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

A Quality by Design approach to investigate tablet dissolution shift upon accelerated stability by multivariate methods.

PubMed

Huang, Jun; Goolcharran, Chimanlall; Ghosh, Krishnendu

2011-05-01

This paper presents the use of experimental design, optimization and multivariate techniques to investigate root-cause of tablet dissolution shift (slow-down) upon stability and develop control strategies for a drug product during formulation and process development. The effectiveness and usefulness of these methodologies were demonstrated through two application examples. In both applications, dissolution slow-down was observed during a 4-week accelerated stability test under 51°C/75%RH storage condition. In Application I, an experimental design was carried out to evaluate the interactions and effects of the design factors on critical quality attribute (CQA) of dissolution upon stability. The design space was studied by design of experiment (DOE) and multivariate analysis to ensure desired dissolution profile and minimal dissolution shift upon stability. Multivariate techniques, such as multi-way principal component analysis (MPCA) of the entire dissolution profiles upon stability, were performed to reveal batch relationships and to evaluate the impact of design factors on dissolution. In Application II, an experiment was conducted to study the impact of varying tablet breaking force on dissolution upon stability utilizing MPCA. It was demonstrated that the use of multivariate methods, defined as Quality by Design (QbD) principles and tools in ICH-Q8 guidance, provides an effective means to achieve a greater understanding of tablet dissolution upon stability. Copyright © 2010 Elsevier B.V. All rights reserved.

The effect of fission-energy Xe ion irradiation on the structural integrity and dissolution of the CeO2 matrix

NASA Astrophysics Data System (ADS)

Popel, A. J.; Le Solliec, S.; Lampronti, G. I.; Day, J.; Petrov, P. K.; Farnan, I.

2017-02-01

This work considers the effect of fission fragment damage on the structural integrity and dissolution of the CeO2 matrix in water, as a simulant for the UO2 matrix of spent nuclear fuel. For this purpose, thin films of CeO2 on Si substrates were produced and irradiated by 92 MeV 129Xe23+ ions to a fluence of 4.8 × 1015 ions/cm2 to simulate fission damage that occurs within nuclear fuels along with bulk CeO2 samples. The irradiated and unirradiated samples were characterised and a static batch dissolution experiment was conducted to study the effect of the induced irradiation damage on dissolution of the CeO2 matrix. Complex restructuring took place in the irradiated films and the irradiated samples showed an increase in the amount of dissolved cerium, as compared to the corresponding unirradiated samples. Secondary phases were also observed on the surface of the irradiated CeO2 films after the dissolution experiment.

Development and validation of a discriminating in vitro dissolution method for a poorly soluble drug, olmesartan medoxomil: comparison between commercial tablets.

PubMed

Bajerski, Lisiane; Rossi, Rochele Cassanta; Dias, Carolina Lupi; Bergold, Ana Maria; Fröehlich, Pedro Eduardo

2010-06-01

A dissolution test for tablets containing 40 mg of olmesartan medoxomil (OLM) was developed and validated using both LC-UV and UV methods. After evaluation of the sink condition, dissolution medium, and stability of the drug, the method was validated using USP apparatus 2, 50 rpm rotation speed, and 900 ml of deaerated H(2)O + 0.5% sodium lauryl sulfate (w/v) at pH 6.8 (adjusted with 18% phosphoric acid) as the dissolution medium. The model-independent method using difference factor (f(1)) and similarity factor (f(2)), model-dependent method, and dissolution efficiency were employed to compare dissolution profiles. The kinetic parameters of drug release were also investigated. The obtained results provided adequate dissolution profiles. The developed dissolution test was validated according to international guidelines. Since there is no monograph for this drug in tablets, the dissolution method presented here can be used as a quality control test for OLM in this dosage form, especially in a batch to batch evaluation.

Experimental study of dissolution of minerals and CO2 sequestration in steel slag.

PubMed

Yadav, Shashikant; Mehra, Anurag

2017-06-01

This study strives to achieve a substantial amount of steel slag carbonation without using any harmful chemicals. For this purpose, experiments were performed in an aqueous medium, in a semi-batch reactor, to investigate the effect of varying reaction conditions during the steel slag CO 2 sequestration process. Further, studying the effect of dissolution on carbonation reactions and the mineralogical changes that subsequently occur within the slag helps provide insight into the parameters that ultimately have an impact on the carbonation rate as well the magnitude of the impact. Copyright © 2017 Elsevier Ltd. 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.

Effects of ammonium on uranium partitioning and kaolinite mineral dissolution.

PubMed

Emerson, Hilary P; Di Pietro, Silvina; Katsenovich, Yelena; Szecsody, Jim

2017-02-01

Ammonia gas injection is a promising technique for the remediation of uranium within the vadose zone. It can be used to manipulate the pH of a system and cause co-precipitation processes that are expected to remove uranium from the aqueous phase and decrease leaching from the solid phase. The work presented in this paper explores the effects of ammonium and sodium hydroxide on the partitioning of uranium and dissolution of the kaolinite mineral in simplified synthetic groundwaters using equilibrium batch sorption and sequential extraction experiments. It shows that there is a significant increase in uranium removal in systems with divalent cations present in the aqueous phase but not in sodium chloride synthetic groundwaters. Further, the initial conditions of the aqueous phase do not affect the dissolution of kaolinite. However, the type of base treatment does have an effect on mineral dissolution. Published by Elsevier Ltd.

Development of In Vitro-In Vivo Correlation for Amorphous Solid Dispersion Immediate-Release Suvorexant Tablets and Application to Clinically Relevant Dissolution Specifications and In-Process Controls.

PubMed

Kesisoglou, Filippos; Hermans, Andre; Neu, Colleen; Yee, Ka Lai; Palcza, John; Miller, Jessica

2015-09-01

Although in vitro-in vivo correlations (IVIVCs) are commonly pursued for modified-release products, there are limited reports of successful IVIVCs for immediate-release (IR) formulations. This manuscript details the development of a Multiple Level C IVIVC for the amorphous solid dispersion formulation of suvorexant, a BCS class II compound, and its application to establishing dissolution specifications and in-process controls. Four different 40 mg batches were manufactured at different tablet hardnesses to produce distinct dissolution profiles. These batches were evaluated in a relative bioavailability clinical study in healthy volunteers. Although no differences were observed for the total exposure (AUC) of the different batches, a clear relationship between dissolution and Cmax was observed. A validated Multiple Level C IVIVC against Cmax was developed for the 10, 15, 20, 30, and 45 min dissolution time points and the tablet disintegration time. The relationship established between tablet tensile strength and dissolution was subsequently used to inform suitable tablet hardness ranges within acceptable Cmax limits. This is the first published report for a validated Multiple Level C IVIVC for an IR solid dispersion formulation demonstrating how this approach can facilitate Quality by Design in formulation development and help toward clinically relevant specifications and in-process controls. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Hydrated calcareous oil-shale ash as potential filter media for phosphorus removal in constructed wetlands.

PubMed

Kaasik, Ago; Vohla, Christina; Mõtlep, Riho; Mander, Ulo; Kirsimäe, Kalle

2008-02-01

The P-retention in hydrated calcareous ash sediment from oil-shale burning thermal power plants in Estonia was studied. Batch experiments indicate good (up to 65 mg P g(-1)) P-binding capacity of the hydrated oil-shale ash sediment, with a removal effectiveness of 67-85%. The high phosphorus sorption potential of hydrated oil-shale ash is considered to be due to the high content of reactive Ca-minerals, of which ettringite Ca6Al2(SO4)3(OH)12.26H2O and portlandite Ca(OH)2 are the most important. The equilibrium dissolution of ettringite provides free calcium ions that act as stable nuclei for phosphate precipitation. The precipitation mechanism of phosphorus removal in hydrated ash plateau sediment is suggested by Ca-phosphate formation in batch experiments at different P-loadings. Treatment with a P-containing solution causes partial-to-complete dissolution of ettringite and portlandite, and precipitation of Ca-carbonate and Ca-phosphate phases, which was confirmed by X-ray diffraction (XRD) and scanning electron microscope (SEM)-EDS studies. Thus, the hydrated oil-shale ash sediment can be considered as a potential filtration material for P removal in constructed wetlands for wastewater treatment.

Quantifying Mass Transfer Processes in Groundwater as a Function of Molecular Structure Variation for Multicomponent NAPL Sources

NASA Astrophysics Data System (ADS)

Abbott, J. B., III; Tick, G. R.; Greenberg, R. R.; Carroll, K. C.

2017-12-01

The remediation of nonaqueous liquid (NAPL) contamination sources in groundwater has been shown to be challenging and have limited success in the field. The presence of multicomponent NAPL sources further complicates the remediation due to variability of mass-transfer (dissolution) behavior as a result of compositional and molecular structure variations between the different compounds within the NAPL phase. This study investigates the effects of the contaminant of concern (COC) composition and the bulk-NAPL components molecular structure (i.e. carbon chain length, aliphatic and aromatic) on dissolution and aqueous phase concentrations in groundwater. The specific COCs tested include trichloroethene (TCE), toluene (TOL), and perfluorooctanoic acid (PFOA). Each COC was tested in a series of binary batch experiments using insoluble bulk NAPL including n-hexane (HEX), n-decane (DEC), and n-hexadecane (HEXDEC). These equilibrium batch tests were performed to understand how different carbon-chain-length (NAPL) systems affect resulting COC aqueous phase concentrations. The experiments were conducted with four different COC mole fractions mixed within the bulk-NAPL derivatives (0.1:0.9, 0.05:0.95, 0.01:0.99, 0.001:0.999). Raoult's Law was used to assess the relative ideality of the mass transfer processes for each binary equilibrium dissolution experiment. Preliminary results indicate that as mole fraction of the COC decreases (composition effects), greater deviance from dissolution ideality occurs. It was also shown that greater variation in molecular structure (i.e. greater carbon chain length of bulk-NAPL with COC and aromatic COC presence) exhibited greater dissolution nonideality via Raoult's Law analysis. For instance, TOL (aromatic structure) showed greater nonideality than TCE (aliphatic structure) in the presence of the different bulk-NAPL derivatives (i.e. of various aliphatic carbon chains lengths). The results suggest that the prediction of aqueous phase concentration, from complex multicomponent NAPL sources, is highly dependent upon both composition and molecular structure variations of COC-NAPL mixtures, and such impacts should be taken into account when designing and evaluating a remediation strategy and/or predicting COC concentrations from a source zone region.

Dissolution and transport of insensitive munitions formulations IMX-101 and IMX-104 in saturated soil columns.

PubMed

Arthur, Jennifer D; Mark, Noah W; Taylor, Susan; Šimůnek, Jiří; Brusseau, Mark L; Dontsova, Katerina M

2018-05-15

Military training exercises can result in deposition of energetic residues on range soils, which ultimately can contaminate groundwater with munitions constituents. Column experiments followed by HYDRUS-1D modeling were conducted to evaluate dissolution and transport of energetic constituents from the new insensitive munitions (IM) formulations IMX-101, a mixture of 3-nitro-1,2,4-triazol-5-one (NTO), nitroguanidine (NQ), and 2, 4-dinitroanisole (DNAN), and IMX-104, a mixture of NTO, 1,3,5-hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and DNAN. NTO and DNAN are emerging contaminants associated with the development of insensitive munitions as replacements for traditional munitions. Flow interruption experiments were performed to investigate dissolution kinetics and sorption non-equilibrium between soil and solution phases. The results indicated that insensitive munitions compounds dissolved in order of their aqueous solubility, consistent with prior dissolution studies conducted in the absence of soil. Initial elution of the high concentration pulse of highly soluble NTO and NQ was followed by lower concentrations, while DNAN had generally lower and more constant concentrations in leachate. The sorption of NTO and NQ was low, while RDX, 1,3,5,7-octahydro-1,3,5,7-tetranitrotetrazocine (HMX, an impurity in technical grade RDX), and DNAN all exhibited appreciable sorption. DNAN transformation was observed, with formation of amino-reduction products 2-ANAN (2-amino-4-nitroanisole) and 4-ANAN (4-amino-2-nitroanisole). HYDRUS-1D model, incorporating one-dimensional advective-dispersive transport with particle dissolution and first-order solute transformation was used to simulate the measured breakthrough curves. Optimized dissolution parameters varied widely but were correlated between compounds in the same formulation. Determined adsorption coefficients generally agreed with values determined from batch and column studies conducted with pure NTO and DNAN, while mass-loss rate coefficients were in better agreement with ones from batch than column studies possibly due to suppression of microbial transformation during elution of high concentrations of explosives. Even in the low organic matter soils selected in this study DNAN experienced significant retardation and transformation, indicating potential for its natural attenuation. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

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

2015-06-16

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

Dissolution of steel slags in aqueous media.

PubMed

Yadav, Shashikant; Mehra, Anurag

2017-07-01

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

The impact of antibacterial handsoap constituents on the dynamics of triclosan dissolution from dry sand.

PubMed

Koehler, Daniel A; Strevett, Keith A; Papelis, Charalambos; Kibbey, Tohren C G

2017-11-01

Triclosan has been widely used as an antibacterial agent in consumer and industrial products, and large quantities continue to be discharged to natural waters annually. The focus of this work was on studying the dynamics of triclosan dissolution following evaporative drying. Warm weather can cause the water in intermittent streams or the unsaturated zone to evaporate, causing nonvolatile compounds to form solid precipitates. Because dissolution of precipitates is a relatively slow process, the dynamics of dissolution following evaporation may play an important role in controlling the release of contaminants to the environment. The specific purpose of the work was to explore the effects of surfactant co-contaminants from an industrial antibiotic handsoap on the dissolution dynamics of triclosan. The work used a fiber optic-based optical cell to conduct stirred-batch dissolution experiments for sands coated with different mass loadings of triclosan. Results show that the presence of surfactants from the hand soap not only increase the apparent equilibrium solubility, but also increase the rate of approach to equilibrium. A model describing the dissolution process was developed, and was found to be consistent with experimental data. Results of the work suggest that even small solubility enhancement by surfactant co-contaminants may have a significant impact on dissolution dynamics. Because waters containing significant quantities of triclosan are also among those most likely to contain surfactant co-contaminants, it is likely that the release of triclosan to the environment following evaporation may be faster in many cases than would be predicted from experiments based on pure triclosan. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Steel slag carbonation in a flow-through reactor system: the role of fluid-flux.

PubMed

Berryman, Eleanor J; Williams-Jones, Anthony E; Migdisov, Artashes A

2015-01-01

Steel production is currently the largest industrial source of atmospheric CO2. As annual steel production continues to grow, the need for effective methods of reducing its carbon footprint increases correspondingly. The carbonation of the calcium-bearing phases in steel slag generated during basic oxygen furnace (BOF) steel production, in particular its major constituent, larnite {Ca2SiO4}, which is a structural analogue of olivine {(MgFe)2SiO4}, the main mineral subjected to natural carbonation in peridotites, offers the potential to offset some of these emissions. However, the controls on the nature and efficiency of steel slag carbonation are yet to be completely understood. Experiments were conducted exposing steel slag grains to a CO2-H2O mixture in both batch and flow-through reactors to investigate the impact of temperature, fluid flux, and reaction gradient on the dissolution and carbonation of steel slag. The results of these experiments show that dissolution and carbonation of BOF steel slag are more efficient in a flow-through reactor than in the batch reactors used in most previous studies. Moreover, they show that fluid flux needs to be optimized in addition to grain size, pressure, and temperature, in order to maximize the efficiency of carbonation. Based on these results, a two-stage reactor consisting of a high and a low fluid-flux chamber is proposed for CO2 sequestration by steel slag carbonation, allowing dissolution of the slag and precipitation of calcium carbonate to occur within a single flow-through system. Copyright © 2014. Published by Elsevier B.V.

Mineral displacement and -dissolution processes and their relevance to rock porosity and permeability in Rotliegend sandstones of the Altmark natural gas field (central Germany) - results from CO2 laboratory batch experiments

NASA Astrophysics Data System (ADS)

Pudlo, Dieter; Enzmann, Frieder; Heister, Katja; Werner, Lars; Ganzer, Leonhard; Reitenbach, Viktor; Henkel, Steven; Albrecht, Daniel; Gaupp, Reinhard

2014-05-01

The Rotliegend reservoir sandstones of the Altmark area (central Germany) comprise the second largest natural gas field of Europe. These sandstones were deposited on a playa-like continental platform with braided river systems, ephemeral lakes and aeolian dunes under semi-arid conditions. Some of the pristine, red coloured deposits suffered intensive late diagenetic alteration and are now preserved as bleached, high porous and permeable sandstones. To evaluate the relevance of distinct fluids and their fluid-rock alteration reactions on such bleaching processes we performed laboratory static batch experiments on the Altmark sandstones. These 4-6 week lasting runs were conducted with CO2 saturated synthetic brines under typical Altmark reservoir conditions (p= 20 MPa, T= 125°C). Thereby mineralogical, petrophysical and (hydro- and geo-) chemical rock features were maintained prior and after the experiments. Chemical data proved the dissolution of carbonate and sulphate minerals during the runs, whereas the variation in abundance of further elements was within the detection limit of analytical accuracy. However, FE-SEM investigations on used, evaporated brines reveal the presence of illite and chlorite minerals within a matrix of Ca-, Si-, Fe, Al-, Na- and S components (carbonate, anhydrite, albite and Fe-(hydr-) oxides ?). By porosity and relative permeability measurements an increase in both rock features was observed after the runs, indicating that mineral dissolution and/or (clay) fine migration/detachment occurred during the experiments. Mineral dissolution, especially of pore-filling cements (e.g. carbonate-, sulphate minerals) is also deduced by BET analysis, in determining the specific surface of the sandstones. The size of these reactive surfaces increased after the experiments, suggesting that after the dissolution of pore-filling cements, formerly armoured grain rimming clay cutans were exposed to potential migrating fluids. These findings are also supported by µ-CT investigations. Here, the achieved 3D modelling data indicate an increase in reactive surface areas exposed to the pore space (which is in accord to the BET observations), as well as an enhancement in rock porosity and permeability after the runs. Moreover, these simulations showed that a remarkable mass (mineral) transfer was induced by the experiments, which led to a displacement of the porosity and permeability distribution in the sandstones and therefore a change in the fluid flow characteristics within the rocks - a parameter most important for every fluid-rock process. These observations are quite astonishing because they suggest that not only fluid velocity (e.g. during fluid flow experiments) might detach and transport grain rimming (clay) minerals, but also that physico-chemical reactions may enforce the release of such solids, even during almost static p-/T-/Xfluid conditions, as used in our experiments.

Retention of neodymium by dolomite at variable ionic strength as probed by batch and column experiments.

PubMed

Emerson, H P; Zengotita, F; Richmann, M; Katsenovich, Y; Reed, D T; Dittrich, T M

2018-10-01

The results presented in this paper highlight the complexity of adsorption and incorporation processes of Nd with dolomite and significantly improve upon previous work investigating trivalent actinide and lanthanide interactions with dolomite. Both batch and mini column experiments were conducted at variable ionic strength. These data highlight the strong chemisorption of Nd to the dolomite surface (equilibrium K d 's > 3000 mL/g) and suggest that equilibrium adsorption processes may not be affected by ionic strength based on similar results at 0.1 and 5.0 M ionic strength in column breakthrough and equilibrium batch (>5 days) results. Mini column experiments conducted over approximately one year also represent a significant development in measurement of sorption of Nd in the presence of flow as previous large-scale column experiments did not achieve breakthrough likely due to the high loading capacity of dolomite for Nd (up to 240 μg/g). Batch experiments in the absence of flow show that the rate of Nd removal increases with increasing ionic strength (up to 5.0 M) with greater removal at greater ionic strength for a 24 h sampling point. We suggest that the increasing ionic strength induces increased mineral dissolution and re-precipitation caused by changes in activity with ionic strength that lead to increased removal of Nd through co-precipitation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Kozeny-Carman permeability relationship with disintegration process predicted from early dissolution profiles of immediate release tablets.

PubMed

Kumari, Parveen; Rathi, Pooja; Kumar, Virender; Lal, Jatin; Kaur, Harmeet; Singh, Jasbir

2017-07-01

This study was oriented toward the disintegration profiling of the diclofenac sodium (DS) immediate-release (IR) tablets and development of its relationship with medium permeability k perm based on Kozeny-Carman equation. Batches (L1-L9) of DS IR tablets with different porosities and specific surface area were prepared at different compression forces and evaluated for porosity, in vitro dissolution and particle-size analysis of the disintegrated mass. The k perm was calculated from porosities and specific surface area, and disintegration profiles were predicted from the dissolution profiles of IR tablets by stripping/residual method. The disintegration profiles were subjected to exponential regression to find out the respective disintegration equations and rate constants k d . Batches L1 and L2 showed the fastest disintegration rates as evident from their bi-exponential equations while the rest of the batches L3-L9 exhibited the first order or mono-exponential disintegration kinetics. The 95% confidence interval (CI 95% ) revealed significant differences between k d values of different batches except L4 and L6. Similar results were also spotted for dissolution profiles of IR tablets by similarity (f 2 ) test. The final relationship between k d and k perm was found to be hyperbolic, signifying the initial effect of k perm on the disintegration rate. The results showed that disintegration profiling is possible because a relationship exists between k d and k perm . The later being relatable with porosity and specific surface area can be determined by nondestructive tests.

Method and apparatus for melting glass batch

DOEpatents

Fassbender, Alexander G.; Walkup, Paul C.; Mudge, Lyle K.

1988-01-01

A glass melting system involving preheating, precalcining, and prefluxing of batch materials prior to injection into a glass furnace. The precursors are heated by convection rather than by radiation in present furnaces. Upon injection into the furnace, batch materials are intimately coated with molten flux so as to undergo or at least begin the process of dissolution reaction prior to entering the melt pool.

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.

Reaction processes and permeability changes during CO2-rich brine flow through fractured Portland cement

NASA Astrophysics Data System (ADS)

Abdoulghafour, H.; Luquot, L.; Gouze, P.

2012-12-01

So far, cement alteration was principally studied experimentally using batch reactor (with static or renewed fluid). All exhibit similar carbonation mechanisms. The acidic solution, formed by the dissolution of the CO2 into the pore water or directly surrounding the cement sample, diffuses into the cement and induces dissolution reactions of the cement hydrates in particular portlandite and CSH. The calcium released by the dissolution of these calcium bearing phases combining with carbonate ions of the fluid forms calcium carbonates. The cement pH, initially around 13, falls to values where carbonate ion is the most dominant element (pH ~ 9), then CaCO3 phases can precipitate. These studies mainly associate carbonation process with a reduction of porosity and permeability. Indeed an increase of volume (about 10%) is expected during the formation of calcite from portlandite (equation 2) assuming a stoichiometric reaction. Here we investigated the cement alteration mechanisms in the frame of a controlled continuous renewal of CO2-rich fluid in a fracture. This situation is that expected when seepage is activated by the mechanical failure of the cement material that initially seals two layers of distinctly different pressure: the storage reservoir and the aquifer above the caprock, for instance. We study the effect of flow rates from quasi-static flow to higher flow rates for well-connected fractures. In the quasi-static case we observed an extensive conversion of portlandite (Ca(OH)2) to calcite in the vicinity of the fracture similar to that observed in the published batch experiments. Eventually, the fracture was almost totally healed. The experiments with constant flow revealed a different behaviour triggered by the continuous renewing of the reactants and withdrawal of reaction products. We showed that calcite precipitation is more efficient for low flow rate. With intermediate flow rate, we measured that permeability increases slowly at the beginning of the experiment and then remains constant due to calcite precipitation in replacement of CSH and CH into fracture border. With higher flow rate, we measured a constant permeability which can be explained by the development of a highly hydrated Si-rich zone which maintains the initial fracture aperture during all over the experiment while noticeable mass is released from the sample. These preliminary results emphasize that more complex behaviours than that envisaged from batch experiments may take place in the vicinity of flowing fractures. We demonstrated that if only micro-cracks appear in the cement well, carbonation reaction may heal these micro-cracks and mitigate leakage whereas conductive fractures allowing high flow may represent a risk of perennial leakage because the net carbonation process, including the calcite precipitation and its subsequent re-dissolution, is sufficiently to heal the fracture. However, the precipitation of Si-rich amorphous phases may maintain the initial fracture aperture and limit the leakage rate. Keywords: leakage, cement alteration, flow rate, fracture, permeability changes, reaction processes.

Fractured cement reactivity during CO2-rich brine leakage: Consequences on hydrodynamic and structural properties

NASA Astrophysics Data System (ADS)

abdelghafour, H.; Luquot, L.; Gouze, P.

2013-12-01

So far, cement alteration was principally studied experimentally using batch reactor (with static or renewed fluid). All exhibit similar carbonation mechanisms. The acidic solution, formed by the dissolution of the CO2 into the pore water or directly surrounding the cement sample, diffuses into the cement and induces dissolution reactions of the cement hydrates in particular portlandite and CSH. The calcium released by the dissolution of these calcium bearing phases combining with carbonate ions of the fluid forms calcium carbonates. The cement pH, initially around 13, falls to values where carbonate ion is the most dominant element (pH ~ 9), then CaCO3 phases can precipitate. These studies mainly associate carbonation process with a reduction of porosity and permeability. Indeed an increase of volume (about 10%) is expected during the formation of calcite from portlandite assuming a stoichiometric reaction. Here we investigated the cement alteration mechanisms in the frame of a controlled continuous renewal of CO2-rich fluid in a fracture. This situation is that expected when seepage is activated by the mechanical failure of the cement material that initially seals two layers of distinctly different pressure: the storage reservoir and the aquifer above the caprock, for instance. We study the effect of flow rates from quasi-static flow to higher flow rates for well-connected fractures. In the quasi-static case we observed an extensive conversion of portlandite (Ca(OH)2) to calcite in the vicinity of the fracture similar to that observed in the published batch experiments. Eventually, the fracture was almost totally healed. The experiments with constant flow revealed a different behavior triggered by the continuous renewing of the reactants and withdrawal of the reaction products. We showed that calcite precipitation is more efficient for low flow rate. With intermediate flow rate, we measured that permeability increases slowly at the beginning of the experiment and then remains constant due to calcite precipitation in replacement of CSH and CH into fracture border. With higher flow rate, we measured a constant permeability which can be explained by the development of a highly hydrated Si-rich zone which maintains the initial fracture aperture during all over the experiment while noticeable mass is released from the sample. These results emphasize that more complex behaviors than that envisaged from batch experiments may take place in the vicinity of flowing fractures. We demonstrated that if only micro-cracks appear in the cement well, carbonation reaction may heal these micro-cracks and mitigate leakage whereas conductive fractures allowing high flow may represent a risk of perennial leakage because the net carbonation process, including the calcite precipitation and its subsequent re-dissolution, is sufficiently to heal the fracture. However, the precipitation of Si-rich amorphous phases may maintain the initial fracture aperture and limit the leakage rate.

Improving the hardness of dry granulated tablets containing sodium lauryl sulfate.

