Bio resorbability of the modified hydroxyapatite in Tris-HCL buffer

NASA Astrophysics Data System (ADS)

Golovanova, O. A.; Izmailov, R. R.; Ghyngazov, S. A.

2016-02-01

The solubility of carbonated hydroxyapatite powders and granulated carbonated hydroxyapatite produced from the synovial biofluid model solution has been studied. The kinetic characteristics of dissolution were determined. It was found that the solubility of carbonated hydroxyapatite is higher as compared to that of hydroxyapatite. The impact of the organic matrix on the rate of sample dissolution was revealed. For HA-gelatin composites, as the gelatin concentration grows, the dissolution rate becomes greater, and a sample of 6.0 g / L concentration has higher resorbability. The results of the research can be used to study the kinetics of dissolution and the biocompatibility of ceramic materials for medicine, namely for reconstructive surgery, dentistry, and development of drug delivery systems.

Dissolution enhancement of a model poorly water-soluble drug, atorvastatin, with ordered mesoporous silica: comparison of MSF with SBA-15 as drug carriers.

PubMed

Maleki, Aziz; Hamidi, Mehrdad

2016-01-01

The purpose of this study was to develop mesoporous silica materials incorporated with poorly water-soluble drug atorvastatin calcium (AC) in order to improve drug dissolution, and intended to be orally administrated. A comparison between 2D-hexagonal silica nanostructured SBA-15 and mesocellular siliceous foam (MSF) with continuous 3D pore system on drug release rate was investigated. AC-loaded mesoporous silicas were characterized thorough N2 adsorption-desorption analysis, Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC) and dynamic light scattering (DLS). Results demonstrated a successful incorporation of AC into the silica-based hosts. The results taken from the drug release tests were also analyzed using different parameters, namely similarity factor (f2), difference factor (f1), dissolution efficiency (DE%), mean dissolution rate (MDR) and dissolution time (tm%). It confirmed a significant enhancement in the release profile of atorvastatin calcium with SBA-15, and MSF as drug carrier. Moreover, in comparison with SBA-15, MSF showed faster release rate of AC in enzyme-free simulated gastric fluid (pH 1.2). We believed that our findings can help the use of mesoporous silica materials in improving bioavailability of poorly water-soluble drugs.

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.

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.

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

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.

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.

Pyrolysis-gas chromatography-mass spectrometry for studying N-vinyl-2-pyrrolidone-co-vinyl acetate copolymers and their dissolution behaviour.

PubMed

Chojnacka, Aleksandra; Ghaffar, Abdul; Feilden, Andrew; Treacher, Kevin; Janssen, Hans-Gerd; Schoenmakers, Peter

2011-11-14

Knowledge on the solubility behaviour and dissolution rate of speciality and commodity polymers is very important for the use of such materials in high-tech applications. We have developed methods for the quantification and characterization of dissolved copolymers of N-vinyl-2-pyrrolidone (VP) and vinyl acetate (VA) during dissolution in water. The methods are based on pyrolysis (Py) performed in a programmed-temperature vaporization injector with subsequent identification and quantification of the components in the pyrolysate using capillary gas chromatography-mass spectrometry (GC-MS). By injecting large volumes and applying cryo-focussing at the top of the column, low detection limits could be achieved. The monomer ratio was found to have the greatest effect on the dissolution rate of the PVP-co-VA copolymers. The material with the highest amount of VA (50%) dissolves significantly slower than the other grades. Size-exclusion chromatography (SEC) and Py-GC-MS were used to measure molecular weights and average chemical compositions, respectively. Combined off-line SEC//Py-GC-MS was used to determine the copolymer composition (VP/VA ratio), as a function of the molecular weight for the pure polymers. In the dissolution experiments, a constant VP/VA ratio across the dissolution curve was observed for all copolymers analysed. This suggests a random distribution of the two monomers over the molecules. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Comparative evaluation of ibuprofen/beta-cyclodextrin complexes obtained by supercritical carbon dioxide and other conventional methods.

PubMed

Hussein, Khaled; Türk, Michael; Wahl, Martin A

2007-03-01

The preparation of drug/cyclodextrin complexes is a suitable method to improve the dissolution of poor soluble drugs. The efficacy of the Controlled Particle Deposition (CPD) as a new developed method to prepare these complexes in a single stage process using supercritical carbon dioxide is therefore compared with other conventional methods. Ibuprofen/beta-cyclodextrin complexes were prepared with different techniques and characterized using FTIR-ATR spectroscopy, powder X-ray diffractometry (PXRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). In addition, the influences of the processing technique on the drug content (HPLC) and the dissolution behavior were studied. Employing the CPD-process resulted in a drug content of 2.8+/-0.22 wt.% in the carrier. The material obtained by CPD showed an improved dissolution rate of ibuprofen at pH 5 compared with the pure drug and its physical mixture with beta-cyclodextrin. In addition CPD material displays the highest dissolution (93.5+/- 2.89% after 75 min) compared to material obtained by co-precipitation (61.3 +/-0.52%) or freeze-drying (90.6 +/-2.54%). This study presents the CPD-technique as a well suitable method to prepare a drug/beta-cyclodextrin complex with improved drug dissolution compared to the pure drug and materials obtained by other methods.

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 analysis would provide a basis for comparison of different rate models and allow for a better means of quantifiably comparing the various models.« less

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 a basis for comparison of different rate models and allow for a better means of quantifiably comparing the various models.

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 analysis would provide a basis for comparison of different rate models and allow for a better means of quantifiably comparing the various models.« 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.

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

Effects of acid deposition on dissolution of carbonate stone during summer storms in the Adirondack Mountains, New York, 1987-89

USGS Publications Warehouse

Schuster, Paul F.; Reddy, Michael M.; Sherwood, S.I.

1994-01-01

This study is part of a long-term research program designed to identify and quantify acid rain damage to carbonate stone. Acidic deposition accelerates the dissolution of carbonate-stone monuments and building materials. Sequential sampling of runoff from carbonate-stone (marble) and glass (reference) microcatchments in the Adirondack Mountains in New York State provided a detailed record of the episodic fluctuations in rain rate and runoff chemistry during individual summer storms. Rain rate and chemical concentrations from carbonate-stone and glass runoff fluctuated three to tenfold during storms. Net calcium-ion concentrations from the carbonatestone runoff, a measure of stone dissolution, typically fluctuated twofold during these storms. High net sulfate and net calcium concentrations in the first effective runoff at the start of a storm indicated that atmospheric pollutants deposited on the stone surface during dry periods formed calcium sulfate minerals, an important process in carbonate stone dissolution. Dissolution of the carbonate stone generally increased up to twofold during coincident episodes of low rain rate (less than 5 millimeters per hour) and decreased rainfall (glass runoff) pH (less than 4.0); episodes of high rain rate (cloudbursts) were coincident with a rapid increase in rainfall pH and also a rapid decrease in the dissolution of carbonate-stone. During a storm, it seems the most important factors causing increased dissolution of carbonate stone are coincident periods of low rain rate and decreased rainfall pH. Dissolution of the carbonate stone decreased slightly as the rain rate exceeded about 5 millimeters per hour, probably in response to rapidly increasing rainfall pH during episodes of high rain rate and shorter contact time between the runoff and the stone surface. High runoff rates resulting from cloudbursts remove calcium sulfate minerals formed during dry periods prior to storms and also remove dissolution products formed in large measure by chemical weathering as a result of episodes of low rain rate and decreased rainfall pH during a storm.

Multicomponent amorphous nanofibers electrospun from hot aqueous solutions of a poorly soluble drug.

PubMed

Yu, Deng-Guang; Gao, Li-Dong; White, Kenneth; Branford-White, Christopher; Lu, Wei-Yue; Zhu, Li-Min

2010-11-01

To design and fabricate multicomponent amorphous electrospun nanofibers for synergistically improving the dissolution rate and permeation profiles of poorly water-soluble drugs. Nanofibers were designed to be composed of a poorly water soluble drug, helicid, a hydrophilic polymer polyvinylpyrrolidone as filament-forming matrix, sodium dodecyl sulfate as transmembrane enhancer and mannitol as taste masking agent, and were prepared from hot aqueous co-dissolving solutions of them. An elevated temperature electrospinning process was developed to fabricate the composite nanofibers, which were characterized using FESEM, DSC, XRD, ATR-FTIR, in vitro dissolution and permeation tests. The composite nanofibers were homogeneous with smooth surfaces and uniform structure, and the components were combined together in an amorphous state because of the favorable interactions such as hydrogen bonding, electrostatic interaction and hydrophobic interactions among them. In vitro dissolution and permeation tests demonstrated that the composite nanofibers had a dissolution rate over 26-fold faster than that of crude helicid particles and a 10-fold higher permeation rate across sublingual mucosa. A new type of amorphous material in the form of nanofibers was prepared from hot aqueous solutions of multiple ingredients using an electrospinning process. The amorphous nanofibers were able to improve the dissolution rate and permeation rate of helicid.

Template occluded SBA-15: An effective dissolution enhancer for poorly water-soluble drug

NASA Astrophysics Data System (ADS)

Tingming, Fu; Liwei, Guo; Kang, Le; Tianyao, Wang; Jin, Lu

2010-09-01

The aim of the present work was to improve the dissolution rate of piroxicam by inclusion into template occluded SBA-15. Our strategy involves directly introducing piroxicam into as-prepared SBA-15 occluded with P123 (EO 20PO 70EO 20) by self assembling method in acetonitrile/methylene chloride mixture solution. Ultraviolet spectrometry experiment and thermogravimetric analysis-differential scanning calorimetry (TG-DSC) profiles show that the piroxicam and P123 contents in the inclusion compound are 12 wt% and 28 wt%, respectively. X-ray powder diffraction and DSC analysis reveal that the included piroxicam is arranged in amorphous form. N 2 adsorption-desorption experiment indicates that the piroxicam has been introduced to the mesopores instead of precipitating at the outside of the silica material. The inclusion compound was submitted to in vitro dissolution tests, the results show that the piroxicam dissolve from template occluded inclusion compound more rapidly, than these from the piroxicam crystalline and template removed samples in all tested conditions. Thus a facile method to improve the dissolution rate of poorly water-soluble drug was established, and this discovery opens a new avenue for the utilization of templates used for the synthesis of mesoporous materials.

Dissolution of Material and Test reactor Fuel in an H-Canyon Dissolver

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

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

2017-01-26

In an amended record of decision for the management of spent nuclear fuel (SNF) at the Savannah River Site, the US Department of Energy has authorized the dissolution and recovery of U from 1000 bundles of Al-clad SNF. The SNF is fuel from domestic and foreign research reactors and is typically referred to as Material Test Reactor (MTR) fuel. Bundles of MTR fuel containing assemblies fabricated from U-Al alloys (or other U compounds) are currently dissolved using a Hg-catalyzed HNO3 flowsheet. Since the development of the existing flowsheet, improved experimental methods have been developed to more accurately characterize the offgasmore » composition and generation rate during laboratory dissolutions. Recently, these new techniques were successfully used to develop a flowsheet for the dissolution of High Flux Isotope Reactor (HFIR) fuel. Using the data from the HFIR dissolution flowsheet development and necessary laboratory experiments, the Savannah River National Laboratory (SRNL) was requested to define flowsheet conditions for the dissolution of MTR fuels. With improved offgas characterization techniques, SRNL will be able define the number of bundles of fuel which can be charged to an H-Canyon dissolver with much less conservatism.« less

Dissolution and fractionation of nut shells in ionic liquids.

PubMed

Carneiro, Aristides P; Rodríguez, Oscar; Macedo, Eugénia A

2017-03-01

The aim of this work was to study the dissolution of raw peanut and chestnut shells in ionic liquids. Dissolution of raw biomass up to 7wt% was achieved under optimized operatory conditions. Quantification of polysaccharides dissolved through quantitative 13 Cq NMR revealed extractions of the cellulosic material to ionic liquids as high as 87%. Regeneration experiments using an antisolvent mixture allowed to recover the cellulosic material and the ionic liquid. The overall mass balance presented very low loss rates (<8%), recoveries of 75% and 95% of cellulosic material from peanut and chestnut shells, respectively, and the recovery of more than 95% of the ionic liquid in both cases. These results show the high potential of using nut shells and ionic liquids for biorefining purposes. Moreover, high recovery of ionic liquids favors the process from an economical point of view. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hydroxyapatite, fluor-hydroxyapatite and fluorapatite produced via the sol-gel method: dissolution behaviour and biological properties after crystallisation.

PubMed

Tredwin, Christopher J; Young, Anne M; Abou Neel, Ensanya A; Georgiou, George; Knowles, Jonathan C

2014-01-01

Hydroxyapatite (HA), fluor-hydroxyapatite (FHA) with varying levels of fluoride ion substitution and fluorapatite (FA) were synthesised by the sol-gel method as possible implant coating or bone-grafting materials. Calcium nitrate and triethyl phosphite were used as precursors under an ethanol-water based solution. Different amounts of ammonium fluoride were incorporated for the preparation of the FHA and FA sol-gels. After heating and powdering the sol-gels, dissolution behaviour was assessed using ion chromatography to measure Ca(2+) and PO4 (3-) ion release. Biological behaviour was assessed using cellular proliferation with human osteosarcoma cells and alamarBlue™ assay. Statistical analysis was performed with a two way analysis of variance and post hoc testing with a Bonferroni correction. Increasing fluoride substitution into an apatite structure decreased the dissolution rate. Increasing the firing temperature of the HA, FHA and FA sol-gels up to 1,000 °C decreased the dissolution rate. There was significantly higher cellular proliferation on highly substituted FHA and FA than on HA or Titanium. The properties of an implant coating or bone grafting material can be tailored to meet specific requirements by altering the amount of fluoride that is incorporated into the original apatite structure. The dissolution behaviour can further be altered by the temperature at which the sol-gel is fired.

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.

Solid-state, triboelectrostatic and dissolution characteristics of spray-dried piroxicam-glucosamine solid dispersions.

PubMed

Adebisi, Adeola O; Kaialy, Waseem; Hussain, Tariq; Al-Hamidi, Hiba; Nokhodchi, Ali; Conway, Barbara R; Asare-Addo, Kofi

2016-10-01

This work explores the use of both spray drying and d-glucosamine HCl (GLU) as a hydrophilic carrier to improve the dissolution rate of piroxicam (PXM) whilst investigating the electrostatic charges associated with the spray drying process. Spray dried PXM:GLU solid dispersions were prepared and characterised (XRPD, DSC, SEM). Dissolution and triboelectric charging were also conducted. The results showed that the spray dried PXM alone, without GLU produced some PXM form II (DSC results) with no enhancement in solubility relative to that of the parent PXM. XRPD results also showed the spray drying process to decrease the crystallinity of GLU and solid dispersions produced. The presence of GLU improved the dissolution rate of PXM. Spray dried PXM: GLU at a ratio of 2:1 had the most improved dissolution. The spray drying process generally yielded PXM-GLU spherical particles of around 2.5μm which may have contributed to the improved dissolution. PXM showed a higher tendency for charging in comparison to the carrier GLU (-3.8 versus 0.5nC/g for untreated material and -7.5 versus 3.1nC/g for spray dried materials). Spray dried PXM and spray dried GLU demonstrated higher charge densities than untreated PXM and untreated GLU, respectively. Regardless of PXM:GLU ratio, all spray dried PXM:GLU solid dispersions showed a negligible charge density (net-CMR: 0.1-0.3nC/g). Spray drying of PXM:GLU solid dispersions can be used to produce formulation powders with practically no charge and thereby improving handling as well as dissolution behaviour of PXM. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Effects of temperature on the removal efficiency of KDP crystal during the process of magnetorheological water-dissolution polishing.

PubMed

Zhang, Yifan; Dai, Yifan; Tie, Guipeng; Hu, Hao

2016-10-10

As a kind of important nonlinear optical element, KDP crystal has great demand in the inertial confinement fusion system. Based on the dissolution mechanism of solid materials, the factors that affect the material removal rate of KDP crystal in magnetorheological (MR) water-dissolution polishing are investigated to improve the machining efficiency. It is found that the material removal rate is proportional to the product of the saturation concentration and diffusion coefficient, and the relationship between the removal efficiency and the temperature meets the unilateral Gaussian function. Polishing experiments are carried out on a magnetorheological finishing (MRF) machine with self-designed MRF fluid heating devices. The experimental results show that practical efficiency-temperature curve is consistent with the theoretical curve, and the maximum machining efficiency increases by about 50% with the rise of temperature from 294 to 302 K. Meanwhile, when the MR fluid temperature is lower than 308 K, the crystal surface quality and surface roughness in different processing temperatures have no remarkable difference with constant crystal temperature (294 K). This research indicates that it is feasible to drastically improve KDP crystal MRF efficiency by controlling the processing temperature.

Modifying Surface Chemistry of Metal Oxides for Boosting Dissolution Kinetics in Water by Liquid Cell Electron Microscopy.

PubMed

Lu, Yue; Geng, Jiguo; Wang, Kuan; Zhang, Wei; Ding, Wenqiang; Zhang, Zhenhua; Xie, Shaohua; Dai, Hongxing; Chen, Fu-Rong; Sui, Manling

2017-08-22

Dissolution of metal oxides is fundamentally important for understanding mineral evolution and micromachining oxide functional materials. In general, dissolution of metal oxides is a slow and inefficient chemical reaction. Here, by introducing oxygen deficiencies to modify the surface chemistry of oxides, we can boost the dissolution kinetics of metal oxides in water, as in situ demonstrated in a liquid environmental transmission electron microscope (LETEM). The dissolution rate constant significantly increases by 16-19 orders of magnitude, equivalent to a reduction of 0.97-1.11 eV in activation energy, as compared with the normal dissolution in acid. It is evidenced from the high-resolution TEM imaging, electron energy loss spectra, and first-principle calculations where the dissolution route of metal oxides is dynamically changed by local interoperability between altered water chemistry and surface oxygen deficiencies via electron radiolysis. This discovery inspires the development of a highly efficient electron lithography method for metal oxide films in ecofriendly water, which offers an advanced technique for nanodevice fabrication.

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 (normalized to specific surface area) were 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57 · 10-10 vs. 1.28 · 10-13 mol m-2 s-1 [log R = -9.81 and -12.89] and 5.79 · 10-10 vs. 3.71 · 10-13 mol m-2 s-1 [log R = -9.24 and -12.43] for K- and Na-compreignacite, respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for U mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. This study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as U in porous geomedia.

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 surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

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 surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

NASA Astrophysics Data System (ADS)

Turchyn, Alexandra V.; DePaolo, Donald J.

2011-11-01

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ 44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ 44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ 44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ 44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

[Dissolution behavior of Fuzi Lizhong pill based on simultaneous determination of two components in Glycyrrhizae Radix et Rhizoma].

PubMed

Jiang, Mao-Yuan; Zhang, Zhen; Shi, Jin-Feng; Zhang, Jin-Ming; Fu, Chao-Mei; Lin, Xia; Liu, Yu-Mei

2018-03-01

To preliminarily investigate the dissolution behavior of Fuzi Lizhong pill, provide the basis for its quality control and lay foundation for in vivo dissolution behavior by determining the dissolution rate of liquiritin and glycyrrhizic acid. High-performance liquid chromatography (HPLC) method for simultaneous content determination of the two active ingredients of liquiritin and glycyrrhizic acid in Fuzi Lizhong pill was established; The dissolution amount of these two active ingredients in fifteen batches of Fuzi Lizhong pill from five manufacturers was obtained at different time points, and then the cumulative dissolution rate was calculated and cumulative dissolution curve was drawn. The similarity of cumulative dissolution curve of different batches was evaluated based on the same factory, and the similarity of cumulative dissolution curve of different factories was evaluated based on the same active ingredients. The dissolution model of Fuzi Lizhong pill based on two kinds of active ingredients was established by fitting with the dissolution data. The best dissolution medium was 0.25% sodium lauryl sulfate. The dissolution behavior of liquiritin and glycyrrhizic acid in Fuzi Lizhong pill was basically the same and sustained release in 48 h. Three batches of the factories (factory 2, factory 3, factory 4 and factory 5) appeared to be similar in dissolution behavior, indicating similarity in dissolution behavior in most factories. Two of the three batches from factory 1 appeared to be not similar in dissolution behavior of liquiritin and glycyrrhizic acid. The dissolution data of the effective ingredients from different factories were same in fitting, and Weibull model was the best model in these batches. Fuzi Lizhong pill in 15 batches from 5 factories showed sustained release in 48 h, proving obviously slow releasing characteristics "pill is lenitive and keeps a long-time efficacy". The generally good dissolution behavior also suggested that quality of different batches from most factories was stable. The dissolution behavior of liquiritin and glycyrrhizic acid in different factories was different, suggesting that the source of medicinal materials and preparation technology parameters in five factories were different. Copyright© by the Chinese Pharmaceutical Association.

On The Molecular Mechanism Of Positive Novolac Resists

NASA Astrophysics Data System (ADS)

Huang, Jian-Ping; Kwei, T. K.; Reiser, Arnost

1989-08-01

A molecular mechanism for the dissolution of novolac is proposed, based on the idea of a critical degree of deprotonation as being the condition for the transfer of polymer into solution. The rate at which the critical deprotonation condition is achieved is controlled by the supply of developer into a thin penetration zone, and depends in particular on the rate of diffusion of the base cations which are the developer component with the lowest mobility. The penetration zone contains phenolate ions and ion-bound water, but it retains the structure of a rigid polymer membrane, as evidenced by the diffusion coefficient of cations in the pene;tration zone which is several orders of magnitude slower than in an open gel of the same material. When the critical degree of deprotonation is reached, the membrane structure unravels and all subsequent events, chain rearrangement and transfer into solution, occur rapidly. The supralinear dependence of dissolution rate on base concentration and the effect of the size of the base cation are plausibly interpreted by the model. The diffusion of developer components is assumed to occur preferentially via hydrophilic sites in the polymer matrix. These sites define a diffusion path which acts like a hydrophilic diffusion channel. Suitably designed hydrophobic molecules can block some of the channels and in this way alter the dissolution rate. They reduce in effect the diffusion crossect ion of the material. Hydrophilic additives, on the other hand, introduce additional channels into the system and promote dissolution. The concept of diffusion channels appears to provide a unified interpretation for a number of common observations.

Bioavailability of indomethacin-saccharin cocrystals.

PubMed

Jung, Min-Sook; Kim, Jeong-Soo; Kim, Min-Soo; Alhalaweh, Amjad; Cho, Wonkyung; Hwang, Sung-Joo; Velaga, Sitaram P

2010-11-01

Pharmaceutical cocrystals are new solid forms with physicochemical properties that appear promising for drug product development. However, the in-vivo bioavailability of cocrystals has rarely been addressed. The cocrystal of indomethacin (IND), a Biopharmaceutical Classification System class II drug, with saccharin (SAC) has been shown to have higher solubility than IND at all pH. In this study, we aimed to evaluate the in-vitro dissolution and in-vivo bioavailability of IND-SAC cocrystals in comparison with IND in a physical mixture and the marketed product Indomee. Scale-up of the cocrystals was undertaken using cooling batch crystallisation without seeding. The chemical and physical purity of the up-scaled material was verified using high-performance liquid chromatography, differential scanning calorimetry and powder X-ray diffraction. The IND-SAC cocrystals and IND plus SAC were mixed with lactose and the formulations were placed into gelatin capsules. In-vitro dissolution studies were then performed using the rotating basket dissolution method. The intrinsic dissolution rate of IND and IND-SAC cocrystals was also determined. Finally, a bioavailability study for the formulations was conducted in beagle dogs. The plasma samples were analysed using high-performance liquid chromatography and the pharmacokinetic data were analysed using standard methodologies.   The bulk cocrystals (i.e. scaled-up material) were chemically and physically pure. The in-vitro dissolution rate of the cocrystals was higher than that of IND and similar to that of Indomee at pH 7.4 and pH 1.2. The in-vivo bioavailability of the IND-SAC cocrystals in dogs was significantly higher (ANOVA, P<0.05) than that of IND but not significantly different from Indomee (ANOVA, P>0.05). The study indicates that the improved aqueous solubility of the cocrystals leads to improved bioavailability of IND. Thus, the cocrystals are a viable alternative solid form that can improve the dissolution rate and bioavailability of poorly soluble drugs. © 2010 The Authors. JPP © 2010 Royal Pharmaceutical Society of Great Britain.

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. Additional analyses including Mg concentrations, microprobe and BET analyses support mineral dissolution rate calculations and stoichiometry considerations. All experimental assays containing endospores show increased forsterite dissolution rates relative to abiotic controls. Forsterite dissolution rates increased by approximately one order of magnitude in dialysis bound, biotic experiments relative to abiotic assays. Homogenous biotic assays exhibited a more complex dissolution rate profile that changes over time. All microbially mediated forsterite dissolution rates returned to abiotic control rates after 10 to 15 days of incubation. This shift in dissolution rate likely corresponds to maximum endospore surface adsorption capacity. The Bacillus subtilis endospore surface serves as a first-order proxy for studying the effect of metabolizing microbe surfaces on silicate dissolution rates. Comparisons with published abiotic, microbial, and organic acid mediated forsterite dissolution rates will provide insight on the importance of bacterial surfaces in primary mineral dissolution processes.

The Influence of Drug Physical State on the Dissolution Enhancement of Solid Dispersions Prepared Via Hot-Melt Extrusion: A Case Study Using Olanzapine

PubMed Central

Pina, Maria Fátima; Zhao, Min; Pinto, João F; Sousa, João J; Craig, Duncan Q M

2014-01-01

In this study, we examine the relationship between the physical structure and dissolution behavior of olanzapine (OLZ) prepared via hot-melt extrusion in three polymers [polyvinylpyrrolidone (PVP) K30, polyvinylpyrrolidone-co-vinyl acetate (PVPVA) 6:4, and Soluplus® (SLP)]. In particular, we examine whether full amorphicity is necessary to achieve a favorable dissolution profile. Drug–polymer miscibility was estimated using melting point depression and Hansen solubility parameters. Solid dispersions were characterized using differential scanning calorimetry, X-ray powder diffraction, and scanning electron microscopy. All the polymers were found to be miscible with OLZ in a decreasing order of PVP>PVPVA>SLP. At a lower extrusion temperature (160°C), PVP generated fully amorphous dispersions with OLZ, whereas the formulations with PVPVA and SLP contained 14%–16% crystalline OLZ. Increasing the extrusion temperature to 180°C allowed the preparation of fully amorphous systems with PVPVA and SLP. Despite these differences, the dissolution rates of these preparations were comparable, with PVP showing a lower release rate despite being fully amorphous. These findings suggested that, at least in the particular case of OLZ, the absence of crystalline material may not be critical to the dissolution performance. We suggest alternative key factors determining dissolution, particularly the dissolution behavior of the polymers themselves. PMID:24765654

Environmental Degradation of Materials: Surface Chemistry Related to Stress Corrosion Cracking

NASA Technical Reports Server (NTRS)

Schwarz, J. A.

1985-01-01

Parallel experiments have been performed in order to develop a comprehensive model for stress cracking (SCC) in structural materials. The central objective is to determine the relationship between the activity and selectivity of the microstructure of structural materials to their dissolution kinetics and experimentally measured SCC kinetics. Zinc was chosen as a prototype metal system. The SCC behavior of two oriented single-crystal disks of zinc in a chromic oxide/sodium sulfate solution (Palmerton solution) were determined. It was found that: (1) the dissolution rate is strongly (hkil)-dependent and proportional to the exposure time in the aggressive environment; and (2) a specific slip system is selectively active to dissolution under applied stress and this slip line controls crack initiation and propagation. As a precursor to potential microgrvity experiments, electrophoretic mobility measurements of zinc particles were obtained in solutions of sodium sulfate (0.0033 M) with concentrations of dissolved oxygen from 2 to 8 ppm. The equilibrium distribution of exposed oriented planes as well as their correlation will determine the particle mobility.

The effect of clay on the dissolution of nuclear waste glass

NASA Astrophysics Data System (ADS)

Lemmens, K.

2001-09-01

In a nuclear waste repository, the waste glass can interact with metals, backfill materials (if present) and natural host rock. Of the various host rocks considered, clays are often reported to delay the onset of the apparent glass saturation, where the glass dissolution rate becomes very small. This effect is ascribed to the sorption of silica or other glass components on the clay. This can have two consequences: (1) the decrease of the silica concentration in solution increases the driving force for further dissolution of glass silica, and (2) the transfer of relatively insoluble glass components (mainly silica) from the glass surface to the clay makes the alteration layer less protective. In recent literature, the latter explanation has gained credibility. The impact of the environmental materials on the glass surface layers is however not well understood. Although the glass dissolution can initially be enhanced by clay, there are arguments to assume that it will decrease to very low values after a long time. Whether this will indeed be the case, depends on the fate of the released glass components in the clay. If they are sorbed on specific sites, it is likely that saturation of the clay will occur. If however the released glass components are removed by precipitation (growth of pre-existing or new secondary phases), saturation of the clay is less likely, and the process can continue until exhaustion of one of the system components. There are indications that the latter mechanism can occur for varying glass compositions in Boom Clay and FoCa clay. If sorption or precipitation prevents the formation of protective surface layers, the glass dissolution can in principle proceed at a high rate. High silica concentrations are assumed to decrease the dissolution rate (by a solution saturation effect or by the impact on the properties of the glass alteration layer). In glass corrosion tests at high clay concentrations, silica concentrations are, however, often higher than the silica concentrations in equilibrium with the glass surface ( C ∗Si, saturation) that are found in absence of clay. Nevertheless, the glass dissolution proceeds at relatively high rate. C ∗Si, saturation seems to be increased by the presence of clay. To understand this, more knowledge is necessary concerning the fate of the released silica and the silica speciation in solution.

Quantification of the resist dissolution process: an in situ analysis using high speed atomic force microscopy

NASA Astrophysics Data System (ADS)

Santillan, Julius Joseph; Shichiri, Motoharu; Itani, Toshiro

2016-03-01

This work focuses on the application of a high speed atomic force microscope (HS-AFM) for the in situ visualization / quantification of the resist dissolution process. This technique, as reported in the past, has provided useful pointers on the formation of resist patterns during dissolution. This paper discusses about an investigation made on the quantification of what we refer to as "dissolution unit size" or the basic units of patterning material dissolution. This was done through the establishment of an originally developed analysis method which extracts the difference between two succeeding temporal states of the material film surface (images) to indicate the amount of change occurring in the material film at a specific span of time. Preliminary experiments with actual patterning materials were done using a positive-tone EUV model resist composed only of polyhydroxystyrene (PHS)-based polymer with a molecular weight of 2,500 and a polydispersity index of 1.2. In the absence of a protecting group, the material was utilized at a 50nm film thickness with post application bake of 90°C/60s. The resulting film is soluble in the alkali-based developer even without exposure. Results have shown that the dissolution components (dissolution unit size) of the PHS-based material are not of fixed size. Instead, it was found that aside from one constantly dissolving unit size, another, much larger dissolution unit size trend also occurs during material dissolution. The presence of this larger dissolution unit size suggests an occurrence of "polymer clustering". Such polymer clustering was not significantly present during the initial stages of dissolution (near the original film surface) but becomes more persistently obvious after the dissolution process reaches a certain film thickness below the initial surface.

Structural and silver/vanadium ratio effects on silver vanadium phosphorous oxide solution formation kinetics: impact on battery electrochemistry.

PubMed

Bock, David C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

2015-01-21

The detailed understanding of non-faradaic parasitic reactions which diminish battery calendar life is essential to the development of effective batteries for use in long life applications. The dissolution of cathode materials including manganese, cobalt and vanadium oxides in battery systems has been identified as a battery failure mechanism, yet detailed dissolution studies including kinetic analysis are absent from the literature. The results presented here provide a framework for the quantitative and kinetic analyses of the dissolution of cathode materials which will aid the broader community in more fully understanding this battery failure mechanism. In this study, the dissolution of silver vanadium oxide, representing the primary battery powering implantable cardioverter defibrillators (ICD), is compared with the dissolution of silver vanadium phosphorous oxide (Ag(w)VxPyOz) materials which were targeted as alternatives to minimize solubility. This study contains the first kinetic analyses of silver and vanadium solution formation from Ag0.48VOPO4·1.9H2O and Ag2VP2O8, in a non-aqueous battery electrolyte. The kinetic results are compared with those of Ag2VO2PO4 and Ag2V4O11 to probe the relationships among crystal structure, stoichiometry, and solubility. For vanadium, significant dissolution was observed for Ag2V4O11 as well as for the phosphate oxide Ag0.49VOPO4·1.9H2O, which may involve structural water or the existence of multiple vanadium oxidation states. Notably, the materials from the SVPO family with the lowest vanadium solubility are Ag2VO2PO4 and Ag2VP2O8. The low concentrations and solution rates coupled with their electrochemical performance make these materials interesting alternatives to Ag2V4O11 for the ICD application.

A dissolution-precipitation mechanism is at the origin of concrete creep in moist environments.

PubMed

Pignatelli, Isabella; Kumar, Aditya; Alizadeh, Rouhollah; Le Pape, Yann; Bauchy, Mathieu; Sant, Gaurav

2016-08-07

Long-term creep (i.e., deformation under sustained load) is a significant material response that needs to be accounted for in concrete structural design. However, the nature and origin of concrete creep remain poorly understood and controversial. Here, we propose that concrete creep at relative humidity ≥ 50%, but fixed moisture content (i.e., basic creep), arises from a dissolution-precipitation mechanism, active at nanoscale grain contacts, as has been extensively observed in a geological context, e.g., when rocks are exposed to sustained loads, in liquid-bearing environments. Based on micro-indentation and vertical scanning interferometry data and molecular dynamics simulations carried out on calcium-silicate-hydrate (C-S-H), the major binding phase in concrete, of different compositions, we show that creep rates are correlated with dissolution rates-an observation which suggests a dissolution-precipitation mechanism as being at the origin of concrete creep. C-S-H compositions featuring high resistance to dissolution, and, hence, creep are identified. Analyses of the atomic networks of such C-S-H compositions using topological constraint theory indicate that these compositions present limited relaxation modes on account of their optimally connected (i.e., constrained) atomic networks.

The Effect of Micro/Nano-metrics Size on the Interaction of Jordanian Aluminosilicate Raw Materials with High pH Solution

NASA Astrophysics Data System (ADS)

Aldabsheh, Islam; Garcia-Valles, Maite; Martinez, Salvador

2014-05-01

Environmental preservation has become a driving force behind the search for new sustainable and environmentally friendly composites to replace conventional concrete produced from ordinary Portland cement (OPC). Current researches concentrate on developing building products (geopolymers) through geopolymerization. The goal is to produce low cost construction materials for green housing. Geopolymerization is the process of polymerizing minerals with high silica and alumina at low temperature by the use of alkali solutions. Dissolution is the most important process for supplying the high initial Al and Si concentrations to produce the gel phase that is responsible for geopolymerization. This study has been focused on the influence of different micrometric particle sizes of three Jordanian raw materials on their dissolution behavior in sodium hydroxide solution. The samples are kaolinite, volcanic tuff and silica sand. The dissolution properties of each material, alone and mixed with the other two materials were studied in different concentrations (5 and 10 M) using (NaOH) at 25ºC, and shaking time for 24 and 168 h. To better understand the dissolution process, the alkaline solution was renewed after the desired time in order to know if the Al-Si raw material is completely dissolved or not. Different analytical techniques were used to characterize raw materials physically, mineralogically, chemically and thermally. All processed samples either centrifuged solutions or solid residues were fully characterized. The leached concentrations of Al and Si were determined by inductively coupled plasma (ICP). X-ray Diffraction Technique (XRD), Scanning Electron Microscopy (SEM), and Thermo Gravimetric Analysis (TGA) were used to evaluate the solid residue characterization compared with the original ones. The three aluminosilicate raw materials have indicated variable degrees of solubility under highly alkaline conditions. The method for the size reduction of the used raw materials achieved by using a ball mill increased the dissolution rate owing to the increased surface area of the material or particle exposed to the solvent. The used Jordanian raw materials are potential to be used for geopolymerization. This work was partly financed by SGR 2009SGR-00444

Particular Film Formation of Phenytoin at Silica Surfaces

PubMed Central

2014-01-01

Given the increasing number of poorly soluble and thus poorly bioavailable active pharmaceutical materials, there is a demand for innovative formulation platforms for such molecules. Thus a focus on enhancing dissolution properties of poorly soluble drugs exists. Within this study, the spin coating of acetone solutions containing 5,5-diphenyl-2,4-imidazolidinedione (phenytoin) in various concentrations is evaluated. The results reveal strong variations of the morphology of deposited phenytoin crystals at silica surfaces. Individual separated particles are obtained on low phenytoin concentrations, and closely packed particular films form when the concentration is increased. As the material is isomorphic, these various morphologies have the same crystalline structure. Dissolution experiments reveal that both the apparent maximum solubility and as the dissolution rate are strongly enhanced compared to bulk powder, suggesting that formulation based on this preparative technique will allow overcoming the low solubility problematic for a variety of drugs. PMID:24417472

Critical material attributes (CMAs) of strip films loaded with poorly water-soluble drug nanoparticles: I. Impact of plasticizer on film properties and dissolution

PubMed Central

Krull, Scott M.; Patel, Hardik V.; Li, Meng; Bilgili, Ecevit; Davé, Rajesh N.

2016-01-01

Recent studies have demonstrated polymer films to be a promising platform for delivery of poorly water-soluble drug particles. However, the impact of critical material attributes, for example plasticizer, on the properties of and drug release from such films has yet to be investigated. In response, this study focuses on the impact of plasticizer and plasticizer concentration on properties and dissolution rate of polymer films loaded with poorly water-soluble drug nanoparticles. Glycerin, triacetin, and polyethylene glycol were selected as film plasticizers. Griseofulvin was used as a model Biopharmaceutics Classification System class II drug and hydroxypropyl methylcellulose was used as a film-forming polymer. Griseofulvin nanoparticles were prepared via wet stirred media milling in aqueous suspension. A depression in film glass transition temperature was observed with increasing plasticizer concentration, along with a decrease in film tensile strength and an increase in film elongation, as is typical of plasticizers. However, the type and amount of plasticizer necessary to produce strong yet flexible films had no significant impact on the dissolution rate of the films, suggesting that film mechanical properties can be effectively manipulated with minimal impact on drug release. Griseofulvin nanoparticles were successfully recovered upon redispersion in water regardless of plasticizer or content, even after up to 6 months’ storage at 40 °C and 75% relative humidity, which contributed to similar consistency in dissolution rate after 6 months’ storage for all films. Good content uniformity (<4% R.S.D. for very small film sample size) was also maintained across all film formulations. PMID:27402100

Understanding the barriers to crystal growth: dynamical simulation of the dissolution and growth of urea from aqueous solution.

PubMed

Piana, Stefano; Gale, Julian D

2005-02-16

Both the dissolution and growth of a molecular crystalline material, urea, has been studied using dynamical atomistic simulation. The kinetic steps of dissolution and growth are clearly identified, and the activation energies for each possible step are calculated. Our molecular dynamics simulations indicate that crystal growth on the [001] face is characterized by a nucleation and growth mechanism. Nucleation on the [001] urea crystal face is predicted to occur at a very high rate, followed by rapid propagation of the steps. The rate-limiting step for crystallization is actually found to be the removal of surface defects, rather than the initial formation of the next surface layer. Through kinetic Monte Carlo modeling of the surface growth, it is found that this crystal face evolves via a rough surface topography, rather than a clean layer-by-layer mechanism.

OPTIMIZATION OF FUROSEMIDE LIQUISOLID TABLETS PREPARATION PROCESS LEADING TO THEIR MASS AND SIZE REDUCTION.

PubMed

Kurek, Mateusz; Woyna-Orlewicz, Krzysztof; Khalid, Mohammad Hassan; Jachowicz, Renata

2016-09-01

The great number of drug substances currently used in solid oral dosage forms is characterized by poor water solubility. Therefore, various methods of dissolution rate enhancement are an important topic of research interest in modem drug technology. The purpose of this study was to enhance the furosemide dissolution rate from liquisolid tablets while maintaining an acceptable size and mass. Two types of dibasic calcium phosphate (Fujicalin®/Emcompress®) and microcrystalline cellulose (Vivapur® 102/Vivapur® 12) were used as carriers and magnesium aluminometasilicate (Neusilin® US2) was used as a coating material. The flowable liquid retention potential for those excipients was tested by measuring the angle of slide. To evaluate the impact of used excipients on tablet properties fourteen tablet formulations were prepared. It was found that LS2 tablets containing spherically granulated dibasic calcium phosphate and magnesium aluminometasilicate exhibit the best dissolution profile and mechanical properties while tablets composed only with Neusilin® US2 was characterized by the smallest size and mass with preserved good mechanical properties and furosemide dissolution.

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.

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

PubMed

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

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.

Critical material attributes (CMAs) of strip films loaded with poorly water-soluble drug nanoparticles: I. Impact of plasticizer on film properties and dissolution.

PubMed

Krull, Scott M; Patel, Hardik V; Li, Meng; Bilgili, Ecevit; Davé, Rajesh N

2016-09-20

Recent studies have demonstrated polymer films to be a promising platform for delivery of poorly water-soluble drug particles. However, the impact of critical material attributes, for example plasticizer, on the properties of and drug release from such films has yet to be investigated. In response, this study focuses on the impact of plasticizer and plasticizer concentration on properties and dissolution rate of polymer films loaded with poorly water-soluble drug nanoparticles. Glycerin, triacetin, and polyethylene glycol were selected as film plasticizers. Griseofulvin was used as a model Biopharmaceutics Classification System class II drug and hydroxypropyl methylcellulose was used as a film-forming polymer. Griseofulvin nanoparticles were prepared via wet stirred media milling in aqueous suspension. A depression in film glass transition temperature was observed with increasing plasticizer concentration, along with a decrease in film tensile strength and an increase in film elongation, as is typical of plasticizers. However, the type and amount of plasticizer necessary to produce strong yet flexible films had no significant impact on the dissolution rate of the films, suggesting that film mechanical properties can be effectively manipulated with minimal impact on drug release. Griseofulvin nanoparticles were successfully recovered upon redispersion in water regardless of plasticizer or content, even after up to 6months' storage at 40°C and 75% relative humidity, which contributed to similar consistency in dissolution rate after 6months' storage for all films. Good content uniformity (<4% R.S.D. for very small film sample size) was also maintained across all film formulations. Copyright © 2016 Elsevier B.V. All rights reserved.

Dissolution rate enhancement of gliclazide by ordered mixing.

PubMed

Saharan, Vikas A; Choudhury, Pratim K

2011-09-01

The poorly water soluble antidiabetic drug gliclazide was selected to study the effect of excipients on dissolution rate enhancement. Ordered mixtures of micronized gliclazide with lactose, mannitol, sorbitol, maltitol and sodium chloride were prepared by manual shaking of glass vials containing the drug and excipient(s). Different water soluble excipients, addition of surfactant and superdisintegrant, drug concentration and carrier particle size influenced the dissolution rate of the drug. Dissolution rate studies of the prepared ordered mixtures revealed an increase in drug dissolution with all water soluble excipients. The order of dissolution rate improvement for gliclazide was mannitol > lactose > maltitol > sorbitol > sodium chloride. Composite granules of the particle size range 355-710 μm were superior in increasing the drug dissolution rate from ordered mixtures. Reducing the carrier particle size decreased the dissolution rate of the drug as well as the increase in drug concentration. Kinetic modeling of drug release data fitted best the Hixson-Crowell model, which indicates that all the ordered mixture formulations followed the cube root law fairly well.

Double layer, diluent and anode effects upon the electrodeposition of aluminium from chloroaluminate based ionic liquids.

PubMed

Abbott, Andrew P; Qiu, Fulian; Abood, Hadi M A; Ali, M Rostom; Ryder, Karl S

2010-02-28

The deposition of aluminium from a chloroaluminate based ionic liquid was studied to elucidate the effect of a diluent (toluene) and electrolyte (LiCl) on the deposit morphology. A wide variety of analytical techniques was applied to this system to determine the speciation and mechanism of material growth. These included: (27)Al NMR, FAB-MS, cyclic voltammetry, chronocoulometry, chronopotentiometry, scanning electron microscopy and atomic force microscopy. It was found that under-potential deposition (upd) causes a change in the way in which metal grows on the electrode surface. Metal grows in two regimes which are believed to be nano-material and bulk material. The addition of toluene causes a change in speciation and a decrease in upd which in turn changes the morphology of the deposit obtained and can lead to mirror finish aluminium. The addition of LiCl has the opposite effect encouraging upd and leading to larger crystallites and a dark grey deposit. It is also shown for the first time that under many conditions the rate of the anodic dissolution process is overall rate controlling and one effect of the addition of toluene is to increase the rate of anodic dissolution.

Model of heterogeneous material dissolution in simulated biological fluid

NASA Astrophysics Data System (ADS)

Knyazeva, A. G.; Gutmanas, E. Y.

2015-11-01

In orthopedic research, increasing attention is being paid to bioresorbable/biodegradable implants as an alternative to permanent metallic bone healing devices. Biodegradable metal based implants possessing high strength and ductility potentially can be used in load bearing sites. Biodegradable Mg and Fe are ductile and Fe possess high strength, but Mg degrades too fast and Fe degrades too slow, Ag is a noble metal and should cause galvanic corrosion of the more active metallic iron - thus, corrosion of Fe can be increased. Nanostructuring should results in higher strength and can result in higher rate of dissolution/degradation from grain boundaries. In this work, a simple dissolution model of heterogeneous three phase nanocomposite material is considered - two phases being metal Fe and Ag and the third - nanopores. Analytical solution for the model is presented. Calculations demonstrate that the changes in the relative amount of each phase depend on mass exchange and diffusion coefficients. Theoretical results agree with preliminary experimental results.

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 carbonate rocks, both in the natural environment, as well as in stone buildings and statuary, where the amount of solutes in pore waters is significant and can vary depending on evaporation and condensation phenomena. References Higgins, S.R.; Hu, X. Self-limiting growth on dolomite: Experimental observations with in situ atomic force microscopy. Geochimica et Cosmochimica Acta, 2005, 69 (8), 2085-2094. Morse, J.W.; Arvidson, R.S. The dissolution kinetics of major sedimentary carbonate minerals. Earth-Science Reviews, 2002, 58, 51-84. Ruiz-Agudo, E.; Kowacz, M.; Putnis, C.V.; Putnis, A. The role of background electrolytes on the kinetics and mechanism of calcite dissolution. Geochimica et Cosmochimica Acta, 2010, 74, 1256-1267.

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.

Extrusion-based, three-dimensional printing of calcium-phosphate scaffolds

NASA Astrophysics Data System (ADS)

Witek, Lukasz

Small or large bone defects, can occur due to a variety of reasons: congenital disorders, infections, tumors, or traumas which can lead to significant disabilities. There is an assortment of bone grafting procedures, each having their own respective advantages and disadvantages and exhibiting certain essential characteristics. Among the available grafts, autogenous (autograft), allograft, xenograft, and alloplasts, all exhibit a minimum of two-thirds of the essential characteristics and have been proven useful in fully or partially repairing skeletal defects. However, different host-to-grafting material responses have been reported and should be taken into consideration when determining treatment options. A large range of physical and chemical properties can be achieved with calcium phosphate based materials, which possess two of the ideal characteristics for grafting procedures: osteoconduction and osseointegration. Calcium phosphate based scaffolds composed of hydroxyapatite (HA), beta-tri-calcium phosphate (beta-TCP), or a combination of both (HA/beta-TCP) were investigated as materials for three-dimensional printing process to create layer-by-layer structures for use as bone regeneration scaffolds. Different calcium-phosphate phases will result in different degrees of in vivo dissolution and/or cell-mediated resorption. There has been a growing interest in BCP because it has been shown that this material improves the formation of new bone inside the implanted scaffold. The literature indicates that the faster dissolution rate of ?-TCP would be greatly responsible of this enhancement. However, in vitro tests indicate that fast dissolution can decrease the mechanical strength of BCP scaffolds. Furthermore, studies reported that HA has higher mechanical strength and lower degradation rate than beta-TCP. Therefore, the HA/beta-TCP ratio is a key parameter controlling the performance of the scaffold for bone repair applications, since it determines degradation rate, calcium (Ca2+) and phosphate (PO4) release and mechanical properties of the material.

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

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

Dissolution of a new explosive formulation containing TNT and HMX: comparison with octol.

PubMed

Monteil-Rivera, Fanny; Deschamps, Stéphane; Ampleman, Guy; Thiboutot, Sonia; Hawari, Jalal

2010-02-15

GIM (Greener Insensitive Material) is a new explosive formulation made of HMX (51.5%), TNT (40.7%), and a binder, ETPE (7.8%), which is currently investigated by the Canadian Department of National Defense for a wider use by the Army. In the present study, dissolution of GIM in water was measured and compared to the dissolution of octol (HMX/TNT: 70/30). Although the presence of ETPE did not prevent completely TNT and HMX from dissolving, GIM appeared to dissolve more slowly than octol. The ETPE was shown to prevent the formulation particles from collapsing and to retard the dissolution of both TNT and HMX by limiting their exposure to water. In both octol and GIM, the dissolution rate of the particles was governed by the compound(s) that are slower to dissolve, i.e. HMX in octol, and HMX and ETPE in GIM. A model based on Fick's diffusion law allowed fitting well the dissolution data of octol but was less appropriate to fit the data of GIM likely due to a physical rearrangement of the solid upon dissolution. The present findings demonstrate that ETPE in GIM decreases the risks of explosives leakage from particles of the new formulation and should facilitate the collecting of non-exploded GIM particles in training sites.

Indomethacin-Kollidon VA64 Extrudates: A Mechanistic Study of pH-Dependent Controlled Release.

PubMed

Tres, Francesco; Treacher, Kevin; Booth, Jonathan; Hughes, Leslie P; Wren, Stephen A C; Aylott, Jonathan W; Burley, Jonathan C

2016-03-07

Because of its weakly acidic nature (pKa of 4.5), indomethacin presents an aqueous solubility that significantly increases when changing from acidic to neutral/alkaline pH (1.5 μg/mL at pH 1.2 and 105.2 μg/mL at pH 7.4). We have therefore investigated the impact of the dissolution medium pH on the dissolution performance of indomethacin:Kollidon VA64 extrudates. The impact of the drug loading on the dissolution properties of these systems was also examined (5%, 15%, 30%, 50%, 70%, and 90% drug loading). Time-resolved Raman spectroscopy along with in-line UV-vis spectrophotometry was employed to directly relate changes in dissolution behavior to physicochemical changes that occur to the extrudate during the test. The dissolution tests were performed in pH 2 HCl (to mimic the stomach conditions), and this was then switched during the experiment to pH 6.8 phosphate buffer (to simulate the poststomach conditions). The rotating disc dissolution rate test was also used to simultaneously measure the dissolution rate of both the drug and the polymer. We found that in pH 2 HCl buffer, for the 15% or higher drug-loaded extrudates, Kollidon VA64 preferentially dissolves from the exterior of the compact leaving an amorphous drug-rich hydrophobic shell, which, similarly to an enteric coating, inhibits the drug release. The in situ formation of an enteric coating has been previously hypothesized, and this has been the first time that is directly observed in a pH-variable dissolution test. The dissolution medium switch to pH 6.8 phosphate buffer, due to the large increase of the aqueous solubility of indomethacin at this pH, leads to rapid dissolution of the material forming the coating and therefore total drug release. In contrast, the 5% extrudate is fully hydrated and quickly dissolves at low pH pointing to a dissolution performance dependent on highly water-soluble Kollidon VA64.

