations using in situ Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Urosevic, Maja; Ruiz-Agudo, Encarnacion; Putnis, Christine V.; Cardell, Carolina; Rodriguez-Navarro, Carlos; Putnis, Andrew

2010-05-01

Dissolution of carbonate minerals is one of the main chemical reactions occurring at shallow levels in the crust of the Earth and has a paramount importance for a wide range of geological and biological processes. Calcite (CaCO3), and to a lesser extent dolomite (CaMg(CO3)2), are the major carbonate minerals in sedimentary rocks and building stone materials. The dissolution of calcite has been thoroughly investigated over a range of conditions and solution compositions. In contrast, dolomite dissolution studies have been traditionally hampered by its low reaction rates compared to calcite and its poorly constrained relationship between cation ordering and reactivity (Morse and Arvidson, 2002). Yet important questions like the so-called 'dolomite problem' (e.g. Higgins and Hu, 2005) remain unresolved and more experimental work is needed in order to understand the role of other dissolved species, such as soluble salts, on the kinetics and mechanism of dolomite dissolution and precipitation. We have explored the effect of different electrolytes on the dissolution rate of dolomite by using in situ Atomic Force Microcopy (AFM). Experiments were carried out by passing alkali halide, nitrate and sulfate salt solutions (NaCl, KCl, LiCl, NaI, NaNO3 and Na2SO4) with different ionic strengths (IS = 10-3, 10-2 and 10-1) over dolomite {1014} cleavage surfaces. We show that all electrolytes tested enhance dolomite dissolution. Moreover, the morphology and density of etch pits are controlled by the presence of different ions in solution. The etch pit spreading rate and dolomite dissolution rate depend on both (1) the nature of the electrolyte and (2) the ionic strength. This is in agreement with recent experimental studies on calcite dissolution (Ruiz-Agudo et al., 2010). This study highlights the role of electrolytes in dolomite dissolution and points to a common behavior for carbonate minerals. Our results suggest that soluble salts may play a critical role in the weathering of

Difference in the Dissolution Behaviors of Tablets Containing Polyvinylpolypyrrolidone (PVPP) Depending on Pharmaceutical Formulation After Storage Under High Temperature and Humid Conditions.

PubMed

Takekuma, Yoh; Ishizaka, Haruka; Sumi, Masato; Sato, Yuki; Sugawara, Mitsuru

Storage under high temperature and humid conditions has been reported to decrease the dissolution rate for some kinds of tablets containing polyvinylpolypyrrolidone (PVPP) as a disintegrant. The aim of this study was to elucidate the properties of pharmaceutical formulations with PVPP that cause a decrease in the dissolution rate after storage under high temperature and humid conditions by using model tablets with a simple composition. Model tablets, which consisted of rosuvastatin calcium or 5 simple structure compounds, salicylic acid, 2-aminodiphenylmethane, 2-aminobiphenyl, 2-(p-tolyl)benzoic acid or 4.4'-biphenol as principal agents, cellulose, lactose hydrate, PVPP and magnesium stearate as additives, were made by direct compression. The model tables were wrapped in paraffin papers and stored for 2 weeks at 40°C/75% relative humidity (RH). Dissolution tests were carried out by the paddle method in the Japanese Pharmacopoeia 16th edition. Model tablets with a simple composition were able to reproduce a decreased dissolution rate after storage at 40°C/75% RH. These tablets showed significantly decreased water absorption activities after storage. In the case of tablets without lactose hydrate by replacing with cellulose, a decreased dissolution rate was not observed. Carboxyl and amino groups in the structure of the principal agent were not directly involved in the decreased dissolution. 2-Benzylaniline tablets showed a remarkably decreased dissolution rate and 2-aminobiphenyl and 2-(p-tolyl)benzoic acid tablets showed slightly decreased dissolution rates, though 4,4'-biphenol tablets did not show a decrease dissolution rate. We demonstrated that additives and structure of the principal agent were involved in the decreased in dissolution rate for tablets with PVPP. The results suggested that one of the reasons for a decreased dissolution rate was the inclusion of lactose hydrate in tablets. The results also indicated that compounds as principal agents with low

25 CFR 11.605 - Dissolution.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 25 Indians 1 2013-04-01 2013-04-01 false Dissolution. 11.605 Section 11.605 Indians BUREAU OF... Domestic Relations § 11.605 Dissolution. (a) The Court of Indian Offenses shall enter a decree of dissolution of marriage if: (1) The court finds that the marriage is irretrievably broken, if the finding is...

25 CFR 11.605 - Dissolution.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 25 Indians 1 2011-04-01 2011-04-01 false Dissolution. 11.605 Section 11.605 Indians BUREAU OF... Domestic Relations § 11.605 Dissolution. (a) The Court of Indian Offenses shall enter a decree of dissolution of marriage if: (1) The court finds that the marriage is irretrievably broken, if the finding is...