PubMed

Moore, Francis; Okelo, Geoffrey; Colón, Ivelisse; Kushner, Joseph

2010-11-15

The impact of the addition of a wetting agent, the surfactant sodium lauryl sulfate (SLS), on the tablet hardness of a dry granulated, solid oral dosage form was investigated. In three batches, SLS was added concurrently with: (1) a poorly soluble, highly hydrophobic active pharmaceutical ingredient (API) and the other excipients prior to the initial blending step, (2) magnesium stearate prior to roller compaction, or (3) magnesium stearate prior to tableting. A fourth batch, which did not contain SLS, served as a control. The maximum hardness of 100 mg, 1/4″-SRC tablets for the four batches--SLS added initially, prior to roller compaction, prior to tableting, and no SLS--were 61±3, 71±3, 89±5, and 86±3N, respectively, suggesting reduced processing of SLS improves tablet hardness by ∼50%. Dissolution of the tablets in 900 ml of simulated gastric fluid with paddles at 75 rpm showed that: (1) there was no impact on the insertion point of SLS into the process on API dissolution, and (2) that the presence of SLS improved dissolution by 5% compared to the control tablets. Adding SLS just prior to tableting can improve tablet hardness and yield similar dissolution performance relative to SLS addition prior to the initial blending step. Copyright © 2010 Elsevier B.V. All rights reserved.

Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy.

PubMed

Fan, Jian-Xin; Wang, Yu-Jun; Liu, Cun; Wang, Li-Hua; Yang, Ke; Zhou, Dong-Mei; Li, Wei; Sparks, Donald L

2014-08-30

The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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

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

NASA Astrophysics Data System (ADS)

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

2018-07-01

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

Olivine Dissolution in Seawater: Implications for CO2 Sequestration through Enhanced Weathering in Coastal Environments

PubMed Central

2017-01-01

Enhanced weathering of (ultra)basic silicate rocks such as olivine-rich dunite has been proposed as a large-scale climate engineering approach. When implemented in coastal environments, olivine weathering is expected to increase seawater alkalinity, thus resulting in additional CO2 uptake from the atmosphere. However, the mechanisms of marine olivine weathering and its effect on seawater–carbonate chemistry remain poorly understood. Here, we present results from batch reaction experiments, in which forsteritic olivine was subjected to rotational agitation in different seawater media for periods of days to months. Olivine dissolution caused a significant increase in alkalinity of the seawater with a consequent DIC increase due to CO2 invasion, thus confirming viability of the basic concept of enhanced silicate weathering. However, our experiments also identified several important challenges with respect to the detailed quantification of the CO2 sequestration efficiency under field conditions, which include nonstoichiometric dissolution, potential pore water saturation in the seabed, and the potential occurrence of secondary reactions. Before enhanced weathering of olivine in coastal environments can be considered an option for realizing negative CO2 emissions for climate mitigation purposes, these aspects need further experimental assessment. PMID:28281750

Retardation of iron-cyanide complexes in the soil of a former manufactured gas plant site.

PubMed

Sut, Magdalena; Repmann, Frank; Raab, Thomas

2015-01-01

The soil in the vicinities of former Manufactured Gas Plant (MGP) sites is commonly contaminated with iron-cyanide complexes (ferric ferrocyanide). The phenomenon of cyanide mobility in soil, according to the literature, is mainly governed by the dissolution and precipitation of ferric ferrocyanide, which is only slightly soluble (<1 mg L(-1)) under acidic conditions. In this paper, retention properties of the sandy loam soil and the potential vertical movement of the solid iron-cyanide complexes, co-existing with the dissolution, sorption and precipitation reactions were investigated. Preliminary research conducted on a former MGP site implied colloidal transport of ferric ferricyanide from the initial deposition in the wastes layer towards the sandy loam material (secondary accumulation), which possibly retarded the mobility of cyanide (CN). A series of batch and column experiments were applied in order to investigate the retardation of iron-cyanide complexes by the sandy loam soil. Batch experiments revealed that in circumneutral pH conditions sandy loam material decreases the potassium ferro- and ferricyanide concentration. In column experiments a minor reduction in CN concentration was observed prior to addition of iron sulfide (FeS) layer, which induced the formation of the Prussian blue colloids in circumneutral pH conditions. Precipitated solid iron-cyanide complexes were mechanically filtered by the coherent structure of the investigated soil. Additionally, the reduction of the CN concentration of the percolation solutions by the sandy loam soil was presumably induced due to the formation of potassium manganese iron-cyanide (K2Mn[Fe(CN)6]).

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

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

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.

Laboratory Scale Experiments and Numerical Modeling of Cosolvent flushing of NAPL Mixtures in Saturated Porous Media

NASA Astrophysics Data System (ADS)

Agaoglu, B.; Scheytt, T. J.; Copty, N. K.

2011-12-01

This study examines the mechanistic processes governing multiphase flow of a water-cosolvent-NAPL system in saturated porous media. Laboratory batch and column flushing experiments were conducted to determine the equilibrium properties of pure NAPL and synthetically prepared NAPL mixtures as well as NAPL recovery mechanisms for different water-ethanol contents. The effect of contact time was investigated by considering different steady and intermittent flow velocities. A modified version of multiphase flow simulator (UTCHEM) was used to compare the multiphase model simulations with the column experiment results. The effect of employing different grid geometries (1D, 2D, 3D), heterogeneity and different initial NAPL saturation configurations were also examined in the model. It is shown that the change in velocity affects the mass transfer rate between phases as well as the ultimate NAPL recovery percentage. The experiments with slow flow rate flushing of pure NAPL and the 3D UTCHEM simulations gave similar effluent concentrations and NAPL cumulative recoveries. The results were less consistent for fast non-equilibrium flow conditions. The dissolution process from the NAPL mixture into the water-ethanol flushing solutions was found to be more complex than dissolution expressions incorporated in the numerical model. The dissolution rate of individual organic compounds (namely Toluene and Benzene) from a mixture NAPL into the ethanol-water flushing solution is found not to correlate with their equilibrium solubility values.The implications of this controlled experimental and modeling study on field cosolvent remediation applications are discussed.

Pattern of elemental release during the granite dissolution can be changed by aerobic heterotrophic bacterial strains isolated from Damma Glacier (central Alps) deglaciated granite sand.

PubMed

Lapanje, Aleš; Wimmersberger, Celine; Furrer, Gerhard; Brunner, Ivano; Frey, Beat

2012-05-01

Colonisation and weathering of freshly deglaciated granite are key processes in initial soil formation and development. We have obtained 438 isolates from granite sand covering glacial toe, 284 isolates at 22°C and 154 at 4°C incubation temperatures, respectively, to obtain cultures for the investigation of their weathering capabilities under laboratory conditions. The isolation of bacteria from granite sand was performed on rich-, intermediate- and low-nutrient-content solid media. Isolates were identified by 16S rRNA gene sequencing. According to the genera-associated weathering capabilities described in the literature and according to their abundance in our culture collection, we selected eight strains to analyse their effects on the weathering dynamics of granite sand during the batch culture experiment. Analysis of culturable bacteria showed higher species richness among isolates from 22°C than from 4°C incubations. In the R2A and 1/100 Ravan media, we observed the highest species richness of isolates obtained at 22°C and 4°C incubation temperatures, respectively. The obtained 16S rRNA sequences revealed the presence of alpha-, beta- and gamma-proteobacteria, Firmicutes, Actinobacteria and Bacteroidetes. The most numerous group of isolates was distantly related to Collimonas representatives, and according to the sequences of the 16S rRNA genes, they can form a new genus. Isolates from this group had the capability of causing increased dissolution rates for Fe, W, Ni and Rb. In general, at each sampling during the 30-day experiment, every strain showed a unique weathering profile resulting from differential rates of the dissolution and the precipitation of different minerals in the batch culture. Consequently, the presence of different strains, their growth stage and changes in proportions of strains in the bacterial community can affect further soil development and the successive colonisation by plants.

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.

Unraveling the Fate and Transport of SrEDTA-2 and Sr+2 in Hanford Sediments

NASA Astrophysics Data System (ADS)

Pace, M. N.; Mayes, M. A.; Jardine, P. M.; Mehlhorn, T. L.; Liu, Q. G.; Yin, X. L.

2004-12-01

Accelerated migration of strontium-90 has been observed in the vadose zone beneath the Hanford tank farm. The goal of this paper is to provide an improved understanding of the hydrogeochemical processes that contribute to strontium transport in the far-field Hanford vadose zone. Laboratory scale batch, saturated packed column experiments, and an unsaturated transport experiment in an undisturbed core were conducted to quantify geochemical and hydrological processes controlling Sr+2 and SrEDTA-2 sorption to Hanford flood deposits. After experimentation, the undisturbed core was disassembled and samples were collected from different bedding units as a function of depth. Sequential extractions were then performed on the samples. It has been suggested that organic chelates such as EDTA may be responsible for the accelerated transport of strontium due to the formation of stable anionic complexes. Duplicate batch and column experiments performed with Sr+2 and SrEDTA-2 suggested that the SrEDTA-2 complex was not stable in the presence of soil and rapid dissociation allowed strontium to be transported as a divalent cation. Batch experiments indicated a decrease in sorption with increasing rock:water ratios, whereas saturated packed column experiments indicated equal retardation in columns of different lengths. This difference between the batch and column experiments is primarily due to the difference between equilibrium conditions where dissolution of cations may compete for sorption sites versus flowing conditions where any dissolved cations are flushed through the system minimizing competition for sorption sites. Unsaturated transport in the undisturbed core resulted in significant Sr+2 retardation despite the presence of physical nonequilibrium. Core disassembly and sequential extractions revealed the mass wetness distribution and reactive mineral phases associated with strontium in the core. Overall, results indicated that strontium will most likely be transported through the Hanford far-field vadose zone as a divalent cation.

Testing of the Defense Waste Processing Facility Cold Chemical Dissolution Method in Sludge Batch 9 Qualification

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

Edwards, T.; Pareizs, J.; Coleman, C.

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) tests the applicability of the digestion methods used by the DWPF Laboratory for elemental analysis of Sludge Receipt and Adjustment Tank (SRAT) Receipt samples and SRAT Product process control samples. DWPF SRAT samples are typically dissolved using a method referred to as the DWPF Cold Chemical or Cold Chem Method (CC), (see DWPF Procedure SW4- 15.201). Testing indicates that the CC method produced mixed results. The CC method did not result in complete dissolution of either the SRAT Receipt ormore » SRAT Product with some fine, dark solids remaining. However, elemental analyses did not reveal extreme biases for the major elements in the sludge when compared with analyses obtained following dissolution by hot aqua regia (AR) or sodium peroxide fusion (PF) methods. The CC elemental analyses agreed with the AR and PF methods well enough that it should be adequate for routine process control analyses in the DWPF after much more extensive side-by-side tests of the CC method and the PF method are performed on the first 10 SRAT cycles of the Sludge Batch 9 (SB9) campaign. The DWPF Laboratory should continue with their plans for further tests of the CC method during these 10 SRAT cycles.« less

The combined effect of wet granulation process parameters and dried granule moisture content on tablet quality attributes.

PubMed

Gabbott, Ian P; Al Husban, Farhan; Reynolds, Gavin K

2016-09-01

A pharmaceutical compound was used to study the effect of batch wet granulation process parameters in combination with the residual moisture content remaining after drying on granule and tablet quality attributes. The effect of three batch wet granulation process parameters was evaluated using a multivariate experimental design, with a novel constrained design space. Batches were characterised for moisture content, granule density, crushing strength, porosity, disintegration time and dissolution. Mechanisms of the effect of the process parameters on the granule and tablet quality attributes are proposed. Water quantity added during granulation showed a significant effect on granule density and tablet dissolution rate. Mixing time showed a significant effect on tablet crushing strength, and mixing speed showed a significant effect on the distribution of tablet crushing strengths obtained. The residual moisture content remaining after granule drying showed a significant effect on tablet crushing strength. The effect of moisture on tablet tensile strength has been reported before, but not in combination with granulation parameters and granule properties, and the impact on tablet dissolution was not assessed. Correlations between the energy input during granulation, the density of granules produced, and the quality attributes of the final tablets were also identified. Understanding the impact of the granulation and drying process parameters on granule and tablet properties provides a basis for process optimisation and scaling. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of Calcium on Microbial Reduction of Solid Phase Uranium (VI)

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

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M.

2007-06-27

The effect of calcium on microbial reduction of a solid phase U(VI), sodium boltwoodite (NaUO2SiO3OH ∙1.5H2O), was evaluated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. Batch experiments were performed in a non-growth bicarbonate medium with lactate as electron donor at pH 7 buffered with PIPES. Calcium increased both the rate and extent of Na-boltwoodite dissolution 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) revealed that microbial reductionmore » of solid phase U(VI) is 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. The overall rates of microbial reduction of solid phase U(VI) can be described by the coupled rates of dissolution and microbial reduction that were both influenced by calcium. The results demonstrated that dissolved U(VI) concentration during microbial reduction was a complex function of solid phase U(VI) dissolution kinetics, aqueous U(VI) speciation, and microbial activity.« less

Short-time dissolution mechanisms of kaolinitic tropical soils

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

Malengreau, N.; Sposito, Garrison

1996-03-01

Previous research on the short-time dissolution behavior of kaolinitic Oxisols suggested pH-dependent kinetics involving ligand-promoted dissolution, metal readsorption, and colloidal dispersion, with soil organic matter conjectured to play a decisive role. A novel combination of spectroscopy, lightscattering, and batch dissolution experiments, conducted at controlled pH and ionic strength over five dissolution periods ranging from 1 to 12 h, was applied to evaluate this mechanism for samples of a representative kaolinitic Oxisol; collected at both forested and cultivated field sites (leading to significant differences in organic matter content and field soil pH). The overall characteristics of the pH-dependent net release kineticsmore » of Al, Fe, and Si by the soil samples, for any dissolution period in the range investigated, were determined by the pH value at which colloid dispersion commenced, which decreased significantly as the soil organic matter content increased. Plots of log(Si/Al released) (or Si/Fe released) vs. -log [H+] ([H+] is proton concentration) were superimposable for all dissolution periods studied, rising to a plateau value above the point of zero net charge of the soils (pH 3.2). Light-scattering and X-ray diffraction data showed conclusively that this plateau represented the release of siliceous colloids containing kaolinite and X-ray amorphous material. X-ray diffraction, UV-visible diffuse reflectance spectroscopy, and electron spin resonance spectroscopy, applied to the soil samples before and after dissolution, and after conventional chemical extractions to remove Al, C, Fe, and Si, showed that kaolinite and iron oxide phases (the latter being highly Al-substituted and present in both coatings and occlusions) were essentially unaltered by dissolution, even at -log [H+] = 2, whereas substantial dissolution loss of soil quartz occurred. Diffuse reflectance spectroscopy gave strong evidence that C in these soils occurs principally in discrete solid phases, not as a reactive coating on mineral surfaces.« less

Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

PubMed

Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

2017-02-15

Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

The influence of citrate and oxalate on 99TcVII, Cs, NpV and UVI sorption to a Savannah River Site soil.

PubMed

Montgomery, D; Barber, K; Edayilam, N; Oqujiuba, K; Young, S; Biotidara, T; Gathers, A; Danjaji, M; Tharayil, N; Martinez, N; Powell, B

2017-06-01

Batch sorption experiments were conducted with 0.5-50 ppb 99 Tc, 133 Cs, 237 Np and U in the presence and absence of citrate and/or oxalate in a 25 g/L Savannah River Site (SRS) soil suspension. Citrate and oxalate were the ligands of choice due to their relevancy to plant exudates, the nuclides were selected for their wide range of biogeochemical behavior, and the soil from SRS was selected as a model Department of Energy (DOE) site soil. Batch samples were continually mixed on a rotary shaker and maintained at a pH of approximately 5. Analysis via ICP-MS indicated that sorption of 237 Np increased with ligand concentration compared to baseline studies, as did sorption of 99 Tc although to a lesser extent. The increased sorption of 237 Np is proposed to be due to a combination of factors that are dependent on the ligand(s) present in the specific system including, ligand dissolution of the soil by citrate and formation of tertiary soil-oxalate-Np complexes. The increased 99 Tc sorption is attributed to the dissolution of the soil by the ligands, leading to an increase in the number of available sorption sites for 99 Tc. Uranium sorption decreased and dissolution of native uranium was also observed with increasing ligand concentration, thought to be a result of the formation of strong U-ligand complexes remaining in the aqueous phase. The majority of these effects were observed at the highest ligand concentrations of 50 mg C /L. No notable changes were observed for the 133 Cs system which is ascribed to the minimal interaction of Cs + with these organic ligands. Copyright © 2017 Elsevier Ltd. All rights reserved.

Non-destructive Determination of Disintegration Time and Dissolution in Immediate Release Tablets by Terahertz Transmission Measurements.

PubMed

Markl, Daniel; Sauerwein, Johanna; Goodwin, Daniel J; van den Ban, Sander; Zeitler, J Axel

2017-05-01

The aim of this study was to establish the suitability of terahertz (THz) transmission measurements to accurately measure and predict the critical quality attributes of disintegration time and the amount of active pharmaceutical ingredient (API) dissolved after 15, 20 and 25 min for commercial tablets processed at production scale. Samples of 18 batches of biconvex tablets from a production-scale design of experiments study into exploring the design space of a commercial tablet manufacturing process were used. The tablet production involved the process steps of high-shear wet granulation, fluid-bed drying and subsequent compaction. The 18 batches were produced using a 4 factor split plot design to study the effects of process changes on the disintegration time. Non-destructive and contactless terahertz transmission measurements of the whole tablets without prior sample preparation were performed to measure the effective refractive index and absorption coefficient of 6 tablets per batch. The disintegration time (R 2  = 0.86) and API dissolved after 15 min (R 2  = 0.96) linearly correlates with the effective refractive index, n eff , measured at terahertz frequencies. In contrast, no such correlation could be established from conventional hardness measurements. The magnitude of n eff represents the optical density of the sample and thus it reflects both changes in tablet porosity as well as granule density. For the absorption coefficient, α eff , we observed a better correlation with dissolution after 20 min (R 2  = 0.96) and a weaker correlation with disintegration (R 2  = 0.83) compared to n eff . The measurements of n eff and α eff provide promising predictors for the disintegration and dissolution time of tablets. The high penetration power of terahertz radiation makes it possible to sample a significant volume proportion of a tablet without any prior sample preparation. Together with the short measurement time (seconds), the potential to measure content uniformity and the fact that the method requires no chemometric models this technology shows clear promise to be established as a process analyser to non-destructively predict critical quality attributes of tablets.

Laboratory batch experiments and geochemical modelling of water-rock-supercritical CO2 reactions in Southern San Joaquin Valley, California oil field sediments: Implications for future carbon capture and sequestration projects.

NASA Astrophysics Data System (ADS)

Mickler, P. J.; Rivas, C.; Freeman, S.; Tan, T. W.; Baron, D.; Horton, R. A.

2015-12-01

Storage of CO2 as supercritical liquid in oil reservoirs has been proposed for enhanced oil recovery and a way to lower atmospheric CO2 levels. The fate of CO2 after injection requires an understanding of mineral dissolution/precipitation reactions occurring between the formation minerals and the existing formation brines at formation temperatures and pressures in the presence of supercritical CO2. In this study, core samples from three potential storage formations, the Vedder Fm. (Rio Bravo oil field), Stevens Fm. (Elk Hills oil field) and Temblor Fm. (McKittrick oil field) were reacted with a synthetic brine and CO2(sc) at reservoir temperature (110°C) and pressure (245-250 bar). A combination of petrographic, SEM-EDS and XRD analyses, brine chemistry, and PHREEQ-C modelling were used to identify geochemical reactions altering aquifer mineralogy. XRD and petrographic analyses identified potentially reactive minerals including calcite and dolomite (~2%), pyrite (~1%), and feldspars (~25-60%). Despite the low abundance, calcite dissolution and pyrite oxidation were dominant geochemical reactions. Feldspar weathering produced release rates ~1-2 orders of magnitude slower than calcite dissolution. Calcite dissolution increased the aqueous concentrations of Ca, HCO3, Mg, Mn and Sr. Silicate weathering increased the aqueous concentrations of Si and K. Plagioclase weathering likely increased aqueous Ca concentrations. Pyrite oxidation, despite attempts to remove O2 from the experiment, increased the aqueous concentration of Fe and SO4. SEM-EDS analysis of post-reaction samples identified mixed-layered illite-smectites associated with feldspar grains suggesting clay mineral precipitation in addition to calcite, pyrite and feldspar dissolution. The Vedder Fm. sample underwent complete disaggregation during the reaction due to cement dissolution. This may adversely affect Vedder Formation CCS projects by impacting injection well integrity.

Fertilizers mobilization in alluvial aquifer: laboratory experiments

NASA Astrophysics Data System (ADS)

Mastrocicco, M.; Colombani, N.; Palpacelli, S.

2009-02-01

In alluvial plains, intensive farming with conspicuous use of agrochemicals, can cause land pollution and groundwater contamination. In central Po River plain, paleo-channels are important links between arable lands and the underlaying aquifer, since the latter is often confined by clay sediments that act as a barrier against contaminants migration. Therefore, paleo-channels are recharge zones of particular interest that have to be protected from pollution as they are commonly used for water supply. This paper focuses on fertilizer mobilization next to a sand pit excavated in a paleo-channel near Ferrara (Italy). The problem is approached via batch test leaking and columns elution of alluvial sediments. Results from batch experiments showed fast increase in all major cations and anions, suggesting equilibrium control of dissolution reactions, limited availability of solid phases and geochemical homogeneity of samples. In column experiments, early elution and tailing of all ions breakthrough was recorded due to preferential flow paths. For sediments investigated in this study, dispersion, dilution and chemical reactions can reduce fertilizers at concentration below drinking standards in a reasonable time frame, provided fertilizer loading is halted or, at least, reduced. Thus, the definition of a corridor along paleo-channels is recommended to preserve groundwater quality.

Fayalite Dissolution and Siderite Formation in Water-Saturated Supercritical CO2

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

Qafoku, Odeta; Kovarik, Libor; Kukkadapu, Ravi K.

2012-11-25

Olivines, a significant constituent of basaltic rocks, have the potential to immobilize permanently CO2 after it is injected in the deep subsurface, due to carbonation reactions occurring between CO2 and the host rock. To investigate the reactions of fayalitic olivine with supercritical CO2 (scCO2) and formation of mineral carbonates, experiments were conducted at temperatures of 35 °C to 80 °C, 90 atm pressure and anoxic conditions. For every temperature, the dissolution of fayalite was examined both in the presence of liquid water and H2O-saturated scCO2. The experiments were conducted in a high pressure batch reactor at reaction time extending upmore » to 85 days. The newly formed products were characterized using a comprehensive suite of bulk and surface characterization techniques X-ray diffraction, Transmission/Emission Mössbauer Spectroscopy, Scanning Electron Microscopy coupled with Focused Ion Beam, and High Resolution Transmission Electron Microscopy. Siderite with rhombohedral morphology was formed at 35 °C, 50 °C, and 80 °C in the presence of liquid water and scCO2. In H2O-saturated scCO2, the formation of siderite was confirmed only at high temperature (80 °C). Characterization of reacted samples in H2O-saturated scCO2 with high resolution TEM indicated that siderite formation initiated inside voids created during the initial steps of fayalite dissolution. Later stages of fayalite dissolution result in the formation of siderite in layered vertical structures, columns or pyramids with a rhombus base morphology.« less

Arsenic mobilization and immobilization in paddy soils

NASA Astrophysics Data System (ADS)

Kappler, A.; Hohmann, C.; Zhu, Y. G.; Morin, G.

2010-05-01

Arsenic is oftentimes of geogenic origin and in many cases bound to iron(III) minerals. Iron(III)-reducing bacteria can harvest energy by coupling the oxidation of organic or inorganic electron donors to the reduction of Fe(III). This process leads either to dissolution of Fe(III)-containing minerals and thus to a release of the arsenic into the environment or to secondary Fe-mineral formation and immobilisation of arsenic. Additionally, aerobic and anaerobic iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation at neutral pH that is usually followed by iron(III) mineral precipitation. We are currently investigating arsenic immobilization by Fe(III)-reducing bacteria and arsenic co-precipitation and immobilization by anaerobic iron(II)-oxidizing bacteria in batch, microcosm and rice pot experiments. Co-precipitation batch experiments with pure cultures of nitrate-dependent Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation, to identify the minerals formed and to analyze the arsenic binding environment in the precipitates. Microcosm and rice pot experiments are set-up with arsenic-contaminated rice paddy soil. The microorganisms (either the native microbial population or the soil amended with the nitrate-dependent iron(II)-oxidizing Acidovorax sp. strain BoFeN1) are stimulated either with iron(II), nitrate, or oxygen. Dissolved and solid-phase arsenic and iron are quantified. Iron and arsenic speciation and redox state in batch and microcosm experiments are determined by LC-ICP-MS and synchrotron-based methods (EXAFS, XANES).

Continuous processing of recombinant proteins: Integration of inclusion body solubilization and refolding using simulated moving bed size exclusion chromatography with buffer recycling.

PubMed

Wellhoefer, Martin; Sprinzl, Wolfgang; Hahn, Rainer; Jungbauer, Alois

2013-12-06

An integrated process which combines continuous inclusion body dissolution with NaOH and continuous matrix-assisted refolding based on closed-loop simulated moving bed size exclusion chromatography was designed and experimentally evaluated at laboratory scale. Inclusion bodies from N(pro) fusion pep6His and N(pro) fusion MCP1 from high cell density fermentation were continuously dissolved with NaOH, filtered and mixed with concentrated refolding buffer prior to refolding by size exclusion chromatography (SEC). This process enabled an isocratic operation of the simulated moving bed (SMB) system with a closed-loop set-up with refolding buffer as the desorbent buffer and buffer recycling by concentrating the raffinate using tangential flow filtration. With this continuous refolding process, we increased the refolding and cleavage yield of both model proteins by 10% compared to batch dilution refolding. Furthermore, more than 99% of the refolding buffer of the raffinate could be recycled which reduced the buffer consumption significantly. Based on the actual refolding data, we compared throughput, productivity, and buffer consumption between two batch dilution refolding processes - one using urea for IB dissolution, the other one using NaOH for IB dissolution - and our continuous refolding process. The higher complexity of the continuous refolding process was rewarded with higher throughput and productivity as well as significantly lower buffer consumption compared to the batch dilution refolding processes. Copyright © 2013 Elsevier B.V. All rights reserved.

Interdisciplinary Research to Elucidate Mechanisms Governing Silver Nanoparticle Fate and Transport in Porous Media

NASA Astrophysics Data System (ADS)

Pennell, K. D.; Mittleman, A.; Taghavy, A.; Fortner, J.; Lantagne, D.; Abriola, L. M.

2014-12-01

Interdisciplinary Research to Elucidate Mechanisms Governing Silver Nanoparticle Fate and Transport in Porous Media Anjuliee M. Mittelman, Amir Taghavy, Yonggang Wang, John D. Fortner, Daniele S. Lantagne, Linda M. Abriola and Kurt D. Pennell* Detailed knowledge of the processes governing nanoparticle transport and reactivity in porous media is essential for accurate predictions of environmental fate, water and wastewater treatment system performance, and assessment of potential risks to ecosystems and water supplies. To address these issues, an interdisciplinary research team combined experimental and mathematical modeling studies to investigate the mobility, dissolution, and aging of silver nanoparticles (nAg) in representative aquifer materials and ceramic filters. Results of one-dimensional column studies, conducted with water-saturated sands maintained at pH 4 or 7 and three levels of dissolved oxygen (DO), revealed that fraction of silver mass eluted as Ag+ increased with increasing DO level, and that the dissolution of attached nAg decreased over time as a result of surface oxidation. A hybrid Eulerain-Lagragian nanoparticle transport model, which incorporates DO-dependent dissolution kinetics and particle aging, was able to accurately simulate nAg mobility and Ag+ release measured in the column experiments. Model sensitivity analysis indicated that as the flow velocity and particle size decrease, nAg dissolution and Ag+ transport processes increasingly govern silver mobility. Consistent results were obtained in studies of ceramic water filters treated with nAg, where silver elution was shown to be governed by nAg dissolution to form Ag+ and subsequent cation exchange reactions. Recent studies explored the effects of surface coating aging on nAg aggregation, mobility and dissolution. Following ultraviolet light, nAg retention in water saturated sand increased by 25-50%, while up to 50% of the applied mass eluted as Ag+ compared to less than 1% for un-aged nAg. In batch experiments, the addition of tert-butyl alcohol, a reactive oxygen species scavenger, reduced nAg aggregation and dissolution by up to 50%, indicating that free radical activity played an important role in the surface coating aging. Taken in concert, these findings demonstrate the value of undertaking

Interdisciplinary Research to Elucidate Mechanisms Governing Silver Nanoparticle Fate and Transport in Porous Media

NASA Astrophysics Data System (ADS)

Pennell, K. D.; Mittleman, A.; Taghavy, A.; Fortner, J.; Lantagne, D.; Abriola, L. M.