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.

Photodissolution of ferrihydrite in the presence of oxalic acid: an in situ ATR-FTIR/DFT study.

PubMed

Bhandari, Narayan; Hausner, Douglas B; Kubicki, James D; Strongin, Daniel R

2010-11-02

The photodissolution of the iron oxyhydroxide, ferrihydrite, in the presence of oxalic acid was investigated with vibrational spectroscopy, density functional theory (DFT) calculations, and batch geochemical techniques that determined the composition of the solution phase during the dissolution process. Specifically, in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR- FTIR) was used to determine the structure of the adsorbed layer during the dissolution process at a solution pH of 4.5. DFT based computations were used to interpret the vibrational data associated with the surface monolayer in order to help determine the structure of the adsorbed complexes. Results showed that at pH 4.5, oxalate adsorbed on ferrihydrite adopted a mononuclear bidentate (MNBD) binding geometry. Photodissolution at pH 4.5 exhibited an induction period where the rate of Fe(II) release was limited by a low concentration of adsorbed oxalate due to the site-blocking of carbonate that was intrinsic to the surface of the ferrihydrite starting material. Oxalate displaced this initial carbonate over time, and the dissolution rate showed a corresponding increase. Irradiation of oxalate/ferrihydrite at pH 4.5 also ultimately led to the appearance of carbonate reaction product (distinct from carbonate intrinsic to the starting material) on the surface.

Microstructure and mechanical properties of 2024-T3 and 7075-T6 aluminum alloys and austenitic stainless steel 304 after being exposed to hydrogen peroxide

NASA Astrophysics Data System (ADS)

Sofyan, Nofrijon Bin Imam

The effect of hydrogen peroxide used as a decontaminant agent on selected aircraft metallic materials has been investigated. The work is divided into three sections; bacterial attachment behavior onto an austenitic stainless steel 304 surface; effect of decontamination process on the microstructure and mechanical properties of aircraft metallic structural materials of two aluminum alloys, i.e. 2024-T3 and 7075-T6, and an austenitic stainless steel 304 as used in galley and lavatory surfaces; and copper dissolution rate into hydrogen peroxide. With respect to bacterial attachment, the results show that surface roughness plays a role in the attachment of bacteria onto metallic surfaces at certain extent. However, when the contact angle of the liquid on a surface increased to a certain degree, detachment of bacteria on that surface became more difficult. In its relation to the decontamination process, the results show that a corrosion site, especially on the austenitic stainless steel 304 weld and its surrounding HAZ area, needs more attention because it could become a source or a harborage of bio-contaminant agent after either incidental or intentional bio-contaminant delivery. On the effect of the decontamination process on the microstructure and mechanical properties of aircraft metallic structural materials, the results show that microstructural effects are both relatively small in magnitude and confined to a region immediately adjacent to the exposed surface. No systematic effect is found on the tensile properties of the three alloys under the conditions examined. The results of this investigation are promising with respect to the application of vapor phase hydrogen peroxide as a decontaminant agent to civilian aircraft, in that even under the most severe circumstances that could occur; only very limited damage was observed. The results from the dissolution of copper by concentrated liquid hydrogen peroxide showed that the rate of copper dissolution increased for the first 15 minutes of the reaction time with an activation energy of 19 kJ/mol, and then the fraction of copper dissolved became constant. This constant dissolution was expected to be due to the formation of copper hydroxide, which was observed to precipitate after the solution settled for some time. However, because the final consumption of hydrogen peroxide was not controlled, the exact reason for this constant dissolution cannot be determined at this time. The value of activation energy is within the range of activation energy found in the literature for other dissolution process. The low activation energy for dissolution of pure copper correlates with the observation of dissolution of copper from intermetallic particles in the aluminum alloys.

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

Biodurability of chrysotile and tremolite asbestos

NASA Astrophysics Data System (ADS)

Oze, C.; Solt, K.

2008-12-01

Chrysotile and tremolite asbestos represent two mineralogical categories of regulated asbestos commonly evaluated in epidemiological, toxicological, and pathological studies. Lung and digestive fluids are undersaturated with respect to chrysotile and tremolite asbestos (i.e. dissolution is thermodynamically favorable), where the dissolution kinetics control the durability of these minerals in respiratory and gastric systems. Here we examined the biodurability of chrysotile and tremolite asbestos in simulated body fluids (SBFs) as a function of mineral surface area over time. Batch experiments in simulated gastric fluid (SGF; HCl and NaCl solution at pH 1.2) and simulated lung fluid (SLF; a modified Gamble's solution at pH 7.4) were performed at 37°C over 720 hours. The rate-limiting step of Si release for both minerals was used to determine and compare dissolution rates. Chrysotile and tremolite asbestos are less biodurable in SGF compared to SLF. Based on equal suspension densities (surface area per volume of solution, m2 L- 1), chrysotile undergoes dissolution approximately 44 times faster than tremolite asbestos in SGF; however, amphibole asbestos dissolves approximately 6 times faster than chrysotile in SLF. Provided identical fiber dimensions, fiber dissolution models demonstrate that chrysotile is more biodurable in SLF and less biodurable in SGF compared to tremolite asbestos. Overall, the methodology employed here provides an alternative means to evaluate asbestos material fiber lifetimes based on mineral surface considerations.

Physical heterogeneity control on effective mineral dissolution rates

NASA Astrophysics Data System (ADS)

Jung, Heewon; Navarre-Sitchler, Alexis

2018-04-01

Hydrologic heterogeneity may be an important factor contributing to the discrepancy in laboratory and field measured dissolution rates, but the governing factors influencing mineral dissolution rates among various representations of physical heterogeneity remain poorly understood. Here, we present multiple reactive transport simulations of anorthite dissolution in 2D latticed random permeability fields and link the information from local grid scale (1 cm or 4 m) dissolution rates to domain-scale (1m or 400 m) effective dissolution rates measured by the flux-weighted average of an ensemble of flow paths. We compare results of homogeneous models to heterogeneous models with different structure and layered permeability distributions within the model domain. Chemistry is simplified to a single dissolving primary mineral (anorthite) distributed homogeneously throughout the domain and a single secondary mineral (kaolinite) that is allowed to dissolve or precipitate. Results show that increasing size in correlation structure (i.e. long integral scales) and high variance in permeability distribution are two important factors inducing a reduction in effective mineral dissolution rates compared to homogeneous permeability domains. Larger correlation structures produce larger zones of low permeability where diffusion is an important transport mechanism. Due to the increased residence time under slow diffusive transport, the saturation state of a solute with respect to a reacting mineral approaches equilibrium and reduces the reaction rate. High variance in permeability distribution favorably develops large low permeability zones that intensifies the reduction in mixing and effective dissolution rate. However, the degree of reduction in effective dissolution rate observed in 1 m × 1 m domains is too small (<1% reduction from the corresponding homogeneous case) to explain several orders of magnitude reduction observed in many field studies. When multimodality in permeability distribution is approximated by high permeability variance in 400 m × 400 m domains, the reduction in effective dissolution rate increases due to the effect of long diffusion length scales through zones with very slow reaction rates. The observed scale dependence becomes complicated when pH dependent kinetics are compared to the results from pH independent rate constants. In small domains where the entire domain is reactive, faster anorthite dissolution rates and slower kaolinite precipitation rates relative to pH independent rates at far-from-equilibrium conditions reduce the effective dissolution rate by increasing the saturation state. However, in large domains where less- or non-reactive zones develop, higher kaolinite precipitation rates in less reactive zones increase the effective anorthite dissolution rates relative to the rates observed in pH independent cases.

Superconcentrated electrolytes for a high-voltage lithium-ion battery

PubMed Central

Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro; Chiang, Ching Hua; Tateyama, Yoshitaka; Yamada, Atsuo

2016-01-01

Finding a viable electrolyte for next-generation 5 V-class lithium-ion batteries is of primary importance. A long-standing obstacle has been metal-ion dissolution at high voltages. The LiPF6 salt in conventional electrolytes is chemically unstable, which accelerates transition metal dissolution of the electrode material, yet beneficially suppresses oxidative dissolution of the aluminium current collector; replacing LiPF6 with more stable lithium salts may diminish transition metal dissolution but unfortunately encounters severe aluminium oxidation. Here we report an electrolyte design that can solve this dilemma. By mixing a stable lithium salt LiN(SO2F)2 with dimethyl carbonate solvent at extremely high concentrations, we obtain an unusual liquid showing a three-dimensional network of anions and solvent molecules that coordinate strongly to Li+ ions. This simple formulation of superconcentrated LiN(SO2F)2/dimethyl carbonate electrolyte inhibits the dissolution of both aluminium and transition metal at around 5 V, and realizes a high-voltage LiNi0.5Mn1.5O4/graphite battery that exhibits excellent cycling durability, high rate capability and enhanced safety. PMID:27354162

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.

Reactive-transport modelling of gypsum dissolution in a coastal karst aquifer in Puglia, southern Italy

NASA Astrophysics Data System (ADS)

Campana, Claudia; Fidelibus, Maria Dolores

2015-11-01

The gypsum coastal aquifer of Lesina Marina (Puglia, southern Italy) has been affected by sinkhole formation in recent decades. Previous studies based on geomorphologic and hydrogeological data ascribed the onset of collapse phenomena to the erosion of material that fills palaeo-cavities (suffosion sinkholes). The change in the hydrodynamic conditions of groundwater induced by the excavation of a canal within the evaporite formation nearly 100 years ago was identified as the major factor in triggering the erosion, while the contribution of gypsum dissolution was considered negligible. A combined reactive-transport/density-dependent flow model was applied to the gypsum aquifer to evaluate whether gypsum dissolution rate is a dominant or insignificant factor in recent sinkhole formation under current hydrodynamic conditions. The conceptual model was first defined with a set of assumptions based on field and laboratory data along a two-dimensional transect of the aquifer, and then a density-dependent, tide-influenced flow model was set up and solved using the numerical code SEAWAT. Finally, the resulting transient flow field was used by the reactive multicomponent transport model PHT3D to estimate the gypsum dissolution rate. The validation tests show that the model accurately represents the real system, and the multi-disciplinary approach provides consistent information about the causes and evolution time of dissolution processes. The modelled porosity development rate is too low to represent a significant contribution to the recent sinkhole formation in the Lesina Marina area, although it justifies cavity formation and cavity position over geological time.

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 does not adequately describe the kinetics of dissolution. The interplay of mineral composition and surface area, solution carbonate chemistry, temperature and pressure are factors the impact carbonate dissolution rates in natural settings. We suggest that these parameters be considered in CO2 mitigation strategies.

Crystallization kinetics of the borax decahydrate

NASA Astrophysics Data System (ADS)

Ceyhan, A. A.; Sahin, Ö.; Bulutcu, A. N.

2007-03-01

The growth and dissolution rates of borax decahydrate have been measured as a function of supersaturation for various particle sizes at different temperature ranges of 13 and 50 °C in a laboratory-scale fluidized bed crystallizer. The values of mass transfer coefficient, K, reaction rate constant, kr and reaction rate order, r were determined. The relative importances of diffusion and integration resistance were described by new terms named integration and diffusion concentration fraction. It was found that the overall growth rate of borax decahydrate is mainly controlled by integration (reaction) steps. It was also estimated that the dissolution region of borax decahydrate, apart from other materials, is controlled by diffusion and surface reaction. Increasing the temperature and particle size cause an increase in the values of kinetic parameters ( Kg, kr and K). The activation energies of overall, reaction and mass transfer steps were determined as 18.07, 18.79 and 8.26 kJmol -1, respectively.

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

Stirring effect on kaolinite dissolution rate

NASA Astrophysics Data System (ADS)

Metz, Volker; Ganor, Jiwchar

2001-10-01

Experiments were carried out measuring kaolinite dissolution rates using stirred and nonstirred flow-through reactors at pHs 2 to 4 and temperatures of 25°C, 50°C, and 70°C. The results show an increase of kaolinite dissolution rate with increasing stirring speed. The stirring effect is reversible, i.e., as the stirring slows down the dissolution rate decreases. The effect of stirring speed on kaolinite dissolution rate is higher at 25°C than at 50°C and 70°C and at pH 4 than at pHs 2 and 3. It is suggested that fine kaolinite particles are formed as a result of stirring-induced spalling or abrasion of kaolinite. These very fine particles have an increased ratio of reactive surface area to specific surface area, which results in enhancement of kaolinite dissolution rate. A balance between production and dissolution of the fine particles explains both the reversibility and the temperature and pH dependence of the stirring effect. Since the stirring effect on kaolinite dissolution rate varies with temperature and pH, measurement of kinetic parameters such as activation energy may be influenced by stirring. Therefore, standard use of nonagitated reaction vessels for kinetic experiments of mineral dissolution and precipitation is recommended, at least for slow reactions that are surface controlled.

Tadalafil inclusion in microporous silica as effective dissolution enhancer: optimization of loading procedure and molecular state characterization.

PubMed

Mehanna, Mohammed M; Motawaa, Adel M; Samaha, Magda W

2011-05-01

Tadalafil is an efficient drug used to treat erectile dysfunction characterized by poor water solubility, which has a negative influence on its bioavailability. Utilization of microporous silica represents an effective and facile technology to increase the dissolution rate of poorly soluble drugs. Our strategy involved directly introducing tadalafil as guest molecule into microporous silica as host material by incipient wetness impregnation method. To optimize tadalafil inclusion, response surface methodology (RSM) using 3(3) factorial design was utilized. Furthermore, to investigate the molecular state of tadalafil, Fourier-transform infrared spectroscopy, differential scanning calorimetery, thermal gravimetrical analysis, nitrogen adsorption, and powder X-ray diffraction (PXRD) were carried out. The results obtained pointed out that the quantity of microporous silica was the predominant factor that increased the loading efficiency. For the optimized formula, the loading efficiency was 42.50 wt %. Adsorption-desorption experiments indicated that tadalafil has been introduced into the micropores. Powder XRD and differential scanning calorimetry analyses revealed that tadalafil is arranged in amorphous form. In addition, the dissolution rate of tadalafil from the microporous silica was faster than that of free drug. Amorphous tadalafil occluded in microporous silica did not crystallize over 3 months. These findings contributed in opening a new strategy concerning the utilization of porous silica for the dissolution rate enhancement. Copyright © 2010 Wiley-Liss, Inc.

Dissolution profile of dolomite in chloric acid solution: The effect of chloric acid concentration and pulp density

NASA Astrophysics Data System (ADS)

Solihin, Indriani, Mubarok, M. Zaki

2018-05-01

Dolomite is one of carbonate minerals that contain magnesium. Magnesium is important element used in many aspects of life such as cofactor of many enzymes in human body, nutrient for plants, and raw material in automotive industry. Dolomite can be processed through low temperature process to obtain magnesium and calcium oxide that is needed in important applications such as base material for making drugs, raw material in the synthesize slow release fertilizer, materials for fire retardant, component for catalyst, etc. One of the important step of this low temperature process is dissolution of dolomite. Optimizing the dissolution process determines the % extraction of magnesium and calcium oxide from dolomite. The dissolution of dolomite from Gresik, East Java Provence Indonesia, in chloric acid solution has been conducted. Chloric acid concentration and pulp density are the variables that were observed. The dissolution of magnesium and calcium from Gresik dolomite was found to be very fast. The stable stage of dissolution can be reached for 5-10 seconds. The % extraction is mainly determined by the molar ratio of chloric acid / dolomite. At molar ratio of chloric acid / dolomite equal or above stoichiometric of dolomite dissolution, % extraction of magnesium is almost 100 %.

Investigating the Effects of Loading Factors on the In Vitro Pharmaceutical Performance of Mesoporous Materials as Drug Carriers for Ibuprofen

PubMed Central

Lai, Junmin; Lin, Wu; Scholes, Peter; Li, Mingzhong

2017-01-01

The aim of the study was to investigate the effects of the loading factors, i.e., the initial drug loading concentration and the ratio of the drug to carriers, on the in vitro pharmaceutical performance of drug-loaded mesoporous systems. Ibuprofen (IBU) was used as a model drug, and two non-ordered mesoporous materials of commercial silica Syloid® 244FP (S244FP) and Neusilin® US2 (NS2) were selected in the study. The IBU-loaded mesoporous samples were prepared by a solvent immersion method with a rotary evaporation drying technique and characterized by polarized light microscopy (PLM), Fourier transform infrared (FTIR) spectroscopy, X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC). Dissolution experiments were performed in simulated gastric media at 37 °C under non-sink conditions. The concentration of IBU in solution was determined by HPLC. The study showed that the dissolution rate of IBU can be improved significantly using the mesoporous S224FP carriers due to the conversion of crystalline IBU into the amorphous form. Both of the loading factors affected the IBU dissolution kinetics. Due to the molecular interaction between the IBU and NS2 carriers, the loading factors had little effects on the drug release kinetics with incomplete drug desorption recovery and insignificant dissolution enhancement. Care and extensive evaluation must therefore be taken when mesoporous materials are chosen as carrier delivery systems. PMID:28772509

A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

PubMed

Bock, David C; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2013-06-01

Silver vanadium oxide (Ag 2 V 4 O 11 , SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag 2 VO 2 PO 4 , SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO 4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most phosphate salts, a lower material solubility of SVPO relative to SVO is anticipated. Thus, the first vanadium dissolution studies of SVPO in battery electrolyte solutions are described herein. The equilibrium solubility of SVPO was ~5 times less than SVO, with a rate constant of dissolution ~3.5 times less than that of SVO. The vanadium dissolution in SVO and SVPO can be adequately described with a diffusion layer model, as supported by the Noyes-Whitney equation. Cells prepared with vanadium-treated anodes displayed higher AC impedance and DC resistance relative to control anodes. These data support the premise that SVPO cells are likely to exhibit reduced cathode solubility and thus less affected by increased cell resistance due to cathode solubility compared to SVO based cells.

Diatom species abundance and morphologically-based dissolution proxies in coastal Southern Ocean assemblages

NASA Astrophysics Data System (ADS)

Warnock, Jonathan P.; Scherer, Reed P.

2015-07-01

Taphonomic processes alter diatom assemblages in sediments, thus potentially negatively impacting paleoclimate records at various rates across space, time, and taxa. However, quantitative taphonomic data is rarely included in diatom-based paleoenvironmental reconstructions and no objective standard exists for comparing diatom dissolution in sediments recovered from marine depositional settings, including the Southern Ocean's opal belt. Furthermore, identifying changes to diatom dissolution through time can provide insight into the efficiency of both upper water column nutrient recycling and the biological pump. This is significant in that reactive metal proxies (e.g. Al, Ti) in the sediments only account for post-depositional dissolution, not the water column where the majority of dissolution occurs. In order to assess the range of variability of responses to dissolution in a typical Southern Ocean diatom community and provide a quantitative guideline for assessing taphonomic variability in diatoms recovered from core material, a sediment trap sample was subjected to controlled, serial dissolution. By evaluating dissolution-induced changes to diatom species' relative abundance, three preservational categories of diatoms have been identified: gracile, intermediate, and robust. The relative abundances of these categories can be used to establish a preservation grade for diatom assemblages. However, changes to the relative abundances of diatom species in sediment samples may reflect taphonomic or ecological factors. In order to address this complication, relative abundance changes have been tied to dissolution-induced morphological change to the areolae of Fragilariopsis curta, a significant sea-ice indicator in Southern Ocean sediments. This correlation allows differentiation between gracile species loss to dissolution versus ecological factors or sediment winnowing. These results mirror a similar morphological dissolution index from a parallel study utilizing Fragilariopsis kerguelensis, suggesting that results are applicable to a broad spectrum of diatoms typically preserved in the sediments.

Different Material States of Pub1 Condensates Define Distinct Modes of Stress Adaptation and Recovery.

PubMed

Kroschwald, Sonja; Munder, Matthias C; Maharana, Shovamayee; Franzmann, Titus M; Richter, Doris; Ruer, Martine; Hyman, Anthony A; Alberti, Simon

2018-06-12

How cells adapt to varying environmental conditions is largely unknown. Here, we show that, in budding yeast, the RNA-binding and stress granule protein Pub1 has an intrinsic property to form condensates upon starvation or heat stress and that condensate formation is associated with cell-cycle arrest. Release from arrest coincides with condensate dissolution, which takes minutes (starvation) or hours (heat shock). In vitro reconstitution reveals that the different dissolution rates of starvation- and heat-induced condensates are due to their different material properties: starvation-induced Pub1 condensates form by liquid-liquid demixing and subsequently convert into reversible gel-like particles; heat-induced condensates are more solid-like and require chaperones for disaggregation. Our data suggest that different physiological stresses, as well as stress durations and intensities, induce condensates with distinct physical properties and thereby define different modes of stress adaptation and rates of recovery. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Dissolution and characterization of HEV NiMH batteries.

PubMed

Larsson, Kristian; Ekberg, Christian; Ødegaard-Jensen, Arvid

2013-03-01

Metal recovery is an essential part of the recycling of hybrid electric vehicle battery waste and the first step in a hydrometallurgical treatment is dissolution of the solid material. The properties of separated battery electrode materials were investigated. Focus was put on both the solid waste and then the dissolution behaviour. The cathode contains metallic nickel that remains undissolved when utilizing non-oxidizing conditions such as hydrochloric or sulphuric acid in combination with a low oxygen atmosphere. In these conditions the cathode active electrode material is fully dissolved. Not dissolving the nickel metal saves up to 37% of the acid consumption for the cathode electrode material. In the commonly used case of oxidizing conditions the nickel metal dissolves and a cobalt-rich phase remains undissolved from the cathode active material. For the anode material a complete and rapid dissolution can be achieved at mild conditions with hydrochloric, nitric or sulphuric acid. Optimal parameters for all cases of dissolution was pH 1 with a reaction time of approximately ≥ 20,000 s. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effects of acid rain and sulfur dioxide on marble dissolution

USGS Publications Warehouse

Schuster, Paul F.; Reddy, Michael M.; Sherwood, Susan I.

1994-01-01

Acid precipitation and the dry deposition of sulfur dioxide (SO2) accelerate damage to carbonate-stone monuments and building materials. This study identified and quantified environmental damage to a sample of Vermont marble during storms and their preceding dry periods. Results from field experiments indicated the deposition of SO2 gas to the stone surface during dry periods and a twofold increase in marble dissolution during coincident episodes of low rain rate and decreased rainfall pH. The study is widely applicable to the analysis of carbonate-stone damage at locations affected by acid rain and air pollution.

Nanosizing of drugs: Effect on dissolution rate

PubMed Central

Dizaj, S. Maleki; Vazifehasl, Zh.; Salatin, S.; Adibkia, Kh.; Javadzadeh, Y.

2015-01-01

The solubility, bioavailability and dissolution rate of drugs are important parameters for achieving in vivo efficiency. The bioavailability of orally administered drugs depends on their ability to be absorbed via gastrointestinal tract. For drugs belonging to Class II of pharmaceutical classification, the absorption process is limited by drug dissolution rate in gastrointestinal media. Therefore, enhancement of the dissolution rate of these drugs will present improved bioavailability. So far several techniques such as physical and chemical modifications, changing in crystal habits, solid dispersion, complexation, solubilization and liquisolid method have been used to enhance the dissolution rate of poorly water soluble drugs. It seems that improvement of the solubility properties ofpoorly water soluble drugscan translate to an increase in their bioavailability. Nowadays nanotechnology offers various approaches in the area of dissolution enhancement of low aqueous soluble drugs. Nanosizing of drugs in the form of nanoparticles, nanocrystals or nanosuspensions not requiring expensive facilities and equipment or complicated processes may be applied as simple methods to increase the dissolution rate of poorly water soluble drugs. In this article, we attempted to review the effects of nanosizing on improving the dissolution rate of poorly aqueous soluble drugs. According to the reviewed literature, by reduction of drug particle size into nanometer size the total effective surface area is increased and thereby dissolution rate would be enhanced. Additionally, reduction of particle size leads to reduction of the diffusion layer thickness surrounding the drug particles resulting in the increment of the concentration gradient. Each of these process leads to improved bioavailability. PMID:26487886

Salt-enhanced chemical weathering of building materials and bacterial mineralization of calcium carbonate as a treatment

NASA Astrophysics Data System (ADS)

Schiro, M.; Ruiz-Agudo, E.; Jroundi, F.; Gonzalez-Muñoz, M. T.; Rodriguez-Navarro, C.

2012-04-01

Salt weathering is an important mechanism contributing to the degradation and loss of stone building materials. In addition to the physical weathering resulting from crystallization pressure, the presence of salts in solution greatly enhances the chemical weathering potential of pore waters. Flow through experiments quantify the dissolution rates of calcite and quartz grains (63-125 micrometer diameter) when subjected to 1.0 ionic strength solutions of MgSO4, MgCl, Na2SO4 or NaCl. Results indicate that the identity of the cation is the primary control over the dissolution rate of both calcite and quartz substrates, with salt-enhanced dissolution occurring most rapidly in Mg2+ bearing solutions. It has been observed that weathering rates of rocks in nature, as well as building stones, are slowed down by naturally occurring or artificially produced patinas. These tend to be bacterially produced, durable mineralized coatings that lend some degree of protection to the underlying stone surface [1]. Our research shows that bacterially produced carbonate coatings can be quite effective at reducing chemical weathering of stone by soluble salts. The calcite-producing-bacteria used in this study were isolated from stone monuments in Granada, Spain [2] and cultivated in an organic-rich culture medium on a variety of artificial and natural substrates (including limestone, marble, sandstone, quartz, calcite single crystals, glass cover-slips, and sintered porous glass). Scanning electron microscopy (FESEM) was used to image bacterial calcite growth and biofilm formation. In-situ atomic force microscopy (AFM) enabled calculation of dissolution rates of untreated and bacterially treated surfaces. 2D-XRD showed the mineralogy and crystallographic orientation of bacterial calcium carbonate. Results indicate that bacterially produced calcite crystals form a coherent, mechanically resistant surface layer in perfect crystallographic continuity with the calcite substrate (self-epitaxy). These calcite biominerals are more resistant to chemical weathering by salt-enhanced dissolution, apparently due to the incorporation of organics (bacterial exopolymeric substances, EPS). Conversely, on silicate substrates, non-oriented vaterite forms, leading to limited protection. These preliminary results indicate that bacterial treatments have a significant potential to protect the stone built cultural heritage. [1] De Muynck et al. (2010) Ecol. Eng. 36, 118-136. [2] Jimenez-Lopez et al. (2007) Chemosphere 68, 1929-1936.

Simultaneous in vitro and in vivo evaluation of both trimethoprim and sulfamethoxazole from certain dosage forms.

PubMed

Meshali, M; El-Sabbagh, H; Ghanem, A; Foda, A

1983-06-01

The dissolution rates of trimethoprim (T), and sulphamethoxazole (S), from different brands of tablets and suspensions were studied at pH = 1.1 and 7.2. The bioavailabilities of both drugs in humans were studied by the urine excretion method. The dissolution rates were dependent on the pH of the dissolution medium, the solubilities of the drugs at the pH involved, the dosage form and the brand studied. While the dissolution rates of T from all brands studied were consistent with their pH-dependent solubility, those of S were not. The dissolution rates of S from suspensions were found to be equal at pH = 7.2, but different at pH = 1.1. A correlation existed between the dissolution rate of T at pH = 1.1 from tablets and the excretion rate in humans. With S, however, no such correlation was observed at either pH.

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.

Resorption Rate Tunable Bioceramic: Si, Zn-Modified Tricalcium Phosphate

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

Wei, Xiang

2006-01-01

This dissertation is organized in an alternate format. Several manuscripts which have already been published or are to be submitted for publication have been included as separate chapters. Chapter 1 is a general introduction which describes the dissertation organization and introduces the human bone and ceramic materials as bone substitute. Chapter 2 is the background and literature review on dissolution behavior of calcium phosphate, and discussion of motivation for this research. Chapter 3 is a manuscript entitled ''Si,Zn-modified tricalcium phosphate: a phase composition and crystal structure study'', which was published in ''Key Engineering Materials'' [1]. Chapter 4 gives more crystalmore » structure details by neutron powder diffraction, which identifies the position for Si and Zn substitution and explains the stabilization mechanism of the structure. A manuscript entitled ''Crystal structure analysis of Si, Zn-modified Tricalcium phosphate by Neutron Powder Diffraction'' will be submitted to Biomaterials [2]. Chapter 5 is a manuscript, entitled ''Dissolution behavior and cytotoxicity test of Si, Zn-modified tricalcium phosphate'', which is to be submitted to Biomaterials [3]. This paper discusses the additives effect on the dissolution behavior of TCP, and cytotoxicity test result is also included. Chapter 6 is the study of hydrolysis process of {alpha}-tricalcium phosphate in the simulated body fluid, and the phase development during drying process is discussed. A manuscript entitled ''Hydrolysis of {alpha}-tricalcium phosphate in simulated body fluid and phase transformation during drying process'' is to be submitted to Biomaterials [4]. Ozan Ugurlu is included as co-authors in these two papers due to his TEM contributions. Appendix A is the general introduction of the materials synthesis, crystal structure and preliminary dissolution result. A manuscript entitled ''Resorption rate tunable bioceramic: Si and Zn-modified tricalcium phosphate'' was published in Ceramic Engineering and Science Proceedings (the 29th International Conference on Advanced Ceramics and Composites - Advances in Bioceramics and Biocomposites) [5].« less

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.

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.

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

NASA Astrophysics Data System (ADS)

Marc, Philippe; Magnaldo, Alastair; Godard, Jérémy; Schaer, Éric

2018-03-01

Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the "true" chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

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.

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.

Freshwater biodissolution rates of limestone in the temperate climate of the Dinaric karst in Slovenia

NASA Astrophysics Data System (ADS)

Mulec, J.; Prelovšek, M.

2015-01-01

Dissolution rates in two freshwater karst systems were determined by using tablets of dense micrite-biopelmicrite Cretaceous limestone. Submerged limestone tablets in riverbeds were subjected to a natural gradient from complete darkness to direct sunlight. Higher light rates significantly (p < 0.05) increased the epilithic biomass of phototrophs and the overall dissolution rates, which were highest at the Unica spring (- 49.2 μm a- 1), but the exact portion of light-dependent dissolution remains elusive. In the karst river Unica, with its big fluctuations in environmental parameters (e.g., discharge), light rates can be used in estimating the dissolution rates enhanced by phototrophs. Natural biofilms in aquatic systems have important implications for landform evolution, and the impact on limestone dissolution rates is comparable with rates of debris falling from steep slopes.

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 affinity for PVPP may be easily affected by airborne water under high temperature and humid conditions. This article is open to POST-PUBLICATION REVIEW. Registered readers (see "For Readers") may comment by clicking on ABSTRACT on the issue's contents page.

Capsule shell material impacts the in vitro disintegration and dissolution behaviour of a green tea extract☆

PubMed Central

Glube, Natalie; Moos, Lea von; Duchateau, Guus

2013-01-01

Purpose In vitro disintegration and dissolution are routine methods used to assess the performance and quality of oral dosage forms. The purpose of the current work was to determine the potential for interaction between capsule shell material and a green tea extract and the impact it can have on the release. Methods A green tea extract was formulated into simple powder-in-capsule formulations of which the capsule shell material was either of gelatin or HPMC origin. The disintegration times were determined together with the dissolution profiles in compendial and biorelevant media. Results All formulations disintegrated within 30 min, meeting the USP criteria for botanical formulations. An immediate release dissolution profile was achieved for gelatin capsules in all media but not for the specified HPMC formulations. Dissolution release was especially impaired for HPMCgell at pH 1.2 and for both HPMC formulations in FeSSIF media suggesting the potential for food interactions. Conclusions The delayed release from studied HPMC capsule materials is likely attributed to an interaction between the catechins, the major constituents of the green tea extract, and the capsule shell material. An assessment of in vitro dissolution is recommended prior to the release of a dietary supplement or clinical trial investigational product to ensure efficacy. PMID:25755998

Capsule shell material impacts the in vitro disintegration and dissolution behaviour of a green tea extract.

PubMed

Glube, Natalie; Moos, Lea von; Duchateau, Guus

2013-01-01

In vitro disintegration and dissolution are routine methods used to assess the performance and quality of oral dosage forms. The purpose of the current work was to determine the potential for interaction between capsule shell material and a green tea extract and the impact it can have on the release. A green tea extract was formulated into simple powder-in-capsule formulations of which the capsule shell material was either of gelatin or HPMC origin. The disintegration times were determined together with the dissolution profiles in compendial and biorelevant media. All formulations disintegrated within 30 min, meeting the USP criteria for botanical formulations. An immediate release dissolution profile was achieved for gelatin capsules in all media but not for the specified HPMC formulations. Dissolution release was especially impaired for HPMCgell at pH 1.2 and for both HPMC formulations in FeSSIF media suggesting the potential for food interactions. The delayed release from studied HPMC capsule materials is likely attributed to an interaction between the catechins, the major constituents of the green tea extract, and the capsule shell material. An assessment of in vitro dissolution is recommended prior to the release of a dietary supplement or clinical trial investigational product to ensure efficacy.

Laboratory study of fungal bioreceptivity of different fractions of composite flooring tiles showing efflorescence.

PubMed

Masaphy, Segula; Lavi, Ido; Sultz, Stephan; Zabari, Limor

2014-06-01

Fungi can grow in extreme habitats, such as natural stone and mineral building materials, sometimes causing deterioration. Efflorescence-concentrated salt deposits-results from water movement through building material; it can damage masonry materials and other bricks. Fungal isolate KUR1, capable of growth on, and dissolution of stone chips composing terrazzo-type floor tiles, was isolated from such tiles showing fiber-like crystalline efflorescence. The isolate's ribosomal DNA sequences were 100 % identical to those of Nigrospora sphaerica. The ability of KUR1 to colonize and degrade the different stone chips composing the tiles was studied in axenic culture experiments. When exposed to each of the different mineral chip types composed of dolomite, calcite, or calcite-apatite mineral in low-nutrition medium, the fungus showed selective nutrient consumption, and different growth and stone mineral dissolution rates. Micromorphological examination of the fungus-colonized chips by electron microscopy showed the production of a fungal biofilm with thin films around the hyphae on the surface of the examined chips and disintegration of the calcite-apatite fraction. More than 70 % dissolution of the introduced powdered (<1 mm particle size) mineral was obtained within 10 days of incubation for the soft calcite-apatite fraction.

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.

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

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

NASA Astrophysics Data System (ADS)

Jin, Lixin; Williams, Erika L.; Szramek, Kathryn J.; Walter, Lynn M.; Hamilton, Stephen K.

2008-02-01

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition. Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO 2. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg 2+/Ca 2+ ratio of 0.4. Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca 2+ and Mg 2+ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg 2+ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.

A dissolution-precipitation mechanism is at the origin of concrete creep in moist environments

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

Pignatelli, Isabella; Kumar, Aditya; Alizadeh, Rouhollah

Long-term creep (i.e., deformation under sustained load) is a significant material response that needs to be accounted for in concrete structural design. However, the nature and origin of concrete creep remain poorly understood and controversial. Here, we propose that concrete creep at relative humidity ≥ 50%, but fixed moisture content (i.e., basic creep), arises from a dissolution-precipitation mechanism, active at nanoscale grain contacts, as has been extensively observed in a geological context, e.g., when rocks are exposed to sustained loads, in liquid-bearing environments. Based on micro-indentation and vertical scanning interferometry data and molecular dynamics simulations carried out on calcium–silicate–hydrate (C–S–H),more » the major binding phase in concrete, of different compositions, we show that creep rates are correlated with dissolution rates—an observation which suggests a dissolution-precipitation mechanism as being at the origin of concrete creep. C–S–H compositions featuring high resistance to dissolution, and, hence, creep are identified. Analyses of the atomic networks of such C–S–H compositions using topological constraint theory indicate that these compositions present limited relaxation modes on account of their optimally connected (i.e., constrained) atomic networks.« less

Formulation and optimization of mouth dissolve tablets containing rofecoxib solid dispersion.

PubMed

Sammour, Omaima A; Hammad, Mohammed A; Megrab, Nagia A; Zidan, Ahmed S

2006-06-16

The purpose of the present investigation was to increase the solubility and dissolution rate of rofecoxib by the preparation of its solid dispersion with polyvinyl pyrrolidone K30 (PVP K30) using solvent evaporation method. Drug-polymer interactions were investigated using differential scanning calorimetry (DSC), x-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). For the preparation of rofecoxib mouth dissolve tablets, its 1:9 solid dispersion with PVP K30 was used with various disintegrants and sublimable materials. In an attempt to construct a statistical model for the prediction of disintegration time and percentage friability, a 3(2) randomized full and reduced factorial design was used to optimize the influence of the amounts of superdisintegrant and subliming agent. The obtained results showed that dispersion of the drug in the polymer considerably enhanced the dissolution rate. The drug-to-carrier ratio was the controlling factor for dissolution improvement. FTIR spectra revealed no chemical incompatibility between the drug and PVP K30. As indicated from XRD and DSC data, rofecoxib was in the amorphous form, which explains the better dissolution rate of the drug from its solid dispersions. Concerning the optimization study, the multiple regression analysis revealed that an optimum concentration of camphor and a higher percentage of crospovidone are required for obtaining rapidly disintegrating tablets. In conclusion, this investigation demonstrated the potential of experimental design in understanding the effect of the formulation variables on the quality of mouth dissolve tablets containing solid dispersion of a hydrophobic drug.

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 laws of our model give rough rates in the range 10-6 -10-5 mol/(m2 s). This estimate is consistent with the range of calcite dissolution rates obtained in a recent work after treatment of literature data, which suggests the universal control of kink site dissolution in short term laboratory works. The weak effects of lattice size on our results also suggest that smoothing of mineral grain surfaces across geological times may be a microscopic explanation for the difference of chemical weathering rate of silicate minerals in laboratory and in the environment.

Alternate Fuel Cycle Technologies/Thorium Fuel Cycle Technology Programs. Quarterly report for period 1 April--30 June 1978

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

Vondra, B.L.

1978-08-01

Voloxidation and dissolution studies: rotary-kiln heat-transfer tests are under way using a small rotary kiln along with the development of a mathematical model to determine kiln-heat-flux profiles necessary to maintain a desired temperature gradient. The erosion/corrosion test for evaluating materials of construction is operational. Fuel from a BWR (Big Rock Point) yielded more fine solid residue on dissolution than in previous tests with PWR fuel. Two additional parametric voloxidation tests with H.B. Robinson fuel compared air vs pure oxygen atmospheres at 550{sup 0}C; overall tritium release and subsequent fuel dissolution were equivalent. Thorium dissolution studies: the dissolution rate of thoriamore » in fluoride-catalyzed 8 to 14 M HNO{sub 3} (100{sup 0}C) was max between 0.04 to 0.06 M HF; at higher fluoride concentrations, ThF{sub 4}.5H{sub 2}O precipitated. The rate of zircaloy dissolution continued to increase with increasing fluoride concentration. Stainless-steel-clad (Th,U)0{sub 2} fuel rods irradiated in the NRX reactor were sheared, voloxidized, and dissolved. {le}10% of the tritium was released during voloxidation in air at 600{sup 0}C. Carbon-14 removal from off-gas and fixation: carbon dioxide removal with Linde 13X molecular sieves to less than 100 ppB was experimentally verified using 300 ppM CO in air. Decontamination factors from 3000 to 7500 were obtained for CO{sub 2} removal in the gas-slurry stirred-tank reactor with CA(OH){sub 2}.or Ba(0H){sub 2}/sup .8H2O./. With Ba(OH){sub 2}.H{sub 2}0{sup 2} in a fixed-bed column, decontamination factors of about 30,000 were obtained.« less

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.

The long-term acceleration of waste glass corrosion: A preliminary review

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

Kielpinski, A.L.

1995-07-01

Whereas a prior conception of glass dissolution assumed a relatively rapid initial dissolution which then slowed to a smaller, fairly constant longer-term rate, some recent work suggests that these two stages are followed by a third phase of dissolution, in which the dissolution rate is accelerated with respect to what had previously been thought of as the final long-term rate. The goals of the present study are to compile experimental data which may have a bearing on this phenomena, and to provide an initial assessment of these data. The Savannah River Technology Center (SRTC) is contracted to develop glass formulationmore » models for vitrification of Hanford low-level waste (LLW), in support of the Hanford Tank Waste Remediation System Technology Development Program. The phenomenon of an increase in corrosion rate, following a period characterized by a low corrosion rate, has been observed by a number of researchers on a number of waste glass compositions. Despite inherent ambiguities arising from SA/V (glass surface area to solution volume ratio) and other effects, valid comparisons can be made in which accelerated corrosion was observed in one test, but not in another. Some glass compositions do not appear to attain a plateau region; it may be that the observation of continued, non-negligible corrosion in these glasses represents a passage from the initial rate to the accelerated rate. The long-term corrosion is a function of the interaction between the glass and its environment, including the leaching solution and the surrounding materials. Reaction path modeling and stability field considerations have been used with some success to predict the changes in corrosion rate over time, due to these interactions. The accelerated corrosion phenomenon highlights the need for such integrated corrosion modeling and the scenario-specific nature of a particular glass composition`s durability.« less

Effects of selective handling of pyritic, acid-forming materials on the chemistry of pore gas and ground water at a reclaimed surface coal mine in Clarion County, PA, USA

USGS Publications Warehouse

Cravotta,, Charles A.; Dugas, Diana L.; Brady, Keith; Kovalchuck, Thomas E.

1994-01-01

A change from dragline to “selective handling” mining methods at a reclaimed surface coal mine in western Pennsylvania did not significantly affect concentrations of metals in ground water because oxidation of pyrite and dissolution of siderite were not abated. Throughout the mine, placement of pyritic material near the land surface facilitated the oxidation of pyrite, causing the consumption of oxygen (O2) and release of acid, iron, and sulfate ions. Locally in the unsaturated zone, water sampled within or near pyritic zones was acidic, with concentrations of sulfate exceeding 3,000 milligrams per liter (mg/L). However, acidic conditions generally did not persist below the water table because of neutralization by carbonate minerals. Dissolution of calcite, dolomite, and siderite in unsaturated and saturated zones produced elevated concentrations of carbon dioxide (CO2), alkalinity, calcium, magnesium, iron, and manganese. Alkalinity concentrations of 600 to 800 mg/L as CaCO3 were common in water samples from the unsaturated zone in spoil, and alkalinities of 100 to 400 mg/L as CaCO3 were common in ground-water samples from the underlying saturated zone in spoil and bedrock. Saturation indices indicated that siderite could dissolve in water throughout the spoil, but that calcite dissolution or precipitation could occur locally. Calcite dissolution could be promoted as a result of pyrite oxidation, gypsum precipitation, and calcium ion exchange for sodium. Calcite precipitation could be promoted by evapotranspiration and siderite dissolution, and corresponding increases in concentrations of alkalinity and other solutes. Partial pressures of O2 (Po2) and CO2 (Pco2) in spoil pore gas indicated that oxidation of pyrite and precipitation of ferric hydroxide, coupled with dissolution of calcite, dolomite, and siderite were the primary reactions affecting water quality. Highest vertical gradients in Po2, particularly in the near-surface zone (0-1 m), did not correlate with concentrations of total sulfur in spoil. This lack of correlation could indicate that total sulfur concentrations in spoil do not reflect the amount of reactive pyrite or that oxidation rates can be controlled more by rates of O2 diffusion than the amount of pyrite. Hence, if placed in O2-rich zones near the land surface, even small amounts of disseminated pyritic material can be relatively significant sources of acid and mineralized water.

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.

A reaction limited in vivo dissolution model for the study of drug absorption: Towards a new paradigm for the biopharmaceutic classification of drugs.

PubMed

Macheras, Panos; Iliadis, Athanassios; Melagraki, Georgia

2018-05-30

The aim of this work is to develop a gastrointestinal (GI) drug absorption model based on a reaction limited model of dissolution and consider its impact on the biopharmaceutic classification of drugs. Estimates for the fraction of dose absorbed as a function of dose, solubility, reaction/dissolution rate constant and the stoichiometry of drug-GI fluids reaction/dissolution were derived by numerical solution of the model equations. The undissolved drug dose and the reaction/dissolution rate constant drive the dissolution rate and determine the extent of absorption when high-constant drug permeability throughout the gastrointestinal tract is assumed. Dose is an important element of drug-GI fluids reaction/dissolution while solubility exclusively acts as an upper limit for drug concentrations in the lumen. The 3D plots of fraction of dose absorbed as a function of dose and reaction/dissolution rate constant for highly soluble and low soluble drugs for different "stoichiometries" (0.7, 1.0, 2.0) of the drug-reaction/dissolution with the GI fluids revealed that high extent of absorption was found assuming high drug- reaction/dissolution rate constant and high drug solubility. The model equations were used to simulate in vivo supersaturation and precipitation phenomena. The model developed provides the theoretical basis for the interpretation of the extent of drug's absorption on the basis of the parameters associated with the drug-GI fluids reaction/dissolution. A new paradigm emerges for the biopharmaceutic classification of drugs, namely, a model independent biopharmaceutic classification scheme of four drug categories based on either the fulfillment or not of the current dissolution criteria and the high or low % drug metabolism. Copyright © 2018. Published by Elsevier B.V.

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 and to elucidate the stoichiometry of the reaction. After the implementation of (i) the obtained f(ΔGr) term in the K-montmorillonte dissolution rate law, (ii) a fraction of highly reactive particles and surfaces and (iii) the cation exchange reactions between the interlayer K+ and the released Al3+, Mg2+, Ca2+ and H+, the simulations agreed with the experimental concentrations at the outlet. This match indicates that fast dissolution of fine particles and highly reactive sites and exchange between the interlayer K and dissolved structural cations (Al and Mg) and protons are responsible for the temporary incongruency of the K-montmorillonite dissolution reaction. As long as dissolution of the bulk sample predominates, the reaction is stoichiometric.

Density functional theory (DFT) study on the hydrolysis behavior of degradable Mg/Mg alloys for biomedical applications

NASA Astrophysics Data System (ADS)

Nezafati, Marjan

Magnesium-based (Mg and/or Mg alloys) materials possess many advantageous physicochemical/biological characteristics such as good biocompatibility and similarity of the mechanical properties to the human bone tissue, which renders this material a promising candidate for the biomedical and implant applications. One of the most attractive features of Mg-based materials is the degradability in the physiological environment. With the burst of research on the biodegradable materials for the healthcare device applications, Mg and its alloys attracted a strong attention in the bioengineering field in recent years. However, the major limitation of applying Mg-based materials to biomedical applications is the fast degradation/corrosion rate with regards to the healing process time-span. In the present thesis, an atomistic model employing the density-functional theory (DFT) has been developed to study the hydrolysis process by understanding the influences of commonly used alloying elements (zinc (Zn), calcium (Ca), aluminum (Al), and yttrium (Y)) and the crystallographic orientation of the dissolution surfaces (basal (0001), prism (1010), and pyramidal (1011) planes) on the corrosion behavior. These parameters are known to strongly impact the initial hydrolysis phenomena of Mg-based materials. To develop the atomistic computational model, we have implemented the Dmol3 software package in conjunction with PBE (Perdew, Burke and Ernzerhof) correlation energy functional in the GGA (generalized gradient approximation) scheme. Throughout the thesis, we performed three sets of calculations, i) surface energy, ii) dissolution potential, and iii) water adsorption computations, to examine the hydrolysis mechanism and the subsequent corrosion/degradation of Mg/Mg alloys. The total energy changes of various Mg-based systems in different conditions for these surface energies, dissolution behavior, and tendency of the system for adsorbing the water molecule were quantified. The results obtained from the atomistic model showed that these structural/compositional parameters (i.e., different types of alloying elements and surface planes) can considerably impact the stability of surfaces that are in contact with the corrosion media. The dissolution potential change computation predicted that Al can prevent the dissolution of Mg atoms from the surface of Mg-Al systems. In addition, it was found that the trend of water adsorption phenomena with different alloying elements/planes can be well-explained by the stability of corrosion surface.

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 increases the mass transfer rate. Correlations derived for mass transfer from solids in liquids under various operating conditions were applied to the Al--Si system. A new correlation for combined natural and forced convection mass transfer from vertical cylinders in cross flow is presented, and a modification is proposed to take into account free stream turbulence in a correlation for forced convection mass transfer from vertical cylinders in cross flow.

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.

Novel topcoat materials with improved receding angles and dissolution properties for ArF immersion lithography

NASA Astrophysics Data System (ADS)

Yun, Sang Geun; Lee, Jin Young; Yang, Young Soo; Shin, Seung Wook; Lee, Sung Jae; Kwon, Hyo Young; Cho, Youn Jin; Choi, Seung Jib; Choi, Sang Jun; Kim, Jong Seob; Chang, Tuwon

2010-04-01

A topcoat material plays a significant role in achieving technology nodes below 45 nm via ArF immersion lithography. Switching the exposure medium between the lens and the photoresist (PR) film from gas (air, n=1) to liquid (H2O, n=1.44) may lead to leaching of the polymer, the photoacid generator (PAG), or the solvent. These substances can contaminate the lens or cause bubbles, which can lead to defects during the patterning. Previously reported topcoat materials mainly use hydrophobic fluoro-compounds and carboxylic acids to provide high dissolution rates (DR) to basic developers as well as high receding contact angles (RCA). Recently, the demand for a new top-coat material has risen since current materials cause water-mark defects and decreases in scan speeds, due to insufficient RCA's. However, RCA and DR are in a trade-off relationship as an increase in RCA generally results in a lower DR. To overcome this, a novel polymer with high-fluorine content was synthesized to produce a topcoat material with improved DR (120 nm/s in 2.38 wt% TMAH) and RCA (>70°). In addition, a strategy to control the pattern profile according to needs of customers was found.

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 future reactive transport modeling.

Dissolution of Hydrocarbon Gas Hydrates in Seawater at 1030-m; Effects of Porosity, Structure, and Compositional Variation as Determined by High-Definition Video and SEM Imaging.