25 CFR 11.605 - Dissolution.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 25 Indians 1 2014-04-01 2014-04-01 false Dissolution. 11.605 Section 11.605 Indians BUREAU OF... Domestic Relations § 11.605 Dissolution. (a) The Court of Indian Offenses shall enter a decree of dissolution of marriage if: (1) The court finds that the marriage is irretrievably broken, if the finding is...

25 CFR 11.605 - Dissolution.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 25 Indians 1 2012-04-01 2011-04-01 true Dissolution. 11.605 Section 11.605 Indians BUREAU OF... Domestic Relations § 11.605 Dissolution. (a) The Court of Indian Offenses shall enter a decree of dissolution of marriage if: (1) The court finds that the marriage is irretrievably broken, if the finding is...

Karst-on-a-chip: microfluidic studies of dissolution of a gypsum fracture

NASA Astrophysics Data System (ADS)

Szymczak, Piotr; Dutka, Filip; Osselin, Florian

2017-04-01

Dissolution of fractured and porous media introduces a positive feedback between fluid transport and chemical reactions at mineral surfaces leading to self-focusing of the flow in pronounced wormhole-like channels [1,2]. We study the flow-induced dissolution in a simple microfluidic setup, with a gypsum block inserted in between two polycarbonate plates, which is the simplest model of a fracture [3]. This gives us a unique opportunity to observe the evolution of the dissolution patterns in-situ and in real-time. By changing the flow rate and the aperture of the fracture we can scan a relatively wide range of Peclet and Damkohler numbers, characterizing the relative magnitude of advection, diffusion and reaction in the system. Additionally, as the aperture is increased, a transition is observed between the fractal and regular dissolution patterns. For small gaps, the patterns are ramified fractals. For larger gaps, the dissolution fingers are found to have regular forms of two different kinds: either linear (for high flow rates) or parabolic (for lower flow rates). The experiments are supplemented with numerical simulations and analytical modeling which allow for a better understanding of evolving flow patterns. In particular, we find the shapes and propagation velocities of dominant fingers for different widths of the system, flow rates and reaction rates. Finally, we comment on the link between the experimentally observed patterns and the natural karst systems - both cave conduits and epikarst solution pipes. [1] Hoefner, M. L. and Fogler, H. S. Pore evolution and channel formation during flow and reaction in porous media. AIChE J. 34, 45-54, 1988 [2] P. Szymczak, A. J. C. Ladd, Wormhole formation in dissolving fractures, J. Geophys. Res., 114, B06203, 2009 [3] F. Osselin, P. Kondratiuk, A Budek, O. Cybulski, P. Garstecki, P. Szymczak Microfluidic observation of the onset of reactive infiltration instability in an analog fracture, Geophys. Res. Lett., 43, 6907

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

DOE PAGES

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.; ...

2018-02-09

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

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

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

Dissolution flowsheet for high flux isotope reactor fuel

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

Foster, T.

2016-09-27

As part of the Spent Nuclear Fuel (SNF) processing campaign, H-Canyon is planning to begin dissolving High Flux Isotope Reactor (HFIR) fuel in late FY17 or early FY18. Each HFIR fuel core contains inner and outer fuel elements which were fabricated from uranium oxide (U 3O 8) dispersed in a continuous Al phase using traditional powder metallurgy techniques. Fuels fabricated in this manner, like other SNF’s processed in H-Canyon, dissolve by the same general mechanisms with similar gas generation rates and the production of H 2. The HFIR fuel cores will be dissolved and the recovered U will be down-blendedmore » into low-enriched U. HFIR fuel was previously processed in H-Canyon using a unique insert in both the 6.1D and 6.4D dissolvers. Multiple cores will be charged to the same dissolver solution maximizing the concentration of dissolved Al. The objective of this study was to identify flowsheet conditions through literature review and laboratory experimentation to safely and efficiently dissolve the HFIR fuel in H-Canyon. Laboratory-scale experiments were performed to evaluate the dissolution of HFIR fuel using both Al 1100 and Al 6061 T6 alloy coupons. The Al 1100 alloy was considered a representative surrogate which provided an upper bound on the generation of flammable (i.e., H 2) gas during the dissolution process. The dissolution of the Al 6061 T6 alloy proceeded at a slower rate than the Al 1100 alloy and was used to verify that the target Al concentration in solution could be achieved for the selected Hg concentration. Mass spectrometry and Raman spectroscopy were used to provide continuous monitoring of the concentration of H 2 and other permanent gases in the dissolution offgas allowing the development of H 2 generation rate profiles. The H 2 generation rates were subsequently used to evaluate if a full HFIR core could be dissolved in an H-Canyon dissolver without exceeding 60% of the calculated lower flammability limit (LFL) for H 2 at a given Hg

pH-Dependent silica nanoparticle dissolution and cargo release.

PubMed

Giovaninni, Giorgia; Moore, Colin J; Hall, Andrew J; Byrne, Hugh J; Gubala, Vladimir