2015-12-01

Interdisciplinary Research to Elucidate Mechanisms Governing Silver Nanoparticle Fate and Transport in Porous Media Anjuliee M. Mittelman, Amir Taghavy, Yonggang Wang, John D. Fortner, Daniele S. Lantagne, Linda M. Abriola and Kurt D. Pennell* Detailed knowledge of the processes governing nanoparticle transport and reactivity in porous media is essential for accurate predictions of environmental fate, water and wastewater treatment system performance, and assessment of potential risks to ecosystems and water supplies. To address these issues, an interdisciplinary research team combined experimental and mathematical modeling studies to investigate the mobility, dissolution, and aging of silver nanoparticles (nAg) in representative aquifer materials and ceramic filters. Results of one-dimensional column studies, conducted with water-saturated sands maintained at pH 4 or 7 and three levels of dissolved oxygen (DO), revealed that fraction of silver mass eluted as Ag+ increased with increasing DO level, and that the dissolution of attached nAg decreased over time as a result of surface oxidation. A hybrid Eulerain-Lagragian nanoparticle transport model, which incorporates DO-dependent dissolution kinetics and particle aging, was able to accurately simulate nAg mobility and Ag+ release measured in the column experiments. Model sensitivity analysis indicated that as the flow velocity and particle size decrease, nAg dissolution and Ag+ transport processes increasingly govern silver mobility. Consistent results were obtained in studies of ceramic water filters treated with nAg, where silver elution was shown to be governed by nAg dissolution to form Ag+ and subsequent cation exchange reactions. Recent studies explored the effects of surface coating aging on nAg aggregation, mobility and dissolution. Following ultraviolet light, nAg retention in water saturated sand increased by 25-50%, while up to 50% of the applied mass eluted as Ag+ compared to less than 1% for un-aged nAg. In batch experiments, the addition of tert-butyl alcohol, a reactive oxygen species scavenger, reduced nAg aggregation and dissolution by up to 50%, indicating that free radical activity played an important role in the surface coating aging. Taken in concert, these findings demonstrate the value of undertaking

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.

Constraining Path-Dependent Processes During Basalt-CO2 Interactions with Observations From Flow-Through and Batch Experiments

NASA Astrophysics Data System (ADS)

Thomas, D.; Garing, C.; Zahasky, C.; Harrison, A. L.; Bird, D. K.; Benson, S. M.; Oelkers, E. H.; Maher, K.

2017-12-01

Predicting the timing and magnitude of CO2 storage in basaltic rocks relies partly on quantifying the dependence of reactivity on flow path and mineral distribution. Flow-through experiments that use intact cores are advantageous because the spatial heterogeneity of pore space and reactive phases is preserved. Combining aqueous geochemical analyses and petrologic characterization with non-destructive imaging techniques (e.g. micro-computed tomography) constrains the relationship between irreversible reactions, pore connectivity and accessible surface area. Our work enhances these capabilities by dynamically imaging flow through vesicular basalts with Positron Emission Tomography (PET) scanning. PET highlights the path a fluid takes by detecting photons produced during radioactive decay of an injected radiotracer (FDG). We have performed single-phase, CO2-saturated flow-through experiments with basaltic core from Iceland at CO2 sequestration conditions (50 °C; 76-90 bar Ptot). Constant flow rate and continuous pressure measurements at the inlet and outlet of the core constrain permeability. We monitor geochemical evolution through cation and anion analysis of outlet fluid sampled periodically. Before and after reaction, we perform PET scans and characterize the core using micro-CT. The PET scans indicate a discrete, localized flow path that appears to be a micro-crack connecting vesicles, suggesting that vesicle-lining minerals are immediately accessible and important reactants. Rapid increases in aqueous cation concentration, pH and HCO3- indicate that the rock reacts nearly immediately after CO2 injection. After 24 hours the solute release decreases, which may reflect a transition to reaction with phases with slower kinetic dissolution rates (e.g. zeolites and glasses to feldspar), a decrease in available reactive surface area or precipitation. We have performed batch experiments using crushed material of the same rock to elucidate the effect of flow path geometry and mineral accessibility on geochemical evolution. Interestingly, surface area-normalized dissolution rates as evinced by SiO2 release in all experiments approach similar values ( 10-15 mol/cm2/s). Our experiments show how imaging techniques are helpful in interpreting path-dependent processes in open systems.

Transport of barium through dolomite rocks under the presence of guar gum and brine salinities of hydraulic fracturing wastewater

NASA Astrophysics Data System (ADS)

Ebrahimi, P.; Vilcaez, J.

2017-12-01

Hydraulic fracturing wastewater (HFW) containing high concentrations of Ba, is commonly disposed into the deep saline aquifers. We investigate the effect of brine salinity, competing cations (Ca and Mg), and guar gum (most common fracturing viscosifier) on the sorption and transport of Ba through dolomite rocks. To this aim, we have conducted batch sorption and core-flooding experiments at both ambient (22°C) and deep subsurface (60°C) temperature conditions. The effect of mineral composition is assessed by comparing batch and core-flooding experimental results obtained with sandstone and dolomite rocks. Batch sorption experiments conducted using powdered dolomite rocks (500-600 µm particle size) revealed that Ba sorption on dolomite greatly decreases with increasing brine salinity (0 - 180,000 mg-NaCl/L), and that at brine salinities of HFW, chloro-complexation reactions between Ba and Cl ions and changes in pH (that results from dolomite dissolution) are the controlling factors of Ba sorption on dolomite. Organo-complexation reactions between Ba and guar gum, and competition of Ba with common cations (Ca and Mg) for hydration sites of dolomite, play a secondary role. This finding is in accordance with core-flooding experimental results, showing that the transport of Ba through synthetic dolomite rocks of high flow properties (25-29.6% porosity, 9.6-13.7 mD permeability), increases with increasing brine salinity (0-180,000 mg-NaCl/L), while the presence of guar gum (50-500 mg/L) does not affect the transport of Ba. On the other hand, core-flooding experiments conducted using natural dolomite core plugs (6.5-8.6% porosity, 0.06-0.3 mD permeability), indicates that guar gum can clog the pore throats of tight dolomite rocks retarding the transport of Ba. Results of our numerical simulation studies indicate that the mechanism of Ba sorption on dolomite can be represented by a sorption model that accounts for both surface complexation reactions on three distinct hydration sites (>CaOHo, >MgOHo, and >CO3Ho), and the kinetic dissolution of dolomite. The presented results are important in understanding the fate of heavy metals present in HFW disposed into deep saline aquifers.

Tomographic analysis of reactive flow induced pore structure changes in column experiments

NASA Astrophysics Data System (ADS)

Cai, Rong; Lindquist, W. Brent; Um, Wooyong; Jones, Keith W.

2009-09-01

We utilize synchrotron X-ray computed micro-tomography to capture and quantify snapshots in time of dissolution and secondary precipitation in the microstructure of Hanford sediments exposed to simulated caustic waste in flow-column experiments. The experiment is complicated somewhat as logistics dictated that the column spent significant amounts of time in a sealed state (acting as a batch reactor). Changes accompanying a net reduction in porosity of 4% were quantified including: (1) a 25% net decrease in pores resulting from a 38% loss in the number of pores <10-4mm in volume and a 13% increase in the number of pores of larger size; and (2) a 38% decrease in the number of throats. The loss of throats resulted in decreased coordination number for pores of all sizes and significant reduction in the number of pore pathways.

Coal fly ash interaction with environmental fluids: Geochemical and strontium isotope results from combined column and batch leaching experiments

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

Brubaker, Tonya M; Stewart, Brian W; Capo, Rosemary C

2013-05-01

The major element and Sr isotope systematics and geochemistry of coal fly ash and its interactions with environmental waters were investigated using laboratory flow-through column leaching experiments (sodium carbonate, acetic acid, nitric acid) and sequential batch leaching experiments (water, acetic acid, hydrochloric acid). Column leaching of Class F fly ash samples shows rapid release of most major elements early in the leaching procedure, suggesting an association of these elements with soluble and surface bound phases. Delayed release of certain elements (e.g., Al, Fe, Si) signals gradual dissolution of more resistant silicate or glass phases as leaching continues. Strontium isotope resultsmore » from both column and batch leaching experiments show a marked increase in {sup 87}Sr/{sup 86}Sr ratio with continued leaching, yielding a total range of values from 0.7107 to 0.7138. For comparison, the isotopic composition of fluid output from a fly ash impoundment in West Virginia falls in a narrow range around 0.7124. The experimental data suggest the presence of a more resistant, highly radiogenic silicate phase that survives the combustion process and is leached after the more soluble minerals are removed. Strontium isotopic homogenization of minerals in coal does not always occur during the combustion process, despite the high temperatures encountered in the boiler. Early-released Sr tends to be isotopically uniform; thus the Sr isotopic composition of fly ash could be distinguishable from other sources and is a useful tool for quantifying the possible contribution of fly ash leaching to the total dissolved load in natural surface and ground waters.« less

Ligand-controlled Fe mobilization catalyzed by adsorbed Fe(II) on Fe(hydr)oxides

NASA Astrophysics Data System (ADS)

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

2017-04-01

Dissolution of Fe(hydr)oxides is a key process in biological iron acquisition. Due to the low solubility of iron oxides in environments with a circumneutral pH, organisms may exude organic compounds catalyzing iron mobilization by reductive and ligand controlled dissolution mechanisms. Recently, we have shown synergistic effects between reductive dissolution and ligand-controlled dissolution that may operate in biological iron acquisition. The synergistic effects were observed in Fe mobilization from single goethite suspensions as well as in suspensions containing calcareous soil[1],[2]. However, how the redox reaction accelerates Fe(hydr)oxide dissolution by ligands is not studied intensively. In our study, we hypothesized that electron transfer to structural Fe(III) labilizes the Fe(hydr)oxide structure, and that this can accelerate ligand controlled dissolution. Systematical batch dissolution experiments were carried out under anoxic conditions at environmentally relevant pH values in which various Fe(hydr)oxides (goethite, hematite, lepidocrocite) interacted with two different types of ligand (desferrioxamine B (DFOB) and N,N'-Di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid monohydrochloride (HBED)). Electron transfer to the structure was induced by adsorbing Fe(II) to the mineral surface at various Fe(II) concentrations. Our results show a distinct catalytic effect of adsorbed Fe(II) on ligand controlled dissolution, even at submicromolar Fe(II) concentrations. We observed the effect for a range of iron oxides, but it was strongest in lepidocrocite, most likely due to anisotropy in conductivity leading to higher near-surface concentration of reduced iron. Our results demonstrate that the catalytic effect of reductive processes on ligand controlled dissolution require a very low degree of reduction making this an efficient process for biological iron acquisition and a potentially important effect in natural iron cycling. References 1. Wang, Z. M.; Schenkeveld, W. D. C.; Kraemer, S. M.; Giammar, D. E. Environ. Sci. Technol. 2015, 49, (12), 7236-7244. 2. Schenkeveld, W. D. C.; Wang, Z. M.; Giammar, D. E.; Kraemer, S. M. Environ. Sci. Technol. 2016, 50, (12), 6381-6388.

Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part II: Siderophore-promoted dissolution

NASA Astrophysics Data System (ADS)

Mikutta, Christian; Kretzschmar, Ruben

2008-02-01

Ferrihydrite (Fh) coprecipitated with exopolymers of plants and microbes may differ in its geochemical reactivity from its abiotic counterpart. We synthesized Fh in the presence and absence of acid polysaccharides (polygalacturonic acid (PGA), alginate, xanthan) and characterized the physical and structural properties of the precipitates formed [Mikutta C., Mikutta R., Bonneville S., Wagner F., Voegelin A., Christl I. and Kretzschmar R. (2008) Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part I: Characterization. Geochim. Cosmochim. Acta]. In this paper, we focus on the reactivity of PGA and alginate coprecipitates and pure Fh, and studied their interaction with the microbial siderophore desferrioxamine B (DFOB) in the presence and absence of low molecular weight organic (LMWO) acid anions (malate, citrate). Batch adsorption and dissolution experiments were performed in the dark at pH 7 in 10 mM NaClO 4 background electrolyte. In the dissolution experiments, different modes of ligand addition were applied (single, simultaneous, stepwise). With an estimated Langmuir sorption maximum of 15 mmol/mol Fe, a PGA coprecipitate with 11% C org sorbed about four times as much DFOB as pure Fh, and the amount of DFOB sorbed was ˜4-fold larger than estimated from the sum of DFOB sorption to pure Fh and PGA alone. The apparent initial dissolution rates, Rapp-initial, and pseudo-first order rate coefficients, k, of the coprecipitates exceeded those of pure Fh by up to two orders of magnitude. Citrate and malate exerted a strong synergistic effect on the DFOB-promoted dissolution of pure Fh, whereas synergistic effects of both anions were absent or negligible for the coprecipitates. Rapp-initial of the citrate and DFOB-promoted dissolution of PGA coprecipitates increased with increasing molar C/Fe ratio of the coprecipitates, independent of the charge of the LMWO ligand. Our results indicate that polyuronates stabilize Fh particles sterically and /or electrostatically, thus increasing the mineral surface area accessible to LMWO ligands. In contrast, pure Fh was coagulated at pH 7 (pH iep of Fh = 7.1), and hence only a small fraction of the Fh surface underwent dissolution. The increase in ligand-accessible surface area of Fh upon coprecipitation with acid polysaccharides seems to primarily control the kinetics of the ligand-promoted dissolution at neutral pH. In pH environments where the solubility of Fe(III) is very low, dissolution rates of Fe(III) (hydr)oxides in such coprecipitates may therefore exceed those of pure minerals by several orders of magnitude, despite a similar crystallinity of the minerals.

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.

A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

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

Chen Zhu; William E. Seyfried

2005-01-01

Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory-measured andmore » field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between lab and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO{sub 2} injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the first year of the project, we have successfully developed a sample preparation method and completed three batch feldspar dissolution experiments at 200 C and 300 bars. The changes of solution chemistry as dissolution experiments progressed were monitored with on-line sampling of the aqueous phase at the constant temperature and pressure. These data allow calculating overall apparent feldspar 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, and electron microprobe was used to characterize the reactants (feldspars before experiments). We experimented with different sample preparation methods for TEM study, and found excellent images and chemical resolution with reactants, which shows promise of the technology and establishes the baseline for comparison with products (feldspars after the experiments). Preliminary electron microscopic characterization shows that the reacted feldspars have etch pits and are covered with secondary sheet silicate phases. Reaction-path geochemical modeling is used to interpret the experimental results. We have established the software and database, and are making great progress. Also during the first year, our education goal of graduate student training has been achieved. 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 second and third year. A Ph. D. student at University of Minnesota is progressing well in conducting the experiments, and is near graduation. With the success of training of graduate students and excellent experimental data in the first year, we anticipate a more fruitful year in the second year.« less

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.

Biopharmaceutic Risk Assessment of Brand and Generic Lamotrigine Tablets.

PubMed

Vaithianathan, Soundarya; Raman, Siddarth; Jiang, Wenlei; Ting, Tricia Y; Kane, Maureen A; Polli, James E

2015-07-06

The therapeutic equivalence of generic and brand name antiepileptic drugs has been questioned by neurologists and the epilepsy community. A potential contributor to such concerns is pharmaceutical quality. The objective was to assess the biopharmaceutic risk of brand name Lamictal 100 mg tablets and generic lamotrigine 100 mg tablets from several manufacturers. Lamotrigine was characterized in terms of the Biopharmaceutics Classification System (BCS), including aqueous solubility and Caco-2 permeability. A panel of pharmaceutical quality tests was also performed on three batches of Lamictal, three batches of Teva generic, and one batch of each of four other generics: appearance, identity, assay, impurity, uniformity of dosage units, disintegration, dissolution, friability, and loss on drying. These market surveillance results indicate that all brand name and generic lamotrigine 100 mg tablets passed all tests and showed acceptable pharmaceutical quality and low biopharmaceutic risk. Lamotrigine was classified as a BCS class IIb drug, exhibiting pH-dependent aqueous solubility and dissolution. At pH 1.2 and 4.5, lamotrigine exhibited high solubility, whereas lamotrigine exhibited low solubility at pH 6.8, including non-sink dissolution. Lamotrigine showed high Caco-2 permeability. The apparent permeability (Papp) of lamotrigine was (73.7 ± 8.7) × 10(-6) cm/s in the apical-to-basolateral (AP-BL) direction and (41.4 ± 1.6) × 10(-6) cm/s in the BL-AP direction, which were higher than metoprolol's AP-BL Papp of (21.2 ± 0.9) × 10(-6) cm/s and BL-AP Papp of (34.6 ± 4.6) × 10(-6) cm/s. Overall, lamotrigine's favorable biopharmaceutics from a drug substance perspective and favorable quality characteristics from a tablet formulation perspective suggest that multisource lamotrigine tablets exhibit a low biopharmaceutic risk.

Enhancement in in vitro anti-angiogenesis activity and cytotoxicity in lung cancer cell by pectin-PVP based curcumin particulates.

PubMed

Gaikwad, Dinanath; Shewale, Rajnita; Patil, Vinit; Mali, Dipak; Gaikwad, Uday; Jadhav, Namdeo

2017-11-01

The aim of this work was to prepare pectin-poly (vinyl pyrrolidone) [PVP] based curcumin particulates to enhance the anticancer potential of curcumin, solubility and allow its localized controlled release. Pectin-PVP based curcumin particulates (PECTIN-PVP CUR) were prepared by spray drying technique in different ratios and were evaluated for surface morphology, micromeritics, flowability, particle size, drug content, in vitro dissolution, inhalable fraction, anti-angiogenesis/angiolysis and cytotoxicity. Results of micromeritic properties, Carr's index, Hausner's ratio and angle of repose were satisfactory. The batch CP3 was considered as optimum, due to excellent flowability, acceptable aggregation and enhanced solubility. The particle size and size distribution data of selected batch CP3 showed 90% of curcumin particulates having size less than 2.74μm, which may deposit to lungs. Twin Impinger studies showed that 29% of respirable fraction was generated, which could be directly delivered to lungs. The in vitro dissolution data showed many fold increase in dissolution rate. Angiolytic activity and MTT assay of PECTIN-PVP CUR have demonstrated enhancement in the anti-tumor potential, compared to curcumin alone. Altogether, PECTIN-PVP CUR were found suitable for local delivery and enhance its anticancer potential of curcumin. Copyright © 2017 Elsevier B.V. All rights reserved.

Degradation characteristics of polylactide in thermophilic anaerobic digestion with hyperthermophilic solubilization condition.

PubMed

Wang, F; Hidaka, T; Oishi, T; Osumi, S; Tsubota, J; Tsuno, H

2011-01-01

To test whether hyperthermophilic treatment promotes polylactide (PLA) dissolution and methane conversion under anaerobic digestion conditions, a single thermophilic control reactor (55 °C) and a two-phase system consisting of a hyperthermophilic reactor (80 °C) and a thermophilic reactor (55 °C) were continuously fed with a mixture of PLA and artificial kitchen garbage. In Runs 1 and 2, the PLA dissolution ratios in the two-phase system were 79.2 ± 6.5% and 85.2 ± 7.0%, respectively, higher than those of the control. Batch experimental results indicated that hyperthermophilic treatment could promote PLA dissolution to a greater degree as compared with single thermophilic treatment and that ammonia addition also had a promotional effect on PLA dissolution. In the two-phase system, after hyperthermophilic treatment, dissolved PLA was converted to methane gas under the subsequent thermophilic condition.

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

Martino, C

The Department of Energy (DOE) recognizes the need for the characterization of High-Level Waste (HLW) saltcake in the Savannah River Site (SRS) F- and H-area tank farms to support upcoming salt processing activities. As part of the enhanced characterization efforts, Tank 25F will be sampled and the samples analyzed at the Savannah River National Laboratory (SRNL). This Task Technical and Quality Assurance Plan documents the planned activities for the physical, chemical, and radiological analysis of the Tank 25F saltcake core samples. This plan does not cover other characterization activities that do not involve core sample analysis and it does notmore » address issues regarding sampling or sample transportation. The objectives of this report are: (1) Provide information useful in projecting the composition of dissolved salt batches by quantifying important components (such as actinides, {sup 137}Cs, and {sup 90}Sr) on a per batch basis. This will assist in process selection for the treatment of salt batches and provide data for the validation of dissolution modeling. (2) Determine the properties of the heel resulting from dissolution of the bulk saltcake. Also note tendencies toward post-mixing precipitation. (3) Provide a basis for determining the number of samples needed for the characterization of future saltcake tanks. Gather information useful towards performing characterization in a manner that is more cost and time effective.« less

pH-oscillations in the bromate-sulfite reaction in semibatch and in gel-fed batch reactors

NASA Astrophysics Data System (ADS)

Poros, Eszter; Kurin-Csörgei, Krisztina; Szalai, István; Rábai, Gyula; Orbán, Miklós

2015-06-01

The simplest bromate oxidation based pH-oscillator, the two component BrO3--SO32- flow system was transformed to operate under semibatch and closed arrangements. The experimental preconditions of the pH-oscillations in semibatch configuration were predicted by model calculations. Using this information as guideline large amplitude (ΔpH˜3), long lasting (11-24 h) pH-oscillations accompanied with only a 20% increase of the volume in the reactor were measured when a mixture of Na2SO3 and H2SO4 was pumped into the solution of BrO3- with a very low rate. Batch-like pH-oscillations, similar in amplitude and period time appeared when the sulfite supply was substituted by its dissolution from a gel layer prepared previously in the reactor in presence of high concentration of Na2SO3. The dissolution vs time curve and the pH-oscillations in the semibatch and closed systems were successfully simulated. Due to the simplicity in composition and in experimental technique, the semibatch and batch-like BrO3--SO32- pH-oscillators may become superior to their CSTR (continuous flow stirred tank reactor) version in some present and future applications.

Concomitant Zn-Cd and Pb retention in a carbonated fluvio-glacial deposit under both static and dynamic conditions.

PubMed

Lassabatere, Laurent; Spadini, Lorenzo; Delolme, Cécile; Février, Laureline; Galvez Cloutier, Rosa; Winiarski, Thierry

2007-11-01

The chemical and physical processes involved in the retention of 10(-2)M Zn, Pb and Cd in a calcareous medium were studied under saturated dynamic (column) and static (batch) conditions. Retention in columns decreased in order: Pb>Cd approximately Zn. In the batch experiments, the same order was observed for a contact time of less than 40h and over, Pb>Cd>Zn. Stronger Pb retention is in accordance with the lower solubility of Pb carbonates. However, the equality of retained Zn and Cd does not fit the solubility constants of carbonated solids. SEM analysis revealed that heavy metals and calcareous particles are associated. Pb precipitated as individualized Zn-Cd-Ca- free carbonated crystallites. All the heavy metals were also found to be associated with calcareous particles, without any change in their porosity, pointing to a surface/lattice diffusion-controlled substitution process. Zn and Cd were always found in concomitancy, though Pb fixed separately at the particle circumferences. The Phreeqc 2.12 interactive code was used to model experimental data on the following basis: flow fractionation in the columns, precipitation of Pb as cerrusite linked to kinetically controlled calcite dissolution, and heavy metal sorption onto proton exchanging sites (presumably surface complexation onto a calcite surface). This model simulates exchanges of metals with surface protons, pH buffering and the prevention of early Zn and Cd precipitation. Both modeling and SEM analysis show a probable significant decrease of calcite dissolution along with its contamination with metals.

Verification Of The Defense Waste Processing Facility's (DWPF) Process Digestion Methods For The Sludge Batch 8 Qualification Sample

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

Click, D. R.; Edwards, T. B.; Wiedenman, B. J.

2013-03-18

This report contains the results and comparison of data generated from inductively coupled plasma – atomic emission spectroscopy (ICP-AES) analysis of Aqua Regia (AR), Sodium Peroxide/Sodium Hydroxide Fusion Dissolution (PF) and Cold Chem (CC) method digestions and Cold Vapor Atomic Absorption analysis of Hg digestions from the DWPF Hg digestion method of Sludge Batch 8 (SB8) Sludge Receipt and Adjustment Tank (SRAT) Receipt and SB8 SRAT Product samples. The SB8 SRAT Receipt and SB8 SRAT Product samples were prepared in the SRNL Shielded Cells, and the SRAT Receipt material is representative of the sludge that constitutes the SB8 Batch ormore » qualification composition. This is the sludge in Tank 51 that is to be transferred into Tank 40, which will contain the heel of Sludge Batch 7b (SB7b), to form the SB8 Blend composition.« less

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.

Preliminary report of the discovery of a new pharmaceutical granulation process using foamed aqueous binders.

PubMed

Keary, Colin M; Sheskey, Paul J

2004-09-01

Spray granulation is commonly used to improve the flow of drug formulation powders by adding liquid binders. We have discovered a new granulation process whereby liquid binders are added as aqueous foam. Initial experiments indicate that foam granulations require less binder than spray granulations, less water is added to the powder mass, rates of addition of foam can be greater than rates of addition of sprayed liquids, and foam can be added in a single batch to the surface of the powder mass for incorporation at some later stage in the process. This new process appears to have no detrimental effects on granulate, tablet, or in vitro drug dissolution properties. In addition, the elimination of spray addition reduces the complexity of the process and avoids the plugging problems associated with spray nozzles. Several formulations were successfully scaled up from laboratory scale (1.5 kg) to pilot scale (15 kg). Process control was good and there was no detrimental effect on tablet and drug dissolution properties. This paper also proposes a working hypothesis of the mechanism by which foam granulation operates.

Solubility and transport of Cr(III) in a historically contaminated soil - Evidence of a rapidly reacting dimeric Cr(III) organic matter complex.

PubMed

Löv, Åsa; Sjöstedt, Carin; Larsbo, Mats; Persson, Ingmar; Gustafsson, Jon Petter; Cornelis, Geert; Kleja, Dan B

2017-12-01

Chromium is a common soil contaminant and, although it has been studied widely, questions about its speciation and dissolutions kinetics remain unanswered. We combined information from an irrigation experiment performed with intact soil columns with data from batch experiments to evaluate solubility and mobilization mechanisms of Cr(III) in a historically contaminated soil (>65 years). Particulate and colloidal Cr(III) forms dominated transport in this soil, but their concentrations were independent of irrigation intensity (2-20 mm h -1 ). Extended X-ray absorption fine structure (EXAFS) measurements indicated that Cr(III) associated with colloids and particles, and with the solid phase, mainly existed as dimeric hydrolyzed Cr(III) bound to natural organic matter. Dissolution kinetics of this species were fast (≤1 day) at low pH (<3) and slightly slower (≤5 days) at neutral pH. Furthermore, it proved possible to describe the solubility of the dimeric Cr(III) organic matter complex with a geochemical equilibrium model using only generic binding parameters, opening the way for use of geochemical models in risk assessments of Cr(III)-contaminated sites. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Coupling fractionation and batch desorption to understand arsenic and fluoride co-contamination in the aquifer system.