NASA Astrophysics Data System (ADS)

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

2002-12-01

We compare dissolution rates of pure, porous, compacted, and oil-contaminated sI methane hydrate and sII methane-ethane hydrate to rates measured previously on pure, compacted, sI methane hydrate and sI carbon dioxide hydrate (Rehder et al., Fall AGU 2001). Laboratory-synthesized test specimens were used in both studies, allowing characterization of test materials prior to their transport and exposure to seawater at 1030-meter depth on the Monterey Canyon seafloor, off coastal Moss Landing, CA. Although pressure and temperature (P-T) conditions at this site are within the nominal P-T equilibrium fields of all gas hydrates tested here, the seawater is undersaturated with respect to the hydrate-forming gas species. Hence, samples dissolve with time, at a rate dependent on water current flow. Four samples were deployed in this second experiment: (1) pure, 30% porous methane hydrate; (2) pure, compacted methane hydrate; (3) pure methane hydrate compacted and then contaminated with a low-T mineral oil; and (4) pure, compacted sII methane-ethane hydrate with methane:ethane molar ratio 0.72. Samples were transferred by pressure vessel at 0 ° C and 15 MPa to the seafloor observatory via the MBARI remotely operated vehicle Ventana. Samples were then exposed to the deep ocean environment and monitored by HDTV camera for several hours at the beginning and end of a 25-hour period. Local current speed and direction were also measured throughout the experiment. Those samples that did not undergo complete dissolution after 25 h were successfully recovered to the laboratory for subsequent analysis by scanning electron microscopy (SEM). Previously, video analysis showed dissolution rates corresponding to 4.0 +/- 0.5 mmole CO2/m2 s for compacted CO2 hydrate samples, and 0.37 +/- 0.03 mmole CH4/m2s for compacted methane hydrate samples (Rehder et al, AGU 2001). The ratio of dissolution rates fits a simple diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site. These calculations assume that dissolution occurred only along the outer (i.e. imaged) surface of the samples. This assumption is now validated by SEM analysis of recovered samples from the second dive, showing little to no internal alteration of compacted material following their partial dissolution. Quantitative comparison of results from the two dives poses challenges due to variations in sample size and orientation. However, both compacted methane hydrate samples from the second dive in fact exhibited comparable behavior to that measured in the previous experiment; the oily sample did not dissolve at a slower rate, as might be expected if a hydrophobic contaminant inhibits seawater contact. Surprisingly, the porous methane hydrate exhibited significantly slower face retreat than its compacted counterparts. The sII methane-ethane hydrate dissolved measurably slower than all other samples, consistent with the solubility properties of its guest components. While these results represent only a first step in emulating the more complex interactions of seawater with naturally occurring hydrate-bearing sediments, such end member studies should aid preliminary modelling investigations of the chemical stability and lifetime of gas hydrates exposed at the seafloor.

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.

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.

[Key physical parameters of hawthorn leaf granules by stepwise regression analysis method].

PubMed

Jiang, Qie-Ying; Zeng, Rong-Gui; Li, Zhe; Luo, Juan; Zhao, Guo-Wei; Lv, Dan; Liao, Zheng-Gen

2017-05-01

The purpose of this study was to investigate the effect of key physical properties of hawthorn leaf granule on its dissolution behavior. Hawthorn leaves extract was utilized as a model drug. The extract was mixed with microcrystalline cellulose or starch with the same ratio by using different methods. Appropriate amount of lubricant and disintegrating agent was added into part of the mixed powder, and then the granules were prepared by using extrusion granulation and high shear granulation. The granules dissolution behavior was evaluated by using equilibrium dissolution quantity and dissolution rate constant of the hypericin as the indicators. Then the effect of physical properties on dissolution behavior was analyzed through the stepwise regression analysis method. The equilibrium dissolution quantity of hypericin and adsorption heat constant in hawthorn leaves were positively correlated with the monolayer adsorption capacity and negatively correlated with the moisture absorption rate constant. The dissolution rate constants were decreased with the increase of Hausner rate, monolayer adsorption capacity and adsorption heat constant, and were increased with the increase of Carr index and specific surface area. Adsorption heat constant, monolayer adsorption capacity, moisture absorption rate constant, Carr index and specific surface area were the key physical properties of hawthorn leaf granule to affect its dissolution behavior. Copyright© by the Chinese Pharmaceutical Association.

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.

Towards a molecular understanding of cellulose dissolution in ionic liquids: anion/cation effect, synergistic mechanism and physicochemical aspects.

PubMed

Li, Yao; Wang, Jianji; Liu, Xiaomin; Zhang, Suojiang

2018-05-07

Cellulose is one of the most abundant bio-renewable materials on the earth and its conversion to biofuels provides an appealing way to satisfy the increasing global energy demand. However, before carrying out the process of enzymolysis to glucose or polysaccharides, cellulose needs to be pretreated to overcome its recalcitrance. In recent years, a variety of ionic liquids (ILs) have been found to be effective solvents for cellulose, providing a new, feasible pretreatment strategy. A lot of experimental and computational studies have been carried out to investigate the dissolution mechanism. However, many details are not fully understood, which highlights the necessity to overview the current knowledge of cellulose dissolution and identify the research trend in the future. This perspective summarizes the mechanistic studies and microscopic insights of cellulose dissolution in ILs. Recent investigations of the synergistic effect of cations/anions and the distinctive structural changes of cellulose microfibril in ILs are also reviewed. Besides, understanding the factors controlling the dissolution process, such as the structure of anions/cations, viscosity of ILs, pretreatment temperature, heating rate, etc. , has been discussed from a structural and physicochemical viewpoint. At the end, the existing problems are discussed and future prospects are given. We hope this article would be helpful for deeper understanding of the cellulose dissolution process in ILs and the rational design of more efficient and recyclable ILs.

Towards a molecular understanding of cellulose dissolution in ionic liquids: anion/cation effect, synergistic mechanism and physicochemical aspects

PubMed Central

Li, Yao; Wang, Jianji

2018-01-01

Cellulose is one of the most abundant bio-renewable materials on the earth and its conversion to biofuels provides an appealing way to satisfy the increasing global energy demand. However, before carrying out the process of enzymolysis to glucose or polysaccharides, cellulose needs to be pretreated to overcome its recalcitrance. In recent years, a variety of ionic liquids (ILs) have been found to be effective solvents for cellulose, providing a new, feasible pretreatment strategy. A lot of experimental and computational studies have been carried out to investigate the dissolution mechanism. However, many details are not fully understood, which highlights the necessity to overview the current knowledge of cellulose dissolution and identify the research trend in the future. This perspective summarizes the mechanistic studies and microscopic insights of cellulose dissolution in ILs. Recent investigations of the synergistic effect of cations/anions and the distinctive structural changes of cellulose microfibril in ILs are also reviewed. Besides, understanding the factors controlling the dissolution process, such as the structure of anions/cations, viscosity of ILs, pretreatment temperature, heating rate, etc., has been discussed from a structural and physicochemical viewpoint. At the end, the existing problems are discussed and future prospects are given. We hope this article would be helpful for deeper understanding of the cellulose dissolution process in ILs and the rational design of more efficient and recyclable ILs. PMID:29780532

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.

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 concentration. Complete dissolution of the Al 1100 and Al 6061 T6 alloys up to a final Al concentration of 2 M was obtained using a 7 M HNO 3 solution containing a 0.002 M Hg catalyst. However, following the dissolutions, solids were observed in the solution. The solids were amorphous, but likely originated from the Si present in the alloys. No crystalline materials, such as Al(NO 3) 3 were observed. During the course of the dissolution experiments, it was determined that delaying the addition of Hg once the HNO 3 solution reached the boiling point can reduce the total offgas and H 2 generation rates. The delay in starting the Hg addition is not necessary for HFIR fuel dissolution, but could be useful in other research reactor dissolution campaigns. The potential to generate flammable concentrations of H 2 in the offgas during a HFIR fuel dissolution was evaluated using the experimental data. The predicted H 2 concentration in the dissolver offgas stream was compared with 60% of the calculated H 2 LFL at 200 °C using several prototypical experiments. The calculations showed that a full HFIR core can be dissolved using nominally 0.002 M Hg to catalyze the dissolution. The margin between the predicted H 2 concentration and the calculated LFL was greater when the solution was allowed to boil for 45 min prior to initiating the Hg addition. When the Hg was increased to 0.004 M, the predicted H 2 concentration exceeded the calculated LFL early in the dissolution. The dissolution experiments also demonstrated that additional Hg (beyond the initial 0.002 M) could be added as the Al concentration increases. The ability to add more Hg during a HFIR fuel dissolution could be beneficial if slow dissolution rates are observed at high Al concentrations. Experimental data were used to demonstrate that the predicted H 2 concentration in a dissolver was below 60% of the calculated LFL at 200 °C when 0.004 M Hg was used to catalyze the dissolution if the Al concentration is conservatively greater than 0.5 M. Data also show that the Hg concentration during a HFIR fuel dissolution can be increased from 0.002 to 0.008 M at an Al concentration of 1.3 M.« less

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 function of the rate constants k being those measured under well-mixed conditions, effective surface area in equivalent homogeneous media Ae,hm, and the heterogeneity factor (1 - exp(-τa/τa,r))α. The heterogeneity factor quantify heterogeneity effects and depends on the relative magnitude of global residence time (τa) and reactive residence time (τa,r), as well as the shape factor α(= 5 σlnκ2) of the gamma distribution for reactive residence times. Exponential forms of rate laws have been used at the micro-scale describing direct interactions among water and mineral surface, and at the catchment scale describing weathering rates and concentration-discharge relationships. These observations highlight the key role of mineral-water contact time in determining dissolution rates at different scales. This work also emphasizes the importance of critical interfaces between reactive and non-reactive zones as determined by the details of spatial patterns and effective surface area as a scaling factor that quantifies dissolution rates in heterogeneous media across scales.

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

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.

Solubilization of the poorly water soluble drug, telmisartan, using supercritical anti-solvent (SAS) process.

PubMed

Park, Junsung; Cho, Wonkyung; Cha, Kwang-Ho; Ahn, Junhyun; Han, Kang; Hwang, Sung-Joo

2013-01-30

Telmisartan is a biopharmaceutical classification system (BCS) class II drug that has extremely low water solubility but is freely soluble in highly alkalized solutions. Few organic solvents can dissolve telmisartan. This solubility problem is the main obstacle achieving the desired bioavailability. Because of its unique characteristics, the supercritical anti-solvent (SAS) process was used to BCS class II drug in a variety of ways including micronization, amorphization and solid dispersion. Solid dispersions were prepared using hydroxypropylmethylcellulose/polyvinylpyrrolidone (HPMC/PVP) at 1:0.5, 1:1, and 1:2 weight ratios of drug to polymer, and pure telmisartan was also treated using the SAS process. Processed samples were characterized for morphology, particle size, crystallinity, solubility, dissolution rate and polymorphic stability. After the SAS process, all samples were converted to the amorphous form and were confirmed to be hundreds nm in size. Solubility and dissolution rate were increased compared to the raw material. Solubility tended to increase with increases in the amount of polymer used. However, unlike the solubility results, the dissolution rate decreased with increases in polymer concentration due to gel layer formation of the polymer. Processed pure telmisartan showed the best drug release even though it had lower solubility compared to other solid dispersions; however, because there were no stabilizers in processed pure telmisartan, it recrystallized after 1 month under severe conditions, while the other solid dispersion samples remained amorphous form. We conclude that after controlling the formulation of solid dispersion, the SAS process could be a promising approach for improving the solubility and dissolution rate of telmisartan. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

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.

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.

Dissolution Mechanisms of LiNi1/3Mn1/3Co1/3O2 Positive Electrode Material from Lithium-Ion Batteries in Acid Solution.

PubMed

Billy, Emmanuel; Joulié, Marion; Laucournet, Richard; Boulineau, Adrien; De Vito, Eric; Meyer, Daniel

2018-05-04

The sustainability through the energy and environmental costs involve the development of new cathode materials, considering the material abundance, the toxicity, and the end of life. Currently, some synthesis methods of new cathode materials and a large majority of recycling processes are based on the use of acidic solutions. This study addresses the mechanistic and limiting aspects on the dissolution of the layered LiNi 1/3 Mn 1/3 Co 1/3 O 2 oxide in acidic solution. The results show a dissolution of the active cathode material in two steps, which leads to the formation of a well-defined core-shell structure inducing an enrichment in manganese on the particle surface. The crucial role of lithium extraction is discussed and considered as the source of a "self-regulating" dissolution process. The delithiation involves a cumulative charge compensation by the cationic and anionic redox reactions. The electrons generated from the compensation of charge conduct to the dissolution by the protons. The delithiation and its implications on the side reactions, by the modification of the potential, explain the structural and compositional evolutions observed toward a composite material MnO 2 ·Li x MO 2 (M = Ni, Mn, and Co). The study shows a clear way to produce new cathode materials and recover transition metals from Li-ion batteries by hydrometallurgical processes.

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 surface area normalizations have been used to normalize the bulk dissolution rate. For each of the treatments, time consistence and grain size dependence of the normalized dissolution rate have been evaluated and the results revealed significant dependences on the magnitude of surface kinetic anisotropy under differing environmental conditions. In general, the normalized dissolution rates are strongly dependent on grain size. Time-consistent normalization treatment varies with the investigated condition. The modeling results suggest that the sphere-, cube-, and BET-normalized dissolution rates are appropriate under the far-from-equilibrium conditions at low pH where these normalizations are time-consistent and are slightly dependent on grain size.

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.

Rapidly absorbed orodispersible tablet containing molecularly dispersed felodipine for management of hypertensive crisis: development, optimization and in vitro/in vivo studies.

PubMed

Basalious, Emad B; El-Sebaie, Wessam; El-Gazayerly, Omaima

2013-01-01

A liquisolid orodispersible tablet of felodipine, a BCS Class II drug, was developed to improve drug dissolution and absorption through the buccal mucosa for management of hypertensive crisis. A 24 full-factorial design was applied to optimize felodipine liquisolid systems (FLSs) having acceptable flow properties and possessing enhanced drug dissolution rates. Four formulation variables; The liquid type, X1 (PG or PEG), drug concentration, X2 (10% and 20%), type of coat, X3 (Aerosil® and Aeroperl®) and excipients ratio, X4 (10 and 20) were included in the design. The systems were assessed for dissolution and flow properties. Following optimization, the formulation components (X1, X2, X3 and X4) were PEG, 10%, Aerosil® and 20, respectively. The optimized FLS was compressed into felodipine liquisolid orodispersible tablet using Prosolv® as carrier material (FLODT-2). The in vitro and in vivo disintegration times of FLODT-2 were 9 and 7 s, respectively. The in vivo pharmacokinetic study using human volunteers showed a significant increase in dissolution and absorption rates of the formulation of FLODT-2 compared to soft gelatin capsules filled with felodipine solution in PEG under the same conditions. Our results proposed that the optimized FLODT formulation could be promising to manage hypertensive crisis.

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.

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

Preparation, characterization and in vivo evaluation of amorphous atorvastatin calcium nanoparticles using supercritical antisolvent (SAS) process.

PubMed

Kim, Min-Soo; Jin, Shun-Ji; Kim, Jeong-Soo; Park, Hee Jun; Song, Ha-Seung; Neubert, Reinhard H H; Hwang, Sung-Joo

2008-06-01

In this work, amorphous atorvastatin calcium nanoparticles were successfully prepared using the supercritical antisolvent (SAS) process. The effect of process variables on particle size and distribution of atorvastatin calcium during particle formation was investigated. Solid state characterization, solubility, intrinsic dissolution, powder dissolution studies and pharmacokinetic study in rats were performed. Spherical particles with mean particle size ranging between 152 and 863 nm were obtained by varying process parameters such as precipitation vessel pressure and temperature, drug solution concentration and feed rate ratio of CO2/drug solution. XRD, TGA, FT-IR, FT-Raman, NMR and HPLC analysis indicated that atorvastatin calcium existed as anhydrous amorphous form and no degradation occurred after SAS process. When compared with crystalline form (unprocessed drug), amorphous atorvastatin calcium nanoparticles were of better performance in solubility and intrinsic dissolution rate, resulting in higher solubility and faster dissolution rate. In addition, intrinsic dissolution rate showed a good correlation with the solubility. The dissolution rates of amorphous atorvastatin calcium nanoparticles were highly increased in comparison with unprocessed drug by the enhancement of intrinsic dissolution rate and the reduction of particle size resulting in an increased specific surface area. The absorption of atorvastatin calcium after oral administration of amorphous atorvastatin calcium nanoparticles to rats was markedly increased.

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 limits. However, some generics dissolved differently than their branded counterparts. This can clearly question the interchangeability between the branded and its generic counterpart or even among generics. PMID:25755988

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.

Effect of the up-front heat treatment of gelatin particles dispersed in calcium phosphate cements on the in vivo material resorption and concomitant bone formation.

PubMed

Yamamoto, Shoko; Matsushima, Yuta; Kanayama, Yoshitaka; Seki, Azusa; Honda, Haruya; Unuma, Hidero; Sakai, Yasuo

2017-03-01

Calcium phosphate cements (CPCs), consisting of a mixture of calcium phosphate powders and setting liquid, have been widely used in orthopedic applications. One of the drawbacks of CPCs is their poor resorbability in the living body, which hinders substitution with natural bones. One of the strategies to facilitate the resorption of CPCs is the incorporation of bioresorbable or water-soluble pore-generating particles (porogens), such as gelatin, in the CPC matrices. In spite of numerous reports, however, little is known about the effect of the dissolution/resorption rate of the porogens on concomitant bone regeneration. In the present study, we prepared preset CPCs dispersed with 10 mass% of low-endotoxin gelatin particles 200-500 μm in diameter having different heat-treatment histories, therefore exhibiting different dissolution rate, and then the obtained CPC/gelatin composites were evaluated for in vivo resorption and concomitant in vivo bone formation behaviors. As the results, the dispersion of gelatin particles markedly promoted in vivo resorption of CPC, and enhanced concomitant bone formation, connective tissue formation, osteoblast proliferation, and vascularization. The dissolution/resorption rate was able to be controlled by changing the up-front heat-treatment temperature. In particular, when CPC/gelatin composites were implanted in distal metaphysis of rabbits, the optimum dissolution/resorption was attained by heat-treating gelatin particles at 383 K for 24 h before dispersing in CPC. Quick resorption of calcium phosphate cement and concomitant bone formation by dispersing properly heat-treated with gelatin particles.

Sensitizers in EUV chemically amplified resist: mechanism of sensitivity improvement

NASA Astrophysics Data System (ADS)

Vesters, Yannick; Jiang, Jing; Yamamoto, Hiroki; De Simone, Danilo; Kozawa, Takahiro; De Gendt, Stefan; Vandenberghe, Geert

2018-03-01

EUV lithography utilizes photons with 91.6 eV energy to ionize resists, generate secondary electrons, and enable electron driven reactions that produce acid in chemically amplified photoresist. Efficiently using the available photons is of key importance. Unlike DUV lithography, where photons are selectively utilized by photoactive compounds, photons at 13.5nm wavelength ionize almost all materials. Nevertheless, specific elements have a significantly higher atomic photon-absorption cross section at 91.6 eV. To increase photon absorption, sensitizer molecules, containing highly absorbing elements, can be added to photoresist formulations. These sensitizers have gained growing attention in recent years, showing significant sensitivity improvement. But there are few experimental evidences that the sensitivity improvement is due to the higher absorption only, as adding metals salts into the resist formulation can induce other mechanisms, like modification of the dissolution rate, potentially affecting patterning performance. In this work, we used different sensitizers in chemically amplified resist. We measured experimentally the absorption of EUV light, the acid yield, the dissolution rate and the patterning performance of the resists. Surprisingly, the absorption of EUV resist was decreased with addition of metal salt sensitizers. Nevertheless, the resist with sensitizer showed a higher acid yield. Sensitizer helps achieving higher PAG conversion to acid, notably due to an increase of the secondary electron generation. Patterning data confirm a significant sensitivity improvement, but at the cost of roughness degradation at high sensitizer loading. This can be explained by the chemical distribution of the sensitizer in the resist combined with a modification of the dissolution contrast, as observed by Dissolution Rate Monitor.

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.

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.

Understanding the structural drivers governing glass-water interactions in borosilicate based model bioactive glasses.

PubMed

Stone-Weiss, Nicholas; Pierce, Eric M; Youngman, Randall E; Gulbiten, Ozgur; Smith, Nicholas J; Du, Jincheng; Goel, Ashutosh

2018-01-01

The past decade has witnessed a significant upsurge in the development of borate and borosilicate based resorbable bioactive glasses owing to their faster degradation rate in comparison to their silicate counterparts. However, due to our lack of understanding about the fundamental science governing the aqueous corrosion of these glasses, most of the borate/borosilicate based bioactive glasses reported in the literature have been designed by "trial-and-error" approach. With an ever-increasing demand for their application in treating a broad spectrum of non-skeletal health problems, it is becoming increasingly difficult to design advanced glass formulations using the same conventional approach. Therefore, a paradigm shift from the "trial-and-error" approach to "materials-by-design" approach is required to develop new-generations of bioactive glasses with controlled release of functional ions tailored for specific patients and disease states, whereby material functions and properties can be predicted from first principles. Realizing this goal, however, requires a thorough understanding of the complex sequence of reactions that control the dissolution kinetics of bioactive glasses and the structural drivers that govern them. While there is a considerable amount of literature published on chemical dissolution behavior and apatite-forming ability of potentially bioactive glasses, the majority of this literature has been produced on silicate glass chemistries using different experimental and measurement protocols. It follows that inter-comparison of different datasets reveals inconsistencies between experimental groups. There are also some major experimental challenges or choices that need to be carefully navigated to unearth the mechanisms governing the chemical degradation behavior and kinetics of boron-containing bioactive glasses, and to accurately determine the composition-structure-property relationships. In order to address these challenges, a simplified borosilicate based model melt-quenched bioactive glass system has been studied to depict the impact of thermal history on its molecular structure and dissolution behavior in water. It has been shown that the methodology of quenching of the glass melt impacts the dissolution rate of the studied glasses by 1.5×-3× depending on the changes induced in their molecular structure due to variation in thermal history. Further, a recommendation has been made to study dissolution behavior of bioactive glasses using surface area of the sample - to - volume of solution (SA/V) approach instead of the currently followed mass of sample - to - volume of solution approach. The structural and chemical dissolution data obtained from bioactive glasses following the approach presented in this paper can be used to develop the structural descriptors and potential energy functions over a broad range of bioactive glass compositions. Realizing the goal of designing third generation bioactive glasses requires a thorough understanding of the complex sequence of reactions that control their rate of degradation (in physiological fluids) and the structural drivers that control them. In this article, we have highlighted some major experimental challenges and choices that need to be carefully navigated in order to unearth the mechanisms governing the chemical dissolution behavior of borosilicate based bioactive glasses. The proposed experimental approach allows us to gain a new level of conceptual understanding about the composition-structure-property relationships in these glass systems, which can be applied to attain a significant leap in designing borosilicate based bioactive glasses with controlled dissolution rates tailored for specific patient and disease states. Copyright © 2017 Acta Materialia Inc. All rights reserved.

In vitro dynamic solubility test: influence of various parameters.

PubMed Central

Thélohan, S; de Meringo, A

1994-01-01

This article discusses the dissolution of mineral fibers in simulated physiological fluids (SPF), and the parameters that affect the solubility measurement in a dynamic test where an SPF runs through a cell containing fibers (Scholze and Conradt test). Solutions simulate either the extracellular fluid (pH 7.6) or the intracellular fluid (pH 4.5). The fibers have various chemical compositions and are either continuously drawn or processed as wool. The fiber solubility is determined by the amount of SiO2 (and occasionally other ions) released in the solution. Results are stated as percentage of the initial silica content released or as dissolution rate v in nm/day. The reproducibility of the test is higher with the less soluble fibers (10% solubility), than with highly soluble fibers (20% solubility). The influence of test parameters, including SPF, test duration, and surface area/volume (SA/V), has been studied. The pH and the inorganic buffer salts have a major influence: industrial glasswool composition is soluble at pH 7.6 but not at pH 4.5. The opposite is true for rock- (basalt) wool composition. For slightly soluble fibers, the dissolution rate v remains constant with time, whereas for highly soluble fibers, the dissolution rate decreases rapidly. The dissolution rates believed to occur are v1, initial dissolution rate, and v2, dissolution rate of the residual fibers. The SA of fibers varies with the mass of the fibers tested, or with the fiber diameter at equal mass. Volume, V, is the chosen flow rate. An increase in the SA/V ratio leads to a decrease in the dissolution rate.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7882964

In vitro dynamic solubility test: influence of various parameters.

PubMed

Thélohan, S; de Meringo, A

1994-10-01

This article discusses the dissolution of mineral fibers in simulated physiological fluids (SPF), and the parameters that affect the solubility measurement in a dynamic test where an SPF runs through a cell containing fibers (Scholze and Conradt test). Solutions simulate either the extracellular fluid (pH 7.6) or the intracellular fluid (pH 4.5). The fibers have various chemical compositions and are either continuously drawn or processed as wool. The fiber solubility is determined by the amount of SiO2 (and occasionally other ions) released in the solution. Results are stated as percentage of the initial silica content released or as dissolution rate v in nm/day. The reproducibility of the test is higher with the less soluble fibers (10% solubility), than with highly soluble fibers (20% solubility). The influence of test parameters, including SPF, test duration, and surface area/volume (SA/V), has been studied. The pH and the inorganic buffer salts have a major influence: industrial glasswool composition is soluble at pH 7.6 but not at pH 4.5. The opposite is true for rock- (basalt) wool composition. For slightly soluble fibers, the dissolution rate v remains constant with time, whereas for highly soluble fibers, the dissolution rate decreases rapidly. The dissolution rates believed to occur are v1, initial dissolution rate, and v2, dissolution rate of the residual fibers. The SA of fibers varies with the mass of the fibers tested, or with the fiber diameter at equal mass. Volume, V, is the chosen flow rate. An increase in the SA/V ratio leads to a decrease in the dissolution rate.(ABSTRACT TRUNCATED AT 250 WORDS)

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.

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...

Roller compaction of different pseudopolymorphic forms of theophylline: Effect on compressibility and tablet properties.

PubMed

Hadzović, Ervina; Betz, Gabriele; Hadzidedić, Seherzada; El-Arini, Silvia Kocova; Leuenberger, Hans

2010-08-30

The effect of roller compaction on disintegration time, dissolution rate and compressibility of tablets prepared from theophylline anhydrate powder, theophylline anhydrate fine powder and theophylline monohydrate was studied. In addition, the influence of adding microcrystalline cellulose, a commonly used excipient, in mixtures with these materials was investigated. Theophylline anhydrate powder was used as a model drug to investigate the influence of different compaction pressures on the tablet properties. Tablets with same porosity were prepared by direct compaction and by roller compaction/re-compaction. Compressibility was characterized by Heckel and modified Heckel equations. Due to the property of polymorphic materials to change their form during milling and compression, X-ray diffraction analysis of theophylline anhydrate powder, theophylline anhydrate fine powder and theophylline monohydrate powders and granules was carried out. After roller compaction the disintegration time and the dissolution rate of the tablets were significantly improved. Compressibility of theophylline anhydrate powder and theophylline anhydrate fine powder was decreased, while theophylline monohydrate showed higher compressibility after roller compaction. Microcrystalline cellulose affected compressibility of theophylline anhydrate powder, theophylline anhydrate fine powder and theophylline monohydrate whereby the binary mixtures showed higher compressibility than the individual materials. X-ray diffraction analyses confirmed that there were no polymorphic/pseudopolymorphic changes after roller compaction. Copyright 2010 Elsevier B.V. All rights reserved.

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.

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.

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.

(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 to nearest-neighbor sites) and dissolution via detachment of clusters.« less

Role of Water Sorption in Tablet Crushing Strength, Disintegration, and Dissolution.

PubMed

Sacchetti, M; Teerakapibal, R; Kim, K; Elder, E J

2017-08-01

Drugs formulated as tablets are subjected to accelerated stability conditions with the goal of identifying a stable formulation that will exhibit a sufficiently long shelf life. Water sorption at a condition such as 40°C/75% RH can result in significant changes in tablet properties such as a decrease in dissolution rate, the cause of which may be difficult to interpret, given the complex nature of ingredients and their interactions in a tablet. In this research, three drugs, displaying a wide range of physicochemical properties, were formulated with commonly used diluents, disintegrants, and binders, using a design of experiments approach. The tablets were stored at accelerated conditions and assessed for content, dissolution, disintegration, and crushing strength, as well as other properties. The research demonstrated many water-induced effects in tablet properties. Due to the experimental design approach that revealed many interactions, it was possible to interpret all of the changes observed in tablet crushing strength, disintegration, and dissolution for the drugs using a common set of physical principles. Specifically, the relevant factors considered were (1) mechanical properties of materials, (2) water sorption surface effects in surface diffusion and capillary condensation, (3) water sorption bulk effects for amorphous materials such as viscous flow/spreading, and (4) water-induced stress on interparticle bonding arising from volume expansion. These physical principles enable a comprehensive interpretation of the complex changes observed in tablet properties, which should be valuable in the design of tablet formulations that will be stable to accelerated storage conditions.

Solubility and chemistry of materials encountered by beryllium mine and ore extraction workers: relation to risk.

PubMed

Deubner, David C; Sabey, Philip; Huang, Wenjie; Fernandez, Diego; Rudd, Abigail; Johnson, William P; Storrs, Jason; Larson, Rod

2011-10-01

Beryllium mine and ore extraction mill workers have low rates of beryllium sensitization and chronic beryllium disease relative to the level of beryllium exposure. The objective was to relate these rates to the solubility and composition of the mine and mill materials. Medical surveillance and exposure data were summarized. Dissolution of BeO, ore materials and beryllium hydroxide, Be(OH)(2) was measured in synthetic lung fluid. The ore materials were more soluble than BeO at pH 7.2 and similar at pH 4.5. Be(OH)(2) was more soluble than BeO at both pH. Aluminum dissolved along with beryllium from ore materials. Higher solubility of beryllium ore materials and Be(OH)(2) at pH 7.2 might shorten particle longevity in the lung. The aluminum content of the ore materials might inhibit the cellular immune response to beryllium.

Dissolution of NTO, DNAN, and Insensitive Munitions Formulations and Their Fates in Soils

DTIC Science & Technology

2014-09-01

3 2 Mass loss measured by high precision liquid chromatography (HPLC) versus measured mass loss by... Liquid Chromatography IM Insensitive Munitions IMX Insensitive Munitions eXplosive k First-Order Transformation Rate Constant kphoto First...Performance Liquid Chromatography U.S. EPA United States Environmental Protection Agency WMRD Weapons and Materials Research Directorate ERDC/CRREL

Aripiprazole-Cyclodextrin Binary Systems for Dissolution Enhancement: Effect of Preparation Technique, Cyclodextrin Type and Molar Ratio

PubMed Central

M. Badr-Eldin, Shaimaa; A. Ahmed, Tarek; R Ismail, Hatem

2013-01-01

Objective(s): The aim of this work was to investigate the effect of the natural and the chemically modified form of cyclodextrins namely; β-cyclodextrin (β-CD) and hydroxypropyl-β-cyclodextrin (HP-β-CD) respectively on the solubility and dissolution rate of aripiprazole; an antipsychotic medication showing poor aqueous solubility. Materials and Methods: Phase solubility of aripiprazole with the studied CDs and the complexation efficiency values (CE) which reflect the solubilizing power of the CDs towards the drug was performed. Solid binary systems of aripiprazole with CDs were prepared by kneading, microwave irradiation and freeze-drying techniques at 1:1 and 1:2 (drug to CD) molar ratios. Drug-CD physical mixtures were also prepared in the same molar ratios for comparison. The dissolution of aripiprazole-binary systems was carried out to select the most appropriate CD type, molar ratio and preparation technique. Results: Phase solubility study indicated formation of higher order complexes and the complexation efficiency values was higher for HP-β-CD compared to β-CD. Drug dissolution study revealed that aripiprazole dissolution was increased upon increasing the CD molar ratio and, the freeze-drying technique was superior to the other studied methods especially when combined with the HP-β-CD. The cyclodextrin type, preparation technique and molar ratio exhibited statistically significant effect on the drug dissolution at P≤ 0.05. Conclusion: The freeze-dried system prepared at molar ratio 1:2 (drug: CD) can be considered as efficient tool for enhancing aripiprazole dissolution with the possibility of improving its bioavailability. PMID:24570827

Integrating In Vitro, Modeling, and In Vivo Approaches to Investigate Warfarin Bioequivalence

PubMed Central

Wen, H; Fan, J; Vince, B; Li, T; Gao, W; Kinjo, M; Brown, J; Sun, W; Jiang, W; Lionberger, R

2017-01-01

We demonstrate the use of modeling and simulation to investigate bioequivalence (BE) concerns raised about generic warfarin products. To test the hypothesis that the loss of isopropyl alcohol and slow dissolution in acidic pH has significant impact on the pharmacokinetics of warfarin sodium tablets, we conducted physiologically based pharmacokinetic absorption modeling and simulation using formulation factors or in vitro dissolution profiles as input parameters. Sensitivity analyses indicated that warfarin pharmacokinetics was not sensitive to solubility, particle size, density, or dissolution rate in pH 4.5, but was affected by dissolution rate in pH 6.8 and potency. Virtual BE studies suggested that stressed warfarin sodium tablets with slow dissolution rate in pH 4.5 but having similar dissolution rate in pH 6.8 would be bioequivalent to the unstressed warfarin sodium tablets. A four‐way, crossover, single‐dose BE study in healthy subjects was conducted to test the same hypothesis and confirmed the simulation conclusion. PMID:28379643

Dynamic leaching studies of 48 MWd/kgU UO2 commercial spent nuclear fuel under oxic conditions

NASA Astrophysics Data System (ADS)

Serrano-Purroy, D.; Casas, I.; González-Robles, E.; Glatz, J. P.; Wegen, D. H.; Clarens, F.; Giménez, J.; de Pablo, J.; Martínez-Esparza, A.

2013-03-01

The leaching of a high-burn-up spent nuclear fuel (48 MWd/KgU) has been studied in a carbonate-containing solution and under oxic conditions using a Continuously Stirred Tank Flow-Through Reactor (CSTR). Two samples of the fuel, one prepared from the centre of the pellet (labelled CORE) and another one from the fuel pellet periphery, enriched with the so-called High Burn-Up Structure (HBS, labelled OUT) have been used.For uranium and actinides, the results showed that U, Np, Am and Cm gave very similar normalized dissolution rates, while Pu showed slower dissolution rates for both samples. In addition, dissolution rates were consistently two to four times lower for OUT sample compared to CORE sample.Considering the fission products release the main results are that Y, Tc, La and Nd dissolved very similar to uranium; while Cs, Sr, Mo and Rb have up to 10 times higher dissolution rates. Rh, Ru and Zr seemed to have lower dissolution rates than uranium. The lowest dissolution rates were found for OUT sample.Three different contributions were detected on uranium release, modelled and attributed to oxidation layer, fines and matrix release.

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.

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.

Effects of alteration product precipitation on glass dissolution

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

Strachan, Denis M.; Neeway, James J.

2014-06-01

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

Citrus bergamia juice: phytochemical and technological studies.

PubMed

Picerno, Patrizia; Sansone, Francesca; Mencherini, Teresa; Prota, Lucia; Aquino, Rita Patrizia; Rastrelli, Luca; Lauro, Maria Rosaria

2011-07-01

Fresh juice from bergamot (Citrus bergamia Risso) has been studied to evaluate the polyphenolic composition by HPLC-DAD analysis and total polyphenols content by UV method. The main constituent, Naringin, has been selected as analytical and biological marker of the juice. Juice has been loaded onto maltodextrin matrix by spray-drying. The produced maltodextrin/juice powder (BMP) showed neither significant change in total polyphenols content nor decrease in antioxidant properties with respect to fresh juice. Moreover, BMP displayed high in vitro dissolution rate of the bioactive constituents in water and in simulated biological fluids. BMP appears as promising functional raw material for food, nutraceutical and pharmaceutical products. With this aim, a formulation study to develop tablets (BMT) for oral administration has been also performed. The produced solid oral dosage form preserved high polyphenols content, showed complete disaggregation in few minutes and satisfying dissolution rate of the bioactive constituents in simulated biological fluids.

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.

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

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.

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 accumulation rate for Florida Bay of 8.7 cm 1000 yr-1 and suggests that sediment dissolution plays a more important role than sediment transport in loss of sediment from Florida Bay. ?? 2006 Estuarine Research Federation.

Feasibility of Using Gluconolactone, Trehalose and Hydroxy-Propyl Gamma Cyclodextrin to Enhance Bendroflumethiazide Dissolution Using Lyophilisation and Physical Mixing Techniques.

PubMed

Saleh, Ashraf; McGarry, Kenneth; Chaw, Cheng Shu; Elkordy, Amal Ali

2018-02-01

Hydrophobic drugs are facing a major challenge in dissolution rate enhancement and solubility in aqueous solutions; therefore, a variety of methods have been used to improve dissolution rate and/or solubility of bendroflumethiazide as a model hydrophobic drug. In this study, two main methods (physical mixing and lyophilisation) were used with gluconolactone, hydroxyl propyl γ-ccyclodextrin, and trehalose to explore this challenge. Bendroflumethiazide, practically insoluble in water, was mixed with one of the three excipients gluconolactone, hydroxyl propyl γ-cyclodextrin, and trehalose in three different ratios 1:1, 1:2, 1:5. To the best of our knowledge, the dissolution of the drug has not been previously enhanced by using either these methods or any of the used excipients. Samples containing drug and each of the excipients were characterized via dissolution testing, Fourier Transform infra-red spectroscopy, differential scanning calorimetry, and scanning electron microscopy. The used methods showed a significant enhancement in dug dissolution rate; physical mixing significantly, p < 0.05, increased the percentage of the drug released with time; for example, bendroflumethiazide dissolution in distilled water was improved from less than 20% to 99.79% within 90 min for physically mixed drug-cyclodextrin 1:5. The lyophilisation process was enhanced and the drug dissolution rate and the highest drug dissolution was achieved for (drug-gluconolactone 1:1) with 98.98% drug release within 90 min. the physical mixing and freeze drying processes significantly increased the percentage of drug release with time.

Jarosite dissolution rates in perchlorate brine

NASA Astrophysics Data System (ADS)

Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

2018-02-01

Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures <250 K, and may exist as metastable or stable liquids for extended time periods, even under current Mars surface conditions. Therefore, jarosite-bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

Corrosion behavior of ODS steels with several chromium contents in hot nitric acid solutions

NASA Astrophysics Data System (ADS)

Tanno, Takashi; Takeuchi, Masayuki; Ohtsuka, Satoshi; Kaito, Takeji

2017-10-01

Oxide dispersion strengthened (ODS) steel cladding tubes have been developed for fast reactors. Tempered martensitic ODS steels with 9 and 11 wt% of chromium (9Cr-, 11Cr-ODS steel) are the candidate material in research being carried out at JAEA. In this work, fundamental immersion tests and electrochemical tests of 9 to 12Cr-ODS steels were systematically conducted in various nitric acid solutions at 95 °C. The corrosion rate decreased exponentially with effective solute chromium concentration (Creff) and nitric acid concentration. Addition of vanadium (V) and ruthenium (Ru) also decreased the corrosion rate. The combination of low Creff and dilute nitric acid could not avoid the active mass dissolution during active domain at the beginning of immersion, and the corrosion rate was high. Higher Creff decreased the partial anodic current during the active domain and assisted the passivation of the surface of the steel. Concentrated nitric acid and addition of Ru and V increased partial cathodic current and shifted the corrosion potential to noble side. These effects should have prevented the active mass dissolution and decreased the corrosion rate.

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.

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 ± 0.12 log mol m-2 s-1), while dissolution slowed in both NaCl solutions (0.1 mol kg-1; -8.23 ± 0.10 log mol m-2 s-1 and (5.7 mol kg-1; -8.44 ± 0.11 log mol m-2 s-1), as well as near-saturated MgSO4 brine (2.7 mol kg-1; -8.35 ± 0.05 log mol m-2 s-1). The slowest calcite dissolution rates observed in the near-saturated NaCl brine. Magnesite dissolution rates were ∼5 times faster in the dilute salt solutions relative to UPW, but similar to UPW (-8.47 ± 0.06 log mol m-2 s-1) in near-saturated Na2SO4 brines (-8.41 ± 0.18 log mol m-2 s-1). Magnesite dissolution slowed significantly in near-saturated CaCl2 brine (-9.78 ± 0.10 log mol m-2 s-1), likely due to the significantly lower water activity in these experiments. Overall, magnesite dissolution rates are slower than calcite dissolution rates and follow the trend: All dilute salt solutions >2.5 mol kg-1 Na2SO4 ≈ UPW > 5.7 mol kg-1 NaCl >> 9 mol kg-1 CaCl2. Calcite rates follow the trend 3 mol kg-1 MgCl2 > 2.5 mol kg-1 Na2SO4 ≈ UPW ≈ all dilute salt solutions >2.7 mol kg-1 MgSO4 ≈ 5.7 mol kg-1 NaCl. Magnesite dissolution rates in salt solutions generally decrease with decreasing aH2O in both chloride and sulfate brines, which indicates water molecules act as ligands and participate in the rate-limiting magnesite dissolution step. However, there is no general trend associated with water activity observed in the calcite dissolution rates. Calcite dissolution accelerates in near-saturated MgCl2, but slows in near-saturated NaCl brine despite both brines having similar water activities (aH2O = 0.73 and 0.75, respectively). High Mg calcite was observed as a reaction product in the near-saturated MgCl2, indicating Mg2+ from solution likely substituted for Ca2+ in the initial calcite, releasing additional Ca2+ into solution and increasing the observed calcite dissolution rate. Calcite dissolution rates also increase slightly as Na2SO4 concentration increases, while calcite dissolution rates slow slightly with increasing concentration of MgSO4 and NaCl. However, all of the carbonate rates vary by less than 0.5 log units and are within or near the standard deviation observed for each set of replicate experiments. Carbonate mineral lifetimes in high salinity brines indicate magnesite may be preferentially preserved compared to calcite on Mars. Therefore, Mg-carbonates that have experienced post-depositional aqueous alteration are more likely to preserve paleoenvironmental indicators and potential biosignatures. Rapid weathering of carbonates in circum-neutral pH sulfate brines may provide a potential source of cations for abundant sulfate minerals observed on Mars, Ceres, and other planetary bodies.

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.

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 surfactant in the media for the poorly water-soluble drug. Creating sink conditions (based on bulk drug solubilities) by using a high concentration of a surfactant in the dissolution medium may not be a proper approach in developing a bio-relevant dissolution method for a poorly water-soluble drug.

Solid-state characterization of mefenamic acid.

PubMed

Panchagnula, Ramesh; Sundaramurthy, Prakash; Pillai, Omathanu; Agrawal, Shrutidevi; Raj, Yasvanth Ashok

2004-04-01

The purpose of this study was to characterize mefenamic acid (MA) from commercial samples and samples crystallized from different solvents. Various techniques used for characterization included microscopy (hot stage microscopy, scanning electron microscopy), intrinsic dissolution rate, differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and powder X-ray diffractometry (pXRD). The commercial samples varied in their crystal habit, thermal behavior, and intrinsic dissolution rate. It was found that the commercial samples were polymorphic Form I, which converted to Form II on heating in a DSC pan. Similarly, compression in an intrinsic dissolution rate (IDR) press resulted in the conversion of Form I to Form II. On the other hand, the samples recrystallized from different solvents under varying conditions yielded different crystal habits. Stirring and degree of supersaturation significantly influenced the crystal habit in all the solvents used in the study. Samples crystallized from ethanol and tetrahydrofuran yielded Form I, which behaved similarly to the commercial samples (M1 and M3). Recrystallization from ethyl acetate at a fast cooling rate yielded Form I, which on melting crystallized to Form II. The form I crystallized from ethyl acetate by fast cooling converted partially to form II on storing at ambient conditions. Forms I and II of MA were enantiotropically related. The results demonstrate the variable material characteristics of the commercial samples of MA and the influence of the crystallizing conditions on the formation of the polymorphs. Copyright 2004 Wiley-Liss, Inc. and the American Pharmacists Association.

Ionic solutions of two-dimensional materials

NASA Astrophysics Data System (ADS)

Cullen, Patrick L.; Cox, Kathleen M.; Bin Subhan, Mohammed K.; Picco, Loren; Payton, Oliver D.; Buckley, David J.; Miller, Thomas S.; Hodge, Stephen A.; Skipper, Neal T.; Tileli, Vasiliki; Howard, Christopher A.

2017-03-01

Strategies for forming liquid dispersions of nanomaterials typically focus on retarding reaggregation, for example via surface modification, as opposed to promoting the thermodynamically driven dissolution common for molecule-sized species. Here we demonstrate the true dissolution of a wide range of important 2D nanomaterials by forming layered material salts that spontaneously dissolve in polar solvents yielding ionic solutions. The benign dissolution advantageously maintains the morphology of the starting material, is stable against reaggregation and can achieve solutions containing exclusively individualized monolayers. Importantly, the charge on the anionic nanosheet solutes is reversible, enables targeted deposition over large areas via electroplating and can initiate novel self-assembly upon drying. Our findings thus reveal a unique solution-like behaviour for 2D materials that enables their scalable production and controlled manipulation.

Low temperature-pressure batch experiments and field push-pull tests: Assessing potential effects of an unintended CO2 release from CCUS projects on groundwater chemistry

NASA Astrophysics Data System (ADS)

Mickler, P. J.; Yang, C.; Lu, J.; Reedy, R. C.; Scanlon, B. R.

2012-12-01

Carbon Capture Utilization and Storage projects (CCUS), where CO2 is captured at point sources such as power stations and compressed into a supercritical liquid for underground storage, has been proposed to reduce atmospheric CO2 and mitigate global climate change. Problems may arise from CO2 releases along discreet pathways such as abandoned wells and faults, upwards and into near surface groundwater. Migrating CO2 may inversely impact fresh water resources by increasing mineral solubility and dissolution rates and mobilizing harmful trace elements including As and Pb. This study addresses the impacts on fresh water resources through a combination of laboratory batch experiments, where aquifer sediment are reacted in their corresponding groundwater in 100% CO2 environments, and field push-pull tests where groundwater is equilibrated with 100% CO2, reacted in-situ in the groundwater system, and pulled out for analyses. Batch experiments were performed on aquifer material from carbonate dominated, mixed carbonate/silicalstic, and siliclastic dominated systems. A mixed silicalstic/carbonate system was chosen for the field based push-pull test. Batch experiment results suggest carbonate dissolution increased the concentration of Ca, Mg, Sr, Ba, Mn, U and HCO3- in groundwater. In systems with significant carbonate content, dissolution continued until carbonate saturation was achieved at approximately 1000 hr. Silicate dissolution increased the conc. of Si, K Ni and Co, but at much lower rates than carbonate dissolution. The elements As, Mo, V, Zn, Se and Cd generally show similar behavior where concentrations initially increase but soon drop to levels at or below the background concentrations (~48 hours). A Push-Pull test on one aquifer system produced similar geochemical behavior but observed reaction rates are higher in batch experiments relative to push-pull tests. Release of CO2 from CCUS sites into overlying aquifer systems may adversely impact groundwater quality primarily through carbonate dissolution which releases Ca and elements that substitute for Ca in crystal lattices. Silicate weathering releases primarily Si and K at lower rates. Chemical changes with the addition of CO2 may initially mobilize As, Mo, V, Zn, Se and Cd but these elements become immobile in the lowered pH water and sorb onto aquifer minerals. A combined laboratory batch experiment and field push-pull test in fresh water aquifers overlying CCUS projects will best characterize the response of the aquifer to increased pCO2. The long experimental duration of the batch experiments may allow reactions to reach equilibrium however; reaction rates may be artificially high due to increased mineral surface areas. Field based push-pull tests offer a more realistic water rock ratio and test a much larger volume of aquifer material but the test must be shorter in duration because the high pCO2 water is subject to mixing with low pCO2 background water and migration away from the test well with groundwater flow. A comparison of the two methods best characterizes the potential effects on groundwater chemistry

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.

A Review: Pharmaceutical and Pharmacokinetic Aspect of Nanocrystalline Suspensions.

PubMed

Shah, Dhaval A; Murdande, Sharad B; Dave, Rutesh H

2016-01-01

Nanocrystals have emerged as a potential formulation strategy to eliminate the bioavailability-related problems by enhancing the initial dissolution rate and moderately super-saturating the thermodynamic solubility. This review contains an in-depth knowledge of, the processing method for formulation, an accurate quantitative assessment of the solubility and dissolution rates and their correlation to observe pharmacokinetic data. Poor aqueous solubility is considered the major hurdle in the development of pharmaceutical compounds. Because of a lack of understanding with regard to the change in the thermodynamic and kinetic properties (i.e., solubility and dissolution rate) upon nanosizing, we critically reviewed the literatures for solubility determination to understand the significance and accuracy of the implemented analytical method. In the latter part, we reviewed reports that have quantitatively studied the effect of the particle size and the surface area change on the initial dissolution rate enhancement using alternative approaches besides the sink condition dissolution. The lack of an apparent relationship between the dissolution rate enhancement and the observed bioavailability are discussed by reviewing the reported in vivo data on animal models along with the particle size and food effect. The review will provide comprehensive information to the pharmaceutical scientist in the area of nanoparticulate drug delivery.

Weathering profiles in soils and rocks on Earth and Mars

NASA Astrophysics Data System (ADS)

Hausrath, E.; Adcock, C. T.; Bamisile, T.; Baumeister, J. L.; Gainey, S.; Ralston, S. J.; Steiner, M.; Tu, V.

2017-12-01

Interactions of liquid water with rock, soil, or sediments can result in significant chemical and mineralogical changes with depth. These changes can include transformation from one phase to another as well as translocation, addition, and loss of material. The resulting chemical and mineralogical depth profiles can record characteristics of the interacting liquid water such as pH, temperature, duration, and abundance. We use a combined field, laboratory, and modeling approach to interpret the environmental conditions preserved in soils and rocks. We study depth profiles in terrestrial field environments; perform dissolution experiments of primary and secondary phases important in soil environments; and perform numerical modeling to quantitatively interpret weathering environments. In our field studies we have measured time-integrated basaltic mineral dissolution rates, and interpreted the impact of pH and temperature on weathering in basaltic and serpentine-containing rocks and soils. These results help us interpret fundamental processes occurring in soils on Earth and on Mars, and can also be used to inform numerical modeling and laboratory experiments. Our laboratory experiments provide fundamental kinetic data to interpret processes occurring in soils. We have measured dissolution rates of Mars-relevant phosphate minerals, clay minerals, and amorphous phases, as well as dissolution rates under specific Mars-relevant conditions such as in concentrated brines. Finally, reactive transport modeling allows a quantitative interpretation of the kinetic, thermodynamic, and transport processes occurring in soil environments. Such modeling allows the testing of conditions under longer time frames and under different conditions than might be possible under either terrestrial field or laboratory conditions. We have used modeling to examine the weathering of basalt, olivine, carbonate, phosphate, and clay minerals, and placed constraints on the duration, pH, and solution chemistry of past aqueous alteration occurring on Mars.

Development of a combined pyro- and hydro-metallurgical route to treat spent zinc-carbon batteries.

PubMed

Baba, A A; Adekola, A F; Bale, R B

2009-11-15

The potential of solvent extraction using Cynanex272 for the recovery of zinc from spent zinc carbon batteries after a prior leaching in hydrochloric acid has been investigated. The elemental analysis of the spent material was carried out by ICP-MS. The major metallic elements are: ZnO (41.30%), Fe(2)O(3) (4.38%), MnO(2) (2.69%), Al(2)O(3) (1.01%), CaO (0.36%) and PbO (0.11%). The quantitative leaching by hydrochloric acid showed that the dissolution rates are significantly influenced by temperature and concentration of the acid solutions. The experimental data for the dissolution rates have been analyzed and were found to follow the shrinking core model for mixed control reaction with surface chemical reaction as the rate-determining step. About 90.3% dissolution was achieved with 4M HCl solution at 80 degrees C with 0.050-0.063 mm particle size within 120 min at 360 rpm. Activation energy value of 22.78 kJ/mol and a reaction order of 0.74 with respect to H(+) ion concentration were obtained for the dissolution process. An extraction yield of 94.23% zinc by 0.032M Cyanex272 in kerosene was obtained from initial 10 g/L spent battery leach liquor at 25+/-2 degrees C and at optimal stirring time of 25 min. Iron has been effectively separated by precipitation prior to extraction using ammoniacal solution at pH 3.5, while lead and other trace elements were firstly separated from Zn and Fe by cementation prior to iron removal and zinc extraction. Finally, the stripping study showed that 0.1M HCl led to the stripping of about 95% of zinc from the organic phase.

Mechanisms by which moisture generates cocrystals.

PubMed

Jayasankar, Adivaraha; Good, David J; Rodríguez-Hornedo, Naír

2007-01-01

The purpose of this study is to determine the mechanisms by which moisture can generate cocrystals when solid particles of cocrystal reactants are exposed to deliquescent conditions (when moisture sorption forms an aqueous solution). It is based on the hypothesis that cocrystallization behavior during water uptake can be derived from solution chemistry using models that describe cocrystal solubility and reaction crystallization of molecular complexes. Cocrystal systems were selected with active pharmaceutical ingredients (APIs) that form hydrates and include carbamazepine, caffeine, and theophylline. Moisture uptake and crystallization behavior were studied by gravimetric vapor sorption, X-ray powder diffraction, and on-line Raman spectroscopy. Results indicate that moisture uptake generates cocrystals of carbamazepine-nicotinamide, carbamazepine-saccharin, and caffeine or theophylline with dicarboxylic acid ligands (oxalic acid, maleic acid, glutaric acid, and malonic acid) when solid mixtures with cocrystal reactants deliquesce. Microscopy studies revealed that the transformation mechanism to cocrystal involves (1) moisture uptake, (2) dissolution of reactants, and (3) cocrystal nucleation and growth. Studies of solid blends of reactants in a macro scale show that the rate and extent of cocrystal formation are a function of relative humidity, moisture uptake, deliquescent material, and dissolution rates of reactants. It is shown that the interplay between moisture uptake and dissolution determines the liquid phase composition, supersaturation, and cocrystal formation rates. Differences in the behavior of deliquescent additives (sucrose and fructose) are associated with moisture uptake and composition of the deliquesced solution. Our results show that deliquescence can transform API to cocrystal or reverse the reaction given the right conditions. Key indicators of cocrystal formation and stability are (1) moisture uptake, (2) cocrystal aqueous solubility, (3) solubility and dissolution of cocrystal reactants, and (4) transition concentration.

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.

Controlled electrophoretic deposition of HAp/β-TCP composite coatings on piranha treated 316L SS for enhanced mechanical and biological properties

NASA Astrophysics Data System (ADS)

Prem Ananth, K.; Nathanael, A. Joseph; Jose, Sujin P.; Oh, Tae Hwan; Mangalaraj, D.; Ballamurugan, A. M.

2015-10-01

Hydroxyapatite (HAp) and β-tricalcium phosphate (β-TCP) bioactive materials have been used as individual coatings on steel implants employed in the fields of orthopedics and dentistry due to their excellent properties, which foster effective healing of the repair site. However, slow dissolution of HAp and fairly little fast dissolution of β-TCP present a major obstacle for such applications and this leads to the focus on the investigation of a mixture of HAp and β-TCP composite that forms biphasic calcium phosphate (BCP). The BCP coatings were achieved by thickness controlled electrophoretic deposition on piranha treated 316L SS. This method is well controlled and the anticipated dissolution rate could be attained with faster formation of new bone at the implant site, when compared to the individual HAp or β-TCP coating. The structural, functional, morphological and elemental composition of the coatings were characterized by using various analytical techniques. The BCP coating has been shown to have a role in obstructing the corrosion to a greater extent when in contact with SBF solution. The BCP coating also shows excellent in vitro and mechanical properties and osteoblasts cellular tests revealed that the coating was more effective in improving biocompatibility. This makes it an ideal candidate material for hard tissue replacement.

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.

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.

APTES-modified mesoporous silicas as the carriers for poorly water-soluble drug. Modeling of diflunisal adsorption and release

NASA Astrophysics Data System (ADS)

Geszke-Moritz, Małgorzata; Moritz, Michał

2016-04-01

Four mesoporous siliceous materials such as SBA-16, SBA-15, PHTS and MCF functionalized with (3-aminopropyl)triethoxysilane were successfully prepared and applied as the carriers for poorly water-soluble drug diflunisal. Several techniques including nitrogen sorption analysis, XRD, TEM, FTIR and thermogravimetric analysis were employed to characterize mesoporous matrices. Adsorption isotherms were analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models. In order to find the best-fit isotherm for each model, both linear and nonlinear regressions were carried out. The equilibrium data were best fitted by the Langmuir isotherm model revealing maximum adsorption capacity of 217.4 mg/g for aminopropyl group-modified SBA-15. The negative values of Gibbs free energy change indicated that the adsorption of diflunisal is a spontaneous process. Weibull release model was employed to describe the dissolution profile of diflunisal. At pH 4.5 all prepared mesoporous matrices exhibited the improvement of drug dissolution kinetics as compared to the dissolution rate of pure diflunisal.

Hydrobiogeochemical interactions in 'anoxic' limestone drains for neutralization of acidic mine drainage

USGS Publications Warehouse

Robbins, E.I.; Cravotta, C.A.; Savela, C.E.; Nord, G.L.

1999-01-01

Processes affecting neutralization of acidic coal mine drainage were evaluated within 'anoxic' limestone drains (ALDs). Influents had pH???3.5 and dissolved oxygen <2 mg/l. Even though effluents were near neutral (pH 6 and alkalinity acidity), two of the four ALDs were failing due to clogging. Mineral-saturation indices indicated the potential for dissolution of calcite and gypsum, and precipitation of Al3+ and Fe3+ compounds. Cleavage mounts of calcite and gypsum that were suspended within the ALDs and later examined microscopically showed dissolution features despite coatings by numerous bacteria, biofilms, and Fe-Al-Si precipitates. In the drain exhibiting the greatest flow reduction, Al-hydroxysulfates had accumulated on limestone surfaces and calcite etch points, thus causing the decline in transmissivity and dissolution. Therefore, where Al loadings are high and flow rates are low, a pre-treatment step is indicated to promote Al removal before diverting acidic mine water into alkalinity-producing materials. ?? 1998 Elsevier Science Ltd.

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.

Dissolution kinetics of iron-, manganese-, and copper-containing synthetic hydroxyapatites

NASA Technical Reports Server (NTRS)

Sutter, B.; Hossner, L. R.; Ming, D. W.

2005-01-01

Micronutrient-substituted synthetic hydroxyapatite (SHA) is being evaluated by the National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program for crop production on long-duration human missions to the International Space Station or for future Lunar or Martian outposts. The stirred-flow technique was utilized to characterize Ca, P, Fe, Mn, and Cu release characteristics from Fe-, Mn-, and Cu-containing SHA in deionized (DI) water, citric acid, and diethylene-triamine-pentaacetic acid (DTPA). Initially, Ca and P release rates decreased rapidly with time and were controlled by a non-SHA calcium phosphate phase(s) with low Ca/P solution molar ratios (0.91-1.51) relative to solid SHA ratios (1.56-1.64). At later times, Ca/P solution molar ratios (1.47-1.79) were near solid SHA ratios and release rates decreased slowly indicating that SHA controlled Ca and P release. Substituted SHA materials had faster dissolution rates relative to unsubstituted SHA. The initial metal release rate order was Mn >> Cu > Fe which followed metal-oxide/phosphate solubility suggesting that poorly crystalline metal-oxides/phosphates were dominating metal release. Similar metal release rates for all substituted SHA (approximately 0.01 cmol kg-1 min-1) at the end of the DTPA experiment indicated that SHA dissolution was supplying the metals into solution and that poorly crystalline metal-oxide/phosphates were not controlling metal release. Results indicate that non-SHA Ca-phosphate phases and poorly crystalline metal-oxide/phosphates will contribute Ca, P, and metals. After these phases have dissolved, substituted SHA will be the source of Ca, P, and metals for plants.

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. Results reported in this communication lend support to our hypothesis that slow secondary mineral precipitation explains part of the well-known apparent discrepancy between lab measured and field estimated feldspar dissolution rates ( Zhu et al., 2004). Here we show how the slow secondary mineral precipitation provides a regulator to explain why the systems are held close to equilibrium and show how the most often-quoted "near equilibrium" explanation for an apparent field-lab discrepancy can work quantitatively. The substantiated hypothesis now offers the promise of reconciling part of the apparent field-lab discrepancy.

Silica coatings on clarithromycin.

PubMed

Bele, Marjan; Dmitrasinovic, Dorde; Planinsek, Odon; Salobir, Mateja; Srcic, Stane; Gaberscek, Miran; Jamnik, Janko

2005-03-03

Pre-crystallized clarithromycin (6-O-methylerythromycin A) particles were coated with silica from the tetraethyl orthosilicate (TEOS)-ethanol-aqueous ammonia system. The coatings had a typical thickness of 100-150 nm and presented about 15 wt.% of the silica-drug composite material. The properties of the coatings depended on reactant concentration, temperature and mixing rate and, in particular, on the presence of a cationic surfactant (cetylpyridinium chloride). In the presence of cetylpyridinium chloride the silica coatings slightly decreased the rate of pure clarithromycin dissolution.

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

Recovery of fissile materials from nuclear wastes

DOEpatents

Forsberg, Charles W.

1999-01-01

A process for recovering fissile materials such as uranium, and plutonium, and rare earth elements, from complex waste feed material, and converting the remaining wastes into a waste glass suitable for storage or disposal. The waste feed is mixed with a dissolution glass formed of lead oxide and boron oxide resulting in oxidation, dehalogenation, and dissolution of metal oxides. Carbon is added to remove lead oxide, and a boron oxide fusion melt is produced. The fusion melt is essentially devoid of organic materials and halogens, and is easily and rapidly dissolved in nitric acid. After dissolution, uranium, plutonium and rare earth elements are separated from the acid and recovered by processes such as PUREX or ion exchange. The remaining acid waste stream is vitrified to produce a waste glass suitable for storage or disposal. Potential waste feed materials include plutonium scrap and residue, miscellaneous spent nuclear fuel, and uranium fissile wastes. The initial feed materials may contain mixtures of metals, ceramics, amorphous solids, halides, organic material and other carbon-containing material.

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.

Modeling solid-state transformations occurring in dissolution testing.

PubMed

Laaksonen, Timo; Aaltonen, Jaakko

2013-04-15

Changes in the solid-state form can occur during dissolution testing of drugs. This can often complicate interpretation of results. Additionally, there can be several mechanisms through which such a change proceeds, e.g. solvent-mediated transformation or crystal growth within the drug material itself. Here, a mathematical model was constructed to study the dissolution testing of a material, which undergoes such changes. The model consisted of two processes: the recrystallization of the drug from a supersaturated liquid state caused by the dissolution of the more soluble solid form and the crystal growth of the stable solid form at the surface of the drug formulation. Comparison to experimental data on theophylline dissolution showed that the results obtained with the model matched real solid-state changes and that it was able to distinguish between cases where the transformation was controlled either by solvent-mediated crystallization or solid-state crystal growth. Copyright © 2013 Elsevier B.V. All rights reserved.

21 CFR 320.1 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-04-01

..., where applicable, content uniformity, disintegration times, and/or dissolution rates. (d) Pharmaceutical..., disintegration times and/or dissolution rates. (e) Bioequivalence means the absence of a significant difference...

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.

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.

Characterization of Two Distinct Amorphous Forms of Valsartan by Solid-State NMR.

PubMed

Skotnicki, Marcin; Apperley, David C; Aguilar, Juan A; Milanowski, Bartłomiej; Pyda, Marek; Hodgkinson, Paul

2016-01-04

Valsartan (VAL) is an antihypertensive drug marketed in an amorphous form. Amorphous materials can have different physicochemical properties depending on preparation method, thermal history, etc., but the nature of such materials is difficult to study by diffraction techniques. This study characterizes two different amorphous forms of valsartan (AR and AM) using solid-state NMR (SSNMR) as a primary investigation tool, supported by solution-state NMR, FT-IR, TMDSC, and dissolution tests. The two forms are found to be clearly distinct, with a significantly higher level of structural arrangement in the AR form, as observed in (13)C, (15)N, and (1)H SSNMR. (13)C and (15)N NMR indicates that the fully amorphous material (AM) contains an approximately equal ratio of cis-trans conformers about the amide bond, whereas the AR form exists mainly as one conformer, with minor conformational "defects". (1)H ultrafast MAS NMR shows significant differences in the hydrogen bonding involving the tetrazole and acid hydrogens between the two materials, while (15)N NMR shows that both forms exist as a 1,2,3,4-tetrazole tautomer. NMR relaxation times show subtle differences in local and bulk molecular mobility, which can be connected with the glass transition, the stability of the glassy material, and its response to aging. Counterintuitively the fully amorphous material is found to have a significantly lower dissolution rate than the apparently more ordered AR material.

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.

Exhumation rates of high pressure metamorphic rocks in subduction channels: The effect of Rheology

NASA Astrophysics Data System (ADS)

Gerya, T. V.; Stöckhert, B.

2002-04-01

Exhumation of high-pressure metamorphic rocks can take place with typical plate velocities of cm/year. This is consistent with a model of forced flow in a subduction channel. The (micro)structural record of exhumed metamorphic rocks indicates that stresses are generally too low to drive deformation of the bulk material by dislocation creep, according to a power-law rheology. Instead deformation appears to be localized in low-strength shear zones, and is dominated by dissolution precipitation creep or fluid assisted granular flow, implying a Newtonian rheology. 1D modeling shows that the effective rheology of the material in the subduction channel has a significant influence on the rate of exhumation. When the subduction flux either equals or exceeds the return flux, the maximum exhumation rate for Newtonian behavior of the material is at least twice as high (~1/3 of the subduction burial rate) compared to that for power-law creep (~1/6 of the subduction burial rate).

What Happens during Natural Protein Fibre Dissolution in Ionic Liquids.

PubMed

Chen, Jingyu; Vongsanga, Kylie; Wang, Xungai; Byrne, Nolene

2014-08-28

Here, we monitor the dissolution of several natural protein fibres such as wool, human hair and silk, in various ionic liquids (ILs). The dissolution of protein-based materials using ILs is an emerging area exploring the production of new materials from waste products. Wool is a keratin fibre, which is extensively used in the textiles industry and as a result has considerable amounts of waste produced each year. Wool, along with human hair, has a unique morphology whereby the outer layer, the cuticle, is heavily cross linked with disulphide bonds, whereas silk does not have this outer layer. Here we show how ILs dissolve natural protein fibres and how the mechanism of dissolution is directly related to the structure and morphology of the wool fibre.

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 use of 10 M HNO{sub 3} containing 0.03-0.05 M KF, 0.5-1.0 g/L Gd, and 1.9 g/L Fe resulted in complete dissolution of the metal in 2.0-3.5 h. When B was used as the neutron poison, 10 M HNO{sub 3} solutions containing 0.05-0.1 M KF, 1.9 g/L Fe, and 1 g/L B resulted in complete dissolution of the metal in 0.75-2.0 h. Dissolution rates estimated using data from the flowsheet demonstrations agreed reasonably well with the measured rates; although, a discrepancy was observed in the Gd system. The presence of 1 g/L Gd or B in the dissolving solution had about the same effect on the dissolution rate. The predominant Pu valence in the dissolving solution was Pu(IV). The concentration of Pu(VI) was evaluated by UV-visible spectroscopy and was estimated to be significantly less than 1 wt %. The offgas generation rates and H{sub 2} concentrations measured in the offgas from experiments performed using 10 M HNO{sub 3} containing 0.05 M KF, 1.9 g/L Fe and either 1 g/L Gd or B were approximately the same. These data support the conclusion that the presence of either 1 g/L Gd or B had the same general effect on the dissolution rate. The calculated offgas generation during the dissolutions was 0.6 mol offgas/mol of Pu. The H{sub 2} concentration measured in the offgas from the dissolution using Gd as the neutron poison was approximately 0.5 vol %. In the B system, the H{sub 2} ranged from nominally 0.8 to 1 vol % which is about the same as measured in the Gd system within the uncertainty of the analysis. The offgas generation rate for the dissolution performed using 10 M HNO{sub 3} containing 0.03 M KF, 0.5 g/L Gd, and 1.9 g/L Fe was approximately a factor of two less than produced in the other dissolutions; however, the concentration of H{sub 2} measured in the offgas was higher. The adjusted concentration ranged from 2.7 to 8.8 vol % as the dissolution proceeded. Higher concentrations of H{sub 2} occur when the Pu dissolution proceeds by a metal/acid reaction rather than nitrate oxidation. The higher H{sub 2} concentration could be attributed to the reduced activity of the fluoride due to complexation with Pu as the dissolution progressed. Dissolution of Pu metal at 20 °C in 10 M HNO{sub 3} containing 0.05 M KF showed that the Pu metal dissolves slowly without any visible gas generation. As the Pu metal dissolves, it forms a more-dense Pu-bearing solution which sank to the bottom of the dissolution vessel. The dissolved Pu did not form a boundary layer around the sample and failed to distribute homogeneously due to minimal (thermally-induced) mixing. This indicates that in the H-Canyon dissolver insert, the Pu will diffuse out of the insert into the bulk dissolver solution where it will disperse. At 35 °C, the Pu metal dissolved without visible gas generation. However, due to thermal currents caused by maintaining the solution at 35 °C, the dissolved Pu distributed evenly throughout the dissolver solution. It did not form a boundary layer around the sample.« less

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 reserved.

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%.

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 measurements and in situ monitoring of the topography of the dissolving surface of diopside in a hydrothermal AFM flow-cell (e.g. [5]). By investigating the dissolution of several cleavages, we will show how these latter techniques represent a powerful tool for studying the anisotropy of diopside dissolution, and determining which face ultimately controls its dissolution rate. An attempt to link these observations to macroscopic determination of diopside dissolution rates as a function of fluid composition will be discussed. [1] Daval et al. (2011) Chem. Geol., 284, 193-209. [2] Dixit & Carroll (2007) Geochem. T, 8, 1-14. [3] Daval et al. (2010) Geochim. Cosmochim. Ac., 74, 2615-2633. [4] Arvidson & Luttge (2010) Chem. Geol., 269, 79-88. [5] Saldi et al. (2009) Geochim. Cosmochim. Ac., 73, 5646-5657.

Preparation of novel porous starch microsphere foam for loading and release of poorly water soluble drug.

PubMed

Jiang, Tongying; Wu, Chao; Gao, Yikun; Zhu, Wenquan; Wan, Long; Wang, Zhanyou; Wang, Siling

2014-02-01

Organic porous material is a promising carrier for enhancing the dissolution of poorly water soluble drug. The aim of the present study was to enhance dissolution and oral bioavailability of lovastatin (LV) by preparing a porous starch microsphere foam (PSM) using a novel method, meanwhile, looking into the mechanism of improving dissolution of LV. PSM was prepared by the W/O emulsion-freeze thawing method. The porous structure of PSM was characterized by scanning electron microscopy (SEM) and nitrogen adsorption/desorption analysis. The adsorption role of nanopores on the drug dissolution and physical state of LV was systematically studied by instrumental analysis, and in vitro and in vivo drug dissolution studies. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay was used to evaluate carrier cytotoxicity. The SEM images of PSM showed nanometer-sized pores. Physical state characterization indicated that porous structure effectively limited the degree of crystallinity of LV. The results of in vitro and in vivo tests testified that PSM accelerated the release of LV and enhanced its oral bioavailability in comparison with crude LV and commercial capsules. The loaded PSM powder indicated a good physical stability under storage for 12 months. MTT assay shows PSM has no toxicity for Caco-2 cell. The preparation was a promising method to produce small and uniform PSM with markedly enhanced dissolution rate and oral bioavailability due to the spatial confinement effect of porous structure. The present work demonstrates the significant potential for the use of PSM as a novel delivery system for poorly water soluble drugs.

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.

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

Cassingham, N.; Corkhill, C. L.; Backhouse, D. J.

The first comprehensive assessment of the dissolution kinetics of simulant Magnox–THORP blended UK high-level waste glass, obtained by performing a range of single-pass flow-through experiments, is reported here. Inherent forward rates of glass dissolution were determined over a temperature range of 23 to 70°C and an alkaline pH range of 8.0 to 12.0. Linear regression techniques were applied to the TST kinetic rate law to obtain fundamental parameters necessary to model the dissolution kinetics of UK high-level waste glass (the activation energy (Ea), pH power law coefficient (η) and the intrinsic rate constant (k0)), which is of importance to themore » post-closure safety case for the geological disposal of vitreous products. The activation energies based on B release ranged from 55 ± 3 to 83 ± 9 kJ mol–1, indicating that Magnox–THORP blend glass dissolution has a surface-controlled mechanism, similar to that of other high- level waste simulant glass compositions such as the French SON68 and LAW in the US. Forward dissolution rates, based on Si, B and Na release, suggested that the dissolution mechanism under dilute conditions, and pH and temperature ranges of this study, was not sensitive to composition as defined by HLW-incorporation rate.« less

Antisolvent crystallization of a cardiotonic drug in ionic liquids: Effect of mixing on the crystal properties

NASA Astrophysics Data System (ADS)

de Azevedo Jacqueline, Resende; Fabienne, Espitalier; Jean-Jacques, Letourneau; Inês, Ré Maria

2017-08-01

LASSBio-294 (3,4-methylenedioxybenzoyl-2-thienylhydrazon) is a poorly soluble drug which has been proposed to have major advantages over other cardiotonic drugs. Poorly water soluble drugs present limited bioavailability due to their low solubility and dissolution rate. An antisolvent crystallization processing can improve the dissolution rate by decreasing the crystals particle size. However, LASSBio-294 is also poorly soluble in organic solvents and this operation is limited. In order to open new perspectives to improve dissolution rate, this work has investigated LASSBio-294 in terms of its antisolvent crystallization in 1-ethyl-3-methylimidazolium methyl phosphonate [emim][CH3O(H)PO2] as solvent and water as antisolvent. Two modes of mixing are tested in stirred vessel with different pre-mixers (Roughton or T-mixers) in order to investigate the mixing effect on the crystal properties (crystalline structure, particle size distribution, residual solvent and in vitro dissolution rate). Smaller drug particles with unchanged crystalline structure were obtained. Despite the decrease of the elementary particles size, the recrystallized particles did not achieve a better dissolution profile. However, this study was able to highlight a certain number of findings such as the impact of the hydrodynamic conditions on the crystals formation and the presence of a gel phase limiting the dissolution rate.

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.

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

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.

Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar

NASA Astrophysics Data System (ADS)

Hellmann, Roland; Tisserand, Delphine

2006-01-01

Here we report on an experimental investigation of the relation between the dissolution rate of albite feldspar and the Gibbs free energy of reaction, Δ Gr. The experiments were carried out in a continuously stirred flow-through reactor at 150 °C and pH (150 °C) 9.2. The dissolution rates R are based on steady-state Si and Al concentrations and sample mass loss. The overall relation between Δ Gr and R was determined over a free energy range of -150 < Δ Gr < -15.6 kJ mol -1. The data define a continuous and highly non-linear, sigmoidal relation between R and Δ Gr that is characterized by three distinct free energy regions. The region furthest from equilibrium, delimited by -150 < Δ Gr < -70 kJ mol -1, represents an extensive dissolution rate plateau with an average rate R¯=1.0×10-8molm-2s-1. In this free energy range the rates of dissolution are constant and independent of Δ Gr, as well as [Si] and [Al]. The free energy range delimited by -70 ⩽ Δ Gr ⩽ -25 kJ mol -1, referred to as the 'transition equilibrium' region, is characterized by a sharp decrease in dissolution rates with increasing Δ Gr, indicating a very strong inverse dependence of the rates on free energy. Dissolution nearest equilibrium, defined by Δ Gr > -25 kJ mol -1, represents the 'near equilibrium' region where the rates decrease as chemical equilibrium is approached, but with a much weaker dependence on Δ Gr. The lowest rate measured in this study, R = 6.2 × 10 -11 mol m -2 s -1 at Δ Gr = -16.3 kJ mol -1, is more than two orders of magnitude slower than the plateau rate. The data have been fitted to a rate equation (adapted from Burch et al. [Burch, T. E., Nagy, K. L., Lasaga, A. C., 1993. Free energy dependence of albite dissolution kinetics at 80 °C and pH 8.8. Chem. Geol.105, 137-162]) that represents the sum of two parallel reactions R=k1[1-exp(-ng)]+k2[1-exp(-g)], where k1 and k2 are rate constants that have been determined by regression, with values 1.02 × 10 -8 and 1.80 × 10 -10 mol m -2 s -1, g ≡ |Δ Gr|/R T is a dimensionless number, and n, m1, and m2 are adjustable fitted parameters ( n = 7.98 × 10 -5, m1 = 3.81 and m2 = 1.17). Based on measurements of the temporal evolution of RSi and RAl for each experiment, steady-state dissolution rates appear to be congruent at all Δ Gr. In contrast, non-steady-state dissolution is incongruent, and is related to Δ Gr. Scanning electron microscopy (SEM) images of post-reaction grain surfaces indicate that dissolution close to equilibrium (Δ Gr > -25 kJ mol -1) resulted in the precipitation of a secondary crystalline phase, but there are no indications that this altered the measured R-Δ Gr relation.

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. Dissolution from the oil body was greatest for compounds with large effective solubilities (benzene) and with large degradation rates (toluene and o-xylene). Anaerobic degradation removed 77% of the BTEX that dissolved into the water phase and aerobic degradation removed 17%. Although goodness-of-fit measures for the alternative conceptual models were not significantly different, predictions made with the models were quite variable. ?? 2003 Elsevier Science B.V. All rights reserved.

Simulating Dissolution of Intravitreal Triamcinolone Acetonide Suspensions in an Anatomically Accurate Rabbit Eye Model

PubMed Central

Horner, Marc; Muralikrishnan, R.

2010-01-01

ABSTRACT Purpose A computational fluid dynamics (CFD) study examined the impact of particle size on dissolution rate and residence of intravitreal suspension depots of Triamcinolone Acetonide (TAC). Methods A model for the rabbit eye was constructed using insights from high-resolution NMR imaging studies (Sawada 2002). The current model was compared to other published simulations in its ability to predict clearance of various intravitreally injected materials. Suspension depots were constructed explicitly rendering individual particles in various configurations: 4 or 16 mg drug confined to a 100 μL spherical depot, or 4 mg exploded to fill the entire vitreous. Particle size was reduced systematically in each configuration. The convective diffusion/dissolution process was simulated using a multiphase model. Results Release rate became independent of particle diameter below a certain value. The size-independent limits occurred for particle diameters ranging from 77 to 428 μM depending upon the depot configuration. Residence time predicted for the spherical depots in the size-independent limit was comparable to that observed in vivo. Conclusions Since the size-independent limit was several-fold greater than the particle size of commercially available pharmaceutical TAC suspensions, differences in particle size amongst such products are predicted to be immaterial to their duration or performance. PMID:20467888

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.

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 apparent modification of silicate dissolution rate over time. In addition, we evidenced that the relation between K-spar dissolution rate and ΔG depends on the crystallographic orientation of the altered surface, and differs from the transition state theory currently implemented into geochemical codes. Importantly, this theoretical curve overestimates the dissolution rates measured in close-to-equilibrium conditions. Taken together, the new findings show promise as a means for improving the accuracy of geochemical simulations. [1] Schott, J., Pokrovsky, O. S., and Oelkers, E. H., 2009. The Link Between Mineral Dissolution/Precipitation Kinetics and Solution Chemistry. Rev Mineral Geochem 70, 207-258. [2] Daval, D., Hellmann, R., Saldi, G. D., Wirth, R., and Knauss, K. G., 2013. Linking nm-scale measurements of the anisotropy of silicate surface reactivity to macroscopic dissolution rate laws: New insights based on diopside. Geochim Cosmochim Acta 107, 121-134.

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.

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.

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.

Dissolution Rates of Allophane, FE-Containing Allophane, and Hisingerite and Implications for Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Ralston, S. J.; Hausrath, E. M.; Tschauner, O.; Rampe, E. B.; Christoffersen, R.

2018-01-01

Investigations with the CheMin Xray Diffractometer (XRD) onboard the Curiosity rover in Gale Crater demonstrate that all rock and soil samples measured to date contain approximately 15-70 weight percentage X-ray amorphous materials. The diffuse scattering hump from the X-ray amorphous materials in CheMin XRD patterns can be fit with a combination of allophane, ferrihydrite, and rhyolitic and basaltic glass. Because of the iron-rich nature of Mars' surface, Fe-rich poorly-crystalline phases, such as hisingerite, may be present in addition to allophane.

Ionic Liquids and Cellulose: Dissolution, Chemical Modification and Preparation of New Cellulosic Materials

PubMed Central

Isik, Mehmet; Sardon, Haritz; Mecerreyes, David

2014-01-01

Due to its abundance and a wide range of beneficial physical and chemical properties, cellulose has become very popular in order to produce materials for various applications. This review summarizes the recent advances in the development of new cellulose materials and technologies using ionic liquids. Dissolution of cellulose in ionic liquids has been used to develop new processing technologies, cellulose functionalization methods and new cellulose materials including blends, composites, fibers and ion gels. PMID:25000264

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 differences in the degree of confinement on the increase in bulk concentration independent of container geometry and polydisperse vs single particle dissolution. We conclude that the constant diffusion-layer thickness assumption is incorrect in principle and should be replaced by the QSM with accurate treatment of confinement in models of diffusion-controlled dissolution.

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.

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.

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 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.

Degradable and porous Fe-Mn-C alloy for biomaterials candidate

NASA Astrophysics Data System (ADS)

Pratesa, Yudha; Harjanto, Sri; Larasati, Almira; Suharno, Bambang; Ariati, Myrna

2018-02-01

Nowadays, degradable implants attract attention to be developed because it can improve the quality of life of patients. The degradable implant is expected to degrade easily in the body until the bone healing process already achieved. However, there is limited material that could be used as a degradable implant, polymer, magnesium, and iron. In the previous study, Fe-Mn-C alloys had succesfully produced austenitic phase. However, the weakness of the alloy is degradation rate of materials was considered below the expectation. This study aimed to produce porous Fe-Mn-C materials to improve degradation rate and reduce the density of alloy without losing it non-magnetic properties. Potassium carbonate (K2CO3) were chosen as filler material to produce foam structure by sintering and dissolution process. Multisteps sintering process under argon gas environment was performed to generate austenite phase. The product showed an increment of the degradation rate of the foamed Fe-Mn-C alloy compared with the solid Fe-Mn-C alloy without losing the Austenitic Structure

Photochemical Tissue Bonding for Military Medical Applications Practical Low Cost Low Damage Blood Vessel Repair: Albumin Stent Bonded With 19xx nm Laser

DTIC Science & Technology

2011-02-24

shape. At higher concentrations, the albumin would not flow through the extruder. Quarter 4 We used our temperature-controlled extruder to create...albumin stents with an outside diameter from 2 mm and various inner lumen diameters. Dissolution studies in flowing blood indicated that the stents 3...at the same rate. Determined that gamma sterilization procedure does not affect dissolution. Determined that flow rate affects the dissolution rate

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.

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

Sodium sulfate - Deposition and dissolution of silica

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.

1989-01-01

The hot-corrosion process for SiO2-protected materials involves deposition of Na2SO4 and dissolution of the protective SiO2 scale. Dew points for Na2SO4 deposition are calculated as a function of pressure, sodium content, and sulfur content. Expected dissolution regimes for SiO2 are calculated as a function of Na2SO4 basicity. Controlled-condition burner-rig tests on quartz verify some of these predicted dissolution regimes. The basicity of Na2SO4 is not always a simple function of P(SO3). Electrochemical measurements of an (Na2O) show that carbon creates basic conditions in Na2SO4, which explains the extensive corrosion of SiO2-protected materials containing carbon, such as SiC.

What Happens during Natural Protein Fibre Dissolution in Ionic Liquids

PubMed Central

Chen, Jingyu; Vongsanga, Kylie; Wang, Xungai; Byrne, Nolene

2014-01-01

Here, we monitor the dissolution of several natural protein fibres such as wool, human hair and silk, in various ionic liquids (ILs). The dissolution of protein-based materials using ILs is an emerging area exploring the production of new materials from waste products. Wool is a keratin fibre, which is extensively used in the textiles industry and as a result has considerable amounts of waste produced each year. Wool, along with human hair, has a unique morphology whereby the outer layer, the cuticle, is heavily cross linked with disulphide bonds, whereas silk does not have this outer layer. Here we show how ILs dissolve natural protein fibres and how the mechanism of dissolution is directly related to the structure and morphology of the wool fibre. PMID:28788183

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. For dynamic column flushing experiments, dissolution rate kinetics can vary significantly with changes in NAPL volume and surface area. However, under conditions whereby NAPL volume and area are not significantly altered during dissolution, mixture nonideality effects may have a greater relative control on dissolution (elution) and MFR behavior compared to kinetic rate limitations. Copyright © 2017 Elsevier B.V. All rights reserved.

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 fraction. For dynamic column flushing experiments, dissolution rate kinetics can vary significantly with changes in NAPL volume and surface area. However, under conditions whereby NAPL volume and area are not significantly altered during dissolution, mixture nonideality effects may have a greater relative control on dissolution (elution) and MFR behavior compared to kinetic rate limitations.

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 occurred in 8-10 M HNO{sub 3} with 0.04-0.05 M KF at 112 to 116 C (boiling). The testing also showed that solutions containing 8-10 M HNO{sub 3}, 0.1-0.2 M KF, and 1-2 g/L B achieved acceptable dissolution rates in the same temperature range. To confirm that conditions identified by the dissolution rate measurements for solutions containing Gd or B can be used to dissolve Pu metal up to 6.75 g/L in the presence of Fe, demonstration experiments were performed using concentrations in the optimal ranges. In two of the demonstration experiments using Gd and in one experiment using B, the offgas generation during the dissolution was measured and samples were analyzed for H{sub 2}. The experimental methods used to perform the dissolution rate measurements and flowsheet demonstrations and a discussion of the results are presented.« less

Use of glancing angle X-ray powder diffractometry to depth-profile phase transformations during dissolution of indomethacin and theophylline tablets.

PubMed

Debnath, Smita; Predecki, Paul; Suryanarayanan, Raj

2004-01-01

The purpose of this study was (i) to develop glancing angle x-ray powder diffractometry (XRD) as a method for profiling phase transformations as a function of tablet depth; and (ii) to apply this technique to (a) study indomethacin crystallization during dissolution of partially amorphous indomethacin tablets and to (b) profile anhydrate --> hydrate transformations during dissolution of theophylline tablets. The intrinsic dissolution rates of indomethacin and theophylline were determined after different pharmaceutical processing steps. Phase transformations during dissolution were evaluated by various techniques. Transformation in the bulk and on the tablet surface was characterized by conventional XRD and scanning electron microscopy, respectively. Glancing angle XRD enabled us to profile these transformations as a function of depth from the tablet surface. Pharmaceutical processing resulted in a decrease in crystallinity of both indomethacin and theophylline. When placed in contact with the dissolution medium, while indomethacin recrystallized, theophylline anhydrate rapidly converted to theophylline monohydrate. Due to intimate contact with the dissolution medium, drug transformation occurred to a greater extent at or near the tablet surface. Glancing angle XRD enabled us to depth profile the extent of phase transformations as a function of the distance from the tablet surface. The processed sample (both indomethacin and theophylline) transformed more rapidly than did the corresponding unprocessed drug. Several challenges associated with the glancing angle technique, that is, the effects of sorbed water, phase transformations during the experimental timescale, and the influence of phase transformation on penetration depth, were addressed. Increased solubility, and consequently dissolution rate, is one of the potential advantages of metastable phases. This advantage is negated if, during dissolution, the metastable to stable transformation rate > dissolution rate. Glancing angle XRD enabled us to quantify and thereby profile phase transformations as a function of compact depth. The technique has potential utility in monitoring surface reactions, both chemical decomposition and physical transformations, in pharmaceutical systems.

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

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 flow and enhanced dissolution of large scCO2 clusters. The three stages of scCO2 depletion, common to experiments with time-independent water-flow paths, are revealed by zoom-in image analysis of individual scCO2 bubbles and clusters. The measured relative permeability of water, affected by scCO2 dissolution and bi-modal permeability, shows a non-monotonic dependence on saturation. The results for experiments with different injection rates imply that the non-equilibrium nature of scCO2 dissolution becomes less important when water flow is relatively low and the time scale for dissolution is large, and more pronounced when heterogeneity is strong.« less

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

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...

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

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.

Theoretical and Numerical Investigation of the Cavity Evolution in Gypsum Rock

NASA Astrophysics Data System (ADS)

Li, Wei; Einstein, Herbert H.

2017-11-01

When water flows through a preexisting cylindrical tube in gypsum rock, the nonuniform dissolution alters the tube into an enlarged tapered tube. A 2-D analytical model is developed to study the transport-controlled dissolution in an enlarged tapered tube, with explicit consideration of the tapered geometry and induced radial flow. The analytical model shows that the Graetz solution can be extended to model dissolution in the tapered tube. An alternative form of the governing equations is proposed to take advantage of the invariant quantities in the Graetz solution to facilitate modeling cavity evolution in gypsum rock. A 2-D finite volume model was developed to validate the extended Graetz solution. The time evolution of the transport-controlled and the reaction-controlled dissolution models for a single tube with time-invariant flow rate are compared. This comparison shows that for time-invariant flow rate, the reaction-controlled dissolution model produces a positive feedback between the tube enlargement and dissolution, while the transport-controlled dissolution does not.

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 has a labilizing effect on the dynamics of the remaining water molecules and thus increases reaction rates.

Analysis of long-term bacterial vs. chemical Fe(III) oxide reduction kinetics

NASA Astrophysics Data System (ADS)

Roden, Eric E.

2004-08-01

Data from studies of dissimilatory bacterial (10 8 cells mL -1 of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L -1) were analyzed in relation to a generalized rate law for mineral dissolution (J t/m 0 = k'(m/m 0) γ, where J t is the rate of dissolution and/or reduction at time t, m 0 is the initial mass of oxide, and m/m 0 is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to predict long-term patterns of reactivity toward enzymatic reduction at circumneutral pH.

Influence of carbides and microstructure of CoCrMo alloys on their metallic dissolution resistance.

PubMed

Valero-Vidal, C; Casabán-Julián, L; Herraiz-Cardona, I; Igual-Muñoz, A

2013-12-01

CoCrMo alloys are passive and biocompatible materials widely used as joint replacements due to their good mechanical properties and corrosion resistance. Electrochemical behaviour of thermal treated CoCrMo alloys with different carbon content in their bulk alloy composition has been analysed. Both the amount of carbides in the CoCrMo alloys and the chemical composition of the simulated body fluid affect the electrochemical properties of these biomedical alloys, thus passive dissolution rate was influenced by the mentioned parameters. Lower percentage of carbon in the chemical composition of the bulk alloy and thermal treatments favour the homogenization of the surface (less amount of carbides), thus increasing the availability of Cr to form the oxide film and improving the corrosion resistance of the alloy. © 2013.

Tertiary carbonate-dissolution cycles on the Sierra Leone Rise, eastern equatorial Atlantic Ocean

USGS Publications Warehouse

Dean, W.E.; Gardner, J.V.; Cepek, P.

1981-01-01

Most of the Tertiary section on Sierra Leone Rise off northwest Africa consists of chalk, marl, and limestone that show cyclic alterations of clay-rich and clay-poor beds about 20-60 cm thick. On the basis of biostratigraphic accumulation rates, the cycles in Oligocene and Miocene chalk have periods which average about 44,000 years, and those in Eocene siliceous limestone have periods of 4000-27,000 years. Several sections were sampled in detail to further define the cycles in terms of content of CaCO3, clay minerals, and relative abundances of calcareous nannofossils. Extending information gained by analyses of Pleistocene cores from the continental margin of northwest Africa to the Tertiary cycles on Sierra Leone Rise, both dilution by noncarbonate material and dissolution of CaCO3 could have contributed to the observed relative variations in clay and CaCO3. However, dissolution of CaCO3 as the main cause of the carbonate-clay cycles on the Sierra Leone Rise, rather than dilution by clay, is suggested by the large amount of change (several thousand percent) in terrigenous influx required to produce the observed variations in amount of clay and by the marked increase in abundance of dissolution-resistant discoasters relative to more easily dissolved coccoliths in low-carbonate parts of cycles. The main cause of dissolution of CaCO3 was shoaling of the carbonate compensation depth (CCD) during the early Neogene and climatically induced fluctuations in the thickness of Antarctic Bottom Water. ?? 1981.

In vitro and in vivo studies on a novel solid dispersion of repaglinide using polyvinylpyrrolidone as the carrier.

PubMed

Yin, Li-Fang; Huang, Shi-Jing; Zhu, Chun-Li; Zhang, Shu-Hui; Zhang, Qiang; Chen, Xi-Jing; Liu, Qing-Wang

2012-11-01

In order to improve the dissolution and absorption of the water insoluble drug repaglinide, a solid dispersion was developed by solvent method using polyvinylpyrrolidone K30 (PVP K30) as the hydrophilic carrier for the first time. Studies indicated that both solubility and the dissolution rate of repaglinide were significantly increased in the solid dispersion system compared with that of repaglinide raw material or physical mixtures. The repaglinide solid dispersions with PVP K30 solid state was characterized by polarizing microscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). DSC and XRD studies indicated that repaglinide existed in an amorphous form in the solid dispersion. FT-IR analysis demonstrated the presence of intermolecular hydrogen bonding between repaglinide and PVP K30 in the solid dispersion. In the in situ gastrointestinal perfusion experiment, solid dispersion was shown to remarkably enhance the absorption of repaglinide in stomach and all segments of intestine. In vivo pharmacokinetic study in rats showed that immediate and complete release of repaglinide from the solid dispersion resulted in rapid absorption that significantly increased the bioavailability and the maximum plasma concentration over repaglinide raw material. These results demonstrated PVP K30 was an appropriate carrier for solid dispersion of repaglinide, with increased dissolution and oral absorption.

Behavior of radioactive materials and safety stock of contaminated sludge.

PubMed

Tsushima, Ikuo

2017-01-28

The radioactive fallout from the Fukushima Dai-ichi nuclear power plant disaster in 2011 has flowed into and accumulated in many wastewater treatment plants (WWTPs) via sewer systems; this has had a negative impact on WWTPs in eastern Japan. The behavior of radioactive materials was analyzed at four WWTPs in the Tohoku and Kanto regions to elucidate the mechanism by which radioactive materials are concentrated during the sludge treatment process from July 2011 to March 2013. Furthermore, numerical simulations were conducted to study the safe handling of contaminated sewage sludge stocked temporally in WWTPs. Finally, a dissolution test was conducted by using contaminated incinerated ash and melted slag derived from sewage sludge to better understand the disposal of contaminated sewage sludge in landfills. Measurements indicate that a large amount of radioactive material accumulates in aeration tanks and is becoming trapped in the concentrated sludge during the sludge condensation process. The numerical simulation indicates that a worker's exposure around contaminated sludge is less than 1 µSv/h when maintaining an isolation distance of more than 10 m, or when shielding with more than 20-cm-thick concrete. The radioactivity level of the eluate was undetectable in 9 out of 12 samples; in the remaining three samples, the dissolution rates were 0.5-2.7%.

Effects of drug-carrier interactions on drug dissolution from binary and ternary matrices

NASA Astrophysics Data System (ADS)

Iqbal, Zafar

For nearly five decades, pharmaceutical researchers have studied solid solutions of drugs in polymers as a potential means to enhance the dissolution of drugs with poor aqueous solubility. This has become of greater importance in recent years because most new potential drug compounds (new chemical entities) exhibit poor water solubility and present great challenges to scientists who must design dosage forms from which the drugs are bioavailable. During the formulation of a solid solution, the drug undergoes physical but not chemical alterations that increase its chemical potential in the formulation relative to that of the pure drug in its stable form. This increased chemical potential is responsible for enhanced dissolution as well as physical instabilities, such as amorphous to crystalline conversions and precipitation within the solid state. The chemical potential is derived from the Gibbs free energy, so it is reasonable to explain the behavior of solid solution systems in terms of thermodynamics. Solid solutions and dispersions have been extensively studied by pharmaceutical scientists, both with regard to manufacturing aspects and the proposal of various models in attempts to explain the physical bases for how these systems work. Recently, Dave and Bellantone proposed a model based on the thermodynamic changes resulting from the formulation of binary solid solutions of a drug in the polymer PVP. Their model introduced a modification of the F-H theory, which was used to quantify the drug-polymer interaction energies and calculate the entropy of mixing of the drug and polymer. In this work, the model of Dave and Bellantone was extended to include three-component systems, consisting of one drug mixed in a carrier matrix consisting of mixture of two polymers or a polymer and a surfactant. For this research, solid solutions were formed using various drug weight fractions in the formulations. The study focused on the following points: (1) Prepare solid solution formulations and perform appropriate physical characterizations. (2) Characterize the increase in drug dissolution rates resulting from solid solution formulations. (3) Relate the initial dissolution rates to the drug solubility. (4) Explain the solubility enhancement from solid solution dosage in terms of the drug polymer interactions using the extended thermodynamic model. Two poorly water soluble drugs, levonorgestrel (LEVO) and ethinyl estradiol (EE) were formulated in seven solid solution preparations comprised of four carrier systems. Materials used as carriers included various combinations of the polymers PVP K-30, Copovidone (COP), Poloxamer 182, and the surfactant TweenRTM 20. Additionally, ibuprofen (IBU) was used in three formulations consisting of various combinations of PVP K-30, Copovidone and TweenRTM 20. Formulations with various drug weight fractions (0.5%--30%) were prepared using the solvent evaporation technique. Each formulation was tested for dissolution using intrinsic dissolution apparatus (USP). The solid solutions were compressed into tablets into the sample die that maintained a constant surface area during the dissolution process. DSC, XRD and NIRS scans identified that the crystalline peaks of the drug disappeared with the addition of the polymer for all ratios of EE, indicating the formation of solid solutions (to within the limits of detection of the equipment). This was also observed for the LEVO dispersions up to 10% drug loading. At higher drug loading, solutions were formed but some small degree crystallinity was also present. For each experiment, the initial dissolution rates were obtained from the slope of the mass dissolved vs. time plots taken at early times, and volume normalized initial dissolution rates RV were calculated by dividing the initial dissolution rate by the volume fraction of the drug in the formulation. Comparison of the RV values for the various formulations with a reference RV (typically that of the pure drug or of the formulation with the highest polymer content) allowed calculation of relative volume normalized dissolution rates (RNV). The various RNV were used in the thermodynamic model for data analyses and to determine the interactions between the drug and carrier molecules. It was generally seen that RNV increased with decreased drug fraction, and was adequately modeled by the equations derived from the extended thermodynamic model. It was concluded that the model proposed for the binary and ternary systems successfully represented the mechanism of drug-polymer interaction and the energy changes taken place within the dispersion systems. The dissolution data analysis and subsequent understanding of physical modifications in the dispersion systems characterized by XRD, NIRS and DSC further substantiated the findings. The understanding of the fundamental physical might help scientists to predict the effects of mixing various drugs and polymers, and the effects of varying ratios.

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.

Effect of the Addition of a Labile Gelatin Component on the Degradation and Solute Release Kinetics of a Stable PEG Hydrogel

PubMed Central

Waldeck, H.; Kao, W. J.

2013-01-01

Characterization of the degradation mechanisms and resulting products of biodegradable materials is critical in understanding the behavior of the material including solute transport and biological response. Previous mathematical analyses of a semi-interpenetrating network (sIPN) containing both labile gelatin and a stable cross-linked poly(ethylene glycol) (PEG) network found that diffusion-based models alone were unable to explain the release kinetics of solutes from the system. In this study, degradation of the sIPN and its effect on solute release and swelling kinetics were investigated. The kinetics of the primary mode of degradation, gelatin dissolution, was dependent on temperature, preparation methods, PEGdA and gelatin concentration, and the weight ratio between the gelatin and PEG. The gelatin dissolution rate positively correlated with both matrix swelling and the release kinetics of high-molecular-weight model compound, FITC-dextran. Coupled with previous in vitro studies, the kinetics of sIPN degradation provided insights into the time-dependent changes in cellular response including adhesion and protein expression. These results provide a facile guide in material formulation to control the delivery of high-molecular-weight compounds with concomitant modulation of cellular behavior. PMID:21801489

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.

AFS-2 FLOWSHEET MODIFICATIONS TO ADDRESS THE INGROWTH OF PU(VI) DURING METAL DISSOLUTION

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

Crapse, K.; Rudisill, T.; O'Rourke, P.