PubMed

Kumar, Manish; Das, Nilotpal; Goswami, Ritusmita; Sarma, Kali Prasad; Bhattacharya, Prosun; Ramanathan, A L

2016-12-01

The present work is an attempt to study As and F+ coevality using laboratory based assays which couples fractionation and batch dissolution experiments. Sequential extraction procedure (SEP) resulting into five "operationally defined phases", was performed on sediment and soil samples collected from the Brahmaputra flood plains, Assam, India. High correlation between the Fe (hydr)oxide fraction and total As content of the soil/sediment sample indicates the involvement of Fe (hydr)oxides as the principal source of As. F - being an anion has high potential to be sorbed onto positively charged surfaces. Findings of the SEP were used to design the batch desorption experiments by controlling the Fe (hydr)oxide content of the soil/sediment. Desorption of As and F - was observed under acidic, neutral and alkaline pH from untreated and Fe (hydr)oxide removed samples. Highest amount of As and F - were found to be released from untreated samples under alkaline pH, while the amount leached from samples with no Fe (hydr)oxide was low. The study showed that the Fe (hydr)oxide fraction commonly found in the soils and sediments, had high affinity for negatively charged species like F - oxyanions of As, AsO 4 3- (arsenate) and AsO 3 3- (arsenite). Fe (hydr)oxide fraction was found to play the major role in co-evolution of As and F - . Two sorption coefficients were proposed based on easily leachable fraction and As present in the groundwater of sampling location for understanding of contamination vulnerability from the leaching. Copyright © 2016 Elsevier Ltd. All rights reserved.

Microbial dissolution of calcite at T = 28 °C and ambient pCO 2

NASA Astrophysics Data System (ADS)

Jacobson, Andrew D.; Wu, Lingling

2009-04-01

This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species ( Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO 2 over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH 4+ as an N source, and H 2PO 4- as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H 2O-CO 2-CaCO 3 system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH 4+ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H 2CO 3 generated by dissolution of atmospheric CO 2 (H 2CO 3 + CaCO 3 → Ca 2+ + 2HCO 3-) and H + released during NH 4+ uptake (H + + CaCO 3 → Ca 2+ + HCO 3-). Reaction with H 2CO 3 and H + supplied ˜45% and 55% of the total Ca 2+ and ˜60% and 40% of the total HCO 3-, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH 4+ was ˜2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H 2CO 3. In lactate bearing reactors, most H + generated by NH 4+ uptake reacted with HCO 3- produced by lactate oxidation to yield CO 2 and H 2O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H 2CO 3 at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because the solubility and dissolution rate of calcite inversely correlate with pH, heterotrophic microbial growth in the presence of nonionic organic matter and NH 4+ appears to have the greatest potential for enhancing calcite weathering relative to abiotic conditions.

Microbial respiration and dissolution precipitation reactions of minerals: thermo-kinetics and reactive transport modelling

NASA Astrophysics Data System (ADS)

Azaroual, M. M.; Parmentier, M.; Andre, L.; Croiset, N.; Pettenati, M.; Kremer, S.

2010-12-01

Microbial processes interact closely with abiotic geochemical reactions and mineralogical transformations in several hydrogeochemical systems. Reactive transport models are aimed to analyze these complex mechanisms integrating as well as the degradation of organic matter as the redox reactions involving successive terminal electron acceptors (TEAPs) mediated by microbes through the continuum of unsaturated zone (soil) - saturated zone (aquifer). The involvement of microbial processes in reactive transport in soil and subsurface geologic greatly complicates the mastery of the major mechanisms and the numerical modelling of these systems. The introduction of kinetic constraints of redox reactions in aqueous phase requires the decoupling of equilibrium reactions and the redefinition of mass balance of chemical elements including the concept of basis species and secondary species of thermodynamic databases used in geochemical modelling tools. An integrated methodology for modelling the reactive transport has been developed and implemented to simulate the transfer of arsenic, denitrification processes and the role of metastable aqueous sulfur species with pyrite and organic matter as electron donors entities. A mechanistic rate law of microbial respiration in various geochemical environments was used to simulate reactive transport of arsenic, nitrate and organic matter combined to the generalized rate law of mineral dissolution - precipitation reactions derived from the transition state theory was used for dissolution - precipitation of silica, aluminosilicate, carbonate, oxyhydroxide, and sulphide minerals. The kinetic parameters are compiled from the literature measurements based on laboratory constrained experiments and field observations. Numerical simulations, using the geochemical software PHREEQC, were performed aiming to identify the key reactions mediated by microbes in the framework of in the first hand the concept of the unsaturated - saturated zones of an artificial recharge of deep aquifers system and in a second hand an acid mine drainage system. A large amount of data is available on the old mine site of Cheni (France). This field data on acid mine drainage are compared to a thermokinetic model including biological kinetics, precipitation-dissolution kinetics and surface complexation on ferrihydrite. The kinetic parameters are from literature and from a fitting on batch biological experiments. The integrated approach combining reaction kinetics and biogeochemical thermodynamic constraints is successfully applied to denitrification experiments in the presence of acetate and pyrite conducted in the laboratory for batch and column systems. The powerful of this coupled approach allows a fine description of the different transition species from nitrate to nitrogen. The fitted kinetic parameters established for modelling these laboratory results are thus extended to simulate the denitrification processes in a field case where organic matter and pyrite FeS2 are the electron donors and O2, NO3, Fe(OH)3, SO4 are the electron acceptors in the framework of a continuum UZ - SZ aiming to identify the stabilized redox zones of acid mine drainage. The detailed results obtained on two actual case studies will be presented.

Dissolution-precipitation reactions and permeability evolution from reactions of CO2-rich aqueous solutions with fractured basalt

NASA Astrophysics Data System (ADS)

Wells, R. K.; Xiong, W.; Bae, Y.; Sesti, E.; Skemer, P. A.; Giammar, D.; Conradi, M.; Ellis, B. R.; Hayes, S. E.

2015-12-01

The injection of CO2 into fractured basalts is one of several possible solutions to mitigate global climate change; however, research on carbonation in natural basalts in relation to carbon sequestration is limited, which impedes our understanding of the processes that may influence the viability of this strategy. We are conducting bench-scale experiments to characterize the mineral dissolution and precipitation and the evolution of permeability in synthetic and natural basalts exposed to CO2-rich fluids. Analytical methods include optical and electron microscopy, electron microprobe, Raman spectroscopy, nuclear magnetic resonance (NMR), and micro X-ray computed tomography (μCT) with variable flow rates. Reactive rock and mineral samples consist of 1) packed powders of olivine or natural basalt, and 2) sintered cores of olivine or a synthetic basalt mixture. Each sample was reacted in a batch reactor at 100 °C, and 100 bars CO2. Magnesite is detected within one day in olivine packed beds, and within 15 days in olivine sintered cores. Forsterite and synthetic basalt sinters were also reacted in an NMR apparatus at 102 °C and 65 bars CO2. Carbonate signatures are observed within 72 days of reaction. Longer reaction times are needed for carbonate precipitation in natural basalt samples. Cores from the Columbia River flood basalt flows that contain Mg-rich olivine and a serpentinized basalt from Colorado were cut lengthwise, the interface mechanically roughened or milled, and edges sealed with epoxy to simulate a fractured interface. The cores were reacted in a batch reactor at 50-150 °C and 100 bars CO2. At lower temperatures, calcite precipitation is rare within the fracture after 4 weeks. At higher temperatures, numerous calcite and aragonite crystals are observed within 1 mm of the fracture entrance along the roughened fracture surface. In flow-through experiments, permeability decreased along the fracture paths within a few hours to several days of flow.

Rapid fusion method for the determination of refractory thorium and uranium isotopes in soil samples

DOE PAGES

Maxwell, Sherrod L.; Hutchison, Jay B.; McAlister, Daniel R.

2015-02-14

Recently, approximately 80% of participating laboratories failed to accurately determine uranium isotopes in soil samples in the U.S Department of Energy Mixed Analyte Performance Evaluation Program (MAPEP) Session 30, due to incomplete dissolution of refractory particles in the samples. Failing laboratories employed acid dissolution methods, including hydrofluoric acid, to recover uranium from the soil matrix. The failures illustrate the importance of rugged soil dissolution methods for the accurate measurement of analytes in the sample matrix. A new rapid fusion method has been developed by the Savannah River National Laboratory (SRNL) to prepare 1-2 g soil sample aliquots very quickly, withmore » total dissolution of refractory particles. Soil samples are fused with sodium hydroxide at 600 ºC in zirconium crucibles to enable complete dissolution of the sample. Uranium and thorium are separated on stacked TEVA and TRU extraction chromatographic resin cartridges, prior to isotopic measurements by alpha spectrometry on cerium fluoride microprecipitation sources. Plutonium can also be separated and measured using this method. Batches of 12 samples can be prepared for measurement in <5 hours.« less

Effect of brine salinity and guar gum on the transport of barium through dolomite rocks: Implications for unconventional oil and gas wastewater disposal.

PubMed

Ebrahimi, Pouyan; Vilcáez, Javier

2018-05-15

This research aimed to elucidate the effect of brine salinity and guar gum on the sorption and transport of Ba in dolomite rocks collected from the Arbuckle formation in Oklahoma, USA. Guar gum represents the most important organic additive used in viscosified fracturing fluids, and Ba constitutes the most common and abundant heavy metal found in unconventional oil and gas (UOG) wastewater. Batch experiments conducted using powdered dolomite rocks (500-600 μm particle size) revealed that at brine salinities of UOG wastewater, chloro-complexation reactions between Ba and Cl ions and pH changes that results from dolomite dissolution are the controlling factors of Ba sorption on dolomite. Competition of Ba with common cations (Ca and Mg) for hydration sites of dolomite, plays a secondary role. Core-flooding experiments conducted to analyze the transport of Ba through natural and synthetic dolomite core plugs are in agreement with the batch sorption experimental results. The transport of Ba through dolomite rocks, increases with increasing brine salinity (0-180,000 mg-NaCl/L). The presence guar gum (50-500 mg/L) does not affect the transport of Ba through dolomite rocks of high flow properties (25-29.6% porosity, 9.6-13.7 mD permeability). However, core-flooding experiments conducted using tight dolomite rocks (6.5-8.6% porosity, 0.06-0.3 mD permeability), revealed that guar gum can retard the transport of Ba by clogging high permeability/porosity regions of tight dolomite rocks. The mechanism of Ba sorption on dolomite can be represented by a sorption model that accounts for both surface complexation reactions on three distinct hydration sites (>CaOH o , >MgOH o , and >CO 3 H o ), and the kinetic dissolution of dolomite. These results are important in understanding and predicting the fate of Ba present in UOG wastewater disposed into deep dolomite saline aquifers. Copyright © 2018 Elsevier Ltd. All rights reserved.

Optimization of the dissolution of molybdenum disks. FY-16 results

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

Tkac, Peter; Rotsch, David A.; Chemerisov, Sergey D.

2016-09-01

Argonne National Laboratory is providing technical development assistance to NorthStar Medical Technologies LLC in its pursuit of two pathways for production of molybdenum-99: the 98Mo(n,γ) 99Mo reaction and the photonuclear reaction, 100Mo(γ,n) 99Mo. Processing of irradiated targets, from either production mode, requires dissolution of the target material in H 2O 2 followed by a concentration step, addition of ferric ion to precipitate impurities, and conversion of the final solution to 5M potassium hydroxide solution of potassium molybdate. Currently, NorthStar is using pressed and sintered Mo disks as targets. Several options are being considered for the design of Mo targets formore » the production of 99Mo using the (γ,n) reaction. In the current design, the target holder contains a series of sintered Mo disks lined up perpendicular to two incident electron beams, one entering from each side of the target stack. In this configuration, the front-most disks absorb most of the heat from the electron beam and need to be thinner to allow for better cooling, while the middle of the target can be thicker. Distribution of the total mass of Mo allows for larger masses of Mo material and thus larger production batches of 99Mo. A limitation of the sintering approach is the production of very thin disks. Recent advances in 3D printing allow for much thinner target components can be achieved than when the traditional press-and-sinter approach is used. We have demonstrated that several factors can play important roles in dissolution behavior: particle size of Mo metal used for production of targets, sintering conditions, degree of open porosity, and thickness of the sintered Mo targets. Here we report experimental results from studies of small-scale dissolution of sintered Mo disks fabricated from various recycled and commercial Mo materials, and dissolution of 3D-printed Mo disks that were fabricated by Oak Ridge National Laboratory (ORNL). We also report on large-scale dissolution studies with 600 g batches of sintered Mo disks.« less

Oxidative Remobilization of Technetium Sequestered by Sulfide-Transformed Nano Zerovalent Iron

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

Fan, Dimin; Anitori, Roberto; Tebo, Bradley M.

2014-06-02

The dissolution of Tc(IV) sulfide and concurrent transformation of sulfidated ZVI during 2 oxidation were examined. Kinetic data obtained with 10 mL batch reactors showed that Tc(VII) 3 reduced by sulfidated nZVI has significantly slower reoxidation rates than Tc(VII) reduced by 4 nZVI only. In a 50 mL batch reactor, initial inhibition of Tc(IV) dissolution was apparent and 5 lasted until 120 hours at S/Fe = 0.112, presumably due to the redox buffer capacity of FeS. This 6 is evidenced by the parallel trends in oxidation-reduction potentials (ORP) and Tc dissolution 7 kinetics. Mӧssbauer spectra and micro X-ray diffraction ofmore » S/Fe = 0.112 suggested the 8 persistence of FeS after 24-h oxidation although X-ray photoelectron spectroscopy indicated 9 substantial surface oxidation. After 120-h oxidation, all characterizations showed complete 10 oxidation of FeS, which further indicates that FeS inhibits Tc oxidation. X-ray absorption 11 spectroscopy for S/Fe = 0.011 showed significantly increasing percentage of TcS2 in the solid 12 phase after 24-h oxidation, indicating TcS2 is more resistant to oxidation than TcO2. At S/Fe = 13 0.112, the XAS results revealed significant transformation of Tc speciation from TcS2 to TcO2 14 after 120-h oxidation at S/Fe = 0.112. Given that no apparent Tc dissolution occurred during this 15 period, the speciation transformation might play a secondary role in hindering Tc oxidation, 16 especially as redox buffer capacity approached depletion.« less

Influence of indigenous and added iron on copper extraction from soil.

PubMed

Di Palma, Luca

2009-10-15

Experimental tests of copper leaching from a low permeability soil are presented and discussed. The objective of the experiments was to investigate the influence of indigenous and added iron in the soil towards copper mobilization. Metals' leaching was performed by flushing (column tests) or washing (batch tests) the soil with an aqueous solution of ethylenediaminetetraacetic acid, EDTA. An excess of EDTA was used in flushing tests (up to a EDTA:Cu molar ratio of about 26.2:1), while, in washing tests, the investigated EDTA vs. copper molar ratios were in the range between 1 (equimolar tests) and 8. Copper extraction yield in flushing tests (up to about 85%) was found to depend upon contact time between the soil and the leaching solution and the characteristics of the conditioning solution. The saturation of the soil with a NaNO(3) solution before the treatment, favoured the flushing process reducing the time of percolation, but resulted in a lower metal extraction during the following percolation of EDTA. The indigenous iron was competitive with copper to form EDTA complexes only when it was present in the organic and oxides-hydroxides fractions. Artificial iron addition to the soil resulted in an increase of both the exchangeable iron and the iron bonded to the organic fraction of the soil, thus increasing the overall amount of iron available to extraction. In both batch and continuous tests, the mechanism of copper extraction was found to involve the former dissolution of metal salts, that lead to an initial high concentration of both copper and selected competitive cations (essentially Ca(2+)), and the following EDTA exchange reaction between calcium and copper complexes. The initial metal salts dissolution was found to be pH-dependant.

Olivine dissolution in the presence of heterotrophic bacteria (Pseudomonas reactants) extracted from Icelandic groundwater of the CO2 injection pilot site

NASA Astrophysics Data System (ADS)

Shirokova, Liudmila; Pokrovsky, Oleg; Benezeth, Pascale; Gerard, Emmanuelle; Menez, Benedicte; Alfredsson, Helgi

2010-05-01

This work is aimed at experimental modeling of the effect of heterotrophic bacteria on dissolution of important rock-forming mineral, olivine, at the conditions of CO2 storage and sequestration. Heterotrophic aerobic gram-negative bacteria were extracted from deep underground water (HK31, 1700 m deep and, t = 25-30°C) of basaltic aquifer located within the Hellisheidi CO2 injection pilot site (Iceland). Following this sampling, we separated, using culture on nutrient agar plates, four different groups of gram-negative aerobic bacteria. The enzymatic activity of studied species has been evaluated using Biolog Ecoplates and their genetic identification was performed using 18-S RNA analysis. The optimal growth conditions of bacteria on Brain Hearth Broth nutrient have been determined as 5 to 37°C and growth media pH varied from 7.0-8.2. Culturing experiments allowed determining the optimal physico-chemical conditions for bacteria experiments in the presence of basic Ca, Mg-containing silicates. Olivine (Fo92) was chosen as typical mineral of basalt, widely considered in carbon dioxide sequestration mechanisms. Dissolution experiments were performed in constant-pH (7 to 9), bicarbonate-buffered (0.001 to 0.05 M) nutrient-diluted media in batch reactors at 0-30 bars of CO2 in the presence of various biomass of Pseudomonas reactants. The release rate of magnesium, silica and iron was measured as a function of time in the presence of live, actively growing, dead (autoclaved or glutaraldehyde-treated) cells and bacteria exometabolites. Both nutrient media diluted 10 times (to 100 mg DOC/L) and inert electrolyte (NaCl, no DOC) were used. Our preliminary results indicate that the pH and dissolved organic matter are the first-order parameters that control the element release from olivine at far from equilibrium conditions. The SEM investigation of reacted surfaces reveal formation of surface roughness with much stronger mineral alteration in the presence of live bacteria compared to experiments with dead biomass. Overall, this work allows better understanding of microbially-affected silicate dissolution in basaltic aquifers and provides a firm methodological basis for constructing the mixed-flow reactors for studying the interaction of heterotrophic bacteria with rock-forming silicates at the environmental conditions of CO2-storage.

Development and validation of a discriminative dissolution method for atorvastatin calcium tablets using in vivo data by LC and UV methods.

PubMed

Machado, J C; Lange, A D; Todeschini, V; Volpato, N M

2014-02-01

A dissolution method to analyze atorvastatin tablets using in vivo data for RP and test pilot (PB) was developed and validated. The appropriate conditions were determined after solubility tests using different media, and sink conditions were established. The conditions used were equipment paddle at 50 rpm and 900 mL of potassium phosphate buffer pH 6.0 as dissolution medium. In vivo release profiles were obtained from the bioequivalence study of RP and the generic candidate PB. The fraction of dose absorbed was calculated using the Loo-Riegelman method. It was necessary to use a scale factor of time similar to 6.0, to associate the values of absorbed fraction and dissolved fraction, obtaining an in vivo-in vitro correlation level A. The dissolution method to quantify the amount of drug dissolved was validated using high-performance liquid chromatography and ultraviolet spectrophotometry, and validated according to the USP protocol. The discriminative power of dissolution conditions was assessed using two different pilot batches of atorvastatin tablets (PA and PB) and RP. The dissolution test was validated and may be used as a discriminating method in quality control and in the development of the new formulations.

Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

2016-10-01

This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

Mg isotope fractionation during microbe-mineral interactions

NASA Astrophysics Data System (ADS)

Kim, Insu; Ryu, Jong-sik; Lee, Kwang-sik; Lee, Dongho

2014-05-01

Magnesium is involved in various biogeochemical processes important to the global climate change over geological time-scale. Mg isotopes allow us to directly trace the Mg cycle in the Earth's surface but the factors controlling Mg isotopic compositions have not fully understood yet. Here, we conducted a batch experiment using two bacterial species (Shewanella putrefaciens and Burkholderia fungorum) and three major Mg-bearing minerals (biotite, dolomite and hornblende). All elemental concentrations increased by 336 h and then reached to steady-state values, of which Mg concentrations varied depending on minerals and bacterial species. This result indicates that the mineral dissolution is affect by the presence of microbes, which either provide organic acids or attach onto mineral surface. The Mg isotopic compositions of initial minerals biotite, dolomite and hornblende are -0.35o of biotite, -0.99o of dolomite, and -0.24o of hornblende, in δ26Mg. Similarly, δ26Mg values increased by 336 h and reached to steady-state values, which also varied with minerals and microbes. During dissolution of three minerals, the light isotope of Mg is preferentially incorporated into the dissolved phases and then the dissolved δ26Mg values become consistent with those of minerals with the time.

Potential for U sequestration with select minerals and sediments via base treatment.

PubMed

Emerson, Hilary P; Di Pietro, Silvina; Katsenovich, Yelena; Szecsody, Jim

2018-06-13

Temporary base treatment is a potential remediation technique for heavy metals through adsorption, precipitation, and co-precipitation with minerals. Manipulation of pH with ammonia gas injection may be especially useful for vadose zone environments as it does not require addition of liquids that would increase the flux towards groundwater. In this research, we conducted laboratory batch experiments to evaluate the changes in uranium mobility and mineral dissolution with base treatments including sodium hydroxide, ammonium hydroxide, and ammonia gas. Our data show that partitioning of uranium to the solid phase increases by several orders of magnitude following base treatment in the presence of different minerals and natural sediments from the Hanford site. The presence of dissolved calcium and carbonate play an important role in precipitation and co-precipitation of uranium at elevated pH. In addition, significant incongruent dissolution of bulk mineral phases occurs and likely leads to precipitation of secondary mineral phases. These secondary phases may remove uranium via adsorption, precipitation, and co-precipitation processes and may coat uranium phases with low solubility minerals as the pH returns to natural conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

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.

Biosorption of Cr(VI) and As(V) at high concentrations by organic and inorganic wastes

NASA Astrophysics Data System (ADS)

María Rivas Pérez, Ivana; Paradelo Núñez, Remigio; Nóvoa Muñoz, Juan Carlos; Arias Estévez, Manuel; José Fernández Sanjurjo, María; Álvarez Rodríguez, Esperanza; Núñez Delgado, Avelino

2016-04-01

The potential reutilization of several wastes as biosorbents for As(V) and Cr(VI) has been assessed in batch-type experiments. The materials studied were one inorganic: mussel shell, and three organic: pine bark, oak ash and hemp waste. Batch experiments were performed in order to determine the removal capacity of the wastes under conditions of high As(V) and Cr(VI) loads. For this, 3 g of each waste material were added with 30 mL NaNO3 0.01 M dissolutions containing 0, 0.5, 1.5, 3 and 6 mmol As(V) L-1 or Cr(VI) L-1, prepared from analytical grade Na2HAsO4 or K2Cr2O7. The resulting suspensions were shaken for 24 h, centrifuged and filtered. Once each batch experiment corresponding to the sorption trials ended, each individual sample was added with 30 mL of NaNO3 0.01 M to desorb As(V) or Cr(VI), shaken for 24 h, centrifuged and filtered as in the sorption trials. Oak ash showed high sorption (>76%) and low desorption (<7%) for As(V), which was lower on mussel shell (<31%), hemp waste (<16%) and pine bark (<9.9%). In turn, pine bark showed the highest Cr(VI) sorption (>98%) with very low desorption (<0.5%), followed by oak ash (27% sorption), and hemp waste and mussel shell, that presented very low Cr(VI) sorption (<10%). Sorption data for both elements were better described by the Freundlich than by the Langmuir model. The variable results obtained for the removal of the two anionic contaminants for a given sorbent suggest that different mechanisms govern removal from the solution in each case. In summary, oak ash would be an efficient sorbent material for As(V), but not for Cr(VI), while pine bark would be the best sorbent for Cr(VI) removal.

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

PubMed

Smetiško, Jelena; Miljanić, Snežana

2017-10-25

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

Enhancement of ibuprofen dissolution via wet granulation with beta-cyclodextrin.

PubMed

Ghorab, M K; Adeyeye, M C

2001-08-01

The purpose was to investigate the effect of wet granulation with beta-cyclodextrin (betaCD) on the enhancement of ibuprofen (IBU) dissolution. The effect of the granulation variables on the physical properties as well as the dissolution of tablets prepared from these granules was also examined. Granulation was performed using three granulating solvents: water, ethanol (95 vol%), and isopropanol. Granules were either oven-dried for 2 h or air-dried for 3 days. The granules or respective physical mixtures were compressed into tablets. Powder X-ray diffraction showed that oven-dried granulation resulted in less amorphous entities thatfacilitated IBU-betaCD complexation in solution and enhanced the dissolution of the corresponding tablets compared to the physical mixture with or without oven drying. In contrast, air-dried granulation did not cause any differences in the X-ray diffraction pattern (crystallinity) or the dissolution compared to the physical mixture without drying. Isopropanol and water, as granulating solvents, enhanced the dissolution of the oven-dried batches more than ethanol. The Differential scanning calorimetry (DSC) and Thermogravimetric analysis (TGA) data showed that tablets prepared from oven-dried granules, but not air-dried granules, had lower AH values and percent loss in weight, respectively, than those prepared from the physical mixture as a result of the expulsion of the water molecules from the betaCD cavity and enhancement of the complexation in solution. These results showed that oven-dried granulation of IBU and betaCD provided faster IBU dissolution than the physical mixture; air-dried granulation did not substantially affect the dissolution of IBU.

Experimental study of terrestrial plant litter interaction with aqueous solutions

NASA Astrophysics Data System (ADS)

Fraysse, F.; Pokrovsky, O. S.; Meunier, J.-D.

2010-01-01

Quantification of silicon and calcium recycling by plants is hampered by the lack of physico-chemical data on reactivity of plant litter in soil environments. We applied a laboratory experimental approach for determining the silica and calcium release rates from litter of typical temperate and boreal plants: pine ( Pinus laricio), birch ( Betula pubescens), larch ( Larix gmelinii), elm ( Ulmus laevis Pall.), tree fern ( Dicksonia squarrosa), and horsetail (Equisetum arvense) in 0.01 M NaCl solutions, pH of 2-10 and temperature equals to 5, 25 and 40 °C. Open system, mixed-flow reactors equipped with dialysis compartment and batch reactors were used. Comparative measurements were performed on intact larch needles and samples grounded during different time, sterilized or not and with addition or not of sodium azide in order to account for the effect of surface to mass ratio and possible microbiological activity on the litter dissolution rates. Litter degradation results suggest that the silica release rate is independent on dissolved organic carbon release (cell breakdown) which implies the presence of phytoliths in a pure "inorganic" pool not complexed with organic matter. Calcium and DOC are released at the very first stage of litter dissolution while Si concentration increases gradually suggesting the presence of Ca and Si in two different pools. The dry-weight normalized dissolution rate at circum-neutral pH range (approx. 1-10 μmol/g DW/day) is 2 orders of magnitude higher than the rates of Si release from common soil minerals (kaolinite, smectite, illite). Minimal Ca release rates evaluated from batch and mixed-flow reactors are comparable with those of most reactive soil minerals such as calcite and apatite, and several orders of magnitude higher than the dissolution rates of major rock-forming silicates (feldspars, pyroxenes). The activation energy for Si liberation from plant litter is approx. 50 kJ/mol which is comparable with that of surface-controlled mineral dissolutions. It is shown that the Si release rate from the above-ground forest biomass is capable of producing the Si concentrations observed in soil solutions of surficial horizons and contribute significantly to the Si flux from the soil to the river.