2014-07-02

In support of the Alternate Feed Stock Two (AFS-2) PuO{sub 2} production campaign, Savannah River National Laboratory (SRNL) conducted a series of experiments concluding that dissolving Pu metal at 95°C using a 6–10 M HNO{sub 3} solution containing 0.05–0.2 M KF and 0–2 g/L B could reduce the oxidation of Pu(IV) to Pu(VI) as compared to dissolving Pu metal under the same conditions but at or near the boiling temperature. This flowsheet was demonstrated by conducting Pu metal dissolutions at 95°C to ensure that PuO{sub 2} solids were not formed during the dissolution. These dissolution parameters can be used formore » dissolving both Aqueous Polishing (AP) and MOX Process (MP) specification materials. Preceding the studies reported herein, two batches of Pu metal were dissolved in the H-Canyon 6.1D dissolver to prepare feed solution for the AFS-2 PuO{sub 2} production campaign. While in storage, UV-visible spectra obtained from an at-line spectrophotometer indicated the presence of Pu(VI). Analysis of the solutions also showed the presence of Fe, Ni, and Cr. Oxidation of Pu(IV) produced during metal dissolution to Pu(VI) is a concern for anion exchange purification. Anion exchange requires Pu in the +4 oxidation state for formation of the anionic plutonium(IV) hexanitrato complex which absorbs onto the resin. The presence of Pu(VI) in the anion feed solution would require a valence adjustment step to prevent losses. In addition, the presence of Cr(VI) would result in absorption of chromate ion onto the resin and could limit the purification of Pu from Cr which may challenge the purity specification of the final PuO{sub 2} product. Initial experiments were performed to quantify the rate of oxidation of Pu(IV) to Pu(VI) (presumed to be facilitated by Cr(VI)) as functions of the HNO{sub 3} concentration and temperature in simulated dissolution solutions containing Cr, Fe, and Ni. In these simulated Pu dissolutions studies, lowering the temperature from near boiling to 95 °C reduced the oxidation rate of Pu(IV) to Pu(VI). For 8.1 M HNO{sub 3} simulated dissolution solutions, at near boiling conditions >35% Pu(VI) was present in 50 h while at 95 °C <10% Pu(VI) was present at 50 h. At near boiling temperatures, eliminating the presence of Cr and varying the HNO{sub 3} concentration in the range of 7–8.5 M had little effect on the rate of conversion of Pu(IV) to Pu(VI). HNO{sub 3} oxidation of Pu(IV) to Pu(VI) in a pure solution has been reported previously. Based on simulated dissolution experiments, this study concluded that dissolving Pu metal at 95°C using a 6 to 10 M HNO{sub 3} solution 0.05–0.2 M KF and 0–2 g/L B could reduce the rate of oxidation of Pu(IV) to Pu(VI) as compared to near boiling conditions. To demonstrate this flowsheet, two small-scale experiments were performed dissolving Pu metal up to 6.75 g/L. No Pu-containing residues were observed in the solutions after cooling. Using Pu metal dissolution rates measured during the experiments and a correlation developed by Holcomb, the time required to completely dissolve a batch of Pu metal in an H-Canyon dissolver using this flowsheet was estimated to require nearly 5 days (120 h). This value is reasonably consistent with an estimate based on the Batch 2 and 3 dissolution times in the 6.1D dissolver and Pu metal dissolution rates measured in this study and by Rudisill et al. Data from the present and previous studies show that the Pu metal dissolution rate decreases by a factor of approximately two when the temperature decreased from boiling (112 to 116°C) to 95°C. Therefore, the time required to dissolve a batch of Pu metal in an H-Canyon dissolver at 95°C would likely double (from 36 to 54 h) and require 72 to 108 h depending on the surface area of the Pu metal. Based on the experimental studies, a Pu metal dissolution flowsheet utilizing 6–10 M HNO{sub 3} containing 0.05–0.2 M KF (with 0–2 g/L B) at 95°C is recommended to reduce the oxidation of Pu(IV) to Pu(VI) as compared to near boiling conditions. The time required to completely dissolve a batch of Pu metal will increase, however, by approximately a factor of two as compared to initial dissolutions at near boiling (assuming the KF concentration is maintained at nominally 0.1 M). By lowering the temperature to 95°C under otherwise the same operating parameters as previous dissolutions, the Pu(VI) concentration should not exceed 15% after a 120 h heating cycle. Increasing the HNO{sub 3} concentration and lowering Pu concentration are expected to further limit the amount of Pu(VI) formed.« less

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

Visualising phase change in a brushite-based calcium phosphate ceramic

PubMed Central

Bannerman, A.; Williams, R. L.; Cox, S. C.; Grover, L. M.

2016-01-01

The resorption of brushite-based bone cements has been shown to be highly unpredictable, with strong dependence on a number of conditions. One of the major factors is phase transformation, with change to more stable phases such as hydroxyapatite affecting the rate of resorption. Despite its importance, the analysis of phase transformation has been largely undertaken using methods that only detect crystalline composition and give no information on the spatial distribution of the phases. In this study confocal Raman microscopy was used to map cross-sections of brushite cylinders aged in Phosphate Buffered Saline, Foetal Bovine Serum, Dulbecco’s – Minimum Essential Medium (with and without serum). Image maps showed the importance of ageing medium on the phase composition throughout the ceramic structure. When aged without serum, there was dissolution of the brushite phase concomitant to the deposition of octacalcium phosphate (OCP) around the periphery of the sample. The deposition of OCP was detectable within five days and reduced the rate of brushite dissolution from the material. The use of serum, even at a concentration of 10vol% prevented phase transformation. This paper demonstrates the value of confocal Raman microscopy in monitoring phase change in biocements; it also demonstrates the problems with assessing material degradation in non-serum containing media. PMID:27604149

Visualising phase change in a brushite-based calcium phosphate ceramic

NASA Astrophysics Data System (ADS)

Bannerman, A.; Williams, R. L.; Cox, S. C.; Grover, L. M.

2016-09-01

The resorption of brushite-based bone cements has been shown to be highly unpredictable, with strong dependence on a number of conditions. One of the major factors is phase transformation, with change to more stable phases such as hydroxyapatite affecting the rate of resorption. Despite its importance, the analysis of phase transformation has been largely undertaken using methods that only detect crystalline composition and give no information on the spatial distribution of the phases. In this study confocal Raman microscopy was used to map cross-sections of brushite cylinders aged in Phosphate Buffered Saline, Foetal Bovine Serum, Dulbecco’s - Minimum Essential Medium (with and without serum). Image maps showed the importance of ageing medium on the phase composition throughout the ceramic structure. When aged without serum, there was dissolution of the brushite phase concomitant to the deposition of octacalcium phosphate (OCP) around the periphery of the sample. The deposition of OCP was detectable within five days and reduced the rate of brushite dissolution from the material. The use of serum, even at a concentration of 10vol% prevented phase transformation. This paper demonstrates the value of confocal Raman microscopy in monitoring phase change in biocements; it also demonstrates the problems with assessing material degradation in non-serum containing media.

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.

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.

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.

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.

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 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 Monte Carlo simulations carried out in this work enabled us to refine this conclusion. Indeed, the simulations 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 bond to nearest-neighbor sites) and dissolution via detachment of clusters.« less

Electrochemical way of molybdenum extraction from the Bimetallic systems of Mo-W

NASA Astrophysics Data System (ADS)

Kudreeva, L. K.; Nauryzbaev, M. K.; Kurbatov, A. P.; Kamysbaev, D. H.; Adilbekova, A. O.; Mukataeva, Z. S.

2015-12-01

Electrochemical dissolution of molybdenum and tungsten was investigated in water- dimethylsulfoxide (DMSO) media at different concentrations of lithium chloride and magnesium perchlorate. The terms of efficient extraction of molybdenum from bimetallic systems of Mo-W have been determined. The polarization curves of the electrooxidation of molybdenum in the solution of 0.25 M LiCl in the DMSO at the different rates of rotations and the scan rate equal to 50 mV/s were obtained. In the presence of the addition of water at the potential of 0.1-0.75 V the small area of polarizability occurs, then with increasing potentials above 1.5 V there is a sharp increase of the oxidation current. Comparison of the current values of anodic dissolution of molybdenum and tungsten showed that the rate of anodic dissolution of molybdenum significantly exceeds the rate of anodic dissolution of tungsten. In the case of molybdenum, the dissolution process is limited by diffusion, in the case of tungsten - by the passive film formation on the electrode surface.

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.

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 the dynamic system of LD steelmaking. In addition, with the inclusion of this submodel, significant improvement in the prediction of the slag composition during the main blow period has been observed.

Investigation of corrosion behavior of biodegradable magnesium alloys using an online-micro-flow capillary flow injection inductively coupled plasma mass spectrometry setup with electrochemical control

NASA Astrophysics Data System (ADS)

Ulrich, A.; Ott, N.; Tournier-Fillon, A.; Homazava, N.; Schmutz, P.

2011-07-01

The development of biodegradable metallic materials designed for implants or medical stents is new and is one of the most interesting new fields in material science. Besides biocompatibility, a detailed understanding of corrosion mechanisms and dissolution processes is required to develop materials with tailored degradation behavior. The materials need to be sufficiently stable as long as they have to fulfill their medical task. However, subsequently they should dissolve completely in a controlled manner in terms of maximum body burden. This study focuses on the elemental and time resolved dissolution processes of a magnesium rare earth elements alloy which has been compared to pure magnesium with different impurity level. The here described investigations were performed using a novel analytical setup based on a micro-flow capillary online-coupled via a flow injection system to a plasma mass spectrometer. Differences in element-specific and time-dependent dissolution were monitored for various magnesium alloys in contact with sodium chloride or mixtures of sodium and calcium chloride as corrosive media. The dissolution behavior strongly depends on bulk matrix elements, secondary alloying elements and impurities, which are usually present even in pure magnesium.

Processing and analysis techniques involving in-vessel material generation

DOEpatents

Schabron, John F [Laramie, WY; Rovani, Jr., Joseph F.

2011-01-25

In at least one embodiment, the inventive technology relates to in-vessel generation of a material from a solution of interest as part of a processing and/or analysis operation. Preferred embodiments of the in-vessel material generation (e.g., in-vessel solid material generation) include precipitation; in certain embodiments, analysis and/or processing of the solution of interest may include dissolution of the material, perhaps as part of a successive dissolution protocol using solvents of increasing ability to dissolve. Applications include, but are by no means limited to estimation of a coking onset and solution (e.g., oil) fractionating.

Processing and analysis techniques involving in-vessel material generation

DOEpatents

Schabron, John F [Laramie, WY; Rovani, Jr., Joseph F.

2012-09-25

In at least one embodiment, the inventive technology relates to in-vessel generation of a material from a solution of interest as part of a processing and/or analysis operation. Preferred embodiments of the in-vessel material generation (e.g., in-vessel solid material generation) include precipitation; in certain embodiments, analysis and/or processing of the solution of interest may include dissolution of the material, perhaps as part of a successive dissolution protocol using solvents of increasing ability to dissolve. Applications include, but are by no means limited to estimation of a coking onset and solution (e.g., oil) fractionating.

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.

Dissolution of a Tetrachloroethene (PCE) pool in an Anaerobic Sand Tank Aquifer System: Bioenhancement, Ecology, and Hydrodynamics

NASA Astrophysics Data System (ADS)

Klemm, Sara; Becker, Jennifer; Seagren, Eric

2017-04-01

Dehalorespiring bacteria that reductively dechlorinate and grow on chlorinated ethenes in the aqueous phase can also achieve treatment of dense nonaqueous phase liquid (DNAPL) contaminants in the subsurface via bioenhanced dissolution, i.e., enhanced mass transfer from the DNAPL to the aqueous phase. Theoretical and experimental analyses predict that a number of interrelated physicochemical processes (e.g., advection and dispersion) and biological factors (e.g., biokinetics and competition) may influence the degree of bioenhancement. This research focused on understanding the interrelated roles that hydrodynamics and ecological interactions among dehalorespiring populations play in determining the distribution of dehalorespiring populations and the impact on bioenhanced dissolution and detoxification. The hypotheses driving this research are that: (1) ecological interactions between different dehalorespiring strains can significantly impact the dissolution rate bioenhancement and extent of dechlorination; and (2) hydrodynamics near the DNAPL pool will affect the outcome of ecological interactions and the potential for bioenhancement and detoxification. These hypotheses were evaluated via a multi-objective modeling and experimental framework focused on quantifying the impact of microbial interactions and hydrodynamics on the dissolution rate bioenhancement and plume detoxification using a model co-culture of Desulfuromonas michiganensis BB1 and Dehalococcoides mccartyi 195. The experiments were performed in a saturated intermediate-scale flow cell (1.2 m), with flow parallel to a tetrachloroethene (PCE) pool. Bioenhancement of PCE dissolution by the two dehalorespirers was evaluated using a steady-state mass balance, and initially resulted in a two- to three-fold increase in the dissolution rate, with cis-dichloroethene (cDCE) as the primary dechlorination product. Quantitative analysis of microbial population distribution and abundance using a 16S rRNA gene-based qPCR approach indicated that Dsm. michiganensis BB1 was the dominant population in the effluent. This was expected based on our previous work characterizing the PCE utilization kinetics of the two populations, and suggests that Dsm. michiganensis BB1 was the dominant population in the aquifer system and controlled PCE dissolution and its bioenhancement. This conclusion is consistent with our numerical modeling predictions for the same conditions, which suggested Dhc. mccartyi 195 had little effect on dissolution and dehalorespiration, but aided detoxification by growing on the cDCE produced by Dsm. michiganensis BB1. Subsequently, the PCE dissolution enhancement increased to six- to seven-fold relative to the abiotic dissolution rate. Quantitative analysis of population distribution and abundance in the porous media and nonreactive tracer studies suggested that microbial growth-induced bioclogging, coupled with inhibition of microbial activity near the DNAPL, resulted in increased flow immediately adjacent to the DNAPL-aqueous interface. The increased flow rate past the DNAPL could explain the observed increase in the PCE dissolution rate and is consistent with our numerical modeling of the system. The research described here is part of a larger project working to improve the fundamental understanding of the impact of hydrodynamics and ecological interactions on DNAPL dissolution rate bioenhancement and plume detoxification. These biotic data build on the baseline abiotic experiments reported in another abstract submitted to Session HS8.1.6.

Improved dissolution and absorption of ketoconazole in the presence of organic acids as pH-modifiers.

PubMed

Adachi, Masashi; Hinatsu, Yuta; Kusamori, Kosuke; Katsumi, Hidemasa; Sakane, Toshiyasu; Nakatani, Manabu; Wada, Koichi; Yamamoto, Akira

2015-08-30

Formulation development of poorly water-soluble compounds can be challenging because of incomplete dissolution that causes low and variable bioavailability. Enhancing compound solubility is important and many techniques have been investigated to that end, but they require specific materials and machinery. This study investigates the incorporation of a pH-modifier as a method to increase compound solubility and uses ketoconazole (KZ), which is weakly basic (pKa: 6.5), as a model compound. Organic acids are effective pH-modifiers and are generally used in pharmaceutical industries. We successfully obtained granules containing variable organic acids (KZ/acid granule) using a high-shear mixer. Dissolution tests of the KZ/acid granule resulted in highly enhanced solubility under non-sink conditions. Adding water-soluble acids, such as citric acid (CA) and tartaric acid, resulted in more than 8-fold higher dissolution at pH 6.0 compared to that of KZ only. The granules containing citric acid (KZ/CA granule) improved the dissolution of KZ after oral administration to rats under low gastric acid conditions, where the bioavailability of the KZ/CA granules at elevated gastric pH was comparable with that of KZ only at gastric acidic pH. The incorporation of organic acids would result in effective therapeutic outcomes independent of gastric pH in patients. In addition, higher bioavailability of KZ was observed after oral administration of KZ/CA granules under gastric acidic pH conditions than that of KZ alone. Thus, CA improved the dissolution and absorption rate of KZ after oral administration. Copyright © 2015 Elsevier B.V. All rights reserved.

Preventing the dissolution of lithium polysulfides in lithium-sulfur cells by using Nafion-coated cathodes.

PubMed

Oh, Soo Jung; Lee, Jun Kyu; Yoon, Woo Young

2014-09-01

The principal drawback of lithium-sulfur batteries is the dissolution of long-chain lithium polysulfides into the electrolyte, which limits cycling performance. To overcome this problem, we focused on the development of a novel cathode as well as anode material and designed Nafion-coated NiCrAl/S as a cathode and lithium powder as an anode. Nafion-coated NiCrAl/S cathode was synthesized using a two-step dip-coating technique. The lithium-powder anode was used instead of a lithium-foil anode to prohibit dendrite growth and to improve on the electrochemical behaviors. The cells showed an initial discharge capacity of about 900 mA g(-1) and a final discharge capacity of 772 mA g(-1) after 100 cycles at 0.1 C-rate. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) demonstrate that using the Nafion-coated NiCrAl/S cathode can suppress the dissolution of long-chain lithium polysulfides. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Gender and the Stability of Same-Sex and Different-Sex Relationships Among Young Adults.

PubMed

Joyner, Kara; Manning, Wendy; Bogle, Ryan

2017-12-01

Most research on the stability of adult relationships has focused on coresidential (cohabiting or married) unions and estimates rates of dissolution for the period of coresidence. Studies examining how the stability of coresidential unions differs by sex composition have typically found that same-sex female couples have higher rates of dissolution than same-sex male couples and different-sex couples. We argue that the more elevated rates of dissolution for same-sex female couples are a by-product of the focus on coresidential unions. We use data from the National Longitudinal Study of Adolescent to Adult Health to compare rates of dissolution based on the total duration of romantic and sexual relationships for same-sex male couples, same-sex female couples, and different-sex couples. Results from hazard models that track the stability of young adult relationships from the time they are formed demonstrate that male couples have substantially higher dissolution rates than female couples and different-sex couples. Results based on models restricted to the period of coresidence corroborate the counterintuitive finding from earlier studies that female couples have the highest rates of dissolving coresidential unions. This study underlines the importance of comparisons between these couple types for a better understanding of the role that institutions and gender play in the stability of contemporary relationships.

Reprint of: Effects of solution degassing on solubility, crystal growth and dissolution-Case study: Salicylic acid in methanol

NASA Astrophysics Data System (ADS)

Seidel, J.; Ulrich, J.

2017-07-01

The influence of dissolved gases on the crystallization parameter solubility, MZW, growth and dissolution rates was investigated experimentally using degassed and non-degassed (air-saturated) solutions. The results of this study show that degassing has no effect on the solubility curve of the used model substance salicylic acid (SA) in methanol (MeOH). This reveals in the assumption that a thermodynamic effect of dissolved gases can be excluded. Growth rates were measured by means of a desupersaturation method and the results indicate that the growth rates of SA are not affected by degassing. The results of the dissolution rate measurements reveal a distinct decrease in dissolution rates for non-degassed solutions compared to degassed solutions, especially, at low temperature (10 °C). To explain this phenomenon the gas solubility, represented by oxygen, in MeOH in dependence on the SA concentration was estimated by means of Hansen Solubility Parameters (HSP) [1]. It was found that the oxygen solubility decreases with increasing SA content which explains the inhibition of crystal dissolution in non-degassed solution compared to degassed solution. Moreover, this kind of 'drowing-out' mechanism would not appear in growth rate measurements, where indeed no effect of degassing could be observed.

Effects of solution degassing on solubility, crystal growth and dissolution-Case study: Salicylic acid in methanol

NASA Astrophysics Data System (ADS)

Seidel, J.; Ulrich, J.

2017-02-01

The influence of dissolved gases on the crystallization parameter solubility, MZW, growth and dissolution rates was investigated experimentally using degassed and non-degassed (air-saturated) solutions. The results of this study show that degassing has no effect on the solubility curve of the used model substance salicylic acid (SA) in methanol (MeOH). This reveals in the assumption that a thermodynamic effect of dissolved gases can be excluded. Growth rates were measured by means of a desupersaturation method and the results indicate that the growth rates of SA are not affected by degassing. The results of the dissolution rate measurements reveal a distinct decrease in dissolution rates for non-degassed solutions compared to degassed solutions, especially, at low temperature (10 °C). To explain this phenomenon the gas solubility, represented by oxygen, in MeOH in dependence on the SA concentration was estimated by means of Hansen Solubility Parameters (HSP) [1]. It was found that the oxygen solubility decreases with increasing SA content which explains the inhibition of crystal dissolution in non-degassed solution compared to degassed solution. Moreover, this kind of 'drowing-out' mechanism would not appear in growth rate measurements, where indeed no effect of degassing could be observed.

Iron dissolution of dust source materials during simulated acidic processing: the effect of sulfuric, acetic, and oxalic acids.

PubMed

Chen, Haihan; Grassian, Vicki H

2013-09-17

Atmospheric organic acids potentially display different capacities in iron (Fe) mobilization from atmospheric dust compared with inorganic acids, but few measurements have been made on this comparison. We report here a laboratory investigation of Fe mobilization of coal fly ash, a representative Fe-containing anthropogenic aerosol, and Arizona test dust, a reference source material for mineral dust, in pH 2 sulfuric acid, acetic acid, and oxalic acid, respectively. The effects of pH and solar radiation on Fe dissolution have also been explored. The relative capacities of these three acids in Fe dissolution are in the order of oxalic acid > sulfuric acid > acetic acid. Oxalate forms mononuclear bidentate ligand with surface Fe and promotes Fe dissolution to the greatest extent. Photolysis of Fe-oxalate complexes further enhances Fe dissolution with the concomitant degradation of oxalate. These results suggest that ligand-promoted dissolution of Fe may play a more significant role in mobilizing Fe from atmospheric dust compared with proton-assisted processing. The role of atmospheric organic acids should be taken into account in global-biogeochemical modeling to better access dissolved atmospheric Fe deposition flux at the ocean surface.

Dissolution-resistance of glass-added hydroxyapatite composites

NASA Astrophysics Data System (ADS)

Seo, Dong Seok; Lee, Jong Kook

2009-04-01

Hydroxyapatite (HA) has generated a great deal of interest as a promising implant material. However, its poor mechanical properties induced by severe dissolution in biological milieu limit medical applications and lead to clinical failure. In this study, HA ceramics with 30P2O5-30CaO-40Na2O glass (1.0 wt.% and 2.5 wt.%) were prepared to improve the resistance of monophase HA. The monophase HA sintered body showed microstructural degradation due to grain boundary dissolution in buffered water. However, the dissolution-resistance of HA/glass composites was significantly improved and showed no apparent evidence of dissolution. This suggests that a less soluble glass phase should be placed at grain boundaries to protect HA from dissolution.

Fractionation of iron isotopes during leaching of natural particles by acidic and circumneutral leaches and development of an optimal leach for marine particulate iron isotopes

NASA Astrophysics Data System (ADS)

Revels, Brandi N.; Zhang, Ruifeng; Adkins, Jess F.; John, Seth G.

2015-10-01

Iron (Fe) is an essential nutrient for life on land and in the oceans. Iron stable isotope ratios (δ56Fe) can be used to study the biogeochemical cycling of Fe between particulate and dissolved phases in terrestrial and marine environments. We have investigated the dissolution of Fe from natural particles both to understand the mechanisms of Fe dissolution, and to choose a leach appropriate for extracting labile Fe phases of marine particles. With a goal of finding leaches which would be appropriate for studying dissolved-particle interactions in an oxic water column, three particle types were chosen including oxic seafloor sediments (MESS-3), terrestrial dust (Arizona Test Dust - A2 Fine), and ocean sediment trap material from the Cariaco basin. Four leaches were tested, including three acidic leaches similar to leaches previously applied to marine particles and sediments (25% acetic acid, 0.01 N HCl, and 0.5 N HCl) and a pH 8 oxalate-EDTA leach meant to mimic the dissolution of particles by organic complexation, as occurs in natural seawater. Each leach was applied for three different times (10 min, 2 h, 24 h) at three different temperatures (25 °C, 60 °C, 90 °C). MESS-3 was also leached under various redox conditions (0.02 M hydroxylamine hydrochloride or 0.02 M hydrogen peroxide). For all three sample types tested, we find a consistent relationship between the amount of Fe leached and leachate δ56Fe for all of the acidic leaches, and a different relationship between the amount of Fe leached and leachate δ56Fe for the oxalate-EDTA leach, suggesting that Fe was released through proton-promoted dissolution for all acidic leaches and by ligand-promoted dissolution for the oxalate-EDTA leach. Fe isotope fractionations of up to 2‰ were observed during acidic leaching of MESS-3 and Cariaco sediment trap material, but not for Arizona Test Dust, suggesting that sample composition influences fractionation, perhaps because Fe isotopes are greatly fractionated during leaching of silicates and clays but only minimally fractionated during dissolution of Fe oxyhydroxides. Two different analytical models were developed to explain the relationship between amount of Fe leached and δ56Fe, one of which assumes mixing between two Fe phases with different δ56Fe and different dissolution rates, and the other of which assumes dissolution of a single phase with a kinetic isotope effect. We apply both models to fit results from the acidic leaches of MESS-3 and find that the fit for both models is very similar, suggesting that isotope data will never be sufficient to distinguish between these two processes for natural materials. Next, we utilize our data to choose an optimal leach for application to marine particles. The oxalate-EDTA leach is well-suited to this purpose because it does not greatly fractionate Fe isotopes for a diversity of particle types over a wide variety of leaching conditions, and because it approximates the conditions by which particulate Fe dissolves in the oceans. We recommend a 2 h leach at 90 °C with 0.1 M oxalate and 0.05 M EDTA at pH 8 to measure labile ;ligand-leachable; particulate δ56Fe on natural marine materials with a range of compositions.

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 codes designed to model tungsten contamination in a variety of surface and groundwater settings.

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

Comparative study of the biodegradability of porous silicon films in simulated body fluid.

PubMed

Peckham, J; Andrews, G T

2015-01-01

The biodegradability of oxidized microporous, mesoporous and macroporous silicon films in a simulated body fluid with ion concentrations similar to those found in human blood plasma were studied using gravimetry. Film dissolution rates were determined by periodically weighing the samples after removal from the fluid. The dissolution rates for microporous silicon were found to be higher than those for mesoporous silicon of comparable porosity. The dissolution rate of macroporous silicon was much lower than that for either microporous or mesoporous silicon. This is attributed to the fact that its specific surface area is much lower than that of microporous and mesoporous silicon. Using an equation adapted from [Surf. Sci. Lett. 306 (1994), L550-L554], the dissolution rate of porous silicon in simulated body fluid can be estimated if the film thickness and specific surface area are known.

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

Developing a quality by design approach to model tablet dissolution testing: an industrial case study.

PubMed

Yekpe, Ketsia; Abatzoglou, Nicolas; Bataille, Bernard; Gosselin, Ryan; Sharkawi, Tahmer; Simard, Jean-Sébastien; Cournoyer, Antoine

2018-07-01

This study applied the concept of Quality by Design (QbD) to tablet dissolution. Its goal was to propose a quality control strategy to model dissolution testing of solid oral dose products according to International Conference on Harmonization guidelines. The methodology involved the following three steps: (1) a risk analysis to identify the material- and process-related parameters impacting the critical quality attributes of dissolution testing, (2) an experimental design to evaluate the influence of design factors (attributes and parameters selected by risk analysis) on dissolution testing, and (3) an investigation of the relationship between design factors and dissolution profiles. Results show that (a) in the case studied, the two parameters impacting dissolution kinetics are active pharmaceutical ingredient particle size distributions and tablet hardness and (b) these two parameters could be monitored with PAT tools to predict dissolution profiles. Moreover, based on the results obtained, modeling dissolution is possible. The practicality and effectiveness of the QbD approach were demonstrated through this industrial case study. Implementing such an approach systematically in industrial pharmaceutical production would reduce the need for tablet dissolution testing.

Impacts of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on the dissolution kinetics of whole-shell biogenic carbonates

NASA Astrophysics Data System (ADS)

Ries, Justin B.; Ghazaleh, Maite N.; Connolly, Brian; Westfield, Isaac; Castillo, Karl D.

2016-11-01

Anthropogenic increase of atmospheric pCO2 since the Industrial Revolution has caused seawater pH to decrease and seawater temperatures to increase-trends that are expected to continue into the foreseeable future. Myriad experimental studies have investigated the impacts of ocean acidification and warming on marine calcifiers' ability to build protective shells and skeletons. No studies, however, have investigated the combined impacts of ocean acidification and warming on the whole-shell dissolution kinetics of biogenic carbonates. Here, we present the results of experiments designed to investigate the effects of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on gross rates of whole-shell dissolution for ten species of benthic marine calcifiers: the oyster Crassostrea virginica, the ivory barnacle Balanus eburneus, the blue mussel Mytilus edulis, the conch Strombus alatus, the tropical coral Siderastrea siderea, the temperate coral Oculina arbuscula, the hard clam Mercenaria mercenaria, the soft clam Mya arenaria, the branching bryozoan Schizoporella errata, and the coralline red alga Neogoniolithon sp. These experiments confirm that dissolution rates of whole-shell biogenic carbonates decrease with calcium carbonate (CaCO3) saturation state, increase with temperature, and vary predictably with respect to the relative solubility of the calcifiers' polymorph mineralogy [high-Mg calcite (mol% Mg > 4) ≥ aragonite > low-Mg calcite (mol% Mg < 4)], consistent with prior studies on sedimentary and inorganic carbonates. Furthermore, the severity of the temperature effects on gross dissolution rates also varied with respect to carbonate polymorph solubility, with warming (10-25 °C) exerting the greatest effect on biogenic high-Mg calcite, an intermediate effect on biogenic aragonite, and the least effect on biogenic low-Mg calcite. These results indicate that both ocean acidification and warming will lead to increased dissolution of biogenic carbonates in future oceans, with shells/skeletons composed of the more soluble polymorphs of CaCO3 being the most vulnerable to these stressors. The effects of saturation state and temperature on gross shell dissolution rate were modeled with an exponential asymptotic function (y =B0 -B2 ·e B1 Ω) that appeals to the general Arrhenius-derived rate equation for mineral dissolution [ r = (C ·e -Ea / RT) (1 - Ω)n]. Although the dissolution curves for the investigated biogenic CaCO3 exhibited exponential asymptotic trends similar to those of inorganic CaCO3, the observation that gross dissolution of whole-shell biogenic CaCO3 occurred (albeit at lower rates) even in treatments that were oversaturated (Ω > 1) with respect to both aragonite and calcite reveals fundamental differences between the dissolution kinetics of whole-shell biogenic CaCO3 and inorganic CaCO3. Thus, applying stoichiometric solubility products derived for inorganic CaCO3 to model gross dissolution of biogenic carbonates may substantially underestimate the impacts of ocean acidification on net calcification (gross calcification minus gross dissolution) of systems ranging in scale from individual organisms to entire ecosystems (e.g., net ecosystem calcification). Finally, these experiments permit rough estimation of the impact of CO2-induced ocean acidification on the gross calcification rates of various marine calcifiers, calculated as the difference between net calcification rates derived empirically in prior studies and gross dissolution rates derived from the present study. Organisms' gross calcification responses to acidification were generally less severe than their net calcification response patterns, with aragonite mollusks (bivalves, gastropods) exhibiting the most negative gross calcification response to acidification, and photosynthesizing organisms, including corals and coralline red algae, exhibiting relative resilience.

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.

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.

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.

Can crystal engineering be as beneficial as micronisation and overcome its pitfalls?: A case study with cilostazol.

PubMed

Sai Gouthami, Kodukula; Kumar, Dinesh; Thipparaboina, Rajesh; Chavan, Rahul B; Shastri, Nalini R

2015-08-01

Improvement in dissolution of the drugs having poor solubility is a challenge in pharmaceutical industry. Micronization is one technique, employed for dissolution enhancement of cilostazol, a BCS class II drug. However, the obtained micronized drug possesses poor flowability. The aim of this study was to improve the dissolution rate and flow properties of cilostazol by crystal engineering, using habit modification method and compare with micronized cilostazol bulk drug. Simulation studies were performed to predict the effect of solvents on cilostazol crystal habit. Cilostazol crystals with different habits were prepared by solvent:anti-solvent crystallization technique. SEM, FTIR, DSC, TGA and PXRD were used for solid state characterization. The results revealed that cilostazol re-crystallized from methanol-hexane system were hexagonal and ethanol-hexane system gave rods. Cilostazol engineered habits showed increased dissolution rate than unprocessed drug but similar dissolution rate when compared to micronized cilostazol. Micronized cilostazol showed a dissolution efficiency of 75.58% where as cilostazol recrystallized from methanol-hexane and ethanol-hexane systems resulted in a dissolution efficiency of 72.63% and 68.63%, respectively. In addition, crystal engineering resulted in improved flow properties of re-crystallized habits when compared to micronized form of the drug. In conclusion, crystal engineering by habit modification show potential for dissolution enhancement with an added advantage of improved flow properties over micronization technique, for poorly soluble drugs like cilostazol. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

The preparation and evaluation of salt forms of linogliride with reduced solubilities as candidates for extended release.

PubMed

Chrzanowski, Frank A; Ahmad, Kaleem

2017-03-01

Salts of linogliride with reduced solubilities were prepared and evaluated as potential candidates for extended-release oral dosage forms. A once-daily dose of 300-800 mg was intended. Seven acids were selected: p-acetamidobenzoic, benzoic, p-hydroxybenzoic, 3-hydroxy-2-naphthoic, 1-napsylic, pamoic, and p-toluenesulfonic acids but only four salts were able to be prepared in suitable quantities for evaluation: linogliride pamoate, p-hydroxybenzoate, 3-hydroxy-2-naphthoate, and 1-napsylate. The pH-solubility profiles of the four new salts, free base, and fumarate salt were compared over the pH 1.43-8.3 range and the intrinsic dissolution rates of the four new salts and the free base were determined at pH 1.43, 4.4, and 7.5. The range of the pH-solubility profile and intrinsic dissolution rates of the p-hydroxybenzoate salt were less than the free base and fumarate and higher than the other three new salts. The pH-solubilities and intrinsic dissolution rates of the 1-napsylate salt were pH-independent. The solubilities and intrinsic dissolution rates of the pamoate and 3-hydroxy-2-naphthoate were higher at pH 1.4-3.4 than at higher pH. At pH 4.4 and higher, the solubilities were essentially the same, in the 1-2 mg/mL range. The intrinsic dissolution rates were also very low and not very different. Dissolution studies with capsules containing 800 mg doses of the pamoate, 1-napsylate, free base, and fumarate performed in a dissolution medium of pH beginning at 2.2 and ending at 6.8 demonstrated that the pamoate and 1-napsylate salt forms dissolved slower and could be useful as extended-release forms.

Improved oral bioavailability of probucol by dry media-milling.

PubMed

Li, Jia; Yang, Yan; Zhao, Meihui; Xu, Hui; Ma, Junyuan; Wang, Shaoning

2017-09-01

The polymer/probucol co-milled mixtures were prepared to improve drug dissolution rate and oral bioavailability. Probucol, a BCS II drug, was co-milled together with Copovidone (Kollidon VA64, VA64), Soluplus, or MCC using the dry media-milling process with planetary ball-milling equipment. The properties of the milled mixtures including morphology, crystal form, vitro drug dissolution and in vivo oral bioavailability in rats were evaluated. Probucol existed as an amorphous in the matrix of the co-milled mixtures containing VA64, which helped to enhance drug dissolution. The ternary mixture composed of VA64, RH40, and probucol showed increased dissolution rates in both sink and non-sink conditions. It also had a higher oral bioavailability compared to the reference formulation. Dry-media milling of binary or ternary mixtures composed of drug, polymer and surfactant possibly have wide applications to improve dissolution rate and oral bioavailability of water-insoluble drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

2018-04-01

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system from external chemical input and/or the existence of a yet to be defined dissolution/precipitation inhibition mechanism.

Engineering Silver Nanoparticles: Towards a Tunable Antimicrobial

NASA Astrophysics Data System (ADS)

Puppala, Hema Lakshmi

Overwhelming production of commercially available products containing silver nanoparticles (AgNPs) underscores the studies determining their fate in the environment. In order to regulate the use, assess the environmental impact and develop eco-responsible silver products, models that can predict AgNP toxicity based on physicochemical properties are vital. With that vision, this thesis developed well-characterized model libraries of uniform AgNPs stabilized with oleate in the range of 2-45 nm diameter with variable surface coating and investigated the dissolution properties that link AgNP structure to antimicrobial activity. High temperature organic synthesis allowed controlled growth of AgNPs (sigma<15%) by an Ostwald ripening mechanism in the first few hours, and followed by size dependent growth rates yielding uniform nanocrystals. Characterization of these materials revealed a crystalline nature, bidentate binding mode of oleate and non-oxidized pristine silver surface. Phase transfer of these AgNPs from organics to water was facilitated by encapsulation and ligand exchange methods using amphiphilic polymers and methoxy poly (ethylene glycol) (mPEGSH) respectively. Among these surface coatings, steric stabilization by mPEGSH not only helped retain their optical properties but also reduced the dissolution (<1(w/w)%) of AgNPs. This enhanced the stability in various environmentally relevant high ionic strength media (such as Hoaglands, EPA hard water and OECD medium), thereby increasing the shelf life. In addition, size, surface coating, pH of the medium and grafting density of the polymer mediated the dissolution of AgNPs. For instance, the rate of dissolution was decreased by 40% when the polymer coating possessed a mushroom conformation and increased with reducing core size. Analogous to dissolution, physicochemical properties also influenced the antimicrobial activity which were studied by minimum inhibitory concentration (MIC) and bactericidal efficacy assays. For example, surface passivation with mPEGSH prevented the oxidation of active silver atoms on the surface, and resulted in reduced toxicity against E. coli. Moreover citrate stabilized AgNPs when surface modified with mPEGSH had reduced toxicity, which was correlated with residual Ag+ in AgNP solution. Therefore this study demonstrates that processes in the environment that increase stability of AgNPs could make them more persistent due to low dissolution. Furthermore, the size and surface chemistry effects of AgNPs studied here make the intrinsic antimicrobial property of silver tunable and hence more versatile. This work also served as a material support for research on investigating toxicity of AgNPs to C. elegans, Daphnia Magna, Populus and Arabidopsis. In the future, this data will be used to develop nanomaterial bioavailability & environmental exposure (nanoBEE) models that predict the environmental impact of AgNPs.

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.

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.

Methods of amorphization and investigation of the amorphous state.

PubMed

Einfal, Tomaž; Planinšek, Odon; Hrovat, Klemen

2013-09-01

The amorphous form of pharmaceutical materials represents the most energetic solid state of a material. It provides advantages in terms of dissolution rate and bioavailability. This review presents the methods of solid- -state amorphization described in literature (supercooling of liquids, milling, lyophilization, spray drying, dehydration of crystalline hydrates), with the emphasis on milling. Furthermore, we describe how amorphous state of pharmaceuticals differ depending on the method of preparation and how these differences can be screened by a variety of spectroscopic (X-ray powder diffraction, solid state nuclear magnetic resonance, atomic pairwise distribution, infrared spectroscopy, terahertz spectroscopy) and calorimetry methods.

Autogenous teeth used for bone grafting: a comparison with traditional grafting materials.

PubMed

Kim, Young-Kyun; Kim, Su-Gwan; Yun, Pil-Young; Yeo, In-Sung; Jin, Seung-Chan; Oh, Ji-Su; Kim, Heung-Joong; Yu, Sun-Kyoung; Lee, Sook-Young; Kim, Jae-Sung; Um, In-Woong; Jeong, Mi-Ae; Kim, Gyung-Wook

2014-01-01

This study evaluated the surface structures and physicochemical characteristics of a novel autogenous tooth bone graft material currently in clinical use. The material's surface structure was compared with a variety of other bone graft materials via scanning electron microscope (SEM). The crystalline structure of the autogenous tooth bone graft material from the crown (AutoBT crown) and root (AutoBT root), xenograft (BioOss), alloplastic material (MBCP), allograft (ICB), and autogenous mandibular cortical bone were compared using x-ray diffraction (XRD) analysis. The solubility of each material was measured with the Ca/P dissolution test. The results of the SEM analysis showed that the pattern associated with AutoBT was similar to that from autogenous cortical bones. In the XRD analysis, AutoBT root and allograft showed a low crystalline structure similar to that of autogenous cortical bones. In the CaP dissolution test, the amount of calcium and phosphorus dissolution in AutoBT was significant from the beginning, while displaying a pattern similar to that of autogenous cortical bones. In conclusion, autogenous tooth bone graft materials can be considered to have physicochemical characteristics similar to those of autogenous bones. Copyright © 2014 Elsevier Inc. All rights reserved.

CO32- concentration and pCO2 thresholds for calcification and dissolution on the Molokai reef flat, Hawaii

USGS Publications Warehouse

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

2006-01-01

The severity of the impact of elevated atmospheric pCO2 to coral reef ecosystems depends, in part, on how sea-water pCO2 affects the balance between calcification and dissolution of carbonate sediments. Presently, there are insufficient published data that relate concentrations of pCO 2 and CO32- to in situ rates of reef calcification in natural settings to accurately predict the impact of elevated atmospheric pCO2 on calcification and dissolution processes. Rates of net calcification and dissolution, CO32- concentrations, and pCO2 were measured, in situ, on patch reefs, bare sand, and coral rubble on the Molokai reef flat in Hawaii. Rates of calcification ranged from 0.03 to 2.30 mmol CaCO3 m-2 h-1 and dissolution ranged from -0.05 to -3.3 mmol CaCO3 m-2 h-1. Calcification and dissolution varied diurnally with net calcification primarily occurring during the day and net dissolution occurring at night. These data were used to calculate threshold values for pCO2 and CO32- at which rates of calcification and dissolution are equivalent. Results indicate that calcification and dissolution are linearly correlated with both CO32- and pCO2. Threshold pCO2 and CO32- values for individual substrate types showed considerable variation. The average pCO2 threshold value for all substrate types was 654??195 ??atm and ranged from 467 to 1003 ??atm. The average CO32- threshold value was 152??24 ??mol kg-1, ranging from 113 to 184 ??mol kg-1. Ambient seawater measurements of pCO2 and CO32- indicate that CO32- and pCO2 threshold values for all substrate types were both exceeded, simultaneously, 13% of the time at present day atmospheric pCO2 concentrations. It is predicted that atmospheric pCO2 will exceed the average pCO2 threshold value for calcification and dissolution on the Molokai reef flat by the year 2100.

Fate of manufactured nanoparticles in environmental systems

NASA Astrophysics Data System (ADS)

Gelabert, A.; Sivry, Y.; Siron, V.; Akrout, A.; Ferrari, R.; Juillot, F.; Menguy, N.; Benedetti, M. F.

2009-12-01

Because of their specific physico-chemical properties, engineered nanoparticles (NPs) have become largely widespread in numerous industrial fields such as biomedicine, cosmetics, and material sciences. However, their growing use could possibly result in the release of various NPs amounts in environmental settings. Thus, an accurate understanding of their behaviour in natural systems is required, and of first importance is an estimation of their persistence and/or physico-chemical modifications since they can greatly alter their fate and bioavailability in the biogeosphere. The present study focuses on dissolution rate estimations for commercial NPs ZnO and TiO2 in natural waters (i.e. filtered Seine river water and seawater). Both NPs were used uncoated and coated with an organic polymer. Native NPs size and shape were investigated using TEM, and appeared as 20-50 nm spheroids, with an associated specific surface area of 37.5 and 57.6 m2/g for ZnO and TiO2, respectivelly. NPs dissolution rates were determined using both ultrafiltration (UF) and Donnan Membrane Techniques (DMT, [1]). The latter method allows a direct in-situ measurement of the free metal ion concentration only (here Zn2+), while the UF membrane small nominal pore size (approx. 2 nm) results in the separation of small inorganic complexes in addition to free metal ions. After a fast dissolution step reaching 1% of total zinc within the first hour for uncoated ZnO NPs in Seine water, precipitation of new mineral phases occurred with the formation of smithonite and hydrozincite as observed by XRD and TEM and confirmed by thermodynamic calculations (Visual Minteq). Interestingly, the behaviour of the coated ZnO NPs is slightly different since the initial dissolution step takes place during the first 72 hours, to reach up to 10% of the total zinc in our system. However, despite this difference in dissolution kinetics, both systems evolve similarly after 3 days, and they reach a steady state after approximatively 3 months of interaction. Moreover, to assess the influence of external parameters to NPs dissolution kinetics, two different pH (7.8 and 8.3) were tested. The obtained results demonstrate a strong dependence on pH, with the slower dissolution rates associated to the higher pH. XPS measurements performed on native uncoated ZnO NPs evidenced the presence of a layer of Zn(OH)2 which accounts for almost 20% of the total Zn in the NPs. This Zn(OH)2 phase, which is more soluble than ZnO, may control the early dissolution steps of the NPs in our systems. This study constitutes an important step for the understanding of the manufactured NPs fate in natural systems. [1] E. J. M. Temminghoff, A. C. C. Plette, R. Van Eck, W. H. Van Riemsdijk, (2000), Anal. Chim. Acta., 417, 149-157

Modeling Thermal Effects for Simulation of Post Exposure Baking (PEB) Process in Positive Photoresist

NASA Astrophysics Data System (ADS)

Asai, Satoru; Hanyu, Isamu; Nunokawa, Mitsuji; Abe, Masayuki

1991-03-01

We studied the thermal effects in a positive photoresist during post exposure baking (PEB). Infrared analysis and the reduced dissolution rate in the exposed resist suggest that the carboxylic acid is decreased and/or that ECA solvent evaporates. In order to simulate the effects, we assume that the concentration of the alkali-soluble material (carboxylic acid) decreases equivalently. Our model explains PEB and enables its effects to be simulated.

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.

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.

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.

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.

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.

A mechanistic understanding of plagioclase dissolution based on Al occupancy and T-O bond length: from geologic carbon sequestration to ambient conditions.

PubMed

Yang, Yi; Min, Yujia; Jun, Young-Shin

2013-11-14

A quantitative description of how the bulk properties of aluminosilicates affect their dissolution kinetics is important in helping people understand the regulation of atmospheric CO2 concentration by silicate weathering and predict the fate and transport of geologically sequestered CO2 through brine-rock interactions. In this study, we employed a structure model based on the C1 space group to illustrate how differences in crystallographic properties of aluminosilicates, such as T-O (Tetrahedral site-Oxygen) bond length and Al/Si ordering, can result in quantifiable variations in mineral dissolution rates. The dissolution rates of plagioclases were measured under representative geologic carbon sequestration (GCS) conditions (90 °C, 100 atm of CO2, 1.0 M NaCl, and pH ∼ 3.1), and used to validate the model. We found that the logarithm of the characteristic time of the breakdown of Al-O-Si linkages in plagioclases follows a good linear relation with the mineral's aluminum content (nAl). The Si release rates of plagioclases can be calculated based on an assumption of dissolution congruency or on the regularity of Al/Si distribution in the constituent tetrahedra of the mineral. We further extended the application of our approach to scenarios where dissolution incongruency arises because of different linkage reactivities in the solid matrix, and compared the model predictions with published data. The application of our results enables a significant reduction of experimental work for determining the dissolution rates of structurally related aluminosilicates, given a reaction environment.

Arsenic release and speciation during the oxidative dissolution of arsenopyrite by O2 in the absence and presence of EDTA.

PubMed

Wang, Shaofeng; Jiao, BeiBei; Zhang, Mingmei; Zhang, Guoqing; Wang, Xin; Jia, Yongfeng

2018-03-15

The oxidative decomposition of arsenopyrite is an important source of As in surface environment. This study investigated the oxidative dissolution of arsenopyrite by O 2 and aqueous arsenic transformation at different pHs, dissolved oxygen (DO) contents, and temperatures in the absence and presence of EDTA. The oxidative dissolution was greatly inhibited at neutral and alkaline pH in the absence of EDTA. However, in the presence of EDTA, the oxidative dissolution rate increased linearly from pH 4 to 7. The highest dissolution rate was 3-4 times higher than that at pH 4 and 1-2 orders of magnitude higher than that at pH 7 in the absence of EDTA. This is possibly due to the lack of Fe oxyhydroxides on the surface of arsenopyrite. In the pH range of 7-10, the oxidative dissolution rate decreased linearly, possibly due to the formation of goethite and/or hematite coating. The oxidation of released arsenite (As III ) to arsenate (As V ) took place simultaneously during the oxidative dissolution of arsenopyrite in the presence of dissolved Fe without EDTA, while no obvious aqueous As III oxidation was observed in the presence of EDTA, indicating that aqueous Fe species play an important role in As III oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessing hydrodynamic effects on jarosite dissolution rates, reaction products, and preservation on Mars

NASA Astrophysics Data System (ADS)

Dixon, Emily M.; Elwood Madden, Andrew S.; Hausrath, Elisabeth M.; Elwood Madden, Megan E.

2015-04-01

Jarosite flow-through dissolution experiments were conducted in ultrapure water (UPW), pH 2 sulfuric acid, and saturated NaCl and CaCl2 brines at 295-298 K to investigate how hydrologic variables may affect jarosite preservation and reaction products on Mars. K+-based dissolution rates in flowing UPW did not vary significantly with flow rate, indicating that mineral surface reactions control dissolution rates over the range of flow rates investigated. In all of the solutions tested, hydrologic variables do not significantly affect extent of jarosite alteration; therefore, jarosite is equally likely to be preserved in flowing or stagnant waters on Mars. However, increasing flow rate did affect the mineralogy and accumulation of secondary reaction products. Iron release rates in dilute solutions increased as the flow rate increased, likely due to nanoscale iron (hydr)oxide transport in flowing water. Anhydrite formed in CaCl2 brine flow-through experiments despite low temperatures, while metastable gypsum and bassanite were observed in batch experiments. Therefore, observations of the hydration state of calcium sulfate minerals on Mars may provide clues to unravel past salinity and hydrologic conditions as well as temperatures and vapor pressures.

Dynamics of altered surface layer formation on dissolving silicates

NASA Astrophysics Data System (ADS)

Daval, Damien; Bernard, Sylvain; Rémusat, Laurent; Wild, Bastien; Guyot, François; Micha, Jean Sébastien; Rieutord, François; Magnin, Valérie; Fernandez-Martinez, Alejandro

2017-07-01

The extrapolation of mineral dissolution kinetics experiments to geological timescales has frequently been challenged by the observation that mineral dissolution rates decrease with time. In the present study, we report a detailed investigation of the early stages of wollastonite dissolution kinetics, linking time-resolved measurements of wollastonite dissolution rate as a function of crystallographic orientation to the evolution of physicochemical properties (i.e., diffusivity, density, and thickness) of amorphous silica-rich layers (ASSLs) that developed on each surface. Batch dissolution experiments conducted at room temperature and at far-from-equilibrium conditions revealed that the initial (i.e., ASSL-free) dissolution rate of wollastonite (R(hkl)) based on Ca release observe the following trend: R(010) ≈R(100) >R(101) >R(001) . A gradual decrease of the dissolution rate of some faces by up to one order of magnitude resulted in a modification of this trend after two days: R(010) ≫R(100) ⩾R(101) ≈R(001) . In parallel, the diffusivity of ASSLs developed on each face was estimated based on the measurement of the concentration profile of a conservative tracer (methylene blue) across the ASSL using nanoSIMS. The apparent diffusion coefficients of methylene blue as a function of the crystallographic orientation (Dapp(hkl)) observe the following trend: Dapp(010) ⩾Dapp(100) >Dapp(101) ≫Dapp(001) , and decreases as a function of time for the (1 0 0) and (1 0 1) faces. Finally, the density of ASSL was estimated based on the modeling of X-ray reflectivity patterns acquired as a function of time. The density of ASSLs developed on the (0 1 0) faces remains low and constant, whereas it increases for the ASSLs developed on the (0 0 1) faces. On the whole, our results suggest that the impact of the formation of ASSLs on the wollastonite dissolution rate is anisotropic: while some crystal faces are weakly affected by the formation of non-passivating ASSLs (e.g., the (0 1 0) face), the dissolution of other faces is hampered by passivating ASSLs within a few hours. The observed passivation is suggested to originate from the progressive densification of the ASSL, which limits the transport of reactive species from and to the dissolving wollastonite surface, as evidenced by the estimated diffusivity of the ASSLs. Because the apparent face-specific diffusivity of the ASSLs is correlated with the face-specific initial (i.e., ASSL-free) dissolution rate of wollastonite, we propose that the extent of ASSL densification (and the resulting impact on ion transport) is (at least partly) controlled by the absolute mineral dissolution rate. Overall, this study argues that the formation and microstructural evolution of ASSLs are likely candidates for mineral ageing, highlighting the need for determining the parameters controlling the spontaneous changes of ASSL diffusivity as a function of the reaction progress.

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.

An interferometric study of the dissolution kinetics of anorthite: The role of reactive surface area

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

Luettge, A.; Bolton, E.W.; Lasaga, A.C.

1999-07-01

An optical interferometry system has been used to study the dynamics of the dissolution of anorthite (010) cleavage surfaces. With this technique, it is possible to measure directly the surface retreat of alumino-silicates as a function of time and thereby the dissolution rate using a new application of interferometry. The dissolution experiments are carried out in a flow-through cell system with a near endmember anorthite (An{sub 98}) from Miyake-Jima, Tokyo, Japan, Perchloric acid solutions (pH 3) were used at a constant temperature of 25 C. After having measured the topography of the original pristine anorthite surface, measurements of the surfacemore » normal retreat were taken after 48,84,120, and 168 hrs of run duration at 15 different regions on the surface. An internal-reference technique allows absolute measurements of the changes in surface height for the very first time. From these measurements, an average bulk rate for dissolution of the (010) anorthite surface is calculated to be 5.7 x 10{sup {minus}13} [moles/cm{sub 2}/sec]. Finally, their directly determined bulk rate for the (010) face is compared with the bulk rates calculated from the rate law obtained from powder experiments and using the BET or total surface area.« less

DNAPL remediation with in situ chemical oxidation using potassium permanganate - Part I. Mineralogy of Mn oxide and its dissolution in organic acids

NASA Astrophysics Data System (ADS)

Li, X. David; Schwartz, Franklin W.

2004-01-01

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 Å. The chemical formula is K 0.854Mn 1.786O 4·1.55H 2O. It has a relatively small specific surface area at 23.6±0.82 m 2/g. Its point of zero charge (pzc) was measured as 3.7±0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m 2/h for citric acid, 1.35 mM/m 2/h for oxalic acid, and 5.176 mM/m 2/h for EDTA. These rates compare with 0.0025 mM/m 2/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant potential in using these organic acids to remove precipitates formed during the oxidation reaction.

Interactions of silicate glasses with aqueous environments under conditions of prolonged contact and flow

NASA Technical Reports Server (NTRS)

Barkatt, Aaron; Saad, E. E.; Adiga, R. B.; Sousanpour, W.; Barkatt, AL.; Feng, X.; O'Keefe, J. A.; Alterescu, S.

1988-01-01

This paper discusses mechanisms involving saturation and reactions that lead to the formation of altered phases in silicate glasses considered for use in geologic repositories for nuclear waste. It is shown that the rate of dissolution of silicate glasses exposed to a broad range of contact times, leachant compositions, and surface-to-volume ratios is strongly affected by the presence of reactive species such as Al, Mg, and Fe. The reactive materials may originate in the leachant or, under conditions of high surface-to-volume ratio, in the glass itself. The effects of glass composition on the course of the corrosion process can be viewed in terms of the formation of a surface layer on the leached glass; the type, composition, and structure of this layer control the dissolution behavior of the glass.

Kinetics of dissolution of sapphire in melts in the CaO-Al2O3-SiO2 system

NASA Astrophysics Data System (ADS)

Shaw, Cliff S. J.; Klausen, Kim B.; Mao, Huahai

2018-05-01

The dissolution rate of sapphire in melts in the CAS system of varying silica activity, viscosity and degree of alumina saturation has been determined at 1600 °C and 1.5 GPa. After an initiation period of up to 1800 s, dissolution is controlled by diffusion of cations through the boundary layer adjacent to the dissolving sapphire. The dissolution rate decreases with increasing silica activity, viscosity and molar Al2O3/CaO. The calculated diffusion matrix for each solvent melt shows that CAS 1 and 9 which have molar Al2O3/CaO of 0.33 and 0.6 and dissolution rate constants of 0.65 × 10-6 and 0.59 × 10-6 m/s0.5 have similar directions and magnitudes of diffusive coupling: DCaO-Al2O3 and DAl2O3-CaO are both negative are approximately equal. The solvent with the fastest dissolution rate: CAS 4, which has a rate constant of 1.5 × 10-6 m/s0.5 and Al2O3/CaO of 0.31 has positive DCaO-Al2O3 and negative DAl2O3-CaO and the absolute values vary by a factor of 4. Although many studies show that aluminium is added to the melts via the reaction: Si4+ =Al3+ + 0.5Ca2+ the compositional profiles show that this reaction is not the only one involved in accommodating the aluminium added during sapphire dissolution. Rather, aluminium is incorporated as both tetrahedrally coordinated Al charge balanced by Ca and as aluminium not charge balanced by Ca (termed Alxs). This reaction: AlIV -Ca =Alxs +CaNBO where CaNBO is a non-bridging oxygen associated with calcium, may involve the formation of aluminium triclusters. The shape of the compositional profiles and oxide-oxide composition paths is controlled by the aluminium addition reaction. When Alxs exceeds 2%, CaO diffusion becomes increasingly anomalous and since the bond strength of Alxs correlates with CaO/CaO + Al2O3, the presence of more than 2% Alxs leads to significantly slower dissolution than when Alxs is absent or at low concentration. Thus, dissolution is controlled by diffusion of cations through the boundary layer, but this diffusion is itself controlled by the structural modifications required by the addition of new components to the melt. Comparison of quartz dissolution rates in similar melts shows that dissolution is much faster for quartz than for sapphire and that dissolution rates show the same correlation with silica activity and viscosity. We suggest that diffusive fluxes are related to changes in melt structure and the nature of the reaction that incorporates the added component. For the slow eigendirection, SiO2 addition occurs by a single reaction whereas Al2O3 addition requires a more complex two part reaction in which Al is accommodated by charge balance with Ca until Al is in excess of that which can be charge balanced. The Alxs incorporation reaction, is slower than the Si incorporation reaction which inhibits sapphire dissolution relative to quartz in melts of the same composition.

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.

The mechanisms of drug release from solid dispersions in water-soluble polymers.

PubMed

Craig, Duncan Q M

2002-01-14

Solid dispersions in water-soluble carriers have attracted considerable interest as a means of improving the dissolution rate, and hence possibly bioavailability, of a range of hydrophobic drugs. However, despite the publication of numerous original papers and reviews on the subject, the mechanisms underpinning the observed improvements in dissolution rate are not yet understood. In this review the current consensus with regard to the solid-state structure and dissolution properties of solid dispersions is critically assessed. In particular the theories of carrier- and drug-controlled dissolution are highlighted. A model is proposed whereby the release behaviour from the dispersions may be understood in terms of the dissolution or otherwise of the drug into the concentrated aqueous polymer layer adjacent to the solid surface, including a derivation of an expression to describe the release of intact particles from the dispersions. The implications of a deeper understanding of the dissolution mechanisms are discussed, with particular emphasis on optimising the choice of carrier and manufacturing method and the prediction of stability problems.

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

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 can be compared to a series of reaction times calculated by assuming that the mass of dolomite missing from the Edwards was removed at rates observed in the Floridan and Madison aquifers. These reaction times (for complete removal of dolomite) range from 2700 to 58,500 yr and span the Pleistocene-Holocene boundary. Finally, an estimated dolomite reaction rate during dedolomitization of the Edwards aquifer based on surface area of exposed dolomite [mmol cm-2s-1 (millimoles per square centimeter per second)] may be approximated from reaction times. This rate is directly a function of the mass of dolomite removed and the surface area exposed per pore volume passing through the rock. The surface area is available from the observed dolomite rhomb size in unaltered rock. The rate of pore fluid movement is obtained from the averaged annual discharge. Rates during formation of the Edwards aquifer calculated from all reaction times range from 10-13 to 10-14 mmol dolomite cm-2s-1. These rates are faster than rates (10-18 mmol cm-2s-1), measured in the pure laboratory system, CaMg(CO3)2CO2H2O, but slower than rates determined in an alpine stream study (10-10 to 10-11 mmol cm-2s-1) where cold glacial melt water flows over dolostone. Dolomite dissolution rates from both the Edwards and other aquifers support the concept that a major part of the Edwards aquifer could have formed within the Holocene. ?? 1990.

Make and break - Facile synthesis of cocrystals and comprehensive dissolution studies

NASA Astrophysics Data System (ADS)

Batzdorf, L.; Zientek, N.; Rump, D.; Fischer, F.; Maiwald, M.; Emmerling, F.

2017-04-01

Mechanochemistry is increasingly used as a 'green alternative' for synthesizing various materials including pharmaceutical cocrystals. Herein, we present the mechanochemical synthesis of three new cocrystals containing the API carbamazepine (cocrystals CBZ:Indometacin 1:1, CBZ:Benzamide 1:1, and CBZ:Nifedipine 1:1). The mechanochemical reaction was investigated in situ documenting a fast and complete reaction within one minute. Online NMR spectroscopy proved the direct influence of the dissolution behaviour of the coformers to the dissolution behaviour of the API carbamazepine. The dissolution behaviour of the organic cocrystals is compared to the behaviour of the pure drug indicating a general applicability of this approach for detailed cocrystal dissolution studies.

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.

Quality-by-design case study: investigation of the role of poloxamer in immediate-release tablets by experimental design and multivariate data analysis.

PubMed

Kaul, Goldi; Huang, Jun; Chatlapalli, Ramarao; Ghosh, Krishnendu; Nagi, Arwinder

2011-12-01

The role of poloxamer 188, water and binder addition rate, on retarding dissolution in immediate-release tablets of a model drug from BCS class II was investigated by means of multivariate data analysis (MVDA) combined with design of experiments (DOE). While the DOE analysis yielded important clues into the cause-and-effect relationship between the responses and design factors, multivariate data analysis of the 40+ variables provided additional information on slowdown in tablet dissolution. A steep dependence of both tablet dissolution and disintegration on the poloxamer and less so on other design variables was observed. Poloxamer was found to increase dissolution rates in granules as expected of surfactants in general but retard dissolution in tablets. The unexpected effect of poloxamer in tablets was accompanied by an increase in tablet-disintegration-time-mediated slowdown of tablet dissolution and by a surrogate binding effect of poloxamer at higher concentrations. It was additionally realized through MVDA that poloxamer in tablets either acts as a binder by itself or promotes binder action of the binder povidone resulting in increased intragranular cohesion. Additionally, poloxamer was found to mediate tablet dissolution on stability as well. In contrast to tablet dissolution at release (time zero), poloxamer appeared to increase tablet dissolution in a concentration-dependent manner on accelerated open-dish stability. Substituting polysorbate 80 as an alternate surfactant in place of poloxamer in the formulation was found to stabilize tablet dissolution.

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 the same conditions as alkali-feldspar dissolution experiments with and without the presence of CO{sub 2} performed in the first year to check the validation of the experiments and analysis. The changes of solution chemistry as dissolution experiments progressed were monitored with on-line sampling of the aqueous phase at the constant temperature and pressure. These data allow calculating overall apparent mineral (feldspars and sandstones) dissolution rates and secondary mineral precipitation rates as a function of saturation states. State-of-the-art atomic resolution transmission electron microscopy (TEM), scanning electron microscopy (SEM), and electron microprobe was used to characterize the products and reactants. Reaction-path geochemical modeling was used to interpret the experimental results of alkali-feldspar dissolution experiments without the presence of CO{sub 2}. Two manuscripts are near completion. Also during the second year, our education goal of graduate student training has been advanced. A Ph. D. student at Indiana University is progressing well in the degree program and has taken geochemical modeling, SEM, and TEM courses, which will facilitate research in the third year. A Ph. D. student at University of Minnesota had graduated. With the success of training of graduate students and excellent experimental data in the second year, we anticipate a more fruitful year in the third year.« less

Formulation, optimization, and evaluation of self-emulsifying drug delivery systems of nevirapine

PubMed Central

Chintalapudi, Ramprasad; Murthy, T. E. G. K.; Lakshmi, K. Rajya; Manohar, G. Ganesh

2015-01-01

Background: The aim of the present study was to formulate and optimize the self-emulsifying drug delivery systems (SEDDS) of nevirapine (NVP) by use of 22 factorial designs to enhance the oral absorption of NVP by improving its solubility, dissolution rate, and diffusion profile. SEDDS are the isotropic mixtures of oil, surfactant, co-surfactant and drug that form oil in water microemulsion when introduced into the aqueous phase under gentle agitation. Materials and Methods: Solubility of NVP in different oils, surfactants, and co-surfactants was determined for the screening of excipients. Pseudo-ternary phase diagrams were constructed by the aqueous titration method, and formulations were developed based on the optimum excipient combinations with the help of data obtained through the maximum micro emulsion region containing combinations of oil, surfactant, and co-surfactant. The formulations of SEDDS were optimized by 22 factorial designs. Results: The optimum formulation of SEDDS contains 32.5% oleic acid, 44.16% tween 20, and 11.9% polyethylene glycol 600 as oil, surfactant, and co-surfactant respectively. The SEDDS was evaluated for the following drug content, self-emulsification time, rheological properties, zeta potential, in vitro diffusion studies, thermodynamic stability studies, and in vitro dissolution studies. An increase in dissolution was achieved by SEDDS compared to pure form of NVP. Conclusion: Overall, this study suggests that the dissolution and oral bioavailability of NVP could be improved by SEDDS technology. PMID:26682191

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

Dissolution chemistry and biocompatibility of silicon- and germanium-based semiconductors for transient electronics.

PubMed

Kang, Seung-Kyun; Park, Gayoung; Kim, Kyungmin; Hwang, Suk-Won; Cheng, Huanyu; Shin, Jiho; Chung, Sangjin; Kim, Minjin; Yin, Lan; Lee, Jeong Chul; Lee, Kyung-Mi; Rogers, John A

2015-05-06

Semiconducting materials are central to the development of high-performance electronics that are capable of dissolving completely when immersed in aqueous solutions, groundwater, or biofluids, for applications in temporary biomedical implants, environmentally degradable sensors, and other systems. The results reported here include comprehensive studies of the dissolution by hydrolysis of polycrystalline silicon, amorphous silicon, silicon-germanium, and germanium in aqueous solutions of various pH values and temperatures. In vitro cellular toxicity evaluations demonstrate the biocompatibility of the materials and end products of dissolution, thereby supporting their potential for use in biodegradable electronics. A fully dissolvable thin-film solar cell illustrates the ability to integrate these semiconductors into functional systems.

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.

[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.

Atom-Probe Tomography, TEM and ToF-SIMS study of borosilicate glass alteration rim: A multiscale approach to investigating rate-limiting mechanisms

NASA Astrophysics Data System (ADS)

Gin, S.; Jollivet, P.; Barba Rossa, G.; Tribet, M.; Mougnaud, S.; Collin, M.; Fournier, M.; Cadel, E.; Cabie, M.; Dupuy, L.

2017-04-01

Significant efforts have been made into understanding the dissolution of silicate glasses and minerals, but there is still debate about the formation processes and the properties of surface layers. Here, we investigate glass coupons of ISG glass - a 6 oxide borosilicate glass of nuclear interest - altered at 90 °C in conditions close to saturation and for durations ranging from 1 to 875 days. Altered glass coupons were characterized from atomic to macroscopic levels to better understand how surface layers become protective. With this approach, it was shown that a rough interface, whose physical characteristics have been modeled, formed in a few days and then propagated into the pristine material at a rate controlled by the reactive transport of water within the growing alteration layer. Several observations such as stiff interfacial B, Na, and Ca profiles and damped profiles within the rest of the alteration layer are not consistent with the classical inter-diffusion model, or with the interfacial dissolution-precipitation model. A new paradigm is proposed to explain these features. Inter-diffusion, a process based on water ingress into the glass and ion-exchange, may only explain the formation of the rough interface in the early stage of glass corrosion. A thin layer of altered glass is formed by this process, and as the layer grows, the accessibility of water to the reactive interface becomes rate-limiting. As a consequence, only the most easily accessible species are dissolved. The others remain undissolved in the alteration layer, probably fixed in highly hydrolysis resistant clusters. A new estimation of water diffusivity in the glass when covered by the passivating layer was determined from the shift between B and H profiles, and was 10-23 m2.s-1, i.e. approximately 3 orders of magnitude lower than water diffusivity in the pristine material. Overall, in the absence of secondary crystalline phases that could consume the major components of the alteration layer (Si, Al), it is assumed that the glass dissolution rate continuously decreases due to the growth of the transport limiting alteration layer, in good agreement with residual rates reported in the literature for this glass. According to our results it can be expected that new kinetic models should emerge from an accurate time dependent budget of water within the nanoporous alteration layer.

The influence of pH on biotite dissolution and alteration kinetics at low temperature

USGS Publications Warehouse

Acker, James G.; Bricker, O.P.

1992-01-01

Biotite dissolution rates in acidic solutions were determined in fluidized-bed reactors and flowthrough columns. Biotite dissolution rates increased inversely as a linear function of pH in the pH range 3-7, where the rate order n = -0.34. Biotite dissolved incongruently over this pH range, with preferential release of magnesium and iron from the octahedral layer. Release of tetrahedral silicon was much greater at pH 3 than at higher pH. Iron release was significantly enhanced by low pH conditions. Solution compositions from a continuous exposure flow-through column of biotite indicated biotite dissolves incongruently at pH 4, consistent with alteration to a vermiculite-type product. Solution compositions from a second intermittent-flow column exhibited elevated cation release rates upon the initiation of each exposure to solution. The presence of strong oxidizing agents, the mineral surface area, and sample preparation methodology also influenced the dissolution or alteration kinetics of biotite. ?? 1992.

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 dissolution of calcite in CO2-saturated solutions at 25°C and 1 atmosphere total pressure

USGS Publications Warehouse

Plummer, Niel; Wigley, T.M.L.

1976-01-01

The dissolution of Iceland spar in CO2-saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.

Effects of coformers on phase transformation and release profiles of carbamazepine cocrystals in hydroxypropyl methylcellulose based matrix tablets.

PubMed

Qiu, Shi; Li, Mingzhong

2015-02-01

The aim of this study was to investigate the effects of coformers on phase transformation and release profiles of carbamazepine (CBZ) cocrystals in hydroxypropyl methylcellulose (HPMC) based matrix tablets. It has been found that selection of different coformers of saccharin (SAC) and cinnamic acid (CIN) can affect the stability of CBZ cocrystals in solution, resulting in significant differences in the apparent solubility of CBZ. The dissolution advantage of CBZ-SAC cocrystals can only be shown for a short period during dissolution because of the fast conversion to its dihydrate form (DH). HPMC can partially inhibit the crystallisation of CBZ DH during dissolution of CBZ-SAC cocrystal. However, the increased viscosity of HPMC dissolution medium reduced the dissolution rate of CBZ-SAC cocrystals. Therefore the CBZ-SAC cocrystal formulation did not show any significant advantage in CBZ release rate. In contrast the improved CBZ dissolution rate of CBZ-CIN cocrystal can be realised in both solution and formulation due to its high stability. In conclusion, exploring and understanding the mechanisms of the phase transformation of pharmaceutical cocrystals in aqueous medium for selection of lead cocrystals is the key for success of product development. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

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.

The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

USGS Publications Warehouse

Bennett, P.C.; Melcer, M.E.; Siegel, D.I.; Hassett, J.P.

1988-01-01

The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH.The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

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.

Behavior of S.A.P. in the Mercury Catalyzed Nitric Acid Dissolution; COMPORTAMENTO DEL S.A.P. ALL'ATTACCO DI SOLUZIONI DI ACIDO NITRICO E NITRATO MERCURICO

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

Beone, G.

1963-10-01

Plates of S.A.P. (sintered Aluminum Powder) were dissolved under different conditions in a nitric acid solution containing mercuric nitrate as a catalyst. These experiments nim at establishing a head-end dissolution process for S.A.P. cladded uranium oxide fuels. The results of preliminary dissolution experiments on simulated fuel rods are also described. The behavior of S.A.P. in the mercury catalyzed nitric acid dissolutions differs strongly from the behavior of aluminum: reaction rates are very low for S.A.P. and the dissolution time borders on being unacceptable in an industrial process. Settling rates of suspended alumina are however favorable. A tentative head end flowsheetmore » lay out for PRO second core fuel elements is included. (auth)« 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.

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.

Pharmaceutical Amorphous Nanoparticles.

PubMed

Jog, Rajan; Burgess, Diane J

2017-01-01

There has been a tremendous revolution in the field of nanotechnology, resulting in the advent of novel drug delivery systems known as nanomedicines for diagnosis and therapy. One of the applications is nanoparticulate drug delivery systems which are used to improve the solubility and oral bioavailability of poorly soluble compounds. This is particularly important because most of the molecules emerging from the drug discovery pipeline in recent years have problems associated with solubility and bioavailability. There has been considerable focus on nanocrystalline materials; however, amorphous nanoparticles have the advantage of synergistic mechanisms of enhancing dissolution rates (due to their nanosize range and amorphous nature) as well as increasing supersaturation levels (due to their amorphous nature). An example of this technology is Nanomorph TM , developed by Soliqus/Abbott, wherein the nanosize drug particles are precipitated in an amorphous form in order to enhance the dissolution rate. This along with other simple and easily scalable manufacturing techniques for amorphous nanoparticles is described. In addition, the mechanisms of formation of amorphous nanoparticles and several physicochemical properties associated with amorphous nanoparticles are critically reviewed. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

A parallel reaction-transport model applied to cement hydration and microstructure development

NASA Astrophysics Data System (ADS)

Bullard, Jeffrey W.; Enjolras, Edith; George, William L.; Satterfield, Steven G.; Terrill, Judith E.

2010-03-01

A recently described stochastic reaction-transport model on three-dimensional lattices is parallelized and is used to simulate the time-dependent structural and chemical evolution in multicomponent reactive systems. The model, called HydratiCA, uses probabilistic rules to simulate the kinetics of diffusion, homogeneous reactions and heterogeneous phenomena such as solid nucleation, growth and dissolution in complex three-dimensional systems. The algorithms require information only from each lattice site and its immediate neighbors, and this localization enables the parallelized model to exhibit near-linear scaling up to several hundred processors. Although applicable to a wide range of material systems, including sedimentary rock beds, reacting colloids and biochemical systems, validation is performed here on two minerals that are commonly found in Portland cement paste, calcium hydroxide and ettringite, by comparing their simulated dissolution or precipitation rates far from equilibrium to standard rate equations, and also by comparing simulated equilibrium states to thermodynamic calculations, as a function of temperature and pH. Finally, we demonstrate how HydratiCA can be used to investigate microstructure characteristics, such as spatial correlations between different condensed phases, in more complex microstructures.

Investigating Dissolution and Precipitation Phenomena with a Smartphone Microscope

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

Lumetta, Gregg J.; Arcia, Edgar

A novel smartphone microscope can be used to observe the dissolution and crystallization of sodium chloride at a microscopic level. Observation of these seemingly simple phenomena through the microscope at 100× magnification can actually reveal some surprising behavior. These experiments offer the opportunity to discuss some basic concepts such as how the morphological features of the crystals dictates how the dissolution process proceeds, and how materials can be purified by re-crystallization techniques.

Mesoporous Silica Molecular Sieve based Nanocarriers: Transpiring Drug Dissolution Research.

PubMed

Pattnaik, Satyanarayan; Pathak, Kamla

2017-01-01

Improvement of oral bioavailability through enhancement of dissolution for poorly soluble drugs has been a very promising approach. Recently, mesoporous silica based molecular sieves have demonstrated excellent properties to enhance the dissolution velocity of poorly water-soluble drugs. Current research in this area is focused on investigating the factors influencing the drug release from these carriers, the kinetics of drug release and manufacturing approaches to scale-up production for commercial manufacture. This comprehensive review provides an overview of different methods adopted for synthesis of mesoporous materials, influence of processing factors on properties of these materials and drug loading methods. The drug release kinetics from mesoporous silica systems, the manufacturability and stability of these formulations are reviewed. Finally, the safety and biocompatibility issues related to these silica based materials are discussed. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Can accurate kinetic laws be created to describe chemical weathering?

NASA Astrophysics Data System (ADS)

Schott, Jacques; Oelkers, Eric H.; Bénézeth, Pascale; Goddéris, Yves; François, Louis

2012-11-01

Knowledge of the mechanisms and rates of mineral dissolution and growth, especially close to equilibrium, is essential for describing the temporal and spatial evolution of natural processes like weathering and its impact on CO2 budget and climate. The Surface Complexation approach (SC) combined with Transition State Theory (TST) provides an efficient framework for describing mineral dissolution over wide ranges of solution composition, chemical affinity, and temperature. There has been a large debate for several years, however, about the comparative merits of SC/TS versus classical growth theories for describing mineral dissolution and growth at near-to-equilibrium conditions. This study considers recent results obtained in our laboratory on oxides, hydroxides, silicates, and carbonates on near-equilibrium dissolution and growth via the combination of complementary microscopic and macroscopic techniques including hydrothermal atomic force microscopy, hydrogen-electrode concentration cell, mixed flow and batch reactors. Results show that the dissolution and precipitation of hydroxides, kaolinite, and hydromagnesite powders of relatively high BET surface area closely follow SC/TST rate laws with a linear dependence of both dissolution and growth rates on fluid saturation state (Ω) even at very close to equilibrium conditions (|ΔG| < 500 J/mol). This occurs because sufficient reactive sites (e.g. at kink, steps, and edges) are available at the exposed faces for dissolution and/or growth, allowing reactions to proceed via the direct and reversible detachment/attachment of reactants at the surface. In contrast, for magnesite and quartz, which have low surface areas, fewer active sites are available for growth and dissolution. Such minerals exhibit rates dependencies on Ω at near equilibrium conditions ranging from linear to highly non-linear functions of Ω, depending on the treatment of the crystals before the reaction. It follows that the form of the f(ΔG) function describing the growth and dissolution of minerals with low surface areas depends on the availability of reactive sites at the exposed faces and thus on the history of the mineral-fluid interaction and the hydrodynamic conditions under which the crystals are reacted. It is advocated that the crystal surface roughness could serve as a proxy of the density of reactive sites. The consequences of the different rate laws on the quantification of loess weathering along the Mississippi valley for the next one hundred years are examined.

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

Biokinetics and internal dosimetry of inhaled metal tritide particles

NASA Astrophysics Data System (ADS)

Wang, Yansheng

1998-12-01

Metal tritides (MT), stable chemical compounds of tritium, are widely used in nuclear engineering facilities. MT particles can be released as aerosols. Inhaling MT particles is a potential occupational radiation hazard. Little information is available on their dissolution behavior, biokinetics, and dosimetry. The objectives of present dissertation are to estimate dissolution rates, to develop biokinetic models, to improve internal dosimetric considerations, and to classify MT materials. This study consisted of three phases: In vitro dissolution in a simulated lung fluid, In vivo rat experiments on retention and clearance, and biokinetic modeling and dosimetric evaluation. There was a supporting study on self- absorption of tritium beta in MT particles. MT materials used in this study were titanium (Ti) and zirconium (Zr) tritides. Results shows considerable self-absorption of beta particles and their energy, even for respirable MT particles smaller than 5 μm. The self-absorption factors should be required for counting MT particle samples and for estimating absorbed dose to tissues. In vitro and in vivo dissolution data indicate that Ti and Zr tritides are poorly soluble materials. Ti tritide belongs to the W class or M type while Zr tritide can be classified as Y class or S type. Due to long retention time of the MT particles, tritium betas directly from the particles contribute over 90% of the absorbed dose to lung. The lung dose contributes most of the effective dose to the whole body. Dissolved tritium including tritiated water (HTO) and organically bound tritium (OBT) has less effect on the lung dose and effective dose. Results on the annual limit on intake (ALI) indicate that the current radiation protection guideline based on HTO is not adequate for inhalation exposure to MT particles and needs to be modified. The biokinetic models developed in this study have predictive powers to estimate the consequences of a human inhalation exposure to MT aerosols. The animal excretory patterns found from in vivo rat studies may provide useful information for nuclear engineering facilities to setup bioassay program in workplace. The applications of the results from this research are limited in their scopes.

Modeling NAPL dissolution from pendular rings in idealized porous media

EPA Science Inventory

The rate of NAPL dissolution often governs the clean-up time for subsurface hazardous waste sites. Most formulations for estimating this rate are empirical and assume that the NAPL is the non-wetting fluid. However, field evidence suggests that some waste sites might be organic...

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

Newell, J; Miller, D; Stone, M

The Savannah River National Laboratory (SRNL) was tasked to provide an assessment of the downstream impacts to the Defense Waste Processing Facility (DWPF) of decisions regarding the implementation of Al-dissolution to support sludge mass reduction and processing. Based on future sludge batch compositional projections from the Liquid Waste Organization's (LWO) sludge batch plan, assessments have been made with respect to the ability to maintain comparable projected operating windows for sludges with and without Al-dissolution. As part of that previous assessment, candidate frits were identified to provide insight into melt rate for average sludge batches representing with and without Al-dissolution flowsheets.more » Initial melt rate studies using the melt rate furnace (MRF) were performed using five frits each for Cluster 2 and Cluster 4 compositions representing average without and with Al-dissolution. It was determined, however, that the REDOX endpoint (Fe{sup 2+}/{Sigma}Fe for the glass) for Clusters 2 and 4 resulted in an overly oxidized feed which negatively affected the initial melt rate tests. After the sludge was adjusted to a more reduced state, additional testing was performed with frits that contained both high and low concentrations of sodium and boron oxides. These frits were selected strictly based on the ability to ascertain compositional trends in melt rate and did not necessarily apply to any acceptability criteria for DWPF processing. The melt rate data are in general agreement with historical trends observed at SRNL and during processing of SB3 (Sludge Batch 3)and SB4 in DWPF. When MAR acceptability criteria were applied, Frit 510 was seen to have the highest melt rate at 0.67 in/hr for Cluster 2 (without Al-dissolution), which is compositionally similar to SB4. For Cluster 4 (with Al-dissolution), which is compositionally similar to SB3, Frit 418 had the highest melt rate at 0.63 in/hr. Based on this data, there appears to be a slight advantage of the Frit 510 based system without Al-dissolution relative to the Frit 418 based system with Al-dissolution. Though the without aluminum dissolution scenario suggests a slightly higher melt rate with frit 510, several points must be taken into consideration: (1) The MRF does not have the ability to assess liquid feeds and, thus, rheology impacts. Instead, the MRF is a 'static' test bed in which a mass of dried melter feed (SRAT product plus frit) is placed in an 'isothermal' furnace for a period of time to assess melt rate. These conditions, although historically effective in terms of identifying candidate frits for specific sludge batches and mapping out melt rate versus waste loading trends, do not allow for assessments of the potential impact of feed rheology on melt rate. That is, if the rheological properties of the slurried melter feed resulted in the mounding of the feed in the melter (i.e., the melter feed was thick and did not flow across the cold cap), melt rate and/or melter operations (i.e., surges) could be negatively impacted. This could affect one or both flowsheets. (2) Waste throughput factors were not determined for Frit 510 and Frit 418 over multiple waste loadings. In order to provide insight into the mission life versus canister count question, one needs to define the maximum waste throughput for both flowsheets. Due to funding limitations, the melt rate testing only evaluated melt rate at a fixed waste loading. (3) DWPF will be processing SB5 through their facility in mid-November 2008. Insight into the over arching questions of melt rate, waste throughput, and mission life can be obtained directly from the facility. It is recommended that processing of SB5 through the facility be monitored closely and that data be used as input into the decision making process on whether to implement Al-dissolution for future sludge batches.« less

Novel hierarchically porous carbon materials obtained from natural biopolymer as host matrixes for lithium-sulfur battery applications.

PubMed

Zhang, Bin; Xiao, Min; Wang, Shuanjin; Han, Dongmei; Song, Shuqin; Chen, Guohua; Meng, Yuezhong

2014-08-13

Novel hierarchically porous carbon materials with very high surface areas, large pore volumes and high electron conductivities were prepared from silk cocoon by carbonization with KOH activation. The prepared novel porous carbon-encapsulated sulfur composites were fabricated by a simple melting process and used as cathodes for lithium sulfur batteries. Because of the large surface area and hierarchically porous structure of the carbon material, soluble polysulfide intermediates can be trapped within the cathode and the volume expansion can be alleviated effectively. Moreover, the electron transport properties of the carbon materials can provide an electron conductive network and promote the utilization rate of sulfur in cathode. The prepared carbon-sulfur composite exhibited a high specific capacity and excellent cycle stability. The results show a high initial discharge capacity of 1443 mAh g(-1) and retain 804 mAh g(-1) after 80 discharge/charge cycles at a rate of 0.5 C. A Coulombic efficiency retained up to 92% after 80 cycles. The prepared hierarchically porous carbon materials were proven to be an effective host matrix for sulfur encapsulation to improve the sulfur utilization rate and restrain the dissolution of polysulfides into lithium-sulfur battery electrolytes.

Influence of pH and temperature on alunite dissolution rates and products

NASA Astrophysics Data System (ADS)

Acero, Patricia; Hudson-Edwards, Karen

2015-04-01

Aluminium is one of the main elements in most mining-affected environments, where it may influence the mobility of other elements and play a key role on pH buffering. Moreover, high concentrations of Al can have severe effects on ecosystems and humans; Al intake, for example, has been implicated in neurological pathologies (e.g., Alzheimer's disease; Flaten, 2001). The behaviour of Al in mining-affected environments is commonly determined, at least partially, by the dissolution of Al sulphate minerals and particularly by the dissolution of alunite (KAl3(SO4)2(OH)6), which is one of the most important and ubiquitous Al sulphates in mining-affected environments (Nordstrom, 2011). The presence of alunite has been described in other acid sulphate environments, including some soils (Prietzel & Hirsch, 1998) and on the surface of Mars (Swayze et al., 2008). Despite the important role of alunite, its dissolution rates and products, and their controlling factors under conditions similar to those found in these environments, remain largely unknown. In this work, batch dissolution experiments have been carried out in order to shed light on the rates, products and controlling factors of alunite dissolution under different pH conditions (between 3 and 8) and temperatures (between 279 and 313K) similar to those encountered in natural systems. The obtained initial dissolution rates using synthetic alunite, based on the evolution of K concentrations, are between 10-9.7 and 10-10.9 mol-m-2-s-1, with the lowest rates obtained at around pH 4.8, and increases in the rates recorded with both increases and decreases in pH. Increases of temperature in the studied range also cause increases in the dissolution rates. The dissolution of alunite dissolution is incongruent, as has been reported for jarosite (isostructural with alunite) by Welch et al. (2008). Compared with the stoichiometric ratio in the bulk alunite (Al/K=3), K tends to be released to the solution preferentially over Al, leading to dissolved Al/K ratios between 0.5 and 2.5. This depletion of Al in the solution is especially clear for the experiments at pH 4.5-4.8 and 8 and it is consistent with the results of elemental quantifications of the same proportions in the reacted alunite surfaces using X-ray Photoelectron Spectroscopy (XPS). REFERENCES Flaten, T.P. (2001): Aluminium as a risk factor in Alzheimzer's disease, with emphasis on drinking water. Brain Research Bulletin 55: 187-196. Nordstrom, D.K. (2011): Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters. Applied Geochemistry 26: 1777-1791. Prietzel, J., & Hirsch, C. (1998). Extractability and dissolution kinetics of pure and soil-added synthesized aluminium hydroxy sulphate minerals. European journal of soil science, 49(4), 669-681. Swayze, G.A., Ehlmann, B.L., Milliken, R.E., Poulet, F., Wray, J.J., Rye, R.O., Clark, R.N., Desborough, G.A., Crowley, J.K., Gondet, B., Mustard, J.F., Seelos, K.D. and Murchie, S.L., 2008. Discovery of the Acid-Sulfate Mineral Alunite in Terra Sirenum, Mars, Using MRO CRISM: Possible Evidence for Acid-Saline Lacustrine Deposits?, American Geophysical Union, Fall Meeting 2008, abstract #P44A-04. Welch, S. A., Kirste, D., Christy, A. G., Beavis, F. R., & Beavis, S. G. (2008): Jarosite dissolution II'Reaction kinetics, stoichiometry and acid flux. Chemical Geology, 254(1), 73-86.

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.

Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques; Castillo, Alain

2005-02-01

Brucite (Mg(OH) 2) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H 2PO 4- > catechol ≥ HCO 3- > ascorbate > citrate > oxalate > acetate ˜ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO 43-, CO 32-, F -, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO 42- and B(OH) 4- with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation. The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.

A study on the dissolution rates of K-Cr(VI)-jarosites: kinetic analysis and implications.

PubMed

Reyes, Iván A; Mireles, Ister; Patiño, Francisco; Pandiyan, Thangarasu; Flores, Mizraim U; Palacios, Elia G; Gutiérrez, Emmanuel J; Reyes, Martín

2016-01-01

The presence of natural and industrial jarosite type-compounds in the environment could have important implications in the mobility of potentially toxic elements such as lead, mercury, arsenic, chromium, among others. Understanding the dissolution reactions of jarosite-type compounds is notably important for an environmental assessment (for water and soil), since some of these elements could either return to the environment or work as temporary deposits of these species, thus would reduce their immediate environmental impact. This work reports the effects of temperature, pH, particle diameter and Cr(VI) content on the initial dissolution rates of K-Cr(VI)-jarosites (KFe3[(SO4)2 - X(CrO4)X](OH)6). Temperature (T) was the variable with the strongest effect, followed by pH in acid/alkaline medium (H3O(+)/OH(-)). It was found that the substitution of CrO4 (2-)in Y-site and the substitution of H3O(+) in M-site do not modify the dissolution rates. The model that describes the dissolution process is the unreacted core kinetic model, with the chemical reaction on the unreacted core surface. The dissolution in acid medium was congruent, while in alkaline media was incongruent. In both reaction media, there is a release of K(+), SO4 (2-) and CrO4 (2-) from the KFe3[(SO4)2 - X(CrO4)X](OH)6 structure, although the latter is rapidly absorbed by the solid residues of Fe(OH)3 in alkaline medium dissolutions. The dissolution of KFe3[(SO4)2 - X(CrO4)X](OH)6 exhibited good stability in a wide range of pH and T conditions corresponding to the calculated parameters of reaction order n, activation energy E A and dissolution rate constants for each kinetic stages of induction and progressive conversion. The kinetic analysis related to the reaction orders and calculated activation energies confirmed that extreme pH and T conditions are necessary to obtain considerably high dissolution rates. Extreme pH conditions (acidic or alkaline) cause the preferential release of K(+), SO4 (2-) and CrO4 (2-) from the KFe3[(SO4)2 - X(CrO4)X](OH)6 structure, although CrO4 (2-) is quickly adsorbed by Fe(OH)3 solid residues. The precipitation of phases such as KFe3[(SO4)2 - X(CrO4)X](OH)6, and the absorption of Cr(VI) after dissolution can play an important role as retention mechanisms of Cr(VI) in nature.

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.

Dissolution kinetics and biodurability of tremolite particles in mimicked lung fluids: Effect of citrate and oxalate

NASA Astrophysics Data System (ADS)

Rozalen, Marisa; Ramos, M. Elena; Huertas, F. Javier; Fiore, Saverio; Gervilla, Fernando

2013-11-01

The effect of citrate and oxalate on tremolite dissolution rate was measured at 37 °C in non-stirred flow-through reactors, using modified Gamble's solutions at pH 4 (macrophages), 7.4 (interstitial fluids) and 5.5 (intermediate check point) containing 0, 0.15, 1.5 and 15 mmol L-1 of citrate or oxalate. The dissolution rates calculated from Si concentration in the output solutions without organic ligands depend on pH, decreasing when the pH increases from -13.00 (pH 4) to -13.35 (pH 7.4) mol g-1 s-1 and following a proton-promoted mechanism. The presence of both ligands enhances dissolution rates at every pH, increasing this effect when the ligand concentration increases. Citrate produces a stronger effect as a catalyst than oxalate, mainly at more acidic pHs and enhances dissolution rates until 20 times for solutions with 15 mmol L-1 citrate. However, at pH 7.4 the effect is lighter and oxalate solutions (15 mmol L-1) only enhances dissolution rates eight times respect to free organic ligand solutions. Dissolution is promoted by the attack to protons and organic ligands to the tremolite surface. Magnesium speciation in oxalate and citrate solutions shows that Mg citrate complexes are more effective than oxalate ones during the alteration of tremolite in magrophages, but this tendency is the opposite for interstitial fluids, being oxalate magnesium complexes stronger. The biodurability estimations show that the destruction of the fibers is faster in acidic conditions (macrophages) than in the neutral solutions (interstitial fluid). At pH 4, both ligands oxalate and citrate reduce the residence time of the fibers with respect to that calculated in absence of ligands. Nevertheless, at pH 7.4 the presence of ligands does not reduce significantly the lifetime of the fibers.

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.

Effect of radiation-induced amorphization on smectite dissolution.

PubMed

Fourdrin, C; Allard, T; Monnet, I; Menguy, N; Benedetti, M; Calas, G

2010-04-01

Effects of radiation-induced amorphization of smectite were investigated using artificial irradiation. Beams of 925 MeV Xenon ions with radiation dose reaching 73 MGy were used to simulate the effects generated by alpha recoil nuclei or fission products in the context of high level nuclear waste repository. Amorphization was controlled by X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. An important coalescence of the smectite sheets was observed which lead to a loss of interparticle porosity. The amorphization is revealed by a loss of long-range structure and accompanied by dehydroxylation. The dissolution rate far-from-equilibrium shows that the amount of silica in solution is two times larger in the amorphous sample than in the reference clay, a value which may be enhanced by orders of magnitude when considering the relative surface area of the samples. Irradiation-induced amorphization thus facilitates dissolution of the clay-derived material. This has to be taken into account for the safety assessment of high level nuclear waste repository, particularly in a scenario of leakage of the waste package which would deliver alpha emitters able to amorphize smectite after a limited period of time.

Evaluating the reliability of equilibrium dissolution assumption from residual gasoline in contact with water saturated sands

NASA Astrophysics Data System (ADS)

Lekmine, Greg; Sookhak Lari, Kaveh; Johnston, Colin D.; Bastow, Trevor P.; Rayner, John L.; Davis, Greg B.

2017-01-01

Understanding dissolution dynamics of hazardous compounds from complex gasoline mixtures is a key to long-term predictions of groundwater risks. The aim of this study was to investigate if the local equilibrium assumption for BTEX and TMBs (trimethylbenzenes) dissolution was valid under variable saturation in two dimensional flow conditions and evaluate the impact of local heterogeneities when equilibrium is verified at the scale of investigation. An initial residual gasoline saturation was established over the upper two-thirds of a water saturated sand pack. A constant horizontal pore velocity was maintained and water samples were recovered across 38 sampling ports over 141 days. Inside the residual NAPL zone, BTEX and TMBs dissolution curves were in agreement with the TMVOC model based on the local equilibrium assumption. Results compared to previous numerical studies suggest the presence of small scale dissolution fingering created perpendicular to the horizontal dissolution front, mainly triggered by heterogeneities in the medium structure and the local NAPL residual saturation. In the transition zone, TMVOC was able to represent a range of behaviours exhibited by the data, confirming equilibrium or near-equilibrium dissolution at the scale of investigation. The model locally showed discrepancies with the most soluble compounds, i.e. benzene and toluene, due to local heterogeneities exhibiting that at lower scale flow bypassing and channelling may have occurred. In these conditions mass transfer rates were still high enough to fall under the equilibrium assumption in TMVOC at the scale of investigation. Comparisons with other models involving upscaled mass transfer rates demonstrated that such approximations with TMVOC could lead to overestimate BTEX dissolution rates and underestimate the total remediation time.

Evaluating the reliability of equilibrium dissolution assumption from residual gasoline in contact with water saturated sands.

PubMed

Lekmine, Greg; Sookhak Lari, Kaveh; Johnston, Colin D; Bastow, Trevor P; Rayner, John L; Davis, Greg B

2017-01-01

Understanding dissolution dynamics of hazardous compounds from complex gasoline mixtures is a key to long-term predictions of groundwater risks. The aim of this study was to investigate if the local equilibrium assumption for BTEX and TMBs (trimethylbenzenes) dissolution was valid under variable saturation in two dimensional flow conditions and evaluate the impact of local heterogeneities when equilibrium is verified at the scale of investigation. An initial residual gasoline saturation was established over the upper two-thirds of a water saturated sand pack. A constant horizontal pore velocity was maintained and water samples were recovered across 38 sampling ports over 141days. Inside the residual NAPL zone, BTEX and TMBs dissolution curves were in agreement with the TMVOC model based on the local equilibrium assumption. Results compared to previous numerical studies suggest the presence of small scale dissolution fingering created perpendicular to the horizontal dissolution front, mainly triggered by heterogeneities in the medium structure and the local NAPL residual saturation. In the transition zone, TMVOC was able to represent a range of behaviours exhibited by the data, confirming equilibrium or near-equilibrium dissolution at the scale of investigation. The model locally showed discrepancies with the most soluble compounds, i.e. benzene and toluene, due to local heterogeneities exhibiting that at lower scale flow bypassing and channelling may have occurred. In these conditions mass transfer rates were still high enough to fall under the equilibrium assumption in TMVOC at the scale of investigation. Comparisons with other models involving upscaled mass transfer rates demonstrated that such approximations with TMVOC could lead to overestimate BTEX dissolution rates and underestimate the total remediation time. Copyright © 2016. Published by Elsevier B.V.

Accelerated Leach Testing of GLASS (ALTGLASS): I. Informatics approach to high level waste glass gel formation and aging

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

Jantzen, Carol M.; Trivelpiece, Cory L.; Crawford, Charles L.

Glass corrosion data from the ALTGLASS™ database were used to determine if gel compositions, which evolve as glass systems corrode, are correlated with the generation of zeolites and subsequent increase in the glass dissolution rate at long times. The gel compositions were estimated based on the difference between the elemental glass starting compositions and the measured elemental leachate concentrations from the long-term product consistency tests (ASTM C1285) at various stages of dissolution, ie, reaction progress. A well-characterized subset of high level waste glasses from the database was selected: these glasses had been leached for 15-20 years at reaction progresses upmore » to ~80%. The gel composition data, at various reaction progresses, were subjected to a step-wise regression, which demonstrated that hydrogel compositions with Si*/Al* ratios of <1.0 did not generate zeolites and maintained low dissolution rates for the duration of the experiments. Glasses that formed hydrogel compositions with Si^*/Al^* ratios ≥1, generated zeolites accompanied by a resumption in the glass dissolution rate. Finally, the role of the gel Si/Al ratio, and the interactions with the leachate, provides the fundamental understanding needed to predict if and when the glass dissolution rate will increase due to zeolitization.« less

Accelerated Leach Testing of GLASS (ALTGLASS): I. Informatics approach to high level waste glass gel formation and aging

DOE PAGES

Jantzen, Carol M.; Trivelpiece, Cory L.; Crawford, Charles L.; ...

2017-02-18

Glass corrosion data from the ALTGLASS™ database were used to determine if gel compositions, which evolve as glass systems corrode, are correlated with the generation of zeolites and subsequent increase in the glass dissolution rate at long times. The gel compositions were estimated based on the difference between the elemental glass starting compositions and the measured elemental leachate concentrations from the long-term product consistency tests (ASTM C1285) at various stages of dissolution, ie, reaction progress. A well-characterized subset of high level waste glasses from the database was selected: these glasses had been leached for 15-20 years at reaction progresses upmore » to ~80%. The gel composition data, at various reaction progresses, were subjected to a step-wise regression, which demonstrated that hydrogel compositions with Si*/Al* ratios of <1.0 did not generate zeolites and maintained low dissolution rates for the duration of the experiments. Glasses that formed hydrogel compositions with Si^*/Al^* ratios ≥1, generated zeolites accompanied by a resumption in the glass dissolution rate. Finally, the role of the gel Si/Al ratio, and the interactions with the leachate, provides the fundamental understanding needed to predict if and when the glass dissolution rate will increase due to zeolitization.« less

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.

Acceleration of chemical weathering related to intensive agriculture: evidence from groundwater dating

NASA Astrophysics Data System (ADS)

Aquilina, Luc; Marçais, Jean; de Dreuzy, Jean-Raynald; Labasque, Thierry; Abbott, Ben; Vergnaud, Virginie; Walter, Christian; Viville, Daniel; Chabaux, François; Pinay, Gilles

2017-04-01

Agricultural pollution is a matter of political and scientific concern throughout the world. Intensive agriculture can cause nutrient contamination of groundwater and surface water. Nutrient pollution causes eutrophication in freshwater and estuarine ecosystems. A secondary effect of agricultural intensification is river acidification. Oxidation of chemical fertilizers such as ammonium (NH4+) to nitrate (NO3-) produces H+ ions that cause leaching of cations from soil and deeper material to maintain charge balance. Monitoring of various rivers in Brittany (western France) revealed that agriculture intensification has led to increased cation export starting in the 1980s. From the cation ratios, we deduced that cation increase comes approximately equally from dissolution of carbonate added to soil (liming practices) and silicate dissolution. Cation export represented about 30% of the soil cation exchange potential. If compensated by liming, it may constitute a non-negligible source to atmospheric CO2 (Aquilina et al., 2012). We further investigated the potential for silicate dissolution through the use of groundwater dating in various sites of Brittany. Coupling chemical analyses to groundwater ages in a large range of aquifers and a large range of depths (down to 110m) allowed us to reconstruct a chronicle for the last 50 yrs of the cation concentrations of groundwater. It clearly shows a contemporaneous increase in sodium and nitrate and a decrease in calcium, with the most dramatic changes occurring during the 70s and 80s. Using groundwater dating, we were also able to determine a silica production geochronometer. A tight and linear relationship between silica concentration and groundwater age (Figure) was observed and allowed a production rate in groundwater to be determined. Except for short residence-times (Kerrien), the silica production rate for different granitic catchments was consistent, ranging from 0.3 to 0.4 mg.L-1.yr-1. To assess the role of anthropogenic activity in silica production rate, we compared production rates from Brittany with catchments in the Vosges Mountains, a relatively pristine area. Dissolution rates were much higher in the Brittany catchments, indicating the effect of human activities on chemical weathering and cation export at the catchment scale. Aquilina L. et al., 2012 - Long-term effects of high nitrogen loads on cation and carbon riverine export in agricultural catchments. Env. Sci & Technology 46-17, 9447-9455..