Comparison of chemiluminescence methods for analysis of hydrogen peroxide and hydroxyl radicals

NASA Astrophysics Data System (ADS)

Pehrman, R.; Amme, M.; Cachoir, C.

2006-01-01

Assessment of alpha radiolysis influence on the chemistry of geologically disposed spent fuel demands analytical methods for radiolytic product determination at trace levels. Several chemiluminescence methods for the detection of radiolytic oxidants hydrogen peroxide and hydroxyl radicals are tested. Two of hydrogen peroxide methods use luminol, catalyzed by either μ-peroxidase or hemin, one uses 10-methyl-9-(p-formylphenyl)-acridinium carboxylate trifluoromethanesulfonate and one potassium periodate. All recipes are tested as batch systems in basic conditions. For hydroxyl radical detection luminophores selected are 3-hydroxyphthalic hydrazide and rutin. Both methods are tested as batch systems. The results are compared and the applicability of the methods for near-field dissolution studies is discussed.

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

Wang, Guohui; Qafoku, Nikolla; Lawter, Amanda R.

A series of batch and column experiments combined with solid phase characterization studies (i.e., quantitative x-ray diffraction and wet chemical extractions) were conducted to address a variety of scientific issues and evaluate the impacts of the potential leakage of carbon dioxide (CO2) from deep subsurface storage reservoirs. The main objective was to gain an understanding of how CO2 gas influences: 1) the aqueous phase pH; and 2) mobilization of major, minor, and trace elements from minerals present in an aquifer overlying potential CO2 sequestration subsurface repositories. Rocks and slightly weathered rocks representative of an unconfined, oxidizing carbonate aquifer within themore » continental US, i.e., the Edwards aquifer in Texas, were used in these studies. These materials were exposed to a CO2 gas stream or were leached with a CO2-saturated influent solution to simulate different CO2 gas leakage scenarios, and changes in aqueous phase pH and chemical composition were measured in the liquid samples collected at pre-determined experimental times (batch experiments) or continuously (column experiments). The results from the strong acid extraction tests confirmed that in addition to the usual elements present in most soils, rocks, and sediments, the Edward aquifer samples contain As, Cd, Pb, Cu, and occasionally Zn, which may potentially be mobilized from the solid to the aqueous phase during or after exposure to CO2. The results from the batch and column experiments confirmed the release of major chemical elements into the contacting aqueous phase (such as Ca, Mg, Ba, Sr, Si, Na, and K); the mobilization and possible rapid immobilization of minor elements (such as Fe, Al, and Mn), which are able to form highly reactive secondary phases; and sporadic mobilization of only low concentrations of trace elements (such as As, Cd, Pb, Cu, Zn, Mo, etc.). The results from this experimental research effort will help in developing a systematic understanding of how CO2 leakage is likely to influence pertinent geochemical processes (e.g., dissolution/precipitation, sorption/desorption) in the aquifer sediments and will support site selection, risk assessment, policy-making, and public education efforts associated with geologic carbon sequestration.« less

Quantification of temperature impacts on the dissolution of chlorinated hydrocarbons into groundwater

NASA Astrophysics Data System (ADS)

Koproch, Nicolas; Popp, Steffi; Köber, Ralf; Beyer, Christof; Bauer, Sebastian; Dahmke, Andreas

2016-04-01

Shallow thermal energy storage has great potential for heat storage especially in urban and industrial areas. However, frequently existing organic groundwater contaminations in such areas were currently seen as exclusion criteria for thermal use of the shallow subsurface, since increased contaminant discharge is feared as consequence of heating. Contaminant discharge is influenced by a complex interaction of processes and boundary conditions as e.g. solubility, dispersion, viscosity and degradation, where there is still a lack of experimental evidence of the temperature dependent interaction. Even existing studies on basic influencing factors as e.g. temperature dependent solubilities show contradictory results. Such knowledge gaps should be reduced to improve the basis and liability of numerical model simulations and the knowledge base to enable a more differentiated and optimized use of resources. For this purpose batch as well as 1- and 2-dimensional experimental studies concerning the temperature dependent release of TCE (trichloroethylene) from a NAPL (non aqueous phase liquid) source are presented and discussed. In addition, this experimental studies are accompanied by a numerical model verification, where extensions of existing numerical model approaches on basis of this obtained experimental results are developed. Firstly, temperature dependent TCE solubility data were collected using batch experiments with significantly better temperature resolution compared to earlier studies, showing a distinct minimum at 35°C and increased solubility towards 5°C and 70°C. Secondly, heated 1-dimensional stainless steel columns homogenously filled with quartz sand were used to quantify source zone depletion and contaminant discharge at 10-70°C. Cumulative mass discharge curves indicated two blob categories with distinct differences in dissolution kinetics. Increasing the temperature showed here an increase of the amount of fast dissolving blobs indicating higher NAPL-water contact areas. Thirdly, heatable 2D-tanks (40 cm x 25 cm x 10 cm) homogenously filled with quartz sand and percolated by distilled H2O were used to investigate the dissolution behavior and plume development of TCE from a residual source zone (5 cm x 5 cm x 10 cm) at 10-70°C. Using NAPL source zone saturation of 5% (Case A) and 20% (Case B) two exemplary cases of a depleted and a fresh source zone were investigated. TCE outflow concentrations in case A increased continuously with increasing temperature, but were controlled by the temperature-dependent solubility in Case B. The experimental results showed that the TCE mass transfer rate has a minimum at about 40°C, if dissolution is non-rate limited and a continuous increase with increasing temperature for rate-limited systems. Implementation of temperature dependent NAPL dissolution and two different blob categories with different mass transfer rate coefficients in the OpenGeoSys code proved successful in reproducing the experimental results. Acknowledgments: The presented work is part of the ANGUS+ project (03EK3022) funded by the German Ministry of Education and Research (BMBF).

Simultaneous leaching of arsenite, arsenate, selenite and selenate, and their migration in tunnel-excavated sedimentary rocks: I. Column experiments under intermittent and unsaturated flow.

PubMed

Tabelin, Carlito Baltazar; Sasaki, Ryosuke; Igarashi, Toshifumi; Park, Ilhwan; Tamoto, Shuichi; Arima, Takahiko; Ito, Mayumi; Hiroyoshi, Naoki

2017-11-01

Rocks excavated in tunnel construction projects for roads and railways throughout Japan often leached out hazardous trace elements like arsenic (As) and selenium (Se) upon their exposure to the environment. In nature, the various oxyanionic species of As and Se not only coexist but also exhibit contrasting adsorption-desorption behaviors, so speciation is a crucial factor in their migration through natural geologic media. In this study, the leaching and transport of arsenite (As III ), arsenate (As V ), selenite (Se IV ) and selenate (Se VI ) in four tunnel-excavated rocks from the Cretaceous-Paleocene Yezo forearc basin were investigated using laboratory column experiments supplemented by batch leaching experiments. The single- and consecutive-batch leaching results revealed that As III , As V , Se IV and Se VI were released simultaneously, which could be attributed to the rapid dissolution of trace evaporite salts found in the rocks. Arsenic in the leachates was also predominated by As V while Se IV and Se VI concentrations were nearly equal, which are both consistent with predictions of equilibrium Eh-pH diagrams. Under intermittent and unsaturated flow, however, periods when As III and Se VI predominated in the effluents were observed. Spatial distributions of As and Se species with depth at the end of the column experiments suggest that migrations of As III , As V and Se IV were delayed, the extent of which depended on the rock. These results indicate that migration and speciation of As and Se in the rocks are controlled by preferential adsorption-desorption reactions, the effects of which were most probably magnified by changes in the pH and concentrations of coexisting ions due to intermittent and unsaturated flow. Copyright © 2017 Elsevier Ltd. All rights reserved.

In Situ NAPL Modification for Contaminant Source-Zone Passivation, Mass Flux Reduction, and Remediation

NASA Astrophysics Data System (ADS)

Mateas, D. J.; Tick, G.; Carroll, K. C.

2016-12-01

A remediation method was developed to reduce the aqueous solubility and mass-flux of target NAPL contaminants through the in-situ creation of a NAPL mixture source-zone. This method was tested in the laboratory using equilibrium batch tests and two-dimensional flow-cell experiments. The creation of two different NAPL mixture source zones were tested in which 1) volumes of relatively insoluble n-hexadecane (HEX) or vegetable oil (VO) were injected into a trichloroethene (TCE) contaminant source-zone; and 2) pre-determined HEX-TCE and VO-TCE mixture ratio source zones were emplaced into the flow cell prior to water flushing. NAPL-aqueous phase batch tests were conducted prior to the flow-cell experiments to evaluate the effects of various NAPL mixture ratios on equilibrium aqueous-phase concentrations of TCE and toluene (TOL) and to design optimal NAPL (HEX or VO) injection volumes for the flow-cell experiments. Uniform NAPL mixture source-zones were able to quickly decrease contaminant mass-flux, as demonstrated by the emplaced source-zone experiments. The success of the HEX and VO injections to also decrease mass flux was dependent on the ability of these injectants to homogeneously mix with TCE source-zone. Upon injection, both HEX and VO migrated away from the source-zone, to some extent. However, the lack of a steady-state dissolution phase and the inefficient mass-flux-reduction/mass-removal behavior produced after VO injection suggest that VO was more effective than HEX for mixing and partitioning within the source-zone region to form a more homogeneous NAPL mixture with TCE. VO appears to be a promising source-zone injectant-NAPL due to its negligible long-term toxicity and lower mobilization potential.

Basic Oxygen Furnace steel slag aggregates for phosphorus treatment. Evaluation of its potential use as a substrate in constructed wetlands.

PubMed

Blanco, Ivan; Molle, Pascal; Sáenz de Miera, Luis E; Ansola, Gemma

2016-02-01

Basic Oxygen Furnace (BOF) steel slag aggregates from NW Spain were tested in batch and column experiments to evaluate its potential use as a substrate in constructed wetlands (CWs). The objectives of this study were to identify the main P removal mechanisms of BOF steel slag and determine its P removal capacity. Also, the results were used to discuss the suitability of this material as a substrate to be used in CWs. Batch experiments with BOF slag aggregates and increasing initial phosphate concentrations showed phosphate removal efficiencies between 84 and 99% and phosphate removal capacities from 0.12 to 8.78 mg P/g slag. A continuous flow column experiment filled with BOF slag aggregates receiving an influent synthetic solution of 15 mg P/L during 213 days showed a removal efficiency greater than 99% and a phosphate removal capacity of 3.1 mg P/g slag. In both experiments the main P removal mechanism was found to be calcium phosphate precipitation which depends on Ca(2+) and OH(-) release from the BOF steel slag after dissolution of Ca(OH)2 in water. P saturation of slag was reached within the upper sections of the column which showed phosphate removal capacities between 1.7 and 2.5 mg P/g slag. Once Ca(OH)2 was completely dissolved in these column sections, removal efficiencies declined gradually from 99% until reaching stable outlet concentrations with P removal efficiencies around 7% which depended on influent Ca(2+) for limited continuous calcium phosphate precipitation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of xylan and lignin removal by batch and flowthrough pretreatment on the enzymatic digestibility of corn stover cellulose.

PubMed

Yang, Bin; Wyman, Charles E

2004-04-05

Compared with batch systems, flowthrough and countercurrent reactors have important potential advantages for pretreating cellulosic biomass, including higher hemicellulose sugar yields, enhanced cellulose digestibility, and reduced chemical additions. Unfortunately, they suffer from high water and energy use. To better understand these trade-offs, comparative data are reported on xylan and lignin removal and enzymatic digestibility of cellulose for corn stover pretreated in batch and flowthrough reactors over a range of flow rates between 160 degrees and 220 degrees C, with water only and also with 0.1 wt% sulfuric acid. Increasing flow with just water enhanced the xylan dissolution rate, more than doubled total lignin removal, and increased cellulose digestibility. Furthermore, adding dilute sulfuric acid increased the rate of xylan removal for both batch and flowthrough systems. Interestingly, adding acid also increased the lignin removal rate with flow, but less lignin was left in solution when acid was added in batch. Although the enzymatic hydrolysis of pretreated cellulose was related to xylan removal, as others have shown, the digestibility was much better for flowthrough compared with batch systems, for the same degree of xylan removal. Cellulose digestibility for flowthrough reactors was related to lignin removal as well. These results suggest that altering lignin also affects the enzymatic digestibility of corn stover. Copyright 2004 Wiley Periodicals, Inc.

Bacteriophage PRD1 batch experiments to study attachment, detachment and inactivation processes

NASA Astrophysics Data System (ADS)

Sadeghi, Gholamreza; Schijven, Jack F.; Behrends, Thilo; Hassanizadeh, S. Majid; van Genuchten, Martinus Th.

2013-09-01

Knowledge of virus removal in subsurface environments is pivotal for assessing the risk of viral contamination of water resources and developing appropriate protection measures. Columns packed with sand are frequently used to quantify attachment, detachment and inactivation rates of viruses. Since column transport experiments are very laborious, a common alternative is to perform batch experiments where usually one or two measurements are done assuming equilibrium is reached. It is also possible to perform kinetic batch experiments. In that case, however, it is necessary to monitor changes in the concentration with time. This means that kinetic batch experiments will be almost as laborious as column experiments. Moreover, attachment and detachment rate coefficients derived from batch experiments may differ from those determined using column experiments. The aim of this study was to determine the utility of kinetic batch experiments and investigate the effects of different designs of the batch experiments on estimated attachment, detachment and inactivation rate coefficients. The experiments involved various combinations of container size, sand-water ratio, and mixing method (i.e., rolling or tumbling by pivoting the tubes around their horizontal or vertical axes, respectively). Batch experiments were conducted with clean quartz sand, water at pH 7 and ionic strength of 20 mM, and using the bacteriophage PRD1 as a model virus. Values of attachment, detachment and inactivation rate coefficients were found by fitting an analytical solution of the kinetic model equations to the data. Attachment rate coefficients were found to be systematically higher under tumbling than under rolling conditions because of better mixing and more efficient contact of phages with the surfaces of the sand grains. In both mixing methods, more sand in the container yielded higher attachment rate coefficients. A linear increase in the detachment rate coefficient was observed with increased solid-water ratio using tumbling method. Given the differences in the attachment rate coefficients, and assuming the same sticking efficiencies since chemical conditions of the batch and column experiments were the same, our results show that collision efficiencies of batch experiments are not the same as those of column experiments. Upscaling of the attachment rate from batch to column experiments hence requires proper understanding of the mixing conditions. Because batch experiments, in which the kinetics are monitored, are as laborious as column experiments, there seems to be no major advantage in performing batch instead of column experiments.

Selected Fe and Mn (nano)oxides as perspective amendments for the stabilization of As in contaminated soils.

PubMed

Michálková, Zuzana; Komárek, Michael; Veselská, Veronika; Číhalová, Sylva

2016-06-01

An amorphous Mn oxide (AMO), nanomaghemite, and nanomagnetite were used as potential amendments reducing the mobility of As in three contrasting contaminated soils differing in origin of As contamination. Adsorption experiments and XPS analyses combined with incubation batch experiments and pH-static leaching tests were used. The AMO showed excellent adsorption capacity for As(V) reaching a maximum of 1.79 mmol g(-1) at pH 7 and 8. Interestingly, the adsorption capacity in this case decreases with decreasing pH, probably as a result of AMO dissolution at lower pH values. Chemical sorption of As(V) onto AMO was further confirmed with XPS. Both Fe nano-oxides proved the highest adsorption capacity at pH 4 reaching 11 mg g(-1) of adsorbed As(V). The AMO was also the most efficient amendment for decreasing As concentrations in soil solutions during 8 weeks of incubation. Additionally, pH-static leaching tests were performed at pH 4, 5, 6, 7, and natural pH (not adjusted) and AMO again proved the highest ability to decrease As content in leachate. On the other hand, strong dissolution of this amendment at lower pH values (especially pH 4) was observed. For that reason, AMO appears as a promising stabilizing agent for As, especially in neutral, alkaline, or slightly acidic soils, where As(V) species are expected to be more mobile.

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

PubMed

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

2016-01-01

The experience of a compromised sense of "self", termed ego-dissolution, is a key feature of the psychedelic experience. This study aimed to validate the Ego-Dissolution Inventory (EDI), a new 8-item self-report scale designed to measure ego-dissolution. Additionally, we aimed to investigate the specificity of the relationship between psychedelics and ego-dissolution. Sixteen items relating to altered ego-consciousness were included in an internet questionnaire; eight relating to the experience of ego-dissolution (comprising the EDI), and eight relating to the antithetical experience of increased self-assuredness, termed ego-inflation. Items were rated using a visual analog scale. Participants answered the questionnaire for experiences with classical psychedelic drugs, cocaine and/or alcohol. They also answered the seven questions from the Mystical Experiences Questionnaire (MEQ) relating to the experience of unity with one's surroundings. Six hundred and ninety-one participants completed the questionnaire, providing data for 1828 drug experiences (1043 psychedelics, 377 cocaine, 408 alcohol). Exploratory factor analysis demonstrated that the eight EDI items loaded exclusively onto a single common factor, which was orthogonal to a second factor comprised of the items relating to ego-inflation (rho = -0.110), demonstrating discriminant validity. The EDI correlated strongly with the MEQ-derived measure of unitive experience (rho = 0.735), demonstrating convergent validity. EDI internal consistency was excellent (Cronbach's alpha 0.93). Three analyses confirmed the specificity of ego-dissolution for experiences occasioned by psychedelic drugs. Firstly, EDI score correlated with drug-dose for psychedelic drugs (rho = 0.371), but not for cocaine (rho = 0.115) or alcohol (rho = -0.055). Secondly, the linear regression line relating the subjective intensity of the experience to ego-dissolution was significantly steeper for psychedelics (unstandardized regression coefficient = 0.701) compared with cocaine (0.135) or alcohol (0.144). Ego-inflation, by contrast, was specifically associated with cocaine experiences. Finally, a binary Support Vector Machine classifier identified experiences occasioned by psychedelic drugs vs. cocaine or alcohol with over 85% accuracy using ratings of ego-dissolution and ego-inflation alone. Our results demonstrate the psychometric structure, internal consistency and construct validity of the EDI. Moreover, we demonstrate the close relationship between ego-dissolution and the psychedelic experience. The EDI will facilitate the study of the neuronal correlates of ego-dissolution, which is relevant for psychedelic-assisted psychotherapy and our understanding of psychosis.

Validation of Dissolution Testing with Biorelevant Media: An OrBiTo Study.

PubMed

Mann, James; Dressman, Jennifer; Rosenblatt, Karin; Ashworth, Lee; Muenster, Uwe; Frank, Kerstin; Hutchins, Paul; Williams, James; Klumpp, Lukas; Wielockx, Kristina; Berben, Philippe; Augustijns, Patrick; Holm, Rene; Hofmann, Michael; Patel, Sanjaykumar; Beato, Stefania; Ojala, Krista; Tomaszewska, Irena; Bruel, Jean-Luc; Butler, James

2017-12-04

Dissolution testing with biorelevant media has become widespread in the pharmaceutical industry as a means of better understanding how drugs and formulations behave in the gastrointestinal tract. Until now, however, there have been few attempts to gauge the reproducibility of results obtained with these methods. The aim of this study was to determine the interlaboratory reproducibility of biorelevant dissolution testing, using the paddle apparatus (USP 2). Thirteen industrial and three academic laboratories participated in this study. All laboratories were provided with standard protocols for running the tests: dissolution in FaSSGF to simulate release in the stomach, dissolution in a single intestinal medium, FaSSIF, to simulate release in the small intestine, and a "transfer" (two-stage) protocol to simulate the concentration profile when conditions are changed from the gastric to the intestinal environment. The test products chosen were commercially available ibuprofen tablets and zafirlukast tablets. The biorelevant dissolution tests showed a high degree of reproducibility among the participating laboratories, even though several different batches of the commercially available medium preparation powder were used. Likewise, results were almost identicalbetween the commercial biorelevant media and those produced in-house. Comparing results to previous ring studies, including those performed with USP calibrator tablets or commercially available pharmaceutical products in a single medium, the results for the biorelevant studies were highly reproducible on an interlaboratory basis. Interlaboratory reproducibility with the two-stage test was also acceptable, although the variability was somewhat greater than with the single medium tests. Biorelevant dissolution testing is highly reproducible among laboratories and can be relied upon for cross-laboratory comparisons.

Approaches for Establishing Clinically Relevant Dissolution Specifications for Immediate Release Solid Oral Dosage Forms.

PubMed

Hermans, Andre; Abend, Andreas M; Kesisoglou, Filippos; Flanagan, Talia; Cohen, Michael J; Diaz, Dorys A; Mao, Y; Zhang, Limin; Webster, Gregory K; Lin, Yiqing; Hahn, David A; Coutant, Carrie A; Grady, Haiyan

2017-11-01

This manuscript represents the perspective of the Dissolution Analytical Working Group of the IQ Consortium. The intent of this manuscript is to highlight the challenges of, and to provide a recommendation on, the development of clinically relevant dissolution specifications (CRS) for immediate release (IR) solid oral dosage forms. A roadmap toward the development of CRS for IR products containing active ingredients with a non-narrow therapeutic window is discussed, within the context of mechanistic dissolution understanding, supported by in-human pharmacokinetic (PK) data. Two case studies present potential outcomes of following the CRS roadmap and setting dissolution specifications. These cases reveal some benefits and challenges of pursuing CRS with additional PK data, in light of current regulatory positions, including that of the US Food and Drug Administration (FDA), who generally favor this approach, but with the understanding that both industry and regulatory agency perspectives are still evolving in this relatively new field. The CRS roadmap discussed in this manuscript also describes a way to develop clinically relevant dissolution specifications based primarily on dissolution data for batches used in pivotal clinical studies, acknowledging that not all IR product development efforts need to be supported by additional PK studies, albeit with the associated risk of potentially unnecessarily tight manufacturing controls. Recommendations are provided on what stages during the life cycle investment into in vivo studies may be valuable. Finally, the opportunities for CRS within the context of post-approval changes, Modeling and Simulation (M&S), and the application of biowaivers, are briefly discussed.

Treatment of mining acidic leachates with indigenous limestone, Zimapan Mexico.

PubMed

Labastida, I; Armienta, M A; Lara-Castro, R H; Aguayo, A; Cruz, O; Ceniceros, N

2013-11-15

An experimental study to evaluate the potential of using indigenous limestones in a passive system to treat acid mine drainage, at a mining zone of Mexico was carried out. Chemical and mineralogical characteristics of four types of native rocks (KIT1, KIT2, KSS, QZ) showed distinct CaCO3 contents. Synthetic aqueous leachates from an old tailings impoundment had a pH of 2.18, 34 mg/L As, 705 mg/L Fetotal, and 3975 mg/L SO4(2-). To evaluate dissolution behavior of rocks, kinetic batch experiments with an acid Fe-rich solution were performed. Decaying kinetic constants adjusting H(+) concentration to a first order exponential process were: KIT1 (k = 2.89), KIT2 (k = 0.89) and KSS (k = 0.47). Infrared spectrum and XRD of precipitates showed schwertmannite formation. To determine As and heavy metals (Fe, Cd, Zn, Al) removal from the synthetic leachates, batch experiments using KIT1 were developed. Arsenic decreased from 34.00 mg/L to 0.04 mg/L, Fe and Al were totally removed, and concentrations of Zn and Cd decreased 88% and 91% respectively. Analyses by IR and SEM-EDS indicate that co-precipitation with Fe-Hydroxides formed upon leachate interaction with limestone is the main As removal process. Chamosite, identified by XRD may participate in the removal of Al, SiO2 and a fraction of Fe. Copyright © 2012 Elsevier B.V. All rights reserved.

Design of a potential colonic drug delivery system of mesalamine.

PubMed

Gohel, Mukesh C; Parikh, Rajesh K; Nagori, Stavan A; Dabhi, Mahesh R

2008-01-01

The aim of the present investigation was to develop a site-specific colonic drug delivery system, built on the principles of the combination of pH and time sensitivity. Press-coated mesalamine tablets with a coat of HPMC E-15 were over-coated with Eudragit S100. The in vitro drug release study was conducted using sequential dissolution technique at pH 1.2, 6.0, 7.2 and 6.4 mimicking different regions of gastrointestinal tract. The optimized batch (F2) showed less than 6% of drug release before reaching colonic pH 6.4 and complete drug release was obtained thereafter within 2 hr. A short-term dissolution stability study demonstrated statistical insignificant difference in drug release.

Arsenic mobilization in shallow aquifers due to CO 2 intrusion from storage reservoirs

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

Xiao, Ting; Dai, Zhenxue; Viswanathan, Hari S.

We developed an integrated framework of combined batch experiments and reactive transport simulations to quantify water-rock-CO 2 interactions and arsenic (As) mobilization responses to CO 2 and/or saline water leakage into USDWs. Experimental and simulation results suggest that when CO 2 is introduced, pH drops immediately that initiates release of As from clay minerals. Calcite dissolution can increase pH slightly and cause As re-adsorption. Thus, the mineralogy of the USDW is ultimately a determining factor of arsenic fate and transport. Salient results suggest that: (1) As desorption/adsorption from/onto clay minerals is the major reaction controlling its mobilization, and clay mineralsmore » could mitigate As mobilization with surface complexation reactions; (2) dissolution of available calcite plays a critical role in buffering pH; (3) high salinity in general hinders As release from minerals; and (4) the magnitude and quantitative uncertainty of As mobilization are predicated on the values of reaction rates and surface area of calcite, adsorption surface areas and equilibrium constants of clay minerals, and cation exchange capacity. Results of this study are intended to improve ability to quantify risks associated with potential leakage of reservoir fluids into shallow aquifers, in particular the possible environmental impacts of As mobilization at carbon sequestration sites.« less

Kinetics of Microbial Reduction of Solid Phase U(VI)

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

Liu, Chongxuan; Jeon, Byong Hun; Zachara, John M.

2006-10-01

Sodium boltwoodite (NaUO2SiO3OH ?1.5H2O) was used to assess the kinetics of microbial reduction of solid phase U(VI) by a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. The bioreduction kinetics was studied with Na-boltwoodite in suspension or within alginate beads. Concentrations of U(VI)tot and cell number were varied to evaluate the coupling of U(VI) dissolution, diffusion, and microbial activity. Batch experiments were performed in a non-growth medium with lactate as electron donor at pH 6.8 buffered with PIPES. Microscopic and spectroscopic analyses with transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and laser-induced fluorescence spectroscopy (LIFS) collectively indicated that solidmore » phase U(VI) was first dissolved and diffused out of grain interiors before it was reduced on bacterial surfaces and/or within the periplasm. The kinetics of solid phase U(VI) bioreduction was well described by a coupled model of bicarbonate-promoted dissolution of Na-boltwoodite, intraparticle uranyl diffusion, and Monod type bioreduction kinetics with respect to dissolved U(VI) concentration. The results demonstrated the intimate coupling of biological, chemical, and physical processes in microbial reduction of solid phase U(VI).« less

Arsenic mobilization in shallow aquifers due to CO 2 intrusion from storage reservoirs

DOE PAGES

Xiao, Ting; Dai, Zhenxue; Viswanathan, Hari S.; ...