Application of tumbling melt granulation (TMG) method to prepare controlled-release fine granules.

PubMed

Maejima, T; Kubo, M; Osawa, T; Nakajima, K; Kobayashi, M

1998-03-01

The tumbling melt granulation (TMG) method was applied to prepare controlled-release fine granules of diltiazem hydrochloride (DH). The entire process, from the preparation of the cores by the adherence of DH to the sucrose crystal to the subsequent coating of the controlled-release layer, was performed without using any solvent. A mixture of meltable material, talc, and ethylcellulose was used for the controlled-release layer and controlled-release fine granules approximately 400 microns in diameter were obtained with excellent producibility. The dissolution rate of DH from these fine granules was similar to that of a once-a-day dosage form obtained in the market; further, the dependency of the dissolution profile on pH of the media was less. Thus, it was concluded that this TMG method was very useful for preparing not only controlled-release beads of granule size (usually 500 to 1400 microns) but also fine granules.

Latent variable modeling to analyze the effects of process parameters on the dissolution of paracetamol tablet

PubMed Central

Sun, Fei; Xu, Bing; Zhang, Yi; Dai, Shengyun; Shi, Xinyuan; Qiao, Yanjiang

2017-01-01

ABSTRACT The dissolution is one of the critical quality attributes (CQAs) of oral solid dosage forms because it relates to the absorption of drug. In this paper, the influence of raw materials, granules and process parameters on the dissolution of paracetamol tablet was analyzed using latent variable modeling methods. The variability in raw materials and granules was understood based on the principle component analysis (PCA), respectively. A multi-block partial least squares (MBPLS) model was used to determine the critical factors affecting the dissolution. The results showed that the binder amount, the post granulation time, the API content in granule, the fill depth and the punch tip separation distance were the critical factors with variable importance in the projection (VIP) values larger than 1. The importance of each unit of the whole process was also ranked using the block importance in the projection (BIP) index. It was concluded that latent variable models (LVMs) were very useful tools to extract information from the available data and improve the understanding on dissolution behavior of paracetamol tablet. The obtained LVMs were also helpful to propose the process design space and to design control strategies in the further research. PMID:27689242

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.

Efficacy of Magnesium Trihydrate of Ursodeoxycholic Acid and Chenodeoxycholic Acid for Gallstone Dissolution: A Prospective Multicenter Trial.

PubMed

Hyun, Jong Jin; Lee, Hong Sik; Kim, Chang Duck; Dong, Seok Ho; Lee, Seung-Ok; Ryu, Ji Kon; Lee, Don Haeng; Jeong, Seok; Kim, Tae Nyeun; Lee, Jin; Koh, Dong Hee; Park, Eun Taek; Lee, In-Seok; Yoo, Byung Moo; Kim, Jin Hong

2015-07-01

Cholecystectomy is necessary for the treatment of symptomatic or complicated gallbladder (GB) stones, but oral litholysis with bile acids is an attractive alternative therapeutic option for asymptomatic or mildly symptomatic patients. This study was conducted to evaluate the efficacy of magnesium trihydrate of ursodeoxycholic acid (UDCA) and chenodeoxycholic acid (CDCA) on gallstone dissolution and to investigate improvements in gallstone-related symptoms. A prospective, multicenter, phase 4 clinical study to determine the efficacy of orally administered magnesium trihydrate of UDCA and CDCA was performed from January 2011 to June 2013. The inclusion criteria were GB stone diameter ≤15 mm, GB ejection fraction ≥50%, radiolucency on plain X-ray, and asymptomatic/mildly symptomatic patients. The patients were prescribed one capsule of magnesium trihydrate of UDCA and CDCA at breakfast and two capsules at bedtime for 6 months. The dissolution rate, response rate, and change in symptom score were evaluated. A total of 237 subjects were enrolled, and 195 subjects completed the treatment. The dissolution rate was 45.1% and the response rate was 47.2% (92/195) after 6 months of administration of magnesium trihydrate of UDCA and CDCA. Only the stone diameter was significantly associated with the response rate. Both the symptom score and the number of patients with symptoms significantly decreased regardless of stone dissolution. Adverse events necessitating discontinuation of the drug, surgery, or endoscopic management occurred in 2.5% (6/237) of patients. Magnesium trihydrate of UDCA and CDCA is a well-tolerated bile acid that showed similar efficacy for gallstone dissolution and improvement of gallstone-related symptoms as that shown in previous studies.

Formation of nano/micro-dispersions with improved dissolution properties upon dispersion of ritonavir melt extrudate in aqueous media.

PubMed

Tho, Ingunn; Liepold, Bernd; Rosenberg, Joerg; Maegerlein, Markus; Brandl, Martin; Fricker, Gert

2010-04-16

The objective of the study was to characterise the aqueous dispersions of ritonavir melt extrudates. More specifically to look into the particular system formed when melt extrudate of a poorly soluble drug dissolved in a hydrophilic polymer matrix containing a surfactant is dispersed in an aqueous medium. Melt extrudates with and without ritonavir were studied. The drug containing extrudate was confirmed to be molecular dispersions of drug in a polymer/surfactant matrix. Particulate dispersions were formed in water from both drug and placebo extrudates. The dispersions were investigated with respect to mean particle size and particle size distribution (photon correlation spectroscopy and optical particle counting), surface charge (zeta potential), particle composition (ultracentrifugation), tendency to form aggregates and precipitate (turbidity), in vitro dissolution rate and drug release. It was concluded that dispersion of melt extrudates in aqueous medium give rise to nano/micro-dispersions. The stability of the nano/micro-dispersion is sensitive to anions and may be subjected to association/aggregation/flocculation as time proceeds after preparation of dispersion. Melt extrudate showed improved dissolution rate and drug release properties compared to crystalline raw material. From studies of single components and physical mixtures of the formulation composition it can be concluded that the drug delivery system itself, namely solid dispersion prepared by melt extrusion technology, plays a key role for the formation of the observed particles. 2010 Elsevier B.V. All rights reserved.

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.

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.

Dynamic Pore-Scale Imaging of Reactive Transport in Heterogeneous Carbonates at Reservoir Conditions Across Multiple Dissolution Regimes

NASA Astrophysics Data System (ADS)

Menke, H. P.; Bijeljic, B.; Andrew, M. G.; Blunt, M. J.

2014-12-01

Sequestering carbon in deep geologic formations is one way of reducing anthropogenic CO2 emissions. When supercritical CO2 mixes with brine in a reservoir, the acid generated has the potential to dissolve the surrounding pore structure. However, the magnitude and type of dissolution are condition dependent. Understanding how small changes in the pore structure, chemistry, and flow properties affect dissolution is paramount for successful predictive modelling. Both 'Pink Beam' synchrotron radiation and a Micro-CT lab source are used in dynamic X-ray microtomography to investigate the pore structure changes during supercritical CO2 injection in carbonate rocks of varying heterogeneity at high temperatures and pressures and various flow-rates. Three carbonate rock types were studied, one with a homogeneous pore structure and two heterogeneous carbonates. All samples are practically pure calcium carbonate, but have widely varying rock structures. Flow-rate was varied in three successive experiments by over an order of magnitude whlie keeping all other experimental conditions constant. A 4-mm carbonate core was injected with CO2-saturated brine at 10 MPa and 50oC. Tomographic images were taken at 30-second to 20-minute time-resolutions during a 2 to 4-hour injection period. A pore network was extracted using a topological analysis of the pore space and pore-scale flow modelling was performed directly on the binarized images with connected pathways and used to track the altering velocity distributions. Significant differences in dissolution type and magnitude were found for each rock type and flowrate. At the highest flow-rates, the homogeneous carbonate was seen to have predominately uniform dissolution with minor dissolution rate differences between the pores and pore throats. Alternatively, the heterogeneous carbonates which formed wormholes at high flow rates. At low flow rates the homogeneous rock developed wormholes, while the heterogeneous samples showed evidence of compact dissolution. This study serves as a unique benchmark for pore-scale reactive transport modelling directly on the binarized Micro-CT images. Dynamic pore-scale imaging methods offer advantages in helping explain the dominant processes at the pore scale so that they may be up-scaled for accurate model prediction.

Glass dissolution as a function of pH and its implications for understanding mechanisms and future experiments

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

Strachan, Denis

For years, we have been using a certain form of the glass dissolution rate equation. In this article, I examine the assumptions that have been made and suggest that the rate equation may be more complex than originally thought. Suggestions of experiments that are needed to correct or validate the exisiting form of the rate equation are made.

Extreme conditions in a dissolving air nanobubble

NASA Astrophysics Data System (ADS)

Yasui, Kyuichi; Tuziuti, Toru; Kanematsu, Wataru

2016-07-01

Numerical simulations of the dissolution of an air nanobubble in water have been performed taking into account the effect of bubble dynamics (inertia of the surrounding liquid). The presence of stable bulk nanobubbles is not assumed in the present study because the bubble radius inevitably passes the nanoscale in the complete dissolution of a bubble. The bubble surface is assumed to be clean because attachment of hydrophobic materials on the bubble surface could considerably change the gas diffusion rate. The speed of the bubble collapse (the bubble wall speed) increases to about 90 m/s or less. The shape of a bubble is kept nearly spherical because the amplitude of the nonspherical component of the bubble shape is negligible compared to the instantaneous bubble radius. In other words, a bubble never disintegrates into daughter bubbles during the dissolution. At the final moment of the dissolution, the temperature inside a bubble increases to about 3000 K due to the quasiadiabatic compression. The bubble temperature is higher than 1000 K only for the final 19 ps. However, the Knudsen number is more than 0.2 for this moment, and the error associated with the continuum model should be considerable. In the final 2.3 ns, only nitrogen molecules are present inside a bubble as the solubility of nitrogen is the lowest among the gas species. The radical formation inside a bubble is negligible because the probability of nitrogen dissociation is only on the order of 10-15. The pressure inside a bubble, as well as the liquid pressure at the bubble wall, increases to about 5 GPa at the final moment of dissolution. The pressure is higher than 1 GPa for the final 0.7 ns inside a bubble and for the final 0.6 ns in the liquid at the bubble wall. The liquid temperature at the bubble wall increases to about 360 K from 293 K at the final stage of the complete dissolution.

Dissolution of cerium(IV)-lanthanide(III) oxides: Comparative effect of chemical composition, temperature, and acidity

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

Horlait, D.; Clavier, N.; Szenknect, S.

2012-03-15

The dissolution of Ce{sub 1-x}Ln{sub x}O{sub 2-x/2} solid solutions was undertaken in various acid media in order to evaluate the effects of several physicochemical parameters such as chemical composition, temperature, and acidity on the reaction kinetics. The normalized dissolution rates (R{sub L,0}) were found to be strongly modified by the trivalent lanthanide incorporation rate, due to the presence of oxygen vacancies decreasing the samples cohesion. Conversely, the nature of the trivalent cation considered only weakly impacted the R{sub L,0} values. The dependence of the normalized dissolution rates on the temperature then appeared to be of the same order of magnitudemore » than that of chemical composition. Moreover, it allowed determining the corresponding activation energy (E{sub A} ≅ 60-85 kJ.mol{sup -1}) which accounts for a dissolution driven by surface-controlled reactions. A similar conclusion was made regarding the acidity of the solution: the partial order related to (H{sub 3}O{sup +}) reaching about 0.7. Finally, the prevailing effect of the incorporation of aliovalent cations in the fluorite-type CeO{sub 2} matrix on the dissolution kinetics precluded the observation of slight effects such as those linked to the complexing agents or to the crystal structure of the samples. (authors)« less

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.

Improving the dissolution properties of curcumin using dense gas antisolvent technology.

PubMed

Kurniawansyah, Firman; Quachie, Lisa; Mammucari, Raffaella; Foster, Neil R

2017-04-15

The dissolution properties of curcumin are notoriously poor and hinder its bioavailability. To improve its dissolution properties, curcumin has been formulated with methyl-β-cyclodextrin and polyvinylpyrrolidone by the atomized rapid injection solvent extraction (ARISE) system. The compounds were co-precipitated from organic solutions using carbon dioxide at 30°C and 95bar as the antisolvent. Curcumin formulations were also produced by physical mixing and freeze drying for comparative purposes. The morphology, crystallinity, solid state molecular interactions, apparent solubility and dissolution profiles of samples were observed. The results indicate that the ARISE process is effective in the preparation of curcumin micro-composites with enhanced dissolution profiles compared to unprocessed material and products from physical mixing and freeze drying. Copyright © 2017 Elsevier B.V. All rights reserved.

Characterization of aqueous interactions of copper-doped phosphate-based glasses by vapour sorption.

PubMed

Stähli, Christoph; Shah Mohammadi, Maziar; Waters, Kristian E; Nazhat, Showan N

2014-07-01

Owing to their adjustable dissolution properties, phosphate-based glasses (PGs) are promising materials for the controlled release of bioinorganics, such as copper ions. This study describes a vapour sorption method that allowed for the investigation of the kinetics and mechanisms of aqueous interactions of PGs of the formulation 50P2O5-30CaO-(20-x)Na2O-xCuO (x=0, 1, 5 and 10mol.%). Initial characterization was performed using (31)P magic angle spinning nuclear magnetic resonance and attenuated total reflectance-Fourier transform infrared spectroscopy. Increasing CuO content resulted in chemical shifts of the predominant Q(2) NMR peak and of the (POP)as and (PO(-)) Fourier transform infrared absorptions, owing to the higher strength of the POCu bond compared to PONa. Vapour sorption and desorption were gravimetrically measured in PG powders exposed to variable relative humidity (RH). Sorption was negligible below 70% RH and increased exponentially with RH from 70 to 90%, where it exhibited a negative correlation with CuO content. Vapour sorption in 0% and 1% CuO glasses resulted in phosphate chain hydration and hydrolysis, as evidenced by protonated Q(0)(1H) and Q(1)(1H) species. Dissolution rates in deionized water showed a linear correlation (R(2)>0.99) with vapour sorption. Furthermore, cation release rates could be predicted based on dissolution rates and PG composition. The release of orthophosphate and short polyphosphate species corroborates the action of hydrolysis and was correlated with pH changes. In conclusion, the agreement between vapour sorption and routine characterization techniques in water demonstrates the potential of this method for the study of PG aqueous reactions. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Influence of drug load on dissolution behavior of tablets containing a poorly water-soluble drug: estimation of the percolation threshold.

PubMed

Wenzel, Tim; Stillhart, Cordula; Kleinebudde, Peter; Szepes, Anikó

2017-08-01

Drug load plays an important role in the development of solid dosage forms, since it can significantly influence both processability and final product properties. The percolation threshold of the active pharmaceutical ingredient (API) corresponds to a critical concentration, above which an abrupt change in drug product characteristics can occur. The objective of this study was to identify the percolation threshold of a poorly water-soluble drug with regard to the dissolution behavior from immediate release tablets. The influence of the API particle size on the percolation threshold was also studied. Formulations with increasing drug loads were manufactured via roll compaction using constant process parameters and subsequent tableting. Drug dissolution was investigated in biorelevant medium. The percolation threshold was estimated via a model dependent and a model independent method based on the dissolution data. The intragranular concentration of mefenamic acid had a significant effect on granules and tablet characteristics, such as particle size distribution, compactibility and tablet disintegration. Increasing the intragranular drug concentration of the tablets resulted in lower dissolution rates. A percolation threshold of approximately 20% v/v could be determined for both particle sizes of the API above which an abrupt decrease of the dissolution rate occurred. However, the increasing drug load had a more pronounced effect on dissolution rate of tablets containing the micronized API, which can be attributed to the high agglomeration tendency of micronized substances during manufacturing steps, such as roll compaction and tableting. Both methods that were applied for the estimation of percolation threshold provided comparable values.

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.

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.

Pharmaceutical Cocrystal of Piroxicam: Design, Formulation and Evaluation

PubMed Central

Panzade, Prabhakar; Shendarkar, Giridhar; Shaikh, Sarfaraj; Balmukund Rathi, Pavan

2017-01-01

Purpose: Cocrystallisation of drug with coformers is a promising approach to alter the solid sate properties of drug substances like solubility and dissolution. The objective of the present work was to prepare, formulate and evaluate the piroxicam cocrystal by screening various coformers. Methods: Cocrystals of piroxicam were prepared by dry grinding method. The melting point and solubility of crystalline phase was determined. The potential cocrystal was characterized by DSC, IR, XRPD. Other pharmaceutical properties like solubility and dissolution rate were also evaluated. Orodispersible tablets of piroxicam cocrystal were formulated, optimized and evaluated using 32 factorial design. Results: Cocrystals of piroxicam-sodium acetate revealed the variation in melting points and solubility. The cocrystals were obtained in 1:1 ratio with sodium acetate. The analysis of Infrared explicitly indicated the shifting of characteristic bands of piroxicam. The X-Ray Powder Diffraction pattern denoted the crystallinity of cocrystals and noteworthy difference in 2θ value of intense peaks. Differential scanning calorimetry spectra of cocrystals indicated altered endotherms corresponding to melting point. The pH solubility profile of piroxicam showed sigmoidal curve, which authenticated the pKa-dependent solubility. Piroxicam cocrystals also exhibited a similar pH-solubility profile. The cocrystals exhibited faster dissolution rate owing to cocrystallization as evident from 30% increase in the extent of dissolution. The orodispersible tablets of piroxicam cocrystals were successfully prepared by direct compression method using crosscarmelose sodium as superdisintegrant with improved disintegration time (30 sec) and dissolution rate. Conclusion: The piroxicam cocrystal with modified properties was prepared with sodium acetate and formulated as orodispersible tablets having faster disintegration and greater dissolution rate. PMID:29071222

Pharmaceutical Cocrystal of Piroxicam: Design, Formulation and Evaluation.

PubMed

Panzade, Prabhakar; Shendarkar, Giridhar; Shaikh, Sarfaraj; Balmukund Rathi, Pavan

2017-09-01

Purpose: Cocrystallisation of drug with coformers is a promising approach to alter the solid sate properties of drug substances like solubility and dissolution. The objective of the present work was to prepare, formulate and evaluate the piroxicam cocrystal by screening various coformers. Methods: Cocrystals of piroxicam were prepared by dry grinding method. The melting point and solubility of crystalline phase was determined. The potential cocrystal was characterized by DSC, IR, XRPD. Other pharmaceutical properties like solubility and dissolution rate were also evaluated. Orodispersible tablets of piroxicam cocrystal were formulated, optimized and evaluated using 3 2 factorial design. Results: Cocrystals of piroxicam-sodium acetate revealed the variation in melting points and solubility. The cocrystals were obtained in 1:1 ratio with sodium acetate. The analysis of Infrared explicitly indicated the shifting of characteristic bands of piroxicam. The X-Ray Powder Diffraction pattern denoted the crystallinity of cocrystals and noteworthy difference in 2θ value of intense peaks. Differential scanning calorimetry spectra of cocrystals indicated altered endotherms corresponding to melting point. The pH solubility profile of piroxicam showed sigmoidal curve, which authenticated the pKa-dependent solubility. Piroxicam cocrystals also exhibited a similar pH-solubility profile. The cocrystals exhibited faster dissolution rate owing to cocrystallization as evident from 30% increase in the extent of dissolution. The orodispersible tablets of piroxicam cocrystals were successfully prepared by direct compression method using crosscarmelose sodium as superdisintegrant with improved disintegration time (30 sec) and dissolution rate. Conclusion: The piroxicam cocrystal with modified properties was prepared with sodium acetate and formulated as orodispersible tablets having faster disintegration and greater dissolution rate.

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…

The improved dissolution performance of a post processing treated spray-dried crystalline solid dispersion of poorly soluble drugs.

PubMed

Chan, Siok-Yee; Toh, Seok-Ming; Khan, Nasir Hayat; Chung, Yin-Ying; Cheah, Xin-Zi

2016-11-01

Solution-mediated transformation has been cited as one of the main problems that deteriorate dissolution performances of solid dispersion (SD). This is mainly attributed by the recrystallization tendency of poorly soluble drug. Eventually, it will lead to extensive agglomeration which is a key process in reducing the dissolution performance of SD and offsets the true benefit of SD system. Here, a post-processing treatment is suggested in order to reduce the recrystallization tendency and hence bring forth the dissolution advantage of SD system. The current study investigates the effect of a post processing treatment on dissolution performance of SD in comparison to their performances upon production. Two poorly soluble drugs were spray dried into SD using polyvinyl alcohol (PVA) as hydrophilic carrier. The obtained samples were post processing treated by exposure to high humidity, i.e. 75% RH at room temperature. The physical properties and release rate of the SD system were characterized upon production and after the post-processing treatment. XRPD, Infrared and DSC results showed partial crystallinity of the fresh SD systems. Crystallinity of these products was further increased after the post-processing treatment at 75% RH. This may be attributed to the high moisture absorption of the SD system that promotes recrystallization process of the drug. However, dissolution efficiencies of the post-treated systems were higher and more consistent than the fresh SD. The unexpected dissolution trend was further supported by the results intrinsic dissolution and solubility studies. An increase of crystallinity in a post humidity treated SD did not exert detrimental effect to their dissolution profiles. A more stabilized system with a preferable enhanced dissolution rate was obtained by exposing the SD to a post processing humidity treatment.

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.

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)

Effects of early sea-floor processes on the taphonomy of temperate shelf skeletal carbonate deposits

NASA Astrophysics Data System (ADS)

Smith, Abigail M.; Nelson, Campbell S.

2003-10-01

Cool-water shelf carbonates differ from tropical carbonates in their sources, modes, and rates of deposition, geochemistry, and diagenesis. Inorganic precipitation, marine cementation, and sediment accumulation rates are absent or slow in cool waters, so that temperate carbonates remain longer at or near the sea bed. Early sea-floor processes, occurring between biogenic calcification and ultimate deposition, thus take on an important role, and there is the potential for considerable taphonomic loss of skeletal information into the fossilised record of cool-water carbonate deposits. The physical breakdown processes of dissociation, breakage, and abrasion are mediated mainly by hydraulic regime, and are always destructive. Impact damage reduces the size of grains, removes structure and therefore information, and ultimately may transform skeletal material into anonymous particles. Abrasion is highly selective amongst and within taxa, their skeletal form and structure strongly influencing resistance to mechanical breakdown. Dissolution and precipitation are the end-members of a two-way chemical equilibrium operating in sea water. In cool waters, inorganic precipitation is rare. There is conflicting opinion about the importance of diagenetic dissolution of carbonate skeletons on the temperate sea floor, but test maceration and early loss of aragonite in particular are reported. Dissolution may relate to undersaturated acidic pore waters generated locally by a combination of microbial metabolisation of organic matter, strong bioturbation, and oxidation of solid phase sulphides immediately beneath the sea floor in otherwise very slowly accumulating skeletal deposits. Laboratory experiments demonstrate that surface-to-volume ratio and skeletal mineralogy are both important in determining skeletal resistance to dissolution. Biological processes on the sea floor include encrustation and bioerosion. Encrustation, a constructive process, may be periodic or seasonal, and can be reversed. It produces both information and material. Bioerosion, in contrast, is destructive and permanent. In temperate areas bioerosion may destroy even very large shells during their long residence at the sea floor, on the order of hundreds to thousands of years. Overall, processes on the temperate sea floor may combine to destroy more carbonate than they produce, and the preservation potential of temperate shelf carbonate into the rock record may be significantly affected. Where preservation does occur in such a destructive regime, the effects of early sea-floor processes will be key determinants of the deposit, resulting in a "taphofacies" characteristic of temperate shelf carbonate sediments.

Solubilization, Solution Equilibria, and Biodegradation of PAH's under Thermophilic Conditions

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

Viamajala, S.; Peyton, B. M.; Richards, L. A.

Biodegradation rates of PAHs are typically low at mesophilic conditions and it is believed that the kinetics of degradation is controlled by PAH solubility and mass transfer rates. Solubility tests were performed on phenanthrene, fluorene and fluoranthene at 20 C, 40 C and 60 C and, as expected, a significant increase in the equilibrium solubility concentration and of the rate of dissolution of these polycyclic aromatic hydrocarbons (PAHs) was observed with increasing temperature. A first-order model was used to describe the PAH dissolution kinetics and the thermodynamic property changes associated with the dissolution process (enthalpy, entropy and Gibb's free energymore » of solution) were evaluated. Further, other relevant thermodynamic properties for these PAHs, including the activity coefficients at infinite dilution, Henry's law constants and octanol-water partition coefficients, were calculated in the temperature range 20-60 C. In parallel with the dissolution studies, three thermophilic Geobacilli were isolated from compost that grew on phenanthrene at 60 C and degraded the PAH more rapidly than other reported mesophiles. Our results show that while solubilization rates of PAHs are significantly enhanced at elevated temperatures, the biodegradation of PAHs under thermophilic conditions is likely mass transfer limited due to enhanced degradation rates.« less

Fabrication, characterization and in vitro evaluation of silibinin nanoparticles: an attempt to enhance its oral bioavailability

PubMed Central

Sahibzada, Muhammad Umar Khayam; Sadiq, Abdul; Khan, Shahzeb; Faidah, Hani S; Naseemullah; Khurram, Muhammad; Amin, Muhammad Usman; Haseeb, Abdul

2017-01-01

Background Silibinin has gained in importance in the past few decades as a hepatoprotector and is used widely as oral therapy for toxic liver damage, liver cirrhosis, and chronic inflammatory liver diseases, as well as for the treatment of different types of cancers. Unfortunately, it has low aqueous solubility and inadequate dissolution, which results in low oral bioavailability. Materials and methods In this study, nanoparticles (NPs) of silibinin, which is a hydrophobic drug, were manufactured using two cost-effective methods. Antisolvent precipitation with a syringe pump (APSP) and evaporative precipitation of nanosuspension (EPN) were used. The prepared NPs were characterized using different analytical techniques such as scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and X-ray powder diffractometry (XRD) and were sifted for their bioavailability through in vitro dissolution and solubility studies. Moreover, the prepared NPs were evaluated for antimicrobial activity against a battery of bacteria and yeast. Results DSC and XRD studies indicated that the prepared NPs were amorphous in nature, with more solubility and dissolution compared to the crystalline form of this drug. NPs prepared through the EPN method had better results than those prepared using the APSP method. Antimicrobial activities of the NPs were improved compared to the unprocessed drugs, while having comparable activities to standard antimicrobial drugs. Conclusion Results indicate that the NPs have significantly increased solubility, dissolution rate, and antimicrobial activities due to the conversion of crystalline structure into amorphous form. PMID:28553075

Role of blooming in determining the storage stability of lipid-based dosage forms.

PubMed

Khan, Nurzalina; Craig, Duncan Q M

2004-12-01

Gelucire 50/13 alone and solid dispersions in this material containing two model drugs (10% w/w caffeine and paracetamol) have been studied with a view to establishing the mechanism underpinning changes in drug-release characteristics as a function of storage time and temperature. The lipid systems were fabricated into tablets and stored for up to 180 days at temperatures of 20 and 37 degrees C. The dispersions were studied using differential scanning calorimetry (DSC), scanning electron microscopy, and dissolution testing. DSC studies indicated that the Gelucire 50/13 exists in two principal melting forms (melting points 38 and 43 degrees C) that undergo transformation to the higher melting form on storage at 37 degrees C. Scanning electron microscopy studies indicated that the systems exhibit "blooming," with crystal formation on the surface being apparent on storage at both temperatures. The dissolution rate increased on storage, with the effect being particularly marked at higher storage temperatures and for the paracetamol systems. However, whereas these changes corresponded well to those seen for the morphology, the correlation between the changes in dissolution and those of the DSC profiles was poor. The study has suggested a novel explanation for the storage instability of Gelucire 50/13 whereby the change in dissolution is associated not with molecular rearrangement as such but with the gross distribution of the constituent components, this in turn altering the physical integrity of the lipid bases. (c) 2004 Wiley-Liss, Inc. and the American Pharmacists Association

Preparation and in vitro/in vivo Evaluation of Lacidipine by Adsorption onto Fumed Silica Using Supercritical Carbon Dioxide.

PubMed

Geng, Yajie; Fu, Qiang; Guo, Bei; Li, Yun; Zhang, Xiangrong; Wang, Xianglin; Zhang, Tianhong

2016-01-01

The aim of this study was to design a silica-supported solid dispersion of lacidipine (LCDP) to enhance the dissolution rate and oral absorption using supercritical CO2 (scCO2) as a solvent. The formulation was characterized using differential scanning calorimetry, powder X-ray diffraction, scanning electron microscopy and fourier transformed infrared spectroscopy. In the dissolution test, LCDP-scCO2 formulation showed a significantly enhanced dissolution compared with LCDPsilica physical mixture and a faster dissolution rate than Lacipil® under different dissolution conditions. In an in vivo test, the area under concentration-time curve and Cmax of LCDP-scCO2 formulation was 9.23 and 23.78 fold greater than LCDP-silica physical mixture (1:15, w/w), respectively, whereas the corresponding values were 1.92 and 2.80 fold greater than Lacipil®, respectively. Our results showed that the solid dispersion prepared by supercritical fluids technology is a feasible method to enhance the oral bioavailability of LCDP.

Vapor deposition and condensate flow on combustion turbine blades - Theoretical model to predict/understand some corrosion rate consequences of molten alkali sulfate deposition in the field or laboratory

NASA Technical Reports Server (NTRS)

Rosner, Daniel E.; Nagarajan, R.

1987-01-01

An analysis is undertaken of aerodynamically- and centrifugally-driven liquid condensate layers on nonisothermal combustion turbines' stator vanes and rotor blades. Attention is given to the quantitative consequences of one possible mechanism for the initiation of 'hot corrosion' in the underlying blade material through a 'fluxing' of the protective oxide coating by the molten salt of the Newtonian condensate film. Illustrative calculations are presented for the condensate streamline pattern and the distributions of the steady-state condensate layer thickness, together with the corresponding oxide dissolution rate, for a test turbine blade.

Hot-melt extrusion microencapsulation of quercetin for taste-masking.

PubMed

Khor, Chia Miang; Ng, Wai Kiong; Kanaujia, Parijat; Chan, Kok Ping; Dong, Yuancai

2017-02-01

Besides its poor dissolution rate, the bitterness of quercetin also poses a challenge for further development. Using carnauba wax, shellac or zein as the shell-forming excipient, this work aimed to microencapsulate quercetin by hot-melt extrusion for taste-masking. In comparison with non-encapsulated quercetin, the microencapsulated powders exhibited significantly reduced dissolution in the simulated salivary pH 6.8 medium indicative of their potentially good taste-masking efficiency in the order of zein > carnauba wax > shellac. In vitro bitterness analysis by electronic tongue confirmed the good taste-masking efficiency of the microencapsulated powders. In vitro digestion results showed that carnauba wax and shellac-microencapsulated powders presented comparable dissolution rate with the pure quercetin in pH 1.0 (gastric) and 6.8 (intestine) medium; while zein-microencapsulated powders exhibited a remarkably slower dissolution rate. Crystallinity of quercetin was slightly reduced after microencapsulation while its chemical structure remained unchanged. Hot-melt extrusion microencapsulation could thus be an attractive technique to produce taste-masked bioactive powders.

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.

Investigating the Dissolution Performance of Amorphous Solid Dispersions Using Magnetic Resonance Imaging and Proton NMR.

PubMed

Tres, Francesco; Coombes, Steven R; Phillips, Andrew R; Hughes, Leslie P; Wren, Stephen A C; Aylott, Jonathan W; Burley, Jonathan C

2015-09-10

We have investigated the dissolution performance of amorphous solid dispersions of poorly water-soluble bicalutamide in a Kollidon VA64 polymeric matrix as a function of the drug loading (5% vs. 30% bicalutamide). A combined suite of state-of-the-art analytical techniques were employed to obtain a clear picture of the drug release, including an integrated magnetic resonance imaging UV-Vis flow cell system and 1H-NMR. Off-line 1H-NMR was used for the first time to simultaneously measure the dissolution profiles and rates of both the drug and the polymer from a solid dispersion. MRI and 1H-NMR data showed that the 5% drug loading compact erodes linearly, and that bicalutamide and Kollidon VA64 are released at approximately the same rate from the molecular dispersion. For the 30% extrudate, data indicated a slower water ingress into the compact which corresponds to a slower dissolution rate of both bicalutamide and Kollidon VA64.

Effect of the microstructure of Ti-5Mo on the anodic dissolution in H/sub 2/SO/sub 4/

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

Kim, Y.J.; Oriani, R.A.

1987-04-01

The effect of microstructure of the Ti-5Mo alloy on its anodic dissolution rate in sulfuric acid solution at various temperatures has been investigated. TiMo alloys exhibit a region of increased dissolution rate in the vicinity of +0.20 V (saturated calomel electrode (SCE)) in 10% H/sub 2/SO/sub 4/, the same potential region in which pure Mo exhibits a large anodic dissolution rate. Aging of Ti-5Mo at 350 C was found to lead to the formation of ..omega.. phase. Heat treatment caused larger passive currents in 10% H/sub 2/SO/sub 4/, but the critical passivation potentials and corrosion potentials were not significantly affected.more » Molybdenum was enriched in the oxide formed on aged Ti-5Mo at +0.23 V (SCE), in comparison with the Mo concentration found in the oxide on as-received Ti-5Mo.« less

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.

Enhanced dissolution and oral bioavailability of valsartan solid dispersions prepared by a freeze-drying technique using hydrophilic polymers.

PubMed

Xu, Wei-Juan; Xie, Hong-Juan; Cao, Qing-Ri; Shi, Li-Li; Cao, Yue; Zhu, Xiao-Yin; Cui, Jing-Hao

2016-01-01

This study aimed to improve the dissolution rate and oral bioavailability of valsartan (VAL), a poorly soluble drug using solid dispersions (SDs). The SDs were prepared by a freeze-drying technique with polyethylene glycol 6000 (PEG6000) and hydroxypropylmethylcellulose (HPMC 100KV) as hydrophilic polymers, sodium hydroxide (NaOH) as an alkalizer, and poloxamer 188 as a surfactant without using any organic solvents. In vitro dissolution rate and physicochemical properties of the SDs were characterized using the USP paddle method, differential scanning calorimetry (DSC), X-ray diffractometry (XRD) and Fourier transform-infrared (FT-IR) spectroscopy, respectively. In addition, the oral bioavailability of SDs in rats was evaluated by using VAL (pure drug) as a reference. The dissolution rates of the SDs were significantly improved at pH 1.2 and pH 6.8 compared to those of the pure drug. The results from DSC, XRD showed that VAL was molecularly dispersed in the SDs as an amorphous form. The FT-IR results suggested that intermolecular hydrogen bonding had formed between VAL and its carriers. The SDs exhibited significantly higher values of AUC 0-24 h and Cmax in comparison with the pure drug. In conclusion, hydrophilic polymer-based SDs prepared by a freeze-drying technique can be a promising method to enhance dissolution rate and oral bioavailability of VAL.

Seabed measurements of modern corrosion rates on the Florida escarpment

USGS Publications Warehouse

Paull, C.K.; Commeau, R.F.; Curray, Joseph R.; Neumann, A.C.

1991-01-01

A mooring containing diverse carbonate and anhydrite substrates was exposed to bottom waters for 9 months at the base of the Florida Escarpment to determine the influence of dissolution on the development of this continental margin. Weight loss was measured on all samples. Etching, pitting, and loss of the original framework components were observed on substrates with known characteristics. Extrapolations of modern dissolution rates predict only about 1.6 meters of corrosion per million years. However, more rapid anhydrite dissolution, up to 1 km per million years, would cause exposed anhydrite beds to undercut and destabilize intercalated limestones. 

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.

Utilization of supercritical carbon dioxide for complex formation of ibuprofen and methyl-beta-cyclodextrin.

PubMed

Charoenchaitrakool, M; Dehghani, F; Foster, N R

2002-06-04

The dissolution rate of a drug into the biological environment can be enhanced by forming complexes with cyclodextrins and their derivatives. In this study, ibuprofen-methyl-beta-cyclodextrin complexes were prepared successfully by passing ibuprofen-laden CO(2) through a methyl-beta-cyclodextrin packed bed. The maximum drug loading obtained in this work was 10.8 wt.%, which was comparable to that of a 1:1 complex (13.6 wt.% of ibuprofen). The complex exhibited instantaneous dissolution profiles in water solution. The enhanced dissolution rate was attributed to the amorphous character and improved wettability of the product.

Investigation of Deteriorated Dissolution of Amorphous Itraconazole: Description of Incompatibility with Magnesium Stearate and Possible Solutions.

PubMed

Démuth, B; Galata, D L; Szabó, E; Nagy, B; Farkas, A; Balogh, A; Hirsch, E; Pataki, H; Rapi, Z; Bezúr, L; Vigh, T; Verreck, G; Szalay, Z; Demeter, Á; Marosi, G; Nagy, Z K

2017-11-06

Disadvantageous crystallization phenomenon of amorphous itraconazole (ITR) occurring in the course of dissolution process was investigated in this work. A perfectly amorphous form (solid dispersion) of the drug was generated by the electroblowing method (with vinylpyrrolidone-vinyl acetate copolymer), and the obtained fibers were formulated into tablets. Incomplete dissolution of the tablets was noticed under the circumstances of the standard dissolution test, after which a precipitated material could be filtered. The filtrate consisted of ITR and stearic acid since no magnesium content was detectable in it. In parallel with dissolution, ITR forms an insoluble associate, stabilized by hydrogen bonding, with stearic acid deriving from magnesium stearate. This is why dissolution curves do not have the plateaus at 100%. Two ways are viable to tackle this issue: change the lubricant (with sodium stearyl fumarate >95% dissolution can be accomplished) or alter the polymer in the solid dispersion to a type being able to form hydrogen bonds with ITR (e.g., hydroxypropyl methylcellulose). This work draws attention to one possible phenomenon that can lead to a deterioration of originally good dissolution of an amorphous solid dispersion.

Catalyst Stability Benchmarking for the Oxygen Evolution Reaction: The Importance of Backing Electrode Material and Dissolution in Accelerated Aging Studies.

PubMed

Geiger, Simon; Kasian, Olga; Mingers, Andrea M; Nicley, Shannon S; Haenen, Ken; Mayrhofer, Karl J J; Cherevko, Serhiy

2017-09-18

In searching for alternative oxygen evolution reaction (OER) catalysts for acidic water splitting, fast screening of the material intrinsic activity and stability in half-cell tests is of vital importance. The screening process significantly accelerates the discovery of new promising materials without the need of time-consuming real-cell analysis. In commonly employed tests, a conclusion on the catalyst stability is drawn solely on the basis of electrochemical data, for example, by evaluating potential-versus-time profiles. Herein important limitations of such approaches, which are related to the degradation of the backing electrode material, are demonstrated. State-of-the-art Ir-black powder is investigated for OER activity and for dissolution as a function of the backing electrode material. Even at very short time intervals materials like glassy carbon passivate, increasing the contact resistance and concealing the degradation phenomena of the electrocatalyst itself. Alternative backing electrodes like gold and boron-doped diamond show better stability and are thus recommended for short accelerated aging investigations. Moreover, parallel quantification of dissolution products in the electrolyte is shown to be of great importance for comparing OER catalyst feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

NASA Technical Reports Server (NTRS)

Eick, M. J.; Grossl, P. R.; Golden, D. C.; Sparks, D. L.; Ming, D. W.

1996-01-01

The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5.

In vitro solubility, dissolution and permeability studies combined with semi-mechanistic modeling to investigate the intestinal absorption of desvenlafaxine from an immediate- and extended release formulation.

PubMed

Franek, F; Jarlfors, A; Larsen, F; Holm, P; Steffansen, B

2015-09-18

Desvenlafaxine is a biopharmaceutics classification system (BCS) class 1 (high solubility, high permeability) and biopharmaceutical drug disposition classification system (BDDCS) class 3, (high solubility, poor metabolism; implying low permeability) compound. Thus the rate-limiting step for desvenlafaxine absorption (i.e. intestinal dissolution or permeation) is not fully clarified. The aim of this study was to investigate whether dissolution and/or intestinal permeability rate-limit desvenlafaxine absorption from an immediate-release formulation (IRF) and Pristiq(®), an extended release formulation (ERF). Semi-mechanistic models of desvenlafaxine were built (using SimCyp(®)) by combining in vitro data on dissolution and permeation (mechanistic part of model) with clinical data (obtained from literature) on distribution and clearance (non-mechanistic part of model). The model predictions of desvenlafaxine pharmacokinetics after IRF and ERF administration were compared with published clinical data from 14 trials. Desvenlafaxine in vivo dissolution from the IRF and ERF was predicted from in vitro solubility studies and biorelevant dissolution studies (using the USP3 dissolution apparatus), respectively. Desvenlafaxine apparent permeability (Papp) at varying apical pH was investigated using the Caco-2 cell line and extrapolated to effective intestinal permeability (Peff) in human duodenum, jejunum, ileum and colon. Desvenlafaxine pKa-values and octanol-water partition coefficients (Do:w) were determined experimentally. Due to predicted rapid dissolution after IRF administration, desvenlafaxine was predicted to be available for permeation in the duodenum. Desvenlafaxine Do:w and Papp increased approximately 13-fold when increasing apical pH from 5.5 to 7.4. Desvenlafaxine Peff thus increased with pH down the small intestine. Consequently, desvenlafaxine absorption from an IRF appears rate-limited by low Peff in the upper small intestine, which "delays" the predicted time to the maximal plasma concentration (tmax), consistent with clinical data. Conversely, desvenlafaxine absorption from the ERF appears rate-limited by dissolution due to the formulation, which tends to negate the influence of pH-dependent permeability on absorption. We suggest that desvenlafaxine Peff is mainly driven by transcellular diffusion of the unionized form. In the case of desvenlafaxine, poor metabolism does not imply low intestinal permeability, as indicated by the BDDCS, merely low duodenal/jejunal permeability. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

A dual coaxial nanocable sulfur composite for high-rate lithium-sulfur batteries.

PubMed

Li, Zhen; Yuan, Lixia; Yi, Ziqi; Liu, Yang; Xin, Ying; Zhang, Zhaoliang; Huang, Yunhui

2014-01-01

Lithium-sulfur batteries have great potential for some high energy applications such as in electric vehicles and smart grids due to their high capacity, natural abundance, low cost and environmental friendliness. But they suffer from rapid capacity decay and poor rate capability. The problems are mainly related to the dissolution of the intermediate polysulfides in the electrolyte, and to the poor conductivity of sulfur and the discharge products. In this work, we propose a novel dual coaxial nanocable sulfur composite fabricated with multi-walled nanotubes (MWCNT), nitrogen-doped porous carbon (NPC) and polyethylene glycol (PEG), i.e. MWCNTs@S/NPC@PEG nanocable, as a cathode material for Li-S batteries. In such a coaxial structure, the middle N-doped carbon with hierarchical porous structure provides a nanosized capsule to contain and hold the sulfur particles; the inner MWCNTs and the outer PEG layer can further ensure the fast electronic transport and prevent the dissolution of the polysulfides into the electrolyte, respectively. The as-designed MWCNT@S/NPC@PEG composite shows good cycling stability and excellent rate capability. The capacity is retained at 527 mA h g(-1) at 1 C after 100 cycles, and 791 mA h g(-1) at 0.5 C and 551 mA h g(-1) at 2 C after 50 cycles. Especially, the high-rate capability is outstanding with 400 mA h g(-1) at 5 C.

Chemical and mechanical bioerosion of boring sponges from Mexican Pacific coral reefs.

PubMed

Nava, Héctor; Carballo, José Luis

2008-09-01

Species richness (S) and frequency of invasion (IF) by boring sponges on living colonies of Pocillopora spp. from National Park Isla Isabel (México, East Pacific Ocean) are presented. Twelve species belonging to the genera Aka, Cliona, Pione, Thoosa and Spheciospongia were found, and 56% of coral colonies were invaded by boring sponges, with Cliona vermifera Hancock 1867 being the most abundant species (30%). Carbonate dissolution rate and sediment production were quantified for C. vermifera and Cliona flavifodina Rützler 1974. Both species exhibited similar rates of calcium carbonate (CaCO3) dissolution (1.2+/-0.4 and 0.5+/-0.2 kg CaCO3 m(-2) year(-1), respectively, mean +/- s.e.m.), and sediment production (3.3+/-0.6 and 4.6+/-0.5 kg CaCO3 m(-2) year(-1)), resulting in mean bioerosion rates of 4.5+/-0.9 and 5.1+/-0.5 kg CaCO3 m(-2) year(-1), respectively. These bioerosion rates are close to previous records of coral calcification per unit of area, suggesting that sponge bioerosion alone can promote disequilibrium in the reef accretion/destruction ratio in localities that are heavily invaded by boring sponges. The proportion of dissolved material by C. vermifera and C. flavifodina (27 and 10.2%, respectively) confirms that chemical bioerosion plays an important role in sponge bioerosion and in the CaCO3 cycle in coral reefs.

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.

The use of tungsten as a chronically implanted material.

PubMed

Shah Idil, A; Donaldson, N

2018-04-01

This review paper shows that tungsten should not generally be used as a chronically implanted material. The metal has a long implant history, from neuroscience, vascular medicine, radiography, orthopaedics, prosthodontics, and various other fields, primarily as a result of its high density, radiopacity, tensile strength, and yield point. However, a crucial material criterion for chronically implanted metals is their long-term resistance to corrosion in body fluids, either by inherently noble metallic surfaces, or by protective passivation layers of metal oxide. The latter is often assumed for elemental tungsten, with references to its 'inertness' and 'stability' common in the literature. This review argues that in the body, metallic tungsten fails this criterion, and will eventually dissolve into the soluble hexavalent form W 6+ , typically represented by the orthotungstate [Formula: see text] (monomeric tungstate) anion. This paper outlines the metal's unfavourable corrosion thermodynamics in the human physiological environment, the chemical pathways to either metallic or metal oxide dissolution, the rate-limiting steps, and the corrosion-accelerating effects of reactive oxidising species that the immune system produces post-implantation. Multiple examples of implant corrosion have been reported, with failure by dissolution to varying extents up to total loss, with associated emission of tungstate ions and elevated blood serum levels measured. The possible toxicity of these corrosion products has also been explored. As the field of medical implants grows and designers explore novel solutions to medical implant problems, the authors recommend the use of alternative materials.

The use of tungsten as a chronically implanted material

NASA Astrophysics Data System (ADS)

Shah Idil, A.; Donaldson, N.

2018-04-01

This review paper shows that tungsten should not generally be used as a chronically implanted material. The metal has a long implant history, from neuroscience, vascular medicine, radiography, orthopaedics, prosthodontics, and various other fields, primarily as a result of its high density, radiopacity, tensile strength, and yield point. However, a crucial material criterion for chronically implanted metals is their long-term resistance to corrosion in body fluids, either by inherently noble metallic surfaces, or by protective passivation layers of metal oxide. The latter is often assumed for elemental tungsten, with references to its ‘inertness’ and ‘stability’ common in the literature. This review argues that in the body, metallic tungsten fails this criterion, and will eventually dissolve into the soluble hexavalent form W6+, typically represented by the orthotungstate WO42- (monomeric tungstate) anion. This paper outlines the metal’s unfavourable corrosion thermodynamics in the human physiological environment, the chemical pathways to either metallic or metal oxide dissolution, the rate-limiting steps, and the corrosion-accelerating effects of reactive oxidising species that the immune system produces post-implantation. Multiple examples of implant corrosion have been reported, with failure by dissolution to varying extents up to total loss, with associated emission of tungstate ions and elevated blood serum levels measured. The possible toxicity of these corrosion products has also been explored. As the field of medical implants grows and designers explore novel solutions to medical implant problems, the authors recommend the use of alternative materials.

Dissolution of spherical cap CO2 bubbles attached to flat surfaces in air-saturated water

NASA Astrophysics Data System (ADS)

Peñas, Pablo; Parrales, Miguel A.; Rodriguez-Rodriguez, Javier

2014-11-01

Bubbles attached to flat surfaces immersed in quiescent liquid environments often display a spherical cap (SC) shape. Their dissolution is a phenomenon commonly observed experimentally. Modelling these bubbles as fully spherical may lead to an inaccurate estimate of the bubble dissolution rate. We develop a theoretical model for the diffusion-driven dissolution or growth of such multi-component SC gas bubbles under constant pressure and temperature conditions. Provided the contact angle of the bubble with the surface is large, the concentration gradients in the liquid may be approximated as spherically symmetric. The area available for mass transfer depends on the instantaneous bubble contact angle, whose dynamics is computed from the adhesion hysteresis model [Hong et al., Langmuir, vol. 27, 6890-6896 (2011)]. Numerical simulations and experimental measurements on the dissolution of SC CO2 bubbles immersed in air-saturated water support the validity of our model. We verify that contact line pinning slows down the dissolution rate, and the fact that any bubble immersed in a saturated gas-liquid solution eventually attains a final equilibrium size. Funded by the Spanish Ministry of Economy and Competitiveness through Grant DPI2011-28356-C03-0.

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.

Variations in Divorce Rates by Community Size: A Test of the Social Integration Explanation.

ERIC Educational Resources Information Center

Shelton, Beth Anne

1987-01-01

Found a strong correlation between residential mobility rate and a measure of marital dissolution. Concluded that community size and marital dissolution correlated positively because of higher levels of residential mobility in large cities and urban areas than in small cities and rural areas. Found high residential mobility both an indicator and a…

CaCO3 dissolution by holothurians (sea cucumber): a case study from One Tree Reef, Great Barrier Reef

NASA Astrophysics Data System (ADS)

Schneider, K.; Silverman, J.; Kravitz, B.; Woolsey, E.; Eriksson, H.; Schneider-Mor, A.; Barbosa, S.; Rivlin, T.; Byrne, M.; Caldeira, K.