2017-06-05

We developed an integrated framework of combined batch experiments and reactive transport simulations to quantify water-rock-CO 2 interactions and arsenic (As) mobilization responses to CO 2 and/or saline water leakage into USDWs. Experimental and simulation results suggest that when CO 2 is introduced, pH drops immediately that initiates release of As from clay minerals. Calcite dissolution can increase pH slightly and cause As re-adsorption. Thus, the mineralogy of the USDW is ultimately a determining factor of arsenic fate and transport. Salient results suggest that: (1) As desorption/adsorption from/onto clay minerals is the major reaction controlling its mobilization, and clay mineralsmore » could mitigate As mobilization with surface complexation reactions; (2) dissolution of available calcite plays a critical role in buffering pH; (3) high salinity in general hinders As release from minerals; and (4) the magnitude and quantitative uncertainty of As mobilization are predicated on the values of reaction rates and surface area of calcite, adsorption surface areas and equilibrium constants of clay minerals, and cation exchange capacity. Results of this study are intended to improve ability to quantify risks associated with potential leakage of reservoir fluids into shallow aquifers, in particular the possible environmental impacts of As mobilization at carbon sequestration sites.« less

Interaction of pesticides with natural and synthetic solids. Evaluation in dynamic and equilibrium conditions.

PubMed

Otalvaro, Julián Ortiz; Brigante, Maximiliano

2018-03-01

Interactions between pesticides (paraquat, glyphosate, 2,4-D, atrazine, and metsulfuron methyl) and soil organic and inorganic components have been studied in batch experiments by performing adsorption, dissolution, and chemical and photochemical degradation under different conditions. The obtained results confirm that the affinity of a pesticide to the solid surface depends on the nature of both and shows that each reactant strongly affects the mobility of the other one, e.g., anionic pesticides promote the dissolution of the solid humic acid but if this last is retained into the inorganic matrix enhances the adsorption of a cationic pesticide. Adsorption also seems to protect the bonded specie to be chemical degraded, such as shown in two pesticide/clay systems at constant pH. The use of mesoporous silicas could result in a good alternative for pesticide remediation. In fact, the solid shows high adsorption capacity towards paraquat and its modification with TiO 2 nanoparticles increases not only the pesticide adsorption but also seems to catalyze its degradation under UV light to less-toxic metabolites. UV-VIS spectroscopy was relevant and novel in such sense. Electrostatic interactions, hydrogen and coordinative bonds formations, surface complexations and hydrophobic associations play a key role in the fate of mentioned pesticides on soil and ground/surface water environments.

Differential Effects of Low-Molecular-Weight Organic Acids on the Mobilization of Soil-Borne Arsenic and Trace Metals.

PubMed

Nworie, Obinna Elijah; Qin, Junhao; Lin, Chuxia

2017-08-21

A batch experiment was conducted to examine the effects of six low-molecular-weight organic acids on the mobilization of arsenic and trace metals from a range of contaminated soils. The results showed that the organic acids behaved differently when reacting with soil-borne As and trace metals. Oxalic acid and acetic acid had the strongest and weakest capacity to mobilize the investigated elements, respectively. The solubilisation of iron oxides by the organic acids appears to play a critical role in mobilizing other trace metals and As. Apart from acidification and complexation, reductive dissolution played a dominant role in the dissolution of iron oxides in the presence of oxalic acid, while acidification tended to be more important for dissolving iron oxides in the presence of other organic acids. The unique capacity of oxalic acid to solubilize iron oxides tended to affect the mobilization of other elements in different ways. For Cu, Mn, and Zn, acidification-driven mobilization was likely to be dominant while complexation might play a major role in Pb mobilization. The formation of soluble Fe and Pb oxalate complexes could effectively prevent arsenate or arsenite from combining with these metals to form solid phases of Fe or Pb arsenate or arsenite.

Interactions Between Biogenic Silica (BSiO2) and Organic Carbon (POC) During the Recycling of Sinking Particles

NASA Astrophysics Data System (ADS)

Moriceau, B.; Goutx, M.; Guigue, C.; Tamburini, C.; Lee, C.; Armstrong, R. A.; Duflos, M.; Charriere, B.; Ragueneau, O.

2006-12-01

Despite recent progress in understanding the ocean's role in the global carbon cycle, we are not yet able to predict the response of ecosystems to climate change and feedbacks of the ocean onto atmospheric CO2. In particular, particle flux dynamics must be represented more faithfully in ocean models. We know that particulate organic carbon (POC) flux is associated with ballast minerals (BSiO2, CaCO3), but the processes controlling the interactions between carbon and ballast minerals during decomposition must be explored further. The present study aims to provide a better understanding of interactions between carbon and BSiO2 during mineralization of sinking particles. Previous studies have provided evidence that the degradation of the external membrane by bacteria increase the BSiO2 dissolution rate. Alternatively, it has been hypothesized that biogenic silica could protect carbon from degradation. To test this hypothesis, an in-vitro batch experiment using the diatom Skeletonema costatum was conducted. In this experiment, carbon degradation, bacterial growth, and BSiO2 dissolution were followed simultaneously. To identify the processes involved and the types of carbon that eventually interact with BSiO2 during mineralization, the concentrations of different lipids and amino acids were also measured. A strong increase of the degradation rate constant of the POC and PON was observed after dissolution of 40 % of initial BSiO2. This increase is associated to a peak of glycine in total amino acids and a switch between free and attached bacteria. These results suggest that carbon degradation is increased when enough of the frustule is dissolved to uncover the glycine contain inside the frustule, this amino acid may trigger an increase in the concentration of attached bacteria, which may in turn increase the degradation rate constant of organic carbon.

Bacteriophage PRD1 batch experiments to study attachment, detachment and inactivation processes.

PubMed

Sadeghi, Gholamreza; Schijven, Jack F; Behrends, Thilo; Hassanizadeh, S Majid; van Genuchten, Martinus Th

2013-09-01

Knowledge of virus removal in subsurface environments is pivotal for assessing the risk of viral contamination of water resources and developing appropriate protection measures. Columns packed with sand are frequently used to quantify attachment, detachment and inactivation rates of viruses. Since column transport experiments are very laborious, a common alternative is to perform batch experiments where usually one or two measurements are done assuming equilibrium is reached. It is also possible to perform kinetic batch experiments. In that case, however, it is necessary to monitor changes in the concentration with time. This means that kinetic batch experiments will be almost as laborious as column experiments. Moreover, attachment and detachment rate coefficients derived from batch experiments may differ from those determined using column experiments. The aim of this study was to determine the utility of kinetic batch experiments and investigate the effects of different designs of the batch experiments on estimated attachment, detachment and inactivation rate coefficients. The experiments involved various combinations of container size, sand-water ratio, and mixing method (i.e., rolling or tumbling by pivoting the tubes around their horizontal or vertical axes, respectively). Batch experiments were conducted with clean quartz sand, water at pH 7 and ionic strength of 20 mM, and using the bacteriophage PRD1 as a model virus. Values of attachment, detachment and inactivation rate coefficients were found by fitting an analytical solution of the kinetic model equations to the data. Attachment rate coefficients were found to be systematically higher under tumbling than under rolling conditions because of better mixing and more efficient contact of phages with the surfaces of the sand grains. In both mixing methods, more sand in the container yielded higher attachment rate coefficients. A linear increase in the detachment rate coefficient was observed with increased solid-water ratio using tumbling method. Given the differences in the attachment rate coefficients, and assuming the same sticking efficiencies since chemical conditions of the batch and column experiments were the same, our results show that collision efficiencies of batch experiments are not the same as those of column experiments. Upscaling of the attachment rate from batch to column experiments hence requires proper understanding of the mixing conditions. Because batch experiments, in which the kinetics are monitored, are as laborious as column experiments, there seems to be no major advantage in performing batch instead of column experiments. Copyright © 2013 Elsevier B.V. All rights reserved.

A Semi-Batch Reactor Experiment for the Undergraduate Laboratory

ERIC Educational Resources Information Center

Derevjanik, Mario; Badri, Solmaz; Barat, Robert

2011-01-01

This experiment and analysis offer an economic yet challenging semi-batch reactor experience. Household bleach is pumped at a controlled rate into a batch reactor containing pharmaceutical hydrogen peroxide solution. Batch temperature, product molecular oxygen, and the overall change in solution conductivity are metered. The reactor simulation…

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

PubMed Central

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

2016-01-01

Aims: The experience of a compromised sense of “self”, termed ego-dissolution, is a key feature of the psychedelic experience. This study aimed to validate the Ego-Dissolution Inventory (EDI), a new 8-item self-report scale designed to measure ego-dissolution. Additionally, we aimed to investigate the specificity of the relationship between psychedelics and ego-dissolution. Method: Sixteen items relating to altered ego-consciousness were included in an internet questionnaire; eight relating to the experience of ego-dissolution (comprising the EDI), and eight relating to the antithetical experience of increased self-assuredness, termed ego-inflation. Items were rated using a visual analog scale. Participants answered the questionnaire for experiences with classical psychedelic drugs, cocaine and/or alcohol. They also answered the seven questions from the Mystical Experiences Questionnaire (MEQ) relating to the experience of unity with one’s surroundings. Results: Six hundred and ninety-one participants completed the questionnaire, providing data for 1828 drug experiences (1043 psychedelics, 377 cocaine, 408 alcohol). Exploratory factor analysis demonstrated that the eight EDI items loaded exclusively onto a single common factor, which was orthogonal to a second factor comprised of the items relating to ego-inflation (rho = −0.110), demonstrating discriminant validity. The EDI correlated strongly with the MEQ-derived measure of unitive experience (rho = 0.735), demonstrating convergent validity. EDI internal consistency was excellent (Cronbach’s alpha 0.93). Three analyses confirmed the specificity of ego-dissolution for experiences occasioned by psychedelic drugs. Firstly, EDI score correlated with drug-dose for psychedelic drugs (rho = 0.371), but not for cocaine (rho = 0.115) or alcohol (rho = −0.055). Secondly, the linear regression line relating the subjective intensity of the experience to ego-dissolution was significantly steeper for psychedelics (unstandardized regression coefficient = 0.701) compared with cocaine (0.135) or alcohol (0.144). Ego-inflation, by contrast, was specifically associated with cocaine experiences. Finally, a binary Support Vector Machine classifier identified experiences occasioned by psychedelic drugs vs. cocaine or alcohol with over 85% accuracy using ratings of ego-dissolution and ego-inflation alone. Conclusion: Our results demonstrate the psychometric structure, internal consistency and construct validity of the EDI. Moreover, we demonstrate the close relationship between ego-dissolution and the psychedelic experience. The EDI will facilitate the study of the neuronal correlates of ego-dissolution, which is relevant for psychedelic-assisted psychotherapy and our understanding of psychosis. PMID:27378878

Dissolution of fluorapatite by Pseudomonas fluorescens P35 resulting in fluorine release

USGS Publications Warehouse

Zhou, Jianping; Wang, Hongmei; Cravotta, Charles A.; Dong, Qiang; Xiang, Xing

2017-01-01

Chemical weathering of fluorine-bearing minerals is widely accepted as the main mechanism for the release of fluorine (F) to groundwater. Here, we propose a potential mechanism of F release via microbial dissolution of fluorapatite (Ca5(PO4)3F), which has been neglected previously. Batch culture experiments were conducted at 30°C with a phosphate-solubilizing bacteria strain, Pseudomonas fluorescens P35, and rock phosphates as the sole source of phosphate for microbial growth in parallel with abiotic controls. Rock phosphates consisted of 55–91% of fluorapatite and 5–10% of dolomite before microbial dissolution as indicated by X-ray diffraction (XRD). Mineral composition and morphology changed after microbial dissolution characterized by the disappearance of dolomite and the development of etched cavities on rock phosphate surfaces. The pH of media used was approximately 7.4 at the beginning and increased gradually to 7.7 in abiotic controls; with the inoculum, the pH decreased to acidic values of 3.7–3.8 after 27 h. Phosphate, calcium, and fluoride were released from the rock phosphate to the acidified medium. At 42 h, the concentration of F reached 8.1–10.3 mg L−1. The elevated F concentration was two times higher than the F levels in groundwater in regions diagnosed with fluorosis, and was toxic to the bacteria, as demonstrated by a precipitous decrease in live cells. Geochemical modeling demonstrated that the oxidation of glucose (the carbon source for microbial growth in the medium) to gluconic acid could decrease the pH to 3.7–3.8 and result in the dissolution of fluorapatite and dolomite. Dolomite and fluorapatite remained unsaturated, while concentrations of dissolved phosphorus (P), calcium (Ca), and F increased throughout the time course Fluorite reached saturation [saturation index (SI) 0.22–0.42] after 42 h in rock phosphate–amended biotic systems. However, fluorite was not detected in XRD patterns of the final residue from microcosms. Given that phosphate-solubilizing bacteria are ubiquitous in soil and groundwater ecosystems, they could play an important role in fluorapatite dissolution and the release of F to groundwater.

Characterization of elemental release during microbe-basalt interactions

NASA Astrophysics Data System (ADS)

Wu, L.; Jacobson, A. D.; Hausner, M.

2006-12-01

This study used batch reactors to characterize the rates, mechanisms, and stoichiometry of elemental release during the interaction of Burkholderia fungorum, a common soil microbe, with Columbia River Flood Basalt at 28°C for 36 d. We especially focused on the release of Ca, Mg, P, Si, and Sr under a variety of biotic and abiotic conditions with the ultimate aim of evaluating how actively metabolizing bacteria might influence basalt weathering on the continents. Four days after inoculating P-limited reactors (those lacking P in the growth medium), pH decreased from ~7 to 4, and glucose was depleted. Theoretical calculations suggest that the lowered pH resulted from the release of organic acids and/or CO2. Purely abiotic control reactors as well as control reactors containing nonviable cells showed constant glucose concentrations and near-neutral pH. Over the entire 36 day period, the P-limited reactors yielded Ca, Mg, Si, and Sr release rates several times higher than those observed in the P-bearing biotic reactors and the abiotic controls. Release rates directly correlate with pH, indicating that proton-promoted dissolution was the dominant reaction mechanism. Ligand- promoted dissolution was probably less important because the P-limited and P-bearing reactors experienced nearly identical rates of microbial growth, but the P-bearing reactors displayed overall lower dissolution rates at near-neutral pH, where presumably, the effect of ligand-promoted dissolution would be most evident. Chemical analyses of bacteria collected at the end of the experiments, combined with mass-balances between the biological and fluid phases, demonstrate that the low P concentration in the biotic reactors was an artifact of P uptake during microbial growth. These findings suggest that when bacteria utilize basalt as a nutrient source, they can potentially elevate the rate of long-term atmospheric CO2 consumption by Ca-Mg silicate weathering by a factor of 5 over the corresponding inorganic rate.

Sulfate Fining Chemistry in Oxidized and Reduced Soda-Lime-Silica Glasses

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

Matyas, Josef; Hrma, Pavel R.

2005-05-13

Various reducing agents were used and their additions were varied to (1) increase glass quality through eliminating defects from silica scum, (2) decrease SOx emissions through changing the kind and quantity of reducing agents, and (3) improve production efficiency through increased flexibility of glass redox control during continuous processing. The work included measuring silica sand dissolution and sulfate decomposition in melts from glass batches. Glass batches were heated at a temperature-increase rate deemed similar to that experienced in the melting furnace. The sulfate decomposition kinetics was investigated with thermogravimetric analysis-differential thermal analysis and evolved gas analysis. Sulfur concentrations in glassesmore » quenched at different temperatures were determined using X-ray fluorescence spectroscopy. The distribution of residual sand (that which was not dissolved during the initial batch reactions) in the glass was obtained as a function of temperature with optical microscopy in thin-sections of melts. The fraction of undissolved sand was measured with X-ray diffraction. The results of the present study helped Visteon Inc. reduce the energy consumption and establish the batch containing 0.118 mass% of graphite as the best candidate for Visteon glass production. The improved glass batch has a lower potential for silica scum formation and for brown fault occurrence in the final glass product. It was established that bubbles trapped in the melt even at 1450 C have a high probability to be refined when reaching the hot zone in the glass furnace. Furthermore, silica sand does not accumulate at the glass surface and dissolves faster in the batch with graphite than in the batch with carbocite.« less

Geochemical modeling of fluid-fluid and fluid-mineral interactions during geological CO2 storage

NASA Astrophysics Data System (ADS)

Zhu, C.; Ji, X.; Lu, P.

2013-12-01

The long time required for effective CO2 storage makes geochemical modeling an indispensable tool for CCUS. One area of geochemical modeling research that is in urgent need is impurities in CO2 streams. Permitting impurities, such as H2S, in CO2 streams can lead to potential capital and energy savings. However, predicting the consequences of co-injection of CO2 and impurities into geological formations requires the understanding of the phase equilibrium and fluid-fluid interactions. To meet this need, we developed a statistical associating fluid theory (SAFT)-based equation of state (EOS) for the H2S-CO2-H2O-NaCl system at 373.15

The Impact of Mineralogy on the Geochemical Alteration of Shales During Hydraulic Fracturing Operations

NASA Astrophysics Data System (ADS)

Maher, K.; Harrison, A. L.; Jew, A. D.; Dustin, M. K.; Kiss, A. M.; Kohli, A. H.; Thomas, D.; Joe-Wong, C. M.; Brown, G. E.; Bargar, J.

2016-12-01

The extraction of oil and gas resources from low permeability shale reservoirs using hydraulic fracturing techniques has increased significantly in recent years. During hydraulic fracturing, large volumes of fluid are injected into subsurface shale formations, which drives substantial fluid-rock interaction that can release contaminants and alter rock permeability. Here, a combined experimental, imaging, and modeling approach was employed to systematically evaluate the impact of shale mineralogy on its physical and chemical alteration when exposed to fracturing fluids of different composition. Batch reactor experiments contained different shales with unique mineralogical compositions that were exposed to simulated hydraulic fracturing fluid. Experiments revealed that the balance between fluid acidity and acid neutralizing capacity of the rock was the strongest control on the evolution of fluid and rock chemistry. Carbonate mineral-rich shales rapidly recovered solution pH to circum-neutral conditions, whereas fluids in contact with carbonate mineral-poor shales remained acidic. The dissolution of shale minerals released metal contaminants, yet the precipitation of Fe(III)-bearing secondary phases helped to attenuate their release via co-precipitation or sorption. Post-reaction imaging illustrated that selective dissolution of carbonate minerals generated secondary porosity, the connectivity of which was dictated by initial carbonate distribution. Conversely, the precipitation of secondary Al- and Fe-bearing phases may occlude porosity, potentially inhibiting transport of water, contaminants, and hydrocarbons. The maturation of secondary Fe-bearing phases from amorphous to crystalline over time suggests that porosity will continue to evolve even after oxidation reactions have effectively ceased. These experiments reveal that the relative abundance and distribution of carbonate minerals is the master variable dictating both porosity alteration and contaminant release from shale formations, implying that the response of a reservoir to hydraulic fracturing can be better assessed using robust mineralogical data.

Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

NASA Astrophysics Data System (ADS)

Kouznetsova, Irina; Mao, Xiaomin; Robinson, Clare; Barry, D. A.; Gerhard, Jason I.; McCarty, Perry L.

2010-09-01

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is able to provide valuable insight into the fundamental processes and their complex interactions during bioremediation of chlorinated ethenes in DNAPL source zones.

Use of spray-cooling technology for development of microencapsulated capsicum oleoresin for the growing pig as an alternative to in-feed antibiotics: a study of release using in vitro models.

PubMed

Meunier, J-P; Cardot, J-M; Manzanilla, E G; Wysshaar, M; Alric, M

2007-10-01

The aim of this study was to develop sustained release microspheres of capsicum oleoresin as an alternative to in-feed additives. Two spray-cooling technologies, a fluidized air bed using a spray nozzle system and a vibrating nozzle system placed on top of a cooling tower, were used to microencapsulate 20% of capsicum oleoresin in a hydrogenated, rapeseed oil matrix. Microencapsulation was intended to reduce the irritating effect of capsicum oleoresin and to control its release kinetics during consumption by the animal. Particles produced by the fluidized air bed process (batch F1) ranged from 180 to 1,000 microm in size. The impact of particle size on release of capsaicin, the main active compound of capsicum oleoresin, was studied after sieving batch F1 to obtain 4 formulations: F1a (180 to 250 microm), F1b (250 to 500 microm), F1c (500 to 710 microm), and F1d (710 to 1,000 microm). The vibrating nozzle system can produce a monodispersive particle size distribution. In this study, particles of 500 to 710 microm were made (batch F2). The release kinetics of the formulations was estimated in a flow-through cell dissolution apparatus (CFC). The time to achieve a 90% dissolution value (T90%) of capsaicin for subbatches of F1 increased with the increase in particle size (P < 0.05), with the greatest value of 165.5 +/- 13.2 min for F1d. The kinetics of dissolution of F2 was slower than all F1 subbatches, with a T90% of 422.7 +/- 30.0 min. Nevertheless, because CFC systems are ill suited for experiments with solid feed and thus limit their predictive values, follow-up studies were performed on F1c and F2 using an in vitro dynamic model that simulated more closely the digestive environment. For both formulations a lower quantity of capsaicin dialyzed was recorded under fed condition vs. fasting condition with 46.9% +/- 1.0 vs. 74.7% +/- 2.7 for F1c and 32.4% +/- 1.4 vs. 44.2% +/- 2.6 for F2, respectively. This suggests a possible interaction between capsaicin and the feed matrix. Moreover, 40.4 +/- 3.9% of the total capsaicin intake in F2 form was dialyzed after 8 h of digestion when feed had been granulated vs. 32.4 +/- 1.4% when feed had not been granulated, which suggests that the feed granulation process could lead to a partial degradation of the microspheres and to a limitation of the sustained release effect. This study demonstrates the potential and the limitations of spray-cooling technology to encapsulate feed additives.

Non-catalytic transfer hydrogenation in supercritical CO2 for coal liquefaction

NASA Astrophysics Data System (ADS)

Elhussien, Hussien

This thesis presents the results of the investigation on developing and evaluating a low temperature (<150°C) non - catalytic process using a hydrogen transfer agent (instead of molecu-lar hydrogen) for coal dissolution in supercritical CO2. The main idea behind the thesis was that one hydrogen atom from water and one hydrogen atom from the hydrogen transfer agent (HTA) were used to hydrogenate the coal. The products of coal dissolution were non-polar and polar while the supercritical CO2, which enhanced the rates of hydrogenation and dissolution of the non-polar molecules and removal from the reaction site, was non-polar. The polar modifier (PM) for CO2 was added to the freed to aid in the dissolution and removal of the polar components. The addition of a phase transfer agent (PTA) allowed a seamless transport of the ions and by-product between the aqueous and organic phases. DDAB, used as the PTA, is an effective phase transfer catalyst and showed enhancement to the coal dissolution process. COAL + DH- +H 2O → COAL.H2 + DHO-- This process has a great feature due to the fact that the chemicals were obtained without requir-ing to first convert coal to CO and H2 units as in indirect coal liquefaction. The experiments were conducted in a unique reactor set up that can be connected through two lines. one line to feed the reactor with supercritical CO 2 and the other connected to gas chromatograph. The use of the supercritical CO2 enhanced the solvent option due to the chemical extraction, in addition to the low environmental impact and energy cost. In this thesis the experiment were conducted at five different temperatures from atmos-pheric to 140°C, 3000 - 6000 psi with five component of feed mixture, namely water, HTA, PTA, coal, and PM in semi batch vessels reactor system with a volume of 100 mL. The results show that the chemicals were obtained without requiring to first convert coal to CO and H2 units as in indirect coal liquefaction. The results show that the conversion was found to be 91.8% at opti-mum feed mixtures values of 3, 1.0 and 5.4 for water: PM, HTA: coal, water: coal respectively. With the oil price increase and growing in energy demand, the coal liquefaction remain affordable and available energy alternative.

Examining Two Types of Best Friendship Dissolution during Early Adolescence

ERIC Educational Resources Information Center

Bowker, Julie C.

2011-01-01

This study examined young adolescents' experiences with best friendship dissolution. Participants were 77 sixth-grade students (M age = 11.63 years, SD = 0.36; 11.00-12.69 age range) who reported on past experiences with (1) "complete dissolutions" (when friendship ties are completely severed), and (2) "downgrade dissolutions"…

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.

Formulation and Evaluation of Mouth Dissolving Tablets of Cinnarizine

PubMed Central

Patel, B. P.; Patel, J. K.; Rajput, G. C.; Thakor, R. S.

2010-01-01

The purpose of this research was to develop mouth dissolve tablets of cinnarizine by effervescent, superdisintegrant addition and sublimation methods. All the three formulations were evaluated for disintegration time, hardness and friability, among these superdisintegrant addition method showed lowest disintegration time; hence it was selected for further studies. Further nine batches (B1-B9) were prepared by using crospovidone, croscarmellose sodium and L-HPC in different concentrations such as 5, 7.5 and 10%. All the formulations were evaluated for weight variation, hardness, friability, drug content, in vitro disintegration time, wetting time, in vitro dissolution. Formulation with 10% L-HPC showed the less disintegration time (25.3 s) and less wetting time (29.1 s). In vitro dissolution studies showed total drug release at the end of 6 min. PMID:21218071

Cocrystal formation in solution: Inducing phase transition by manipulating the amount of cocrystallizing agent

NASA Astrophysics Data System (ADS)

Gagniere, Emilie; Mangin, Denis; Puel, François; Valour, Jean-Pierre; Klein, Jean-Paul; Monnier, Olivier

2011-02-01

The purpose of this work was to assess the possibility of inducing solution mediated phase transition (SMPT) by manipulating the amount of the cocrystallizing agent. The cocrystal, composed of an active pharmaceutical ingredient (carbamazepine, CBZ) and its cocrystallizing agent (a vitamin—nicotinamide, NCT), was selected as a model compound. Batch experiments were performed in a stirred vessel. The solute concentrations of both CBZ and NCT were monitored using in situ ATR-FTIR spectroscopy. The introduction of NCT in dry form allowed a shift in the phase diagram, leading to an SMPT from CBZ crystals toward cocrystals. The concentration profiles gave information on the phase transition kinetics, i.e., the kinetics of nucleation, growth and dissolution mechanisms of the solid phases involved. Several situations were analyzed. This procedure could also be used to correct a process deviation that led to CBZ crystals instead of cocrystals.

Enhancing tablet disintegration characteristics of a highly water-soluble high-drug-loading formulation by granulation process.

PubMed

Pandey, Preetanshu; Levins, Christopher; Pafiakis, Steve; Zacour, Brian; Bindra, Dilbir S; Trinh, Jade; Buckley, David; Gour, Shruti; Sharif, Shasad; Stamato, Howard

2018-07-01

The objective of this study was to improve the disintegration and dissolution characteristics of a highly water-soluble tablet matrix by altering the manufacturing process. A high disintegration time along with high dependence of the disintegration time on tablet hardness was observed for a high drug loading (70% w/w) API when formulated using a high-shear wet granulation (HSWG) process. Keeping the formulation composition mostly constant, a fluid-bed granulation (FBG) process was explored as an alternate granulation method using a 2 (4-1) fractional factorial design with two center points. FBG batches (10 batches) were manufactured using varying disingtegrant amount, spray rate, inlet temperature (T) and atomization air pressure. The resultant final blend particle size was affected significantly by spray rate (p = .0009), inlet T (p = .0062), atomization air pressure (p = .0134) and the interaction effect between inlet T*spray rate (p = .0241). The compactibility of the final blend was affected significantly by disintegrant amount (p < .0001), atomization air pressure (p = .0013) and spray rate (p = .05). It was observed that the fluid-bed batches gave significantly lower disintegration times than the HSWG batches, and mercury intrusion porosimetry data revealed that this was caused by the higher internal pore structure of tablets manufactured using the FBG batches.

Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite

NASA Technical Reports Server (NTRS)

Beiersdorfer, R. E.; Ming, D. W.; Galindo, C., Jr.

2003-01-01

c1inoptilolite-rich tuff-hydroxyapatite mixture (zeoponic substrate) has the potential to serve as a synthetic soil-additive for plant growth. Essential plant macro-nutrients such as calcium, phosphorous, magnesium, ammonium and potassium are released into solution via dissolution of the hydroxyapatite and cation exchange on zeolite charged sites. Plant growth experiments resulting in low yield for wheat have been attributed to a Ca deficiency caused by a high degree of cation exchange by the zeolite. Batch-equilibration experiments were performed in order to determine if the Ca deficiency can be remedied by the addition of a second Ca-bearing, soluble, mineral such as calcite, dolomite or wollastonite. Variations in the amount of calcite, dolomite or wollastonite resulted in systematic changes in the concentrations of Ca and P. The addition of calcite, dolomite or wollastonite to the zeoponic substrate resulted in an exponential decrease in the phosphorous concentration in solution. The exponential rate of decay was greatest for calcite (5.60 wt. % -I), intermediate for wollastonite (2.85 wt.% -I) and least for dolomite (1.58 wt.% -I). Additions of the three minerals resulted in linear increases in the calcium concentration in solution. The rate of increase was greatest for calcite (3.64), intermediate for wollastonite (2.41) and least for dolomite (0.61). The observed changes in P and Ca concentration are consistent with the solubilities of calcite, dolomite and wollastonite and with changes expected from a common ion effect with Ca. Keywords: zeolite, zeoponics, common-ion effect, clinoptilolite, hydroxyapatite

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.

Evaluating Impacts of CO2 Gas Intrusion Into a Confined Sandstone aquifer: Experimental Results

DOE PAGES

Qafoku, Nikolla; Lawter, Amanda R.; Shao, Hongbo; ...

2014-12-31

Deep subsurface storage and sequestration of CO2 has been identified as a potential mitigation technique for rising atmospheric CO2 concentrations. Sequestered CO2 represents a potential risk to overlying aquifers if the CO2 leaks from the deep storage reservoir. Experimental and modeling work is required to evaluate potential risks to groundwater quality and develop a systematic understanding of how CO2 leakage may cause important changes in aquifer chemistry and mineralogy by promoting dissolution/precipitation, adsorption/desorption, and redox reactions. Sediments from the High Plains aquifer in Kansas, United States, were used in this investigation, which is part of the National Risk Assessment Partnershipmore » Program sponsored by the US Department of Energy. This aquifer was selected to be representative of consolidated sand and gravel/sandstone aquifers overlying potential CO2 sequestration repositories within the continental US. In this paper, we present results from batch experiments conducted at room temperature and atmospheric pressure with four High Plains aquifer sediments. Batch experiments simulate sudden, fast, and short-lived releases of the CO2 gas as would occur in the case of well failure during injection. Time-dependent release of major, minor, and trace elements were determined by analyzing the contacting solutions. Characterization studies demonstrated that the High Plains aquifer sediments were abundant in quartz and feldspars, and contained about 15 to 20 wt% montmorillonite and up to 5 wt% micas. Some of the High Plains aquifer sediments contained no calcite, while others had up to about 7 wt% calcite. The strong acid extraction tests confirmed that in addition to the usual elements present in most soils, rocks, and sediments, the High Plains aquifer sediments had appreciable amounts of As, Cd, Pb, Cu, and occasionally Zn, which potentially may be mobilized from the solid to the aqueous phase during or after exposure to CO2. However, the results from the batch experiments showed that the High Plains sediments mobilized only low concentrations of trace elements (potential contaminants), which were detected occasionally in the aqueous phase during these experiments. Importantly, these occurrences were more frequent in the calcite-free sediment. Results from these investigations provide useful information to support site selection, risk assessment, and public education efforts associated with geological CO2 storage and sequestration.« less

Empirical kinetics and their role in elucidating the utility of transition-state theory to mineral–water reactions. A comment upon, ''Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite'' by V. W. Truesdale

DOE PAGES

Icenhower, Jonathan P.

2015-06-23

Transition-state theory (TST) is a successful theory for understanding many different types of reactions, but its application to mineral-water systems has not been successful, especially as the system approaches saturation with respect to a rate-limiting phase. A number of investigators have proposed alternate frameworks for using the kinetic rate data to construct models of dissolution, including Truesdale (Aquat Geochem, 2015; this issue). This alternate approach has been resisted, in spite of self-evident discrepancies between TST expectations and the data. The failure of TST under certain circumstances is a result of the presence of metastable intermediaries or reaction layers that formmore » on the surface of reacting solids, and these phenomena are not anticipated by the current theory. Furthermore, alternate approaches, such as the shrinking object model advocated by Truesdale, represent a potentially important avenue for advancing the science of dissolution kinetics.« less

Solubility and cation exchange in phosphate rock and saturated clinoptilolite mixtures

NASA Technical Reports Server (NTRS)

Allen, E. R.; Hossner, L. R.; Ming, D. W.; Henninger, D. L.

1993-01-01

Mixtures of zeolite and phosphate rock (PR) have the potential to provide slow-release fertilization of plants in synthetic soils by dissolution and ion-exchange reactions. This study was conducted to examine solubility and cation-exchange relationships in mixtures of PR and NH4- and K-saturated clinoptilolite (Cp). Batch-equilibration experiments were designed to investigate the effect of PR source, the proportion of exchangeable K and NH4, and the Cp to PR ratio on solution N, P, K, and Ca concentrations. The dissolution and cation-exchange reactions that occurred after mixing NH4- and K-saturated Cp with PR increased the solubility of the PR and simultaneously released NH4 and K into solution. The more reactive North Carolina (NC) PR rendered higher solution concentrations of NH4 and K when mixed with Cp than did Tennessee (TN) PR. Solution P concentrations for the Cp-NC PR mixture and the Cp-TN PR mixture were similar. Solution concentrations of N, P, K, and Ca and the ratios of these nutrients in solution varied predictably with the type of PR, the Cp/PR ratio, and the proportions of exchangeable K and NH4 on the Cp. Our research indicated that slow-release fertilization using Cp/PR media may provide adequate levels of N, P, and K to support plant growth. Solution Ca concentrations were lower than optimum for plant growth.

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

Poros, Eszter; Kurin-Csörgei, Krisztina; Szalai, István

The simplest bromate oxidation based pH-oscillator, the two component BrO{sub 3}{sup −}–SO{sub 3}{sup 2–} flow system was transformed to operate under semibatch and closed arrangements. The experimental preconditions of the pH-oscillations in semibatch configuration were predicted by model calculations. Using this information as guideline large amplitude (ΔpH∼3), long lasting (11–24 h) pH-oscillations accompanied with only a 20% increase of the volume in the reactor were measured when a mixture of Na{sub 2}SO{sub 3} and H{sub 2}SO{sub 4} was pumped into the solution of BrO{sub 3}{sup −} with a very low rate. Batch-like pH-oscillations, similar in amplitude and period time appearedmore » when the sulfite supply was substituted by its dissolution from a gel layer prepared previously in the reactor in presence of high concentration of Na{sub 2}SO{sub 3}. The dissolution vs time curve and the pH-oscillations in the semibatch and closed systems were successfully simulated. Due to the simplicity in composition and in experimental technique, the semibatch and batch-like BrO{sub 3}{sup −}–SO{sub 3}{sup 2–} pH-oscillators may become superior to their CSTR (continuous flow stirred tank reactor) version in some present and future applications.« less

Mechanisms of siderophore sorption to smectite and siderophore-enhanced release of structural Fe 3+

NASA Astrophysics Data System (ADS)

Haack, Elizabeth A.; Johnston, Cliff T.; Maurice, Patricia A.

2008-07-01

Sorption of the trihydroxamate siderophores desferrioxamine-B and -D (DFOB and DFOD, respectively) and of the monohydroxamate ligand acetohydroxamic acid (aHA) to smectite were examined in batch sorption studies (pH 5.5, 0.1 M ionic strength) coupled with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Both DFOB and DFOD, which have similar molecular structures but different charge properties (cationic versus neutral, respectively) showed a high affinity for smectite. In contrast, the smaller aHA molecule did not sorb appreciably. XRD analysis indicated that DFOB and DFOD each absorbed in the interlamellar region of the clay to give d-spacings of 13.4-13.7 Å at equilibrium solution concentrations <250 μM. FTIR spectra of sorbed DFOB and DFOD indicated that the conformation of each species was distinct from its conformation in the crystalline or dissolved states. At elevated initial solution concentrations of 500-1500 μM, DFOB formed a bilayer in the clay interlayer. Changes in the FTIR spectra of the DFOB-loaded clay samples at these higher surface loadings were consistent with the presence of a metal-siderophore complex in the interlayer. DFOB and DFOD both enhanced Fe and Al release from smectite, but aHA did not. Possible dissolution mechanisms are discussed in light of the FTIR and batch dissolution results.

Do lab-derived distribution coefficient values of pesticides match distribution coefficient values determined from column and field-scale experiments? A critical analysis of relevant literature.

PubMed

Vereecken, H; Vanderborght, J; Kasteel, R; Spiteller, M; Schäffer, A; Close, M

2011-01-01

In this study, we analyzed sorption parameters for pesticides that were derived from batch and column or batch and field experiments. The batch experiments analyzed in this study were run with the same pesticide and soil as in the column and field experiments. We analyzed the relationship between the pore water velocity of the column and field experiments, solute residence times, and sorption parameters, such as the organic carbon normalized distribution coefficient ( ) and the mass exchange coefficient in kinetic models, as well as the predictability of sorption parameters from basic soil properties. The batch/column analysis included 38 studies with a total of 139 observations. The batch/field analysis included five studies, resulting in a dataset of 24 observations. For the batch/column data, power law relationships between pore water velocity, residence time, and sorption constants were derived. The unexplained variability in these equations was reduced, taking into account the saturation status and the packing status (disturbed-undisturbed) of the soil sample. A new regression equation was derived that allows estimating the values derived from column experiments using organic matter and bulk density with an value of 0.56. Regression analysis of the batch/column data showed that the relationship between batch- and column-derived values depends on the saturation status and packing of the soil column. Analysis of the batch/field data showed that as the batch-derived value becomes larger, field-derived values tend to be lower than the corresponding batch-derived values, and vice versa. The present dataset also showed that the variability in the ratio of batch- to column-derived value increases with increasing pore water velocity, with a maximum value approaching 3.5. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.

The function of Sn(II)-apatite as a Tc immobilizing agent

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

Asmussen, R. Matthew; Neeway, James J.; Lawter, Amanda R.

2016-11-01

Technetium-99 is a radioactive contaminant of high concern at many nuclear waste storage sites. At the U.S. Department of Energy Hanford Site, 99Tc is a component of low-activity waste (LAW) fractions of the nuclear tank waste, which are highly caustic, high ionic strength and have high concentrations of chromate. Removal of 99Tc from LAW streams would greatly benefit the site remediation process. In this study, we investigated the removal of 99Tc(VII), as pertechnetate, from deionized water (DIW) and a LAW simulant using two solid sorbents, tin (II) apatite (Sn-A) and SnCl2 through batch sorption testing and solid phase characterization. Sn-Amore » showed higher levels of removal of Tc from both DIW and LAW simulant compared with the SnCl2. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/XEDS) and X-ray adsorption spectroscopy (XAS) of Sn-A following batch experiments in DIW showed that TcO4- is reduced to Tc(IV) on the Sn-A surface with no incorporation into the lattice structure of Sn-A. The performance of Sn-A in the LAW simulant was lowered due to a combined effect of the high alkalinity, which lead to an increased dissolution of Sn from the Sn-A, and a preference for the reduction of Cr(VI) over Tc(VII).« less

Statistical modeling methods to analyze the impacts of multiunit process variability on critical quality attributes of Chinese herbal medicine tablets.

PubMed

Sun, Fei; Xu, Bing; Zhang, Yi; Dai, Shengyun; Yang, Chan; Cui, Xianglong; Shi, Xinyuan; Qiao, Yanjiang

2016-01-01

The quality of Chinese herbal medicine tablets suffers from batch-to-batch variability due to a lack of manufacturing process understanding. In this paper, the Panax notoginseng saponins (PNS) immediate release tablet was taken as the research subject. By defining the dissolution of five active pharmaceutical ingredients and the tablet tensile strength as critical quality attributes (CQAs), influences of both the manipulated process parameters introduced by an orthogonal experiment design and the intermediate granules' properties on the CQAs were fully investigated by different chemometric methods, such as the partial least squares, the orthogonal projection to latent structures, and the multiblock partial least squares (MBPLS). By analyzing the loadings plots and variable importance in the projection indexes, the granule particle sizes and the minimal punch tip separation distance in tableting were identified as critical process parameters. Additionally, the MBPLS model suggested that the lubrication time in the final blending was also important in predicting tablet quality attributes. From the calculated block importance in the projection indexes, the tableting unit was confirmed to be the critical process unit of the manufacturing line. The results demonstrated that the combinatorial use of different multivariate modeling methods could help in understanding the complex process relationships as a whole. The output of this study can then be used to define a control strategy to improve the quality of the PNS immediate release tablet.

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.

Application of biosurfactants, rhamnolipid, and surfactin, for enhanced biodegradation of diesel-contaminated water and soil.

PubMed

Whang, Liang-Ming; Liu, Pao-Wen G; Ma, Chih-Chung; Cheng, Sheng-Shung

2008-02-28

This study investigated potential application of two biosurfactants, surfactin (SF) and rhamnolipid (RL), for enhanced biodegradation of diesel-contaminated water and soil with a series of bench-scale experiments. The rhamnolipid used in this study, a commonly isolated glycolipid biosurfactant, was produced by Pseudomonas aeruginosa J4, while the surfactin, a lipoprotein type biosurfactant, was produced by Bacillus subtilis ATCC 21332. Both biosurfactants were able to reduce surface tension to less than 30 dynes/cm from 72 dynes/cm with critical micelle concentration (CMC) values of 45 and 50 mg/L for surfactin and rhamnolipid, respectively. In addition, the results of diesel dissolution experiments also demonstrated their ability in increasing diesel solubility with increased biosurfactant addition. In diesel/water batch experiments, an addition of 40 mg/L of surfactin significantly enhanced biomass growth (2500 mg VSS/L) as well as increased diesel biodegradation percentage (94%), compared to batch experiments with no surfactin addition (1000 mg VSS/L and 40% biodegradation percentage). Addition of surfactin more than 40 mg/L, however, decreased both biomass growth and diesel biodegradation efficiency, with a worse diesel biodegradation percentage (0%) at 400 mg/L of SF addition. Similar trends were also observed for both specific rate constants of biomass growth and diesel degradation, as surfactin addition increased from 0 to 400 mg/L. Addition of rhamnolipid to diesel/water systems from 0 to 80 mg/L substantially increased biomass growth and diesel biodegradation percentage from 1000 to 2500 mg VSS/L and 40 to 100%, respectively. Rhamnolipid addition at a concentration of 160 mg/L provided similar results to those of an 80 mg/L addition. Finally, potential application of surfactin and rhamnolipid in stimulating indigenous microorganisms for enhanced bioremediation of diesel-contaminated soil was also examined. The results confirmed their enhancing capability on both efficiency and rate of diesel biodegradation in diesel/soil systems.

Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS): A rapid test for enteric coating thickness and integrity of controlled release pellet formulations.

PubMed

Alfarsi, Anas; Dillon, Amy; McSweeney, Seán; Krüse, Jacob; Griffin, Brendan; Devine, Ken; Sherry, Patricia; Henken, Stephan; Fitzpatrick, Stephen; Fitzpatrick, Dara

2018-06-10

There are no rapid dissolution based tests for determining coating thickness, integrity and drug concentration in controlled release pellets either during production or post-production. The manufacture of pellets requires several coating steps depending on the formulation. The sub-coating and enteric coating steps typically take up to six hours each followed by additional drying steps. Post production regulatory dissolution testing also takes up to six hours to determine if the batch can be released for commercial sale. The thickness of the enteric coating is a key factor that determines the release rate of the drug in the gastro-intestinal tract. Also, the amount of drug per unit mass decreases with increasing thickness of the enteric coating. In this study, the coating process is tracked from start to finish on an hourly basis by taking samples of pellets during production and testing those using BARDS (Broadband Acoustic Resonance Dissolution Spectroscopy). BARDS offers a rapid approach to characterising enteric coatings with measurements based on reproducible changes in the compressibility of a solvent due to the evolution of air during dissolution. This is monitored acoustically via associated changes in the frequency of induced acoustic resonances. A steady state acoustic lag time is associated with the disintegration of the enteric coatings in basic solution. This lag time is pH dependent and is indicative of the rate at which the coating layer dissolves. BARDS represents a possible future surrogate test for conventional USP dissolution testing as its data correlates directly with the thickness of the enteric coating, its integrity and also with the drug loading as validated by HPLC. Copyright © 2018 Elsevier B.V. All rights reserved.

Real-time imaging as an emerging process analytical technology tool for monitoring of fluid bed coating process.

PubMed

Naidu, Venkata Ramana; Deshpande, Rucha S; Syed, Moinuddin R; Wakte, Pravin S

2018-07-01

A direct imaging system (Eyecon TM ) was used as a Process Analytical Technology (PAT) tool to monitor fluid bed coating process. Eyecon TM generated real-time onscreen images, particle size and shape information of two identically manufactured laboratory-scale batches. Eyecon TM has accuracy of measuring the particle size increase of ±1 μm on particles in the size range of 50-3000 μm. Eyecon TM captured data every 2 s during the entire process. The moving average of D90 particle size values recorded by Eyecon TM were calculated for every 30 min to calculate the radial coating thickness of coated particles. After the completion of coating process, the radial coating thickness was found to be 11.3 and 9.11 μm, with a standard deviation of ±0.68 and 1.8 μm for Batch 1 and Batch 2, respectively. The coating thickness was also correlated with percent weight build-up by gel permeation chromatography (GPC) and dissolution. GPC indicated weight build-up of 10.6% and 9.27% for Batch 1 and Batch 2, respectively. In conclusion, weight build-up of 10% can also be correlated with 10 ± 2 μm increase in the coating thickness of pellets, indicating the potential applicability of real-time imaging as an endpoint determination tool for fluid bed coating process.

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

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.

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

Cresap, D.A.; Halverson, D.S.

In the Fluorinel Dissolution Process (FDP) upgrade, excess hydrofluoric acid in the dissolver product must be complexed with aluminum nitrate (ANN) to eliminate corrosion concerns, adjusted with nitrate to facilitate extraction, and diluted with water to ensure solution stability. This is currently accomplished via batch processing in large vessels. However, to accommodate increases in projected throughput and reduce water production in a cost-effective manner, a semi-continuous system (In-line Complexing (ILC)) has been developed. The major conclusions drawn from tests demonstrating the feasibility of this concept are given in this report.

DIissolution of low enriched uranium from the experimental breeder reactor-II fuel stored at the Idaho National Laboratory

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

Daniel, G.; Rudisill, T.; Almond, P.

The Idaho National Laboratory (INL) is actively engaged in the development of electrochemical processing technology for the treatment of fast reactor fuels using irradiated fuel from the Experimental Breeder Reactor-II (EBR-II) as the primary test material. The research and development (R&D) activities generate a low enriched uranium (LEU) metal product from the electrorefining of the EBR-II fuel and the subsequent consolidation and removal of chloride salts by the cathode processor. The LEU metal ingots from past R&D activities are currently stored at INL awaiting disposition. One potential disposition pathway is the shipment of the ingots to the Savannah River Sitemore » (SRS) for dissolution in H-Canyon. Carbon steel cans containing the LEU metal would be loaded into reusable charging bundles in the H-Canyon Crane Maintenance Area and charged to the 6.4D or 6.1D dissolver. The LEU dissolution would be accomplished as the final charge in a dissolver batch (following the dissolution of multiple charges of spent nuclear fuel (SNF)). The solution would then be purified and the 235U enrichment downblended to allow use of the U in commercial reactor fuel. To support this potential disposition path, the Savannah River National Laboratory (SRNL) developed a dissolution flowsheet for the LEU using samples of the material received from INL.« less

Solid-state characterization of nevirapine.

PubMed

Sarkar, Mahua; Perumal, O P; Panchagnula, R

2008-09-01

The purpose of this investigation is to characterize nevirapine from commercial samples and samples crystallized from different solvents under various conditions. The solid-state behavior of nevirapine samples was investigated using a variety of complementary techniques such as microscopy (optical, polarized, hot stage microscopy), differential scanning calorimeter, thermogravimetric analysis, Fourier transform infrared spectroscopy and powder X-ray diffractometry. The commercial samples of nevirapine had the same polymorphic crystalline form with an anhedral crystal habit. Intrinsic dissolution of nevirapine was similar for both the commercial batches. Powder dissolution showed pH dependency, with maximum dissolution in acidic pH and there was no significant effect of particle size. The samples recrystallized from different solvent systems with varying polarity yielded different crystal habits. Stirring and degrees of supersaturation influenced the size and shape of the crystals. The recrystallized samples did not produce any new polymorphic form, but weak solvates with varying crystal habit were produced. Recrystallized samples showed differences in the x-ray diffractograms. However, all the samples had the same internal crystal lattice as revealed from their similar melting points and heat of fusion. The intrinsic dissolution rate of recrystallized samples was lower than the commercial sample. It was found that the compression pressure resulted in desolvation and partial conversion of the crystal form. After compression, the recrystallized samples showed similar x-ray diffractograms to the commercial sample. Amorphous form showed slightly higher aqueous solubility than the commercial crystalline form.

Design and Optimization of Floating Drug Delivery System of Acyclovir

PubMed Central

Kharia, A. A.; Hiremath, S. N.; Singhai, A. K.; Omray, L. K.; Jain, S. K.

2010-01-01

The purpose of the present work was to design and optimize floating drug delivery systems of acyclovir using psyllium husk and hydroxypropylmethylcellulose K4M as the polymers and sodium bicarbonate as a gas generating agent. The tablets were prepared by wet granulation method. A 32 full factorial design was used for optimization of drug release profile. The amount of psyllium husk (X1) and hydroxypropylmethylcellulose K4M (X2) were selected as independent variables. The times required for 50% (t50%) and 70% (t70%) drug dissolution were selected as dependent variables. All the designed nine batches of formulations were evaluated for hardness, friability, weight variation, drug content uniformity, swelling index, in vitro buoyancy, and in vitro drug release profile. All formulations had floating lag time below 3 min and constantly floated on dissolution medium for more than 24 h. Validity of the developed polynomial equation was verified by designing two check point formulations (C1 and C2). The closeness of predicted and observed values for t50% and t70% indicates validity of derived equations for the dependent variables. These studies indicated that the proper balance between psyllium husk and hydroxypropylmethylcellulose K4M can produce a drug dissolution profile similar to the predicted dissolution profile. The optimized formulations followed Higuchi's kinetics while the drug release mechanism was found to be anomalous type, controlled by diffusion through the swollen matrix. PMID:21694992

Design and optimization of floating drug delivery system of acyclovir.

PubMed

Kharia, A A; Hiremath, S N; Singhai, A K; Omray, L K; Jain, S K

2010-09-01

The purpose of the present work was to design and optimize floating drug delivery systems of acyclovir using psyllium husk and hydroxypropylmethylcellulose K4M as the polymers and sodium bicarbonate as a gas generating agent. The tablets were prepared by wet granulation method. A 3(2) full factorial design was used for optimization of drug release profile. The amount of psyllium husk (X1) and hydroxypropylmethylcellulose K4M (X2) were selected as independent variables. The times required for 50% (t(50%)) and 70% (t(70%)) drug dissolution were selected as dependent variables. All the designed nine batches of formulations were evaluated for hardness, friability, weight variation, drug content uniformity, swelling index, in vitro buoyancy, and in vitro drug release profile. All formulations had floating lag time below 3 min and constantly floated on dissolution medium for more than 24 h. Validity of the developed polynomial equation was verified by designing two check point formulations (C1 and C2). The closeness of predicted and observed values for t(50%) and t(70%) indicates validity of derived equations for the dependent variables. These studies indicated that the proper balance between psyllium husk and hydroxypropylmethylcellulose K4M can produce a drug dissolution profile similar to the predicted dissolution profile. The optimized formulations followed Higuchi's kinetics while the drug release mechanism was found to be anomalous type, controlled by diffusion through the swollen matrix.

Are multisource levothyroxine sodium tablets marketed in Egypt interchangeable?

PubMed

Abou-Taleb, Basant A; Bondok, Maha; Nounou, Mohamed Ismail; Khalafallah, Nawal; Khalil, Saleh

2018-02-01

A clinical study was initiated in response to patients' complaints, supported by the treating physicians, of suspected differences in efficacy among multisource levothyroxine sodium tablets marketed in Egypt. The study design was a multiple dose (100μg levothyroxine sodium tablet once daily for 6 months) and involved 50 primary hypothyroidism female patients (5 equal groups). Tablets administered included five tablet batches (two brands, three origin locations) purchased from local pharmacies in Alexandria. Assessment parameters (measured on consecutive visits) included the thyroid stimulating hormone, total and free levothyroxine. Tablet dissolution rate was determined (BP/EP 2014 & USP 2014). In vitro vs in vivovs correlations were developed. Clinical and pharmaceutical data confirmed inter-brand and inter-source differences in efficacy. Correlations examined indicated potential usefulness of in vitro dissolution test in detecting poor performing levothyroxine sodium tablets during shelf life. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Oral Disintegration Tablets of Stavudine for HIV Management: A New Technological Approach

PubMed Central

Sankar, V.; Ramakrishna, B.; Devi, P. Shalini; Karthik, S.

2012-01-01

Stavudine oral disintegration tablets were formulated to minimize the bitter taste and to reduce the first-pass hepatic metabolism. The various precompression parameters like the angle of repose, bulk density, compressibility index and Hausner's ratio were determined for the powder blend. In this study, 14 formulations of stavudine oral disintegration tablet were prepared by direct compression method. The tablets were evaluated for weight variation, percentage friability, disintegration time, hardness, wetting time and water absorption ratio. The in vitro dissolution study results of the batch S1 (stavudine+crospovidone+sodium starch glycollate) are encouraging as highest dissolution rate (99.2% in 100 min) and lowest time of disintegration (56 s) was achieved. The in vivo drug release studies were carried out in rabbits and the relative bioavailability of formulation S1 was found to be 2.83 times greater than that of conventional tablets. PMID:23798782

Oral Disintegration Tablets of Stavudine for HIV Management: A New Technological Approach.

PubMed

Sankar, V; Ramakrishna, B; Devi, P Shalini; Karthik, S

2012-11-01

Stavudine oral disintegration tablets were formulated to minimize the bitter taste and to reduce the first-pass hepatic metabolism. The various precompression parameters like the angle of repose, bulk density, compressibility index and Hausner's ratio were determined for the powder blend. In this study, 14 formulations of stavudine oral disintegration tablet were prepared by direct compression method. The tablets were evaluated for weight variation, percentage friability, disintegration time, hardness, wetting time and water absorption ratio. The in vitro dissolution study results of the batch S1 (stavudine+crospovidone+sodium starch glycollate) are encouraging as highest dissolution rate (99.2% in 100 min) and lowest time of disintegration (56 s) was achieved. The in vivo drug release studies were carried out in rabbits and the relative bioavailability of formulation S1 was found to be 2.83 times greater than that of conventional tablets.