2012-12-01

Holothurians (sea cucumbers) are among the largest and most important deposit feeder in coral reefs. They play a role in nutrient and CaCO3 cycling within the reef structure. As a result of their digestive process they secrete alkalinity due to CaCO3 dissolution and organic matter degradation forming CO2 and ammonium. In a survey at station DK13 on One Three Reef we found that the population density of holothurians was > 1 individual m-2. The dominant sea cucumber species Holothuria leucospilota was collected from DK13. The increase in alkalinity due to CaCO3 dissolution in aquaria incubations was measured to be 47±7 μmol kg-1 in average per individual. Combining this dissolution rate with the sea cucumbers concentrations at DK13 suggest that they may account for a dissolution rate of 34.9±17.8 mmol m-2 day-1, which is equivalent to about half of night time community dissolution measured in DK13. This indicates that in reefs where the sea cucumber population is healthy and protected from fishing they can be locally important in the CaCO3 cycle. Preliminary result suggests that the CaCO3 dissolution rates are not affected by the chemistry of the sea water they are incubated in. Measurements of the empty digestive track volume of two sea cucumbers H. atra and Stichopus herrmanni were 36 ± 4 ml and 151 ± 14 ml, respectively. Based on these measurements it is estimated that these species process 19 ± 2kg and 80 ± 7kg CaCO3 sand yr-1 per individual, respectively. The annual dissolution rates of H. atra and S. herrmanni are 6.5±1.9g and 9.6±1.4g, respectively, suggest that 0.05±0.02% and 0.1±0.02% of the CaCO3 processed through their gut annually is dissolved. During the incubations the CaCO3 dissolution was 0.07±0.01%, 0.04±0.01% and 0.21±0.05% of the fecal casts for H. atra, H. leucospilota and S. herrmanni, respectively. Our result that the primary parameter determining the CaCO3 dissolution by sea cucumber is the amount of carbonate send in their gut. This suggests that sea cucumber dissolution in the future is not expected to change due to ocean acidification, but as calcification diminishes the proportion of CaCO3 dissolved by Holothurians (in protected reefs) in the coral reefs may increase.

Rates of zinc and trace metal release from dissolving sphalerite at pH 2.0-4.0

USGS Publications Warehouse

Stanton, M.R.; Gemery-Hill, P. A.; Shanks, Wayne C.; Taylor, C.D.

2008-01-01

High-Fe and low-Fe sphalerite samples were reacted under controlled pH conditions to determine nonoxidative rates of release of Zn and trace metals from the solid-phase. The release (solubilization) of trace metals from dissolving sphalerite to the aqueous phase can be characterized by a kinetic distribution coefficient, (Dtr), which is defined as [(Rtr/X(tr)Sph)/(RZn/X(Zn) Sph)], where R is the trace metal or Zn release rate, and X is the mole fraction of the trace metal or Zn in sphalerite. This coefficient describes the relationship of the sphalerite dissolution rate to the trace metal mole fraction in the solid and its aqueous concentration. The distribution was used to determine some controls on metal release during the dissolution of sphalerite. Departures from the ideal Dtr of 1.0 suggest that some trace metals may be released via different pathways or that other processes (e.g., adsorption, solubility of trace minerals such as galena) affect the observed concentration of metals. Nonoxidative sphalerite dissolution (mediated by H+) is characterized by a "fast" stage in the first 24-30 h, followed by a "slow" stage for the remainder of the reaction. Over the pH range 2.0-4.0, and for similar extent of reaction (reaction time), sphalerite composition, and surface area, the rates of release of Zn, Fe, Cd, Cu, Mn and Pb from sphalerite generally increase with lower pH. Zinc and Fe exhibit the fastest rates of release, Mn and Pb have intermediate rates of release, and Cd and Cu show the slowest rates of release. The largest variations in metal release rates occur at pH 2.0. At pH 3.0 and 4.0, release rates show less variation and appear less dependent on the metal abundance in the solid. For the same extent of reaction (100 h), rates of Zn release range from 1.53 ?? 10-11 to 5.72 ?? 10-10 mol/m2/s; for Fe, the range is from 4.59 ?? 10-13 to 1.99 ?? 10-10 mol/m2/s. Trace metal release rates are generally 1-5 orders of magnitude slower than the Zn or Fe rates. Results indicate that the distributions of Fe and Cd are directly related to the rate of sphalerite dissolution throughout the reaction at pH 3.0 and 4.0 because these two elements substitute readily into sphalerite. These two metals are likely to be more amenable to usage in predictive acid dissolution models because of this behavior. The Pb distribution shows no strong relation to sphalerite dissolution and appears to be controlled by pH-dependent solubility, most likely related to trace amounts of galena. The distribution of Cu is similar to that of Fe but is the most-dependent of all metals on its mole fraction ratio (Zn:Cu) in sphalerite. The Mn distributions suggest an increase in the rate of Mn release relative to sphalerite dissolution occurs in low Mn samples as pH increases. The Mn distribution in high Mn samples is nearly independent of pH and sphalerite dissolution at pH 2.0 but shows a dependence on these two parameters at higher pH (3.0-4.0).

Dissolution corrosion of 316L austenitic stainless steels in contact with static liquid lead-bismuth eutectic (LBE) at 500 °C

NASA Astrophysics Data System (ADS)

Lambrinou, Konstantina; Charalampopoulou, Evangelia; Van der Donck, Tom; Delville, Rémi; Schryvers, Dominique

2017-07-01

This work addresses the dissolution corrosion behaviour of 316L austenitic stainless steels. For this purpose, solution-annealed and cold-deformed 316L steels were simultaneously exposed to oxygen-poor (<10-8 mass%) static liquid lead-bismuth eutectic (LBE) for 253-3282 h at 500 °C. Corrosion was consistently more severe for the cold-drawn steels than the solution-annealed steel, indicating the importance of the steel thermomechanical state. The thickness of the dissolution-affected zone was non-uniform, and sites of locally-enhanced dissolution were occasionally observed. The progress of LBE dissolution attack was promoted by the interplay of certain steel microstructural features (grain boundaries, deformation twin laths, precipitates) with the dissolution corrosion process. The identified dissolution mechanisms were selective leaching leading to steel ferritization, and non-selective leaching; the latter was mainly observed in the solution-annealed steel. The maximum corrosion rate decreased with exposure time and was found to be inversely proportional to the depth of dissolution attack.

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, which can play an important role in the regulation of silica fluxes in terrestrial aquatic environments.

Influence of sodium lauryl sulfate and tween 80 on carbamazepine-nicotinamide cocrystal solubility and dissolution behaviour.

PubMed

Li, Mingzhong; Qiao, Ning; Wang, Ke

2013-10-11

The influence of the surfactants of sodium lauryl sulfate (SLS) and Tween 80 on carbamazepine-nicotinamide (CBZ-NIC) cocrystal solubility and dissolution behaviour has been studied in this work. The solubility of the CBZ-NIC cocrystal was determined by measuring the eutectic concentrations of the drug and the coformer. Evolution of the intrinsic dissolution rate (IDR) of the CBZ-NIC cocrystal was monitored by the UV imaging dissolution system during dissolution. Experimental results indicated that SLS and Tween 80 had little influence upon the solubility of the CBZ-NIC cocrystal but they had totally opposite effects on the IDR of the CBZ-NIC cocrystal during dissolution. SLS significantly increased the IDR of the CBZ-NIC cocrystal while Tween 80 decreased its IDR.

Influence of Sodium Lauryl Sulfate and Tween 80 on Carbamazepine–Nicotinamide Cocrystal Solubility and Dissolution Behaviour

PubMed Central

Li, Mingzhong; Qiao, Ning; Wang, Ke

2013-01-01

The influence of the surfactants of sodium lauryl sulfate (SLS) and Tween 80 on carbamazepine–nicotinamide (CBZ–NIC) cocrystal solubility and dissolution behaviour has been studied in this work. The solubility of the CBZ–NIC cocrystal was determined by measuring the eutectic concentrations of the drug and the coformer. Evolution of the intrinsic dissolution rate (IDR) of the CBZ–NIC cocrystal was monitored by the UV imaging dissolution system during dissolution. Experimental results indicated that SLS and Tween 80 had little influence upon the solubility of the CBZ–NIC cocrystal but they had totally opposite effects on the IDR of the CBZ–NIC cocrystal during dissolution. SLS significantly increased the IDR of the CBZ–NIC cocrystal while Tween 80 decreased its IDR. PMID:24300560

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.

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.

Dual pH durability studies of man-made vitreous fiber (MMVF).

PubMed Central

Bauer, J F; Law, B D; Hesterberg, T W

1994-01-01

Dissolution of fibers in the deep lung may involve both extracellular and intracellular mechanisms. This process was modeled in vitro for each environment using an experimental flow-through system to characterize both total dissolution and specific chemical changes for three representative MMVF's: a glasswool, a slagwool, and a refractory ceramic fiber (RCF). Synthetic physiological fluids at pH 4 and at pH 7.6 were used to simulate macrophage intraphagolysosomal, and extracellular environments, respectively. Actual commercial fiber, sized to rat-respirable dimension, having an average fiber diameter of 1 micron and an average length between 15 and 25 microns, was used in the experiments. Fiber dissolution was monitored through change in chemistry of the fluid collected after percolation at a constant rate through a thin bed of sample. There are great differences in total fiber dissolution rates for the different fibers. Slagwool and RCF dissolve more rapidly at pH 4 than at pH 7.6, while the reverse is true for glasswool. Dissolution is sometimes accompanied by a noticeable change in fiber morphology or dimension, and sometimes by no change. There is strong dependency on pH, which affects not only total fiber dissolution, but also the leaching of specific chemical components. This effect is different for each type of fiber, indicating that specific fiber chemistry largely controls whether a fiber dissolves or leaches more rapidly under acidic or neutral conditions. Both total dissolution rates and calculated fiber composition changes are valuable guides to interpreting in vivo behavior of man-made vitreous fibers, and demonstrate the usefulness of in vitro acellular experiments in understanding overall fiber persistence. Images Figure 3. A Figure 3. B Figure 4. A Figure 4. B Figure 4. C PMID:7882957

Solutal convection induced by dissolution. Influence on erosion dynamics and interface shaping.

NASA Astrophysics Data System (ADS)

Berhanu, Michael; Philippi, Julien; Cohen, Caroline; Derr, Julien; Courrech du Pont, Sylvain

2017-04-01

Rock fractures invaded by a water flow, are often subjected to dissolution, which let grow and evolve the initial fracture network, by evacuating the eroded minerals under a solute form. In the case of fast kinetic of dissolution, local erosion rate is set by the advection of the solute. The erosion velocity decreases indeed with the solute concentration at the interface and vanishes when this concentration reaches the saturation value. Even in absence of an imposed or external flow, advection can drive the dissolution, when buoyancy effects due to gravity induce a solutal convection flow, which controls the erosive dynamics and modifies the shape of the dissolving interface. Here, we investigate using model experiments with fast dissolving materials and numerical simulations in simplified situations, solutal convection induced by dissolution. Results are interpreted regarding a linear stability analysis of the corresponding solutal Rayleigh-Benard instability. A dissolving surface is suspended above a water height, initially at rest. In a first step, solute flux is transported through a growing diffusion layer. Then after an onset time, once the layer exceeds critical width, convection flow starts under the form of falling plumes. A dynamic equilibrium results in average from births and deaths of intermittent plumes, setting the size of the solute concentration boundary layer at the interface and thus the erosion velocity. Solutal convection can also induce a pattern on the dissolving interface. We show experimentally with suspended and inclined blocks of salt and sugar, that in a linear stage, the first wavelength of the dissolution pattern corresponds to the wavelength of the convection instability. Then pattern evolves to more complex shapes due to non-linear interactions between the flow and the eroded interface. More generally, we inquire what are the conditions to observe a such solutal convection instability in geological situations and if the properties of dissolution patterns can be related to the characteristic of the convective flow. C. Oltéan, F. Golfier and M.A. Buès, Numerical and experimental investigation of buoyancy-driven dissolution in vertical fracture, J. Geophys. Res. Solid Earth, 118(5), 2038-2048 (2013) C. Cohen, M. Berhanu, J. Derr and S. Courrech du Pont, Erosion patterns on dissolving and melting bodies (2015 Gallery of Fluid motion), Phys. Rev. Fluids, 1, 050508 (2016) T. S. Sullivan, Y. Liu, and R. E. Ecke, Turbulent solutal convection and surface patterning in solid dissolution, Phys. Rev. E 54, 486 (1996)

Scaling of Convective Mixing in Porous Media

NASA Astrophysics Data System (ADS)

Hidalgo, Juan J.; Fe, Jaime; Cueto-Felgueroso, Luis; Juanes, Ruben

2012-12-01

Convective mixing in porous media is triggered by a Rayleigh-Bénard-type hydrodynamic instability as a result of an unstable density stratification of fluids. While convective mixing has been studied extensively, the fundamental behavior of the dissolution flux and its dependence on the system parameters are not yet well understood. Here, we show that the dissolution flux and the rate of fluid mixing are determined by the mean scalar dissipation rate. We use this theoretical result to provide computational evidence that the classical model of convective mixing in porous media exhibits, in the regime of high Rayleigh number, a dissolution flux that is constant and independent of the Rayleigh number. Our findings support the universal character of convective mixing and point to the need for alternative explanations for nonlinear scalings of the dissolution flux with the Rayleigh number, recently observed experimentally.

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.

The erosion of carbonate stone by acid rain: Laboratory and field investigations

USGS Publications Warehouse

Baedecker, P.A.; Reddy, M.M.

1993-01-01

One of the goals of research on the effects of acidic deposition on carbonate stone surfaces is to define the incremental impact of acidic deposition relative to natural weathering processes on the rate of carbonate stone erosion. If rain that impacts carbonate stone surfaces is resident on the surface long enough to approach chemical equilibrium, the incremental effect of hydrogen ion is expected to be small (i.e., 6% for a rain of pH 4.0). Under nonequilibrium (i.e., high flow rate) conditions, kinetic considerations suggest that the incremental effect of hydrogen ion deposition could be quite significant. Field run-off experiments involving the chemical analysis of rain collected from inclined stone slabs have been used to evaluate stone dissolution processes under ambient conditions of wet and dry deposition of acidic species. The stoichiometry of the reaction of stone with hydrogen ion is difficult to define from the field data due to scatter in the data attributed to hydrodynamic effects. Laboratory run-off experiments show that the stoichiometry is best defined by a reaction with H+ in which CO2 is released from the system. The baseline effect caused by water in equilibrium with atmospheric CO2 is identical in the field and in laboratory simulation. The experiments show that the solutions are close enough to equilibrium for the incremental effect of hydrogen ion to be minor (i.e., 24% for marble for a rain of pH 4.0) relative to dissolution due to water and carbonic acid reactions. Stone erosion rates based on physical measurement are approximately double the recession rates that are due to dissolution (estimated from the observed calcium content of the run-off solutions). The difference may reflect the loss of granular material not included in recession estimates based on the run-off data. Neither the field nor the laboratory run-off experiments indicate a pH dependence for the grain-removal process.

The influence of dissolved H2O content in supercritical carbon dioxide to the inclusion complexes formation of ketoprofen/β-cyclodextrin

NASA Astrophysics Data System (ADS)

Goenawan, Joshua; Trisanti, P. N.; Sumarno

2015-12-01

This work studies the relation between dissolved H2O content in supercritical carbon dioxide (SC-CO2) with the formation of ketoprofen (KP)/β-cyclodextrin(CD) inclusion complexes. The process involves a physical mixture of these two compounds into contact with the supercritical carbon dioxide which had been previously saturated with H2O over a certain duration. The pressure used for saturation process is 130 bar and saturation temperature was ranged between 30 °C to 50 °C. The inclusion process was achieved by keeping it for 2 hours at 160 bar and 200 bar with inclusion temperature of 50 °C. The results enable us to suggest explanations for the inclusion formation. The inclusion complexes can be formed by contacting the dissolved H2O in SC-CO2 to the physical mixture of KP and CD. An increase in the temperature of saturation process resulted in an increase of dissolved H2O content in the supercritical carbon dioxide. The increasing levels of this water soluble resulted an increase in the inclusion complexes that has been formed. The formation of inclusion complexes includes the water molecules enhancing the emptying of the CD cavities and being replaced by KP, towards a more stable energy state. The drug release used for analyzing the dissolution rate of the KP/CD complexes. The results vary from 79,85% to 99,98% after 45 minutes which is above the rate that has been assigned by Farmakope Indonesia at 70% dissolution rate for KP. The use of SC-CO2 offers a new methods for increasing the rate of dissolution of drugs that are hydrophobic such as KP. CO2 used as a supercritical fluid because of its relatively low cost, easily obtainable supercritical conditions, and lack of toxicity. The material samples were characterized by DSC and Spectrophotometer UV-vis technique.

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 dissolution will decrease due to the role of water as a ligand in the reaction. Apparent dissolution rate constants in the dilute NaCl solution (1.89 × 10-12 ± 1 × 10-13 mol mineral m-2 s-1) are slightly greater than those in the dilute CaCl2 solutions (1.18 × 10-12 ± 9 × 10-14 mol mineral m-2 s-1). We attribute this effect to the exchange of Na with Ca in the nontronite interlayer. An apparent activation energy of 54.6 ± 1.0 kJ/mol was calculated from apparent dissolution rate constants in dilute CaCl2-containing solutions at temperatures of 4.0 °C, 25.0 °C, and 45.0 °C: 2.33 × 10-13 ± 1.3 × 10-14 mol mineral m-2 s-1 (4.0 °C), 1.18 × 10-12 ± 9 × 10-14 mol mineral m-2 s-1 (25.0 °C), and 4.98 × 10-12 ± 3.8 × 10-13 mol mineral m-2 s-1 (45.0 °C). The greatly decreased dissolution of nontronite in brines and at low temperatures suggests that any martian nontronite found to be perceptibly weathered may have experienced very long periods of water-rock interaction with brines at the low temperatures prevalent on Mars, with important implications for the paleoclimate and long-term potential habitability of Mars.

A probabilistic assessment of calcium carbonate export and dissolution in the modern ocean

NASA Astrophysics Data System (ADS)

Battaglia, Gianna; Steinacher, Marco; Joos, Fortunat

2016-05-01

The marine cycle of calcium carbonate (CaCO3) is an important element of the carbon cycle and co-governs the distribution of carbon and alkalinity within the ocean. However, CaCO3 export fluxes and mechanisms governing CaCO3 dissolution are highly uncertain. We present an observationally constrained, probabilistic assessment of the global and regional CaCO3 budgets. Parameters governing pelagic CaCO3 export fluxes and dissolution rates are sampled using a Monte Carlo scheme to construct a 1000-member ensemble with the Bern3D ocean model. Ensemble results are constrained by comparing simulated and observation-based fields of excess dissolved calcium carbonate (TA*). The minerals calcite and aragonite are modelled explicitly and ocean-sediment fluxes are considered. For local dissolution rates, either a strong or a weak dependency on CaCO3 saturation is assumed. In addition, there is the option to have saturation-independent dissolution above the saturation horizon. The median (and 68 % confidence interval) of the constrained model ensemble for global biogenic CaCO3 export is 0.90 (0.72-1.05) Gt C yr-1, that is within the lower half of previously published estimates (0.4-1.8 Gt C yr-1). The spatial pattern of CaCO3 export is broadly consistent with earlier assessments. Export is large in the Southern Ocean, the tropical Indo-Pacific, the northern Pacific and relatively small in the Atlantic. The constrained results are robust across a range of diapycnal mixing coefficients and, thus, ocean circulation strengths. Modelled ocean circulation and transport timescales for the different set-ups were further evaluated with CFC11 and radiocarbon observations. Parameters and mechanisms governing dissolution are hardly constrained by either the TA* data or the current compilation of CaCO3 flux measurements such that model realisations with and without saturation-dependent dissolution achieve skill. We suggest applying saturation-independent dissolution rates in Earth system models to minimise computational costs.

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 BCS II weak acids in developing in vitro bioequivalence dissolution methodology. PMID:19183104

Investigation and simulation of dissolution with concurrent degradation under healthy and hypoalbuminaemic simulated parenteral conditions- case example Amphotericin B.

PubMed

Díaz de León-Ortega, Ricardo; D'Arcy, Deirdre M; Bolhuis, A; Fotaki, N

2018-06-01

Guidance on dissolution testing for parenteral formulations is limited and not often related in vivo performance. Critically ill patients represent a target cohort, frequently hypoalbuminaemic, to whom certain parenteral formulations are administered. Amphotericin B (AmB) is a poorly soluble, highly protein-bound drug, available as lipid-based formulations and used in critical illness. The aim of this study was to develop media representing hypoalbuminaemic and healthy plasma, and to understand and simulate the dissolution profile of AmB in biorelevant media. Dissolution media were prepared with bovine serum albumin (BSA) in Krebs-Ringer buffer, and tested in a flow through cell apparatus and a bottle/stirrer setup. Drug activity was tested against Candida albicans. BSA concentration was positively associated with solubility, degradation rate and maximum amount dissolved and negatively associated with dissolution rate constant and antifungal activity. In the bottle/stirrer setup, a biexponential model successfully described simultaneous dissolution and degradation and increased in agitation reduced the discriminatory ability of the test. The hydrodynamics provided by the flow-through cell apparatus was not adequate to dissolve the drug. Establishing discriminating test methods with albumin present in the dissolution media, representing the target population, supports future development of biorelevant and clinically relevant tests for parenteral formulations. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Sucralose as co-crystal co-former for hydrochlorothiazide: development of oral disintegrating tablets.

PubMed

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

2016-08-01

Development of oral disintegrating tablets requires enhancement of drug dissolution and selection of sweetener. Co-crystallization of drugs with inert co-former is an emerging technique for enhancing dissolution rate. The benefit of this technique will become even greater if one of the sweeteners can act as co-crystal co-former to enhance dissolution and mask the taste. Accordingly, the objective of this work was to investigate the efficacy of sucralose as a potential co-crystal co-former for enhancing the dissolution rate of hydrochlorothiazide. This was extended to prepare oral disintegrating tablets. Co-crystallization was achieved after dissolving hydrochlorothiazide with increasing molar ratios of sucralose in the least amount of acetone. The co-crystallization products were characterized using Fourier transform infrared spectroscopy, differential thermal analysis and powder X-ray diffraction. These measurements indicated that co-crystallization process started at a drug sucralose molar ratio of 1:1 and completed at 1:2. The developed co-crystals exhibited faster drug dissolution compared with the control, with co-crystal containing the drug with sucralose at 1:2 molar ratio being optimum. The later was used to prepare fast disintegrating tablets. These tablets had acceptable physical characteristics and showed fast disintegration with subsequent rapid dissolution. The study introduced sucralose as co-crystal co-former for enhanced dissolution and masking the taste.

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.

An investigation into the use of polymer blends to improve the printability of and regulate drug release from pharmaceutical solid dispersions prepared via fused deposition modeling (FDM) 3D printing.

PubMed

Alhijjaj, Muqdad; Belton, Peter; Qi, Sheng

2016-11-01

FDM 3D printing has been recently attracted increasing research efforts towards the production of personalized solid oral formulations. However, commercially available FDM printers are extremely limited with regards to the materials that can be processed to few types of thermoplastic polymers, which often may not be pharmaceutically approved materials nor ideal for optimizing dosage form performance of poor soluble compounds. This study explored the use of polymer blends as a formulation strategy to overcome this processability issue and to provide adjustable drug release rates from the printed dispersions. Solid dispersions of felodipine, the model drug, were successfully fabricated using FDM 3D printing with polymer blends of PEG, PEO and Tween 80 with either Eudragit E PO or Soluplus. As PVA is one of most widely used polymers in FDM 3D printing, a PVA based solid dispersion was used as a benchmark to compare the polymer blend systems to in terms of processability. The polymer blends exhibited excellent printability and were suitable for processing using a commercially available FDM 3D printer. With 10% drug loading, all characterization data indicated that the model drug was molecularly dispersed in the matrices. During in vitro dissolution testing, it was clear that the disintegration behavior of the formulations significantly influenced the rates of drug release. Eudragit EPO based blend dispersions showed bulk disintegration; whereas the Soluplus based blends showed the 'peeling' style disintegration of strip-by-strip. The results indicated that interplay of the miscibility between excipients in the blends, the solubility of the materials in the dissolution media and the degree of fusion between the printed strips during FDM process can be used to manipulate the drug release rate of the dispersions. This brings new insight into the design principles of controlled release formulations using FDM 3D printing. Copyright © 2016 Elsevier B.V. All rights reserved.

Phagosomal pH and glass fiber dissolution in cultured nasal epithelial cells and alveolar macrophages: a preliminary study.

PubMed Central

Johnson, N F

1994-01-01

The dissolution rate of glass fibers has been shown to be pH sensitive using in vitro lung fluid simulant models. The current study investigated whether there is a difference in phagosomal pH (ppH) between rat alveolar macrophages (AM) and rat nasal epithelial cells (RNEC) and whether such a difference would influence the dissolution of glass fibers. The ppH was measured in cultured AM and RNEC using flow cytometric, fluorescence-emission rationing techniques with fluorescein-labeled, amorphous silica particles. Glass fiber dissolution was determined in AM and RNEC cultured for 3 weeks with fast dissolving glass fibers (GF-A) or slow dissolving ones (GF-B). The mean diameters of GF-A were 2.7 microns and of GF-B, 2.6 microns, the average length of both fibers was approximately 22 to 25 microns. Dissolution was monitored by measuring the length and diameter of intracellular fibers and estimating the volume, assuming a cylindrical morphology. The ppH of AM was 5.2 to 5.8, and the ppH of RNEC was 7.0 to 7.5. The GF-A dissolved more slowly in RNEC than in AM, and no dissolution was evident in either cell type with GF-B. The volume loss with GF-A after a 3-week culture with AM was 66% compared to 45% for cultured RNEC. These results are different from those obtained using in vitro lung fluid-simulant models where dissolution is faster at higher pH. This difference suggests that dissolution rates of glass fibers in AM should not be applied to the dissolution of fibers in epithelial cells. Images Figure 1. a Figure 1. b Figure 2. a Figure 2. b Figure 3. a Figure 3. b PMID:7882965

To evaluate the change in release from solid dispersion using sodium lauryl sulfate and model drug sulfathiazole.

PubMed

Dave, Rutesh H; Patel, Hardikkumar H; Donahue, Edward; Patel, Ashwinkumar D

2013-10-01

The solubility of drugs remains one of the most challenging aspects of formulation development. There are numerous ways to improve the solubility of drugs amongst which the most promising strategy is solid dispersion. Different ratios of sulfathiazole: PVP-K29/32: sodium lauryl sulfate (SLS) were prepared (1:1:0.1, 1:1:0.5, 1:1:1) and various methods were employed to characterize the prepared solid dispersions, namely modulated differential scanning calorimeter, X-ray powder diffraction, Fourier Transformed Infrared Spectroscopy and dissolution studies. Lack of crystallinity was observed in internal and external systems suggesting a loss of crystallinity, whereas the physical mixtures showed a characteristic peak of sulfathiazole. In vitro dissolution results clearly showed that the incorporation of a relatively small amount of surfactants (5, 20 or 33% w/w) into a solid dispersion can improve its dissolution rates compared to binary solid dispersion (SD) alone and pure sulfathiazole. In all ratios solid dispersion internal shows a higher dissolution rate compared to a physical mixture and solid dispersion external which suggests that the way that the surfactant is incorporated into the solid dispersion plays an important role in changing the solubility of a drug. The solubilization mechanism is mainly responsible for this higher dissolution rate when we incorporate the SLS in SD.

Dissolution-modulating mechanism of pH modifiers in solid dispersion containing weakly acidic or basic drugs with poor water solubility.

PubMed

Tran, Phuong Ha-Lien; Tran, Thao Truong-Dinh; Lee, Kyoung-Ho; Kim, Dong-Jin; Lee, Beom-Jin

2010-05-01

Although the solid dispersion method has been known to increase the dissolution rate of poorly water-soluble drugs by dispersing them in hydrophilic carriers, one obstacle of the solid dispersion method is its limited solubilization capacity, especially for pH-dependent soluble drugs. pH-modified solid dispersion, in which pH modifiers are incorporated, may be a useful method for increasing the dissolution rate of weakly acidic or basic drugs. Sufficient research, including the most recent reports, was undertaken in this review. How could the inclusion of the pH the pH modifiers in the solid dispersion system change drug structural behaviors, molecular interactions, microenvironmental pH, and/or release rate of pH modifiers, relating with the enhanced dissolution of weakly acidic or weakly basic drugs with poor water solubility? These questions have been investigated to determine the dissolution-modulating mechanism of pH modifiers in solid dispersion containing weakly acidic or basic drugs. It is believed that step-by-step mechanistic approaches could provide the ultimate solution for solubilizing several poorly water-soluble drugs with pH-dependent solubility from a solid dispersion system, as well as provide ideas for developing future dosage systems.

Relative contributions of copper oxide nanoparticles and dissolved copper to Cu uptake kinetics of Gulf killifish (Fundulus grandis) embryos

USGS Publications Warehouse

Jiang, Chuanjia; Castellon, Benjamin T.; Matson, Cole W.; Aiken, George R.; Hsu-Kim, Heileen

2017-01-01

The toxicity of soluble metal-based nanomaterials may be due to the uptake of metals in both dissolved and nanoparticulate forms, but the relative contributions of these different forms to overall metal uptake rates under environmental conditions are not quantitatively defined. Here, we investigated the linkage between the dissolution rates of copper(II) oxide (CuO) nanoparticles (NPs) and their bioavailability to Gulf killifish (Fundulus grandis) embryos, with the aim of quantitatively delineating the relative contributions of nanoparticulate and dissolved species for Cu uptake. Gulf killifish embryos were exposed to dissolved Cu and CuO NP mixtures comprising a range of pH values (6.3–7.5) and three types of natural organic matter (NOM) isolates at various concentrations (0.1–10 mg-C L–1), resulting in a wide range of CuO NP dissolution rates that subsequently influenced Cu uptake. First-order dissolution rate constants of CuO NPs increased with increasing NOM concentration and for NOM isolates with higher aromaticity, as indicated by specific ultraviolet absorbance (SUVA), while Cu uptake rate constants of both dissolved Cu and CuO NP decreased with NOM concentration and aromaticity. As a result, the relative contribution of dissolved Cu and nanoparticulate CuO species for the overall Cu uptake rate was insensitive to NOM type or concentration but largely determined by the percentage of CuO that dissolved. These findings highlight SUVA and aromaticity as key NOM properties affecting the dissolution kinetics and bioavailability of soluble metal-based nanomaterials in organic-rich waters. These properties could be used in the incorporation of dissolution kinetics into predictive models for environmental risks of nanomaterials.

Influence of calcium on microbial reduction of solid phase uranium(VI).

PubMed

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M; Wang, Zheming

2007-08-15

The effect of calcium on the dissolution and microbial reduction of a representative solid phase uranyl [U(VI)], sodium boltwoodite (NaUO(2)SiO(3)OH . 1.5H(2)O), was investigated to evaluate the rate-limiting step of microbial reduction of the solid phase U(VI). Microbial reduction experiments were performed in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1, in a bicarbonate medium with lactate as electron donor at pH 6.8 buffered with PIPES. Calcium increased the rate of Na-boltwoodite dissolution and U(VI) bioavailability by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) collectively revealed that microbial reduction of solid phase U(VI) was a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. Under studied experimental conditions, the overall rate of microbial reduction of solid phase U(VI) was limited by U(VI) dissolution reactions in solutions without calcium and limited by microbial reduction in solutions with calcium. Generally, the overall rate of microbial reduction of solid phase U(VI) was determined by the coupling of solid phase U(VI) dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) that were all affected by calcium. (c) 2007 Wiley Periodicals, Inc.

Incinerator ash dissolution model for the system: Plutonium, nitric acid and hydrofluoric acid

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

Brown, E V

1988-06-01

This research accomplished two goals. The first was to develop a computer program to simulate a cascade dissolver system. This program would be used to predict the bulk rate of dissolution in incinerator ash. The other goal was to verify the model in a single-stage dissolver system using Dy/sub 2/O/sub 3/. PuO/sub 2/ (and all of the species in the incinerator ash) was assumed to exist as spherical particles. A model was used to calculate the bulk rate of plutonium oxide dissolution using fluoride as a catalyst. Once the bulk rate of PuO/sub 2/ dissolution and the dissolution rate ofmore » all soluble species were calculated, mass and energy balances were written. A computer program simulating the cascade dissolver system was then developed. Tests were conducted on a single-stage dissolver. A simulated incinerator ash mixture was made and added to the dissolver. CaF/sub 2/ was added to the mixture as a catalyst. A 9M HNO/sub 3/ solution was pumped into the dissolver system. Samples of the dissolver effluent were analyzed for dissolved and F concentrations. The computer program proved satisfactory in predicting the F concentrations in the dissolver effluent. The experimental sparge air flow rate was predicted to within 5.5%. The experimental percentage of solids dissolved (51.34%) compared favorably to the percentage of incinerator ash dissolved (47%) in previous work. No general conclusions on model verification could be reached. 56 refs., 11 figs., 24 tabs.« less

Atomic force microscopy of atomic-scale ledges and etch pits formed during dissolution of quartz

NASA Technical Reports Server (NTRS)

Gratz, A. J.; Manne, S.; Hansma, P. K.

1991-01-01

The processes involved in the dissolution and growth of crystals are closely related. Atomic force microscopy (AFM) of faceted pits (called negative crystals) formed during quartz dissolution reveals subtle details of these underlying physical mechanisms for silicates. In imaging these surfaces, the AFM detected ledges less than 1 nm high that were spaced 10 to 90 nm apart. A dislocation pit, invisible to optical and scanning electron microscopy measurements and serving as a ledge source, was also imaged. These observations confirm the applicability of ledge-motion models to dissolution and growth of silicates; coupled with measurements of dissolution rate on facets, these methods provide a powerful tool for probing mineral surface kinetics.

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

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

In 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 paper is to study effects of these variables on three model waste glasses (SON68, ISG, AFCI). To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH(RT) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. The results from these tests were then used to parameterize a kinetic rate model based on transition state theory. Both the absolute dissolution rates andmore » the rate model parameters are compared with previous results. Discrepancies in the absolute dissolution rates as compared to those obtained using other test methods are discussed. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies. The results were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), which is capable of providing a robust uncertainty analysis. 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, the effect of glass composition on the rate parameter values could possibly be obtained. This would allow for the possibility of predicting the forward dissolution rate of glass based solely on composition« less

Process for liquefying carbonaceous materials of high molecular weight and for separating liquefaction products

DOEpatents

Malek, John M.

1977-01-01

Process characterized by comprising successively a dissolution zone fed with carbonaceous solids and with a solvent, a high pressure hydrogenation zone provided with a source of hydrogen, and a hydrogenation products separation zone, wherein the improvement consists mainly in chemical upgrading of the liquidform products derived from the separation zone, and recycling a part of the upgraded products to the dissolution zone, this recycled part being of either positively acidic or positively basic properties for enhancing the dissolution - decomposition of base-acid structures present in the carbonaceous solid feed.

The development of carbamazepine-succinic acid cocrystal tablet formulations with improved in vitro and in vivo performance.

PubMed

Ullah, Majeed; Hussain, Izhar; Sun, Changquan Calvin

2016-01-01

The use of soluble cocrystal for delivering drugs with low solubility, although a potentially effective approach, often suffers the problem of rapid disproportionation during dissolution, which negates the solubility advantages offered by the cocrystal. This necessitates their robust stabilization in order for successful use in a tablet dosage form. The cocrystal between carbamezepine and succinic acid (CBZ-SUC) exhibits a higher aqueous solubility than its dihydrate, which is the stable form of CBZ in water. Using this model system, we demonstrate an efficient and material-sparing tablet formulation screening approach enabled by intrinsic dissolution rate measurements. Three tablet formulations capable of stabilizing the cocrystal both under accelerated condition of 40 °C and 75% RH and during dissolution were developed using three different polymers, Soluplus® (F1), Kollidon VA/64 (F2) and Hydroxypropyl methyl cellulose acetate succinate (F3). When compared to a marketed product, Epitol® 200 mg tablets (F0), drug release after 60 min from formulations F1 (∼82%), F2 (∼95%) and F3 (∼95%) was all higher than that from Epitol® (79%) in a modified simulated intestinal fluid. Studies in albino rabbits show correspondingly better bioavailability of F1-F3 than Epitol.

Oxidation of platinum nickel nanowires to improve durability of oxygen-reducing electrocatalysts

DOE PAGES

Alia, Shaun M.; Pylypenko, Svitlana; Dameron, Arrelaine; ...

2016-01-12

In this study, the impact of heat treating platinum-coated nickel (Pt-Ni) nanowires in oxygen is examined to determine the effect on oxygen reduction (ORR) activity and durability. Pt-Ni nanowires exhibit promising ORR mass activities (3 times greater than Pt nanoparticles, 1.5 times greater than U.S. Department of Energy target) both before and after potential cycling for all but the highest annealing temperatures explored. The annealing of Pt-Ni nanowires in oxygen with increasing temperature is found to reduce surface area and ORR activity in comparison to the untreated material, but also reduces activity losses following durability testing. Following potential cycling, unannealedmore » Pt-Ni nanowires show significant losses in surface area (23%) and specific activity (18%) while Pt-Ni nanowires annealed at 200°C show modest increases in surface area (2%) and specific activity (6%) after potential cycling. Increasing annealing temperatures also show a clear trend of decreasing Ni dissolution rates. While oxygen annealing has shown the ability to improve durability of Pt-Ni nanowires, significant Ni dissolution was observed in all samples and suggests oxide passivation while showing promise for improved durability, when employed by itself is insufficient to prevent all contamination concerns involving Ni dissolution.« less

Net loss of CaCO3 from coral reef communities due to human induced seawater acidification

USGS Publications Warehouse

Andersson, A.J.; Kuffner, I.B.; MacKenzie, F.T.; Jokiel, P.L.; Rodgers, K.S.; Tan, A.

2009-01-01

Acidification of seawater owing to oceanic uptake of atmospheric CO2 originating from human activities such as burning of fossil fuels and land-use changes has raised serious concerns regarding its adverse effects on corals and calcifying communities. Here we demonstrate a net loss of calcium carbonate (CaCO3) material as a result of decreased calcification and increased carbonate dissolution from replicated subtropical coral reef communities (n=3) incubated in continuous-flow mesocosms subject to future seawater conditions. The calcifying community was dominated by the coral Montipora capitata. Daily average community calcification or Net Ecosystem Calcification (NEC=CaCO3 production – dissolution) was positive at 3.3 mmol CaCO3 m−2 h−1 under ambient seawater pCO2 conditions as opposed to negative at −0.04 mmol CaCO3 m−2h−1 under seawater conditions of double the ambient pCO2. These experimental results provide support for the conclusion that some net calcifying communities could become subject to net dissolution in response to anthropogenic ocean acidification within this century. Nevertheless, individual corals remained healthy, actively calcified (albeit slower than at present rates), and deposited significant amounts of CaCO3 under the prevailing experimental seawater conditions of elevated pCO2.

Net Loss of CaCO3 from a subtropical calcifying community due to seawater acidification: Mesocosm-scale experimental evidence

USGS Publications Warehouse

Andersson, A.J.; Kuffner, I.B.; MacKenzie, F.T.; Jokiel, P.L.; Rodgers, K.S.; Tan, A.

2009-01-01

Acidification of seawater owing to oceanic uptake of atmospheric CO 2 originating from human activities such as burning of fossil fuels and land-use changes has raised serious concerns regarding its adverse effects on corals and calcifying communities. Here we demonstrate a net loss of calcium carbonate (CaCO3) material as a result of decreased calcification and increased carbonate dissolution from replicated subtropical coral reef communities (N=3) incubated in continuous-flow mesocosms subject to future seawater conditions. The calcifying community was dominated by the coral Montipora capitata. Daily average community calcification or Net Ecosystem Calcification (NECC=CaCO3 production - dissolution) was positive at 3.3 mmol CaCO3 m-2 h-1 under ambient seawater pCO2 conditions as opposed to negative at -0.04 mmol CaCO3 m-2 h-1 under seawater conditions of double the ambient pCO2. These experimental results provide support for the conclusion that some net calcifying communities could become subject to net dissolution in response to anthropogenic ocean acidification within this century. Nevertheless, individual corals remained healthy, actively calcified (albeit slower than at present rates), and deposited significant amounts of CaCO3 under the prevailing experimental seawater conditions of elevated pCO2.

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

Functional assessment of four types of disintegrants and their effect on the spironolactone release properties.

PubMed

Rojas, John; Guisao, Santiago; Ruge, Vanesa

2012-12-01

Spironolactone is a drug derived from sterols that exhibits an incomplete oral absorption due to its low water solubility and slow dissolution rate. In this study, formulations of spironolactone with four disintegrants named as croscarmellose sodium, crospovidone, sodium starch glycolate and microcrystalline cellulose II (MCCII) were conducted. The effect of those disintegrants on the tensile strength, disintegration time and dissolution rate of spironolactone-based compacts was evaluated using a factorial design with three categorical factors (filler, lubricant, and disintegrant). The swelling values, water uptake and water sorption studies of these disintegrants all suggested that MCCII compacts disintegrate by a wicking mechanism similar to that of crospovidone, whereas a swelling mechanism was dominant for sodium starch glycolate and croscarmellose sodium. The disintegration time of MCCII and sodium starch glycolate remained unchanged with magnesium stearate. However, this lubricant delayed the disintegration time of crospovidone and croscarmellose sodium. MCCII presented the fastest disintegration time independent of the medium and lubricant employed. The water sorption ratio and swelling values determined sodium starch glycolate followed by croscarmellose sodium as the largest swelling materials, whereas crospovidone and MCCII where the least swelling disintegrants. The swelling property of sodium starch glycolate and croscarmellose sodium was strongly affected by the medium pH. The disintegration time of spironolactone compacts was faster when starch was used as a filler due to the formation of soft compacts. In this case, the type of filler employed rather than the disintegrant had a major effect on the disintegration and dissolution times of spironolactone.

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, 6907-6915, 2016

Chlorite, Biotite, Illite, Muscovite, and Feldspar Dissolution Kinetics at Variable pH and Temperatures up to 280 C

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

Carroll, S.; Smith, M.; Lammers, K.

2016-10-05

Summary Sheet silicates and clays are ubiquitous in geothermal environments. Their dissolution is of interest because this process contributes to scaling reactions along fluid pathways and alteration of fracture surfaces, which could affect reservoir permeability. In order to better predict the geochemical impacts on long-term performance of engineered geothermal systems, we have measured chlorite, biotite, illite, and muscovite dissolution and developed generalized kinetic rate laws that are applicable over an expanded range of solution pH and temperature for each mineral. This report summarizes the rate equations for layered silicates where data were lacking for geothermal systems.

The effect of polymorphism on powder compaction and dissolution properties of chemically equivalent oxytetracycline hydrochloride powders.

PubMed

Liebenberg, W; de Villiers, M M; Wurster, D E; Swanepoel, E; Dekker, T G; Lötter, A P

1999-09-01

In South Africa, oxytetracycline is identified as an essential drug; many generic products are on the market, and many more are being developed. In this study, six oxytetracycline hydrochloride powders were obtained randomly from manufacturers, and suppliers were compared. It was found that compliance to a pharmacopoeial monograph was insufficient to ensure the optimum dissolution performance of a simple tablet formulation. Comparative physicochemical raw material analysis showed no major differences with regard to differential scanning calorimetry (DSC), infrared (IR) spectroscopy, powder dissolution, and particle size. However, the samples could be divided into two distinct types with respect to X-ray powder diffraction (XRD) and thus polymorphism. The two polymorphic forms had different dissolution properties in water or 0.1 N hydrochloride acid. This difference became substantial when the dissolution from tablets was compared. The powders containing form A were less soluble than that containing form B.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

NASA Astrophysics Data System (ADS)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Evaluation of SLS: APG mixed surfactant systems as carrier for solid dispersion.

PubMed

Patel, Ashok R; Joshi, Vishal Y

2008-01-01

The present investigation aims at studying the effect of mixed surfactant system of sodium lauryl sulphate (SLS) and alkyl polyglucosides (C(10)APG, C(12)APG and C(12/14)APG) on dissolution rate enhancement of poorly water soluble drug. Aceclofenac--a non-steroidal anti-inflammatory agent was used as a model drug as it has limited water solubility. The influence of the surfactant concentration in various blends on dissolution rate of Solid Dispersion (SD), prepared using solution method with ethanol as the solvent was studied and the advantage of mixed surfactant systems over the individual surfactants was illustrated by differences in the in-vitro dissolution profiles of SD. Physico chemical evaluation (critical micellar concentration, zeta potential and beta-parameter calculations) was carried out to study the mixed surfactant systems. Solid mixtures were characterized by Infrared spectroscopy (FT-IR); X-ray diffraction studies (XRD) and scanning electron microscopy (SEM). It was seen that the dissolution rate of aceclofenac from SD increased with the increase in the APG proportion relative to SLS with the optimum ratio of 0.2 SLS:0.8 APG showing the best effect in all cases. Results obtained from physico-chemical evaluation (the decrease in the value of critical micelle concentration and higher negative value of beta-parameters) suggested the existence of synergism between surfactants blends. The observed results in the dissolution rate enhancement could be attributed to the drug--surfactant interactions as evident from FT-IR, SEM and XRD results.

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.

Mechanistic understanding of the link between Sodium Starch Glycolate properties and the performance of tablets made by wet granulation.

PubMed

Wren, S A C; Alhusban, F; Barry, A R; Hughes, L P

2017-08-30

The impact of varying Sodium Starch Glycolate (SSG) grade and wet granulation intensity on the mechanism of disintegration and dissolution of mannitol-based Immediate Release (IR) placebo tablets was investigated. MRI and 1 H NMR provided mechanistic insight, and revealed a four-fold range in both tablet disintegration and dissolution rates. MRI was used to quantify the rates of change in tablet volumes and the data fitted to a hydration/erosion model. Reduced levels of cross-linking change SSG from a swelling to a gelling matrix. The tablet hydration and dissolution rates are related to the viscosity at the tablet-solution interface, with high viscosities limiting mass transport. Copyright © 2017 Elsevier B.V. All rights reserved.

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

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 reaction kinetics should be acknowledged when using reactive transport models, especially when modeling kinetically controlled pH-buffering processes between a CO2 leakage an a receptor like a ground water well. Currently, further experiments for the determination of the dolomite dissolution kinetics are being performed. Here, the knowledge of the dissolution rate constants can be even more important compared to the (still) fast calcite dissolution. This study is being funded by the German Federal Ministry of Education and Research (BMBF), EnBW Energie Baden-Württemberg AG, E.ON Energie AG, E.ON Gas Storage AG, RWE Dea AG, Vattenfall Europe Technology Research GmbH, Wintershall Holding AG and Stadtwerke Kiel AG as part of the CO2-MoPa joint project in the framework of the Special Program GEOTECHNOLOGIEN. Literature Lasaga, A. C., 1984. Chemical Kinetics of Water-Rock Interactions. Journal of Geophysical Research 89, 4009-4025. Palandri, J. L. and Kharaka, Y. K., 2004. A compilation of rate parameters of water-mineral interaction kinetics for application to geochemical modeling. USGS, Menlo Park, CA, USA. v. Grinsven, J. J. M. and Riemsdijk, W. H., 1992. Evaluation of batch and column techniques to measure weathering rates in soils. Geoderma 52, 41-57.

In-vitro studies of enteric coated diclofenac sodium-carboxymethylcellulose microspheres.

PubMed

Arica, B; Arica, M Y; Kaş, H S; Hincal, A A; Hasirci, V

1996-01-01

MIcrospheres containing diclofenac sodium (DS) were prepared using carboxymethylcellulose (CMC) as the main support material (1.0, 2.0, 3.0% (w/v)) and aluminum chloride as the crosslinker. Drug to polymer ratios of 1:1, 1:2 and 1:4 were used to obtain a range of microspheres. The microspheres were then coated with an enteric coating material, Eudragit S-100, efficiency, % yield value, particle sizes an in-vitro dissolution behaviour were investigated. The surface of the enteric coated microspheres seemed to be all covered with Eudragit S-100 from scanning electron microscopy observation. It was also observed that increasing the CMC concentration led to an increase in the encapsulation efficiency, % yield value and particle size and decreased the release rate. Eudragit S-100 coating did not significantly alter the size but the release rate was significantly lower even when the lower concentration solution was used.

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.

Fenofibrate Nanocrystals Embedded in Oral Strip-Films for Bioavailability Enhancement

PubMed Central

Barvaliya, Manish; Zhang, Lu; Anovadiya, Ashish; Brahmbhatt, Harshad; Paul, Parimal; Tripathi, Chandrabhanu

2018-01-01

The aim of the present study was to make a fenofibrate (FNB) nanocrystal (NC) by wet media milling, characterizations and formulates into oral strip-films (OSFs). Mechanical properties, redispersion study, and solid-state characterizations results suggested that reduction of drug crystal size at nanoscale and incorporation into OSFs does not affect the solid-state properties of the drug. In vitro dissolution kinetics showed enhanced dissolution rate was easily manipulated by changing the thickness of the OSF. In situ UV-imaging was used to monitor drug dissolution qualitatively and quantitatively in real time. Results confirm that the intrinsic dissolution rates and surface drug concentration measured with this device were in agreement with the USP-IV dissolution profiles. In vivo pharmacokinetics in rabbits showed a significant difference in the pharmacokinetics parameter (1.4 fold increase bioavailability) of FNB NC-loaded OSFs as compared to the marketed formulation “Tricor” and as-received (pristine) drug. This approach of drug nanocrystallization and incorporation into OSFs may have significant applications in cost-effective tools for bioavailability enhancement of FNB. PMID:29438297

Dissolution characteristics of sericite in chalcopyrite bioleaching and its effect on copper extraction

NASA Astrophysics Data System (ADS)

Dong, Ying-bo; Li, Hao; Lin, Hai; Zhang, Yuan

2017-04-01

The effects of sericite particle size, rotation speed, and leaching temperature on sericite dissolution and copper extraction in a chalcopyrite bioleaching system were examined. Finer particles, appropriate temperature and rotation speed for Acidithiobacillus ferrooxidans resulted in a higher Al3+ dissolution concentration. The Al3+ dissolution concentration reached its highest concentration of 38.66 mg/L after 48-d leaching when the sericite particle size, temperature, and rotation speed were -43 μm, 30°C, and 160 r/min, respectively. Meanwhile, the sericite particle size, rotation speed, and temperature can affect copper extraction. The copper extraction rate is higher when the sericite particle size is finer. An appropriately high temperature is favorable for copper leaching. The dissolution of sericite fitted the shrinking core model, 1-(2/3) α-(1- α)2/3 = k 1 t, which indicates that internal diffusion is the decision step controlling the overall reaction rate in the leaching process. Scanning electron microscopy analysis showed small precipitates covered on the surface of sericite after leaching, which increased the diffusion resistance of the leaching solution and dissolved ions.

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 and were helpful in elucidating the mechanism of generation of amorphous nanodroplets.