Application of oxybutynin selective sensors for monitoring the dissolution profile and assay of pharmaceutical dosage forms.

PubMed

El Hamshary, Marwa S; Salem, Omar H; El Nashar, Rasha M

2010-01-01

Two ion-selective sensors of the plastic membrane type were prepared for the determination of oxybutynin hydrochloride (OxCl). They depend on the incorporation of the ion-associates with phosphotungestic acid or phosphomolybdic acid in a PVC matrix. A comparative study is made between their performance characteristics in batch and FIA conditions. The sensors have nearly the same usable concentration, temperature and pH range. They have a wide range of selectivity and can be applied for the determination of the relevant drug with nearly the same precision and accuracy in vitro. Dissolution testing was applied using the sensors; this offers a simple, rapid, cheap way out of sophisticated and high cost instruments used in the pharmacopeial method using HPLC. The investigated drug was determined in its pure and pharmaceutical preparations. The results were accurate and precise, as indicated by the recovery values and coefficients of variation.

Natural soil mediated photo Fenton-like processes in treatment of pharmaceuticals: Batch and continuous approach.

PubMed

Changotra, Rahil; Rajput, Himadri; Dhir, Amit

2017-12-01

This paper manifests the potential viability of soil as a cost-free catalyst in photo-Fenton-like processes for treating pharmaceuticals at large scale. Naturally available soil without any cost intensive modification was utilized as a catalyst to degrade pharmaceuticals, specifically ornidazole (ORZ) and ofloxacin (OFX). Soil was characterized and found enriched with various iron oxides like hematite, magnetite, goethite, pyrite and wustite, which contributes toward enhanced dissolution of Fe 3+ than Fe 2+ in the aqueous solution resulting in augmented rate of photo-Fenton reaction. The leached iron concentration in solution was detected during the course of experiments. The degradation of ORZ and OFX was assessed in solar induced batch experiments using H 2 O 2 as oxidant and 95% ORZ and 92% OFX removal was achieved. Elevated efficiencies were achieved due to Fe 2+ /Fe 3+ cycling, producing more hydroxyl radical leading to the existence of homogeneous and heterogeneous reactions simultaneously. The removal efficiency of solar photo-Fenton like process was also compared to photo-Fenton process with different irradiation sources (UV-A and UV-B) and were statistically analysed. Continuous-scale studies were conducted employing soil either in the form of soil beads or as a thin layer spread on the surface of baffled reactor. Soil beads were found to have satisfactory reusability and stability. 84 and 79% degradation of ORZ and OFX was achieved using soil as thin layer while with soil beads 71 and 68% degradation, respectively. HPLC and TOC study confirmed the efficient removal of both the compounds. Toxicity assessment demonstrates the inexistence of toxic intermediates during the reaction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic limitations on tracer partitioning in ganglia dominated source zones.

PubMed

Ervin, Rhiannon E; Boroumand, Ali; Abriola, Linda M; Ramsburg, C Andrew

2011-11-01

Quantification of the relationship between dense nonaqueous phase liquid (DNAPL) source strength, source longevity and spatial distribution is increasingly recognized as important for effective remedial design. Partitioning tracers are one tool that may permit interrogation of DNAPL architecture. Tracer data are commonly analyzed under the assumption of linear, equilibrium partitioning, although the appropriateness of these assumptions has not been fully explored. Here we focus on elucidating the nonlinear and nonequilibrium partitioning behavior of three selected alcohol tracers - 1-pentanol, 1-hexanol and 2-octanol in a series of batch and column experiments. Liquid-liquid equilibria for systems comprising water, TCE and the selected alcohol illustrate the nonlinear distribution of alcohol between the aqueous and organic phases. Complete quantification of these equilibria facilitates delineation of the limits of applicability of the linear partitioning assumption, and assessment of potential inaccuracies associated with measurement of partition coefficients at a single concentration. Column experiments were conducted under conditions of non-equilibrium to evaluate the kinetics of the reversible absorption of the selected tracers in a sandy medium containing a uniform entrapped saturation of TCE-DNAPL. Experimental tracer breakthrough data were used, in conjunction with mathematical models and batch measurements, to evaluate alternative hypotheses for observed deviations from linear equilibrium partitioning behavior. Analyses suggest that, although all tracers accumulate at the TCE-DNAPL/aqueous interface, surface accumulation does not influence transport at concentrations typically employed for tracer tests. Moreover, results reveal that the kinetics of the reversible absorption process are well described using existing mass transfer correlations originally developed to model aqueous boundary layer resistance for pure-component NAPL dissolution. Copyright © 2011 Elsevier B.V. All rights reserved.

Laboratory-scale experiments and numerical modeling of cosolvent flushing of multi-component NAPLs in saturated porous media

NASA Astrophysics Data System (ADS)

Agaoglu, Berken; Scheytt, Traugott; Copty, Nadim K.

2012-10-01

This study examines the mechanistic processes governing multiphase flow of a water-cosolvent-NAPL system in saturated porous media. Laboratory batch and column flushing experiments were conducted to determine the equilibrium properties of pure NAPL and synthetically prepared NAPL mixtures as well as NAPL recovery mechanisms for different water-ethanol contents. The effect of contact time was investigated by considering different steady and intermittent flow velocities. A modified version of multiphase flow simulator (UTCHEM) was used to compare the multiphase model simulations with the column experiment results. The effect of employing different grid geometries (1D, 2D, 3D), heterogeneity and different initial NAPL saturation configurations was also examined in the model. It is shown that the change in velocity affects the mass transfer rate between phases as well as the ultimate NAPL recovery percentage. The experiments with low flow rate flushing of pure NAPL and the 3D UTCHEM simulations gave similar effluent concentrations and NAPL cumulative recoveries. Model simulations over-estimated NAPL recovery for high specific discharges and rate-limited mass transfer, suggesting a constant mass transfer coefficient for the entire flushing experiment may not be valid. When multi-component NAPLs are present, the dissolution rate of individual organic compounds (namely, toluene and benzene) into the ethanol-water flushing solution is found not to correlate with their equilibrium solubility values.

Temperature effect on the acid-base behaviour of Na-montmorillonite.

PubMed

Duc, Myriam; Carteret, Cédric; Thomas, Fabien; Gaboriaud, Fabien

2008-11-15

We report a study of the acid-base properties of Na-montmorillonite suspensions at temperatures from 25 degrees C to 80 degrees C, by continuous and batch potentiometric methods, combined with analysis of the dissolved and readsorbed species. The batch titration curves reveal that the dissolution processes of Na-montmorillonite and silica-rich secondary phases are increasingly predominant, respectively at acid and basic pH, and according to the temperature. The continuous titration curves are less affected by these side reactions. In the absence of a common intersection point, the thermodynamic analysis of the curves was based on the shift of the PZNPC with the ionic strength. This shift was not significantly altered by the temperature, by comparison with the dissociation product of water in the same conditions. Therefore we concluded that protonation-deprotonation of the dissociable sites at the edges of the clay platelets is not significantly temperature dependent.

Dissolution and dissolution/permeation experiments for predicting systemic exposure following oral administration of the BCS class II drug clarithromycin.

PubMed

Kristin, Forner; René, Holm; Boontida, Morakul; Buraphacheep, Junyaprasert Varaporn; Maximilian, Ackermann; Johanna, Mazur; Peter, Langguth

2017-04-01

In order to save time and resources in early drug development, in vitro methods that correctly predict the formulation effect on oral drug absorption are necessary. The aim of this study was to 1) evaluate various BCS class II drug formulations with in vitro methods and in vivo in order to 2) determine which in vitro method best correlates with the in vivo results. Clarithromycin served as model compound in formulations with different particle sizes and content of excipients. The performed in vitro experiments were dissolution and dissolution/permeation experiments across two types of membrane, Caco-2 cells and excised rat intestinal sheets. The in vivo study was performed in rats. The oral absorption was enhanced by downsizing drug particles and by increasing the excipient concentration. This correlated strongly with the flux across Caco-2 cells but not with the other in vitro experiments. The insufficient correlation with the dissolution experiments can be partly explained by excipient caused problems during the filtration step. The very poor correlation of the in vivo data with the flux across excised rat intestinal sheets might be due to an artificially enlarged mucus layer ex vivo. In conclusion, downsizing BCS class II drug particles and the addition of surfactants enhanced the in vivo absorption, which was best depicted by dissolution/permeation experiments across Caco-2 cells. This setup is proposed as best model to predict the in vivo formulation effect. Also, this is the first study to evaluate the impact of the nature of the permeation membrane in dissolution/permeation experiments. Copyright © 2017 Elsevier B.V. All rights reserved.

The dissolution kinetics of major elements in municipal solid waste incineration bottom ash particles

NASA Astrophysics Data System (ADS)

Bendz, David; Tüchsen, Peter L.; Christensen, Thomas H.

2007-12-01

Leaching and tracer experiments in batches at L/S 20 were performed with 3-month-old MSWI bottom ash separated into eight different particle sizes. The time-dependent leaching of major elements (Ca 2+, K +, Na +, Cl - and SO 4- 2 ) was monitored for up to 747 h. Physical properties of the particles, the specific surface (BET), pore volume and pore volume distribution over pore sizes (BJH) were determined for all particle classes by N 2 adsorption/desorption experiments. Some common features of physical pore structure for all particles were revealed. The specific surface and the particle pore volume were found to be negatively correlated with particle size, ranging from 3.2 m 2/g to 25.7 m 2/g for the surface area and from 0.0086 cm 3/g to 0.091 cm 3/g for the pore volume. Not surprisingly, the specific surface area was found to be the major material parameter that governed the leaching behavior for all elements (Ca 2+, K +, Na +, Cl - and SO 4- 2 ) and particle sizes. The diffusion resistance was determined independently by separate tracer (tritium) experiments. Diffusion gave a significant contribution to the apparent leaching kinetics for all elements during the first 10-40 h (depending on the particle size) of leaching and surface reaction was the overall rate controlling mechanism at late times for all particle sizes. For Ca 2+ and SO 4- 2 , the coupled effect of diffusion resistance and the degree of undersaturation in the intra particle pore volume was found to be a major rate limiting dissolution mechanism for both early and late times. The solubility control in the intra particulate porosity may undermine any attempt to treat bottom ash by washing out the sulfate. Even for high liquid/solid ratios, the solubility in the intra-particular porosity will limit the release rate.

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.

Integrated continuous dissolution, refolding and tag removal of fusion proteins from inclusion bodies in a tubular reactor.

PubMed

Pan, Siqi; Zelger, Monika; Jungbauer, Alois; Hahn, Rainer

2014-09-20

An integrated continuous tubular reactor system was developed for processing an autoprotease expressed as inclusion bodies. The inclusion bodies were suspended and fed into the tubular reactor system for continuous dissolving, refolding and precipitation. During refolding, the dissolved autoprotease cleaves itself, separating the fusion tag from the target peptide. Subsequently, the cleaved fusion tag and any uncleaved autoprotease were precipitated out in the precipitation step. The processed exiting solution results in the purified soluble target peptide. Refolding and precipitation yields performed in the tubular reactor were similar to batch reactor and process was stable for at least 20 h. The authenticity of purified peptide was also verified by mass spectroscopy. Productivity (in mg/l/h and mg/h) calculated in the tubular process was twice and 1.5 times of the batch process, respectively. Although it is more complex to setup a tubular than a batch reactor, it offers faster mixing, higher productivity and better integration to other bioprocessing steps. With increasing interest of integrated continuous biomanufacturing, the use of tubular reactors in industrial settings offers clear advantages. Copyright © 2014 Elsevier B.V. All rights reserved.

Isolation, characterization and investigation of Cordia dichotoma fruit polysaccharide as a herbal excipient.

PubMed

Pawar, Harshal Ashok; Jadhav, Pravin

2015-01-01

The objective of the present research work was to isolate, purify and characterize Cordia dichotoma gum and investigate its disintegration property in oral tablets. The isolated gum was tested for physicochemical characteristics such as solubility, pH (1% w/w in water), swelling index, loss on drying, ash value, bulk and tapped density, Carr's index, Hausner's ratio and angle of repose. The Orodispersible tablets of valsartan were prepared by direct compression method and evaluated for average weight (mg), drug content (%), thickness (mm), hardness (kg/cm(2)), friability (%), wetting time (sec), water absorption ratio (%) and disintegration time (sec). FTIR studies revealed that there was no interaction between drug, gum and other excipients used in the study. The F4 batch with disintegration time 26.34 ± 0.78 s and in vitro release 99.64 ± 0.43% was selected as optimized formulation. This formulation was compared with conventional marketed formulation and was found superior. Batch F4 was subjected to stability studies for three months and was tested for its disintegration time, drug contents and dissolution behaviour. Batch F4 was found stable for three months at accelerated temperature. Copyright © 2014 Elsevier B.V. All rights reserved.

Mechanistic study of lead desorption during the leaching process of ion-absorbed rare earths: pH effect and the column experiment

NASA Astrophysics Data System (ADS)

Xue, Q.; Tang, J., Sr.; Chen, H.

2017-12-01

High concentrations of ammonium sulfate, often used in the in-situ mining process, can result in a decrease of pH in the environment and dissolution of rare earth metals. Ammonium sulfate can also cause desorption of toxic heavy metals, leading to environmental and human health implications. In this study, the desorption behavior and fraction changes of lead in the ion-absorbed rare earth ore were studied using batch desorption experiments and column leaching tests. Results from batch desorption experiments showed that the desorption process of lead included fast and slow stages, and followed an Elovich model well. The desorption rate and the proportion of lead content in the solution to the total lead in the soil were observed to increase with a decrease in the initial pH of the ammonium sulfate solution. The lead in soil included an acid extractable fraction, reducible fraction, oxidizable fraction, and a residual fraction, with the predominant fractions being the reducible and acid extractable fractions. 96% of the extractable fraction in soil were desorbed into solution at pH=3.0, and the content of the reducible fraction was observed to initially increase (when pH>4.0) and then decrease (when pH<4.0) with a decrease in pH. Column leaching tests indicated that the content of lead in the different fractions of soil followed the trend of reducible fraction > oxidizable fraction > acid extractable fraction > residual fraction after the simulating leaching mining process. The change in pH was also found to have a larger influence on the acid extractable and reducible fractions than the other two fractions. The proportion of the extractable fraction being leached was ca. 86%, and the reducible fraction was enriched along the migration direction of the leaching liquid. These results suggest that certain lead fractions may desorb again and contaminate the environment via acid rain, which provides significant information for environmental assessment and remediation after mining process.

Statistical modeling methods to analyze the impacts of multiunit process variability on critical quality attributes of Chinese herbal medicine tablets

PubMed Central

Sun, Fei; Xu, Bing; Zhang, Yi; Dai, Shengyun; Yang, Chan; Cui, Xianglong; Shi, Xinyuan; Qiao, Yanjiang

2016-01-01

The quality of Chinese herbal medicine tablets suffers from batch-to-batch variability due to a lack of manufacturing process understanding. In this paper, the Panax notoginseng saponins (PNS) immediate release tablet was taken as the research subject. By defining the dissolution of five active pharmaceutical ingredients and the tablet tensile strength as critical quality attributes (CQAs), influences of both the manipulated process parameters introduced by an orthogonal experiment design and the intermediate granules’ properties on the CQAs were fully investigated by different chemometric methods, such as the partial least squares, the orthogonal projection to latent structures, and the multiblock partial least squares (MBPLS). By analyzing the loadings plots and variable importance in the projection indexes, the granule particle sizes and the minimal punch tip separation distance in tableting were identified as critical process parameters. Additionally, the MBPLS model suggested that the lubrication time in the final blending was also important in predicting tablet quality attributes. From the calculated block importance in the projection indexes, the tableting unit was confirmed to be the critical process unit of the manufacturing line. The results demonstrated that the combinatorial use of different multivariate modeling methods could help in understanding the complex process relationships as a whole. The output of this study can then be used to define a control strategy to improve the quality of the PNS immediate release tablet. PMID:27932865

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.

Leaching of boron, arsenic and selenium from sedimentary rocks: II. pH dependence, speciation and mechanisms of release.

PubMed

Tabelin, Carlito Baltazar; Hashimoto, Ayaka; Igarashi, Toshifumi; Yoneda, Tetsuro

2014-03-01

Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite. Copyright © 2013 Elsevier B.V. All rights reserved.

Release kinetics of vanadium from vanadium (III, IV and V) oxides: Effect of pH, temperature and oxide dose.

PubMed

Hu, Xingyun; Yue, Yuyan; Peng, Xianjia

2018-05-01

Batch experiments were performed to derive the rate laws for the proton-promoted dissolution of the main vanadium (III, IV and V) oxides at pH 3.1-10.0. The release rates of vanadium are closely related to the aqueous pH, and several obvious differences were observed in the release behavior of vanadium from the dissolution of V 2 O 5 and vanadium(III, IV) oxides. In the first 2hr, the release rates of vanadium from V 2 O 3 were r=1.14·([H + ]) 0.269 at pH 3.0-6.0 and r=0.016·([H + ]) -0.048 at pH 6.0-10.0; the release rates from VO 2 were r=0.362·([H + ]) 0.129 at pH 3.0-6.0 and r=0.017·([H + ]) -0.097 at pH 6.0-10.0; and the release rates from V 2 O 5 were r=0.131·([H + ]) -0.104 at pH 3.1-10.0. The release rates of vanadium from the three oxides increased with increasing temperature, and the effect of temperature was different at pH 3.8, pH 6.0 and pH 7.7. The activation energies of vanadium (III, IV and V) oxides (33.4-87.5kJ/mol) were determined at pH 3.8, pH6.0 and pH 7.7, showing that the release of vanadium from dissolution of vanadium oxides follows a surface-controlled reaction mechanism. The release rates of vanadium increased with increasing vanadium oxides dose, albeit not proportionally. This study, as part of a broader study of the release behavior of vanadium, can help to elucidate the pollution problem of vanadium and to clarify the fate of vanadium in the environment. Copyright © 2017. Published by Elsevier B.V.

Characterising and correcting batch variation in an automated direct infusion mass spectrometry (DIMS) metabolomics workflow.

PubMed

Kirwan, J A; Broadhurst, D I; Davidson, R L; Viant, M R

2013-06-01

Direct infusion mass spectrometry (DIMS)-based untargeted metabolomics measures many hundreds of metabolites in a single experiment. While every effort is made to reduce within-experiment analytical variation in untargeted metabolomics, unavoidable sources of measurement error are introduced. This is particularly true for large-scale multi-batch experiments, necessitating the development of robust workflows that minimise batch-to-batch variation. Here, we conducted a purpose-designed, eight-batch DIMS metabolomics study using nanoelectrospray (nESI) Fourier transform ion cyclotron resonance mass spectrometric analyses of mammalian heart extracts. First, we characterised the intrinsic analytical variation of this approach to determine whether our existing workflows are fit for purpose when applied to a multi-batch investigation. Batch-to-batch variation was readily observed across the 7-day experiment, both in terms of its absolute measurement using quality control (QC) and biological replicate samples, as well as its adverse impact on our ability to discover significant metabolic information within the data. Subsequently, we developed and implemented a computational workflow that includes total-ion-current filtering, QC-robust spline batch correction and spectral cleaning, and provide conclusive evidence that this workflow reduces analytical variation and increases the proportion of significant peaks. We report an overall analytical precision of 15.9%, measured as the median relative standard deviation (RSD) for the technical replicates of the biological samples, across eight batches and 7 days of measurements. When compared against the FDA guidelines for biomarker studies, which specify an RSD of <20% as an acceptable level of precision, we conclude that our new workflows are fit for purpose for large-scale, high-throughput nESI DIMS metabolomics studies.

Application of the flow-through time-resolved analysis technique to trace element determination in ostracod shells

NASA Astrophysics Data System (ADS)

Börner, Nicole; De Baere, Bart; Francois, Roger; Frenzel, Peter; Schwalb, Antje

2014-05-01

Trace element analyses of ostracod shells are a vital tool for paleoenvironmental reconstructions from lake sediments (Börner et al., 2013). Conventional batch dissolution ICP-MS is the most common way for analyzing trace elements in ostracod shells. However, due to dissolution or secondary overgrowth the primary signal may be masked. Resulting variations in trace element composition have been identified to be in the order of a magnitude range. Therefore, the application of the newly developed flow-through technique will be assessed. The flow-through time-resolved analysis technique allows to chemically separate mineral phases of different solubility such as, in particular, original shell calcite from overgrowth calcite, and thus to correct the measurements for the biogenic signal. During a flow-through experiment, eluent is continuously pumped through a sample column, typically a filter in which the ostracod valves are loaded. The gradual dissolution of the substrate is controlled by a combination of eluent type, eluent temperature and eluent flow rate. The dissolved sample then flows directly to a mass spectrometer. The resulting data is a chromatogram, featuring different mineral phases dissolving as time progresses. Hence, the flow-through technique provides a detailed geochemical fingerprint of the substrate and therefore additional data relative to conventional methods. To calibrate this technique for the application to ostracods we use ostracod shells from Southern Tibetan Plateau lakes, which feature an alkaline environment but show highly diverse hydrochemistry. Cleaned as well as uncleaned ostracod shells show similarity in their trace element signals, allowing measurements without prior cleaning of the shells, and thus more time-efficient sample throughput. Measurements of unclean shells are corrected for the biogenic signal using an equation from Klinkhammer et al. (2004). Another advantage is that the measurements can be carried out on single ostracod shells, as not every single sediment sample contains enough adult intact specimens of all required genera, making batch cleaning dissolution impossible. The flow-through time-resolved analysis technique gives an accurate and high-resolution dataset. The trace elemental data for living ostracods compared to the hydrological data from each sampling site provides a calibration dataset for further hydrological and thus climatological reconstruction of a sediment core from Nam Co. Mg/Ca and Sr/Ca ratios in ostracod shells will provide information about past water temperature and salinity resulting from changes in precipitation vs. evaporation ratios and monsoon activity. Further, we will exploit Mn/Ca, Fe/Ca and U/Ca ratios as redox indicators to reconstruct oxygenation cycles and Ba/Ca ratios to detect changes in productivity and/or salinity. This reconstruction should provide a more extensive insight in past climatic change, e.g. precipitation - evaporation balance, lake level and circulation changes, and the recording of environmental signatures by ostracod shells. Börner, N., De Baere, B., Yang, Q., Jochum, K.P., Frenzel, P., Andreae, M.O., Schwalb, A., 2013. Ostracod shell chemistry as proxy for paleoenvironmental change. Quaternary International 313-314, 17-37. Klinkhammer, G.P., Haley, B.A., Mix, A.C., Benway, H., Cheseby, M., 2004. Evaluation of automated flow-through time-resolved analysis of foraminifera for Mg/Ca paleothermometry. Paleoceanography 19, PA4030.

Its ovr b/n u n me: technology use, attachment styles, and gender roles in relationship dissolution.

PubMed

Weisskirch, Robert S; Delevi, Raquel

2012-09-01

Relationship dissolution now occurs through technologies like text messaging, e-mail, and social networking sites (SNS). Individuals who experience relationship dissolution via technology may differ in their attachment pattern and gender role attitudes from those who have not had that experience. One hundred five college students (males=21 and females=84) completed an online questionnaire about technology-mediated breakups, attachment style, and gender role attitudes. More than a quarter of the sample had experienced relationship dissolution via technology. Attachment anxiety predicted those subject to technology-mediated breakups. Attachment avoidance and less traditional gender roles were associated with increased likelihood of technology use in relationship dissolution. Implications are discussed in regards to future research and practice.

A need for a standardization in anaerobic digestion experiments? Let's get some insight from meta-analysis and multivariate analysis.

PubMed

Lavergne, Céline; Jeison, David; Ortega, Valentina; Chamy, Rolando; Donoso-Bravo, Andrés

2018-09-15

An important variability in the experimental results in anaerobic digestion lab test has been reported. This study presents a meta-analysis coupled with multivariate analysis aiming to assess the impact of this experimental variability in batch and continuous operation at mesophilic and thermophilic anaerobic digestion of waste activated sludge. An analysis of variance showed that there was no significant difference between mesophilic and thermophilic conditions in both continuous and batch conditions. Concerning the operation mode, the values of methane yield were significantly higher in batch experiment than in continuous reactors. According to the PCA, for both cases, the methane yield is positive correlated to the temperature rises. Interestingly, in the batch experiments, the higher the volatile solids in the substrate was, the lowest was the methane production, which is correlated to experimental flaws when setting up those tests. In continuous mode, unlike the batch test, the methane yield is strongly (positively) correlated to the organic content of the substrate. Experimental standardization, above all, in batch conditions are urgently necessary or move to continuous experiments for reporting results. The modeling can also be a source of disturbance in batch test. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of Mineralogy on Dissolution and Speciation of Iron Containing Mineral Oxides in Atmospheric Aerosol Dust

NASA Astrophysics Data System (ADS)

Hettiarachchi, E.; Rubasinghege, G. R. S.; Reynolds, R. L.; Goldstein, H. L.; Moskowitz, B. M.

2017-12-01

Iron is one of the important trace elements for the life. Though it is the fourth most abundant element in the terrestrial crust, given higher pH ( 8.5) in the ocean, the direct dissolution of iron from the Earth crust is limited. Despite this limitation, ocean contains about 2 nM of dissolved iron that is 20-fold greater. Therefore, it is hypothesized most iron comes to the ocean via atmosphere, and dissolution occurs in the acidic atmospheric environments. The current work focuses on the effect of minerology on atmospheric processing of Fe-containing mineral dust using four authentic dust samples, collected from different parts of the world, along with three model systems, hematite (α-Fe2O3), magnetite (Fe3O4) and ilmenite (FeTiO3). Here, spectroscopic methods are combined with batch reactor studies to investigate total iron dissolution and speciation, with a specific focus on source material i.e. particle size, mineralogy, and environmental conditions, i.e. pH, temperature and solar flux. Our data suggests that the presence of Ti metal enhances the dissolution of iron regardless the total %Fe in the mineral. The surface area normalized total iron dissolution in ilmenite, under the dark conditions, in the presence of nitric acid (HNO3) is 3-fold higher than that of hematite. In authentic samples, similar effects were observed for samples containing %Ti. Further, 74% of the dissolved iron in ilmenite remained as Fe(II), bioavailable iron, whereas it was only 60% for magnetite and 8% for hematite. In this study, these results were used to interpret similar trends observed for authentic dust samples with high magnetite content. Thus, the findings of the current study highlight important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol.

Dynamic processes occurring at the Cr IIIaq-manganite (γ-MnOOH) interface: simultaneous adsorption, microprecipitation, oxidation/reduction, and dissolution

NASA Astrophysics Data System (ADS)

Weaver, Robert M.; Hochella, Michael F.; Ilton, Eugene S.

2002-12-01

The complex interaction between Cr IIIaq and manganite (γ-MnOOH) was systematically studied at room temperature over a pH range of 3 to 6, and within a concentration range of 10 -4 to 10 -2 M CrOH 2+aq. Solution compositional changes during batch reactions were characterized by inductively coupled plasma spectroscopy and ultraviolet-visible spectrophotometry. The manganites were characterized before and after reaction with X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), high-resolution field-emission SEM, and energy-dispersive spectroscopy analysis. Fluid-cell atomic force microscopy was used to follow these metal-mineral interactions in situ. The reactions are characterized by (1) sorption of Cr III and the surface-catalyzed microprecipitation of Cr III-hydroxy hydrate on manganite surfaces, (2) the acidic dissolution of the manganite, and (3) the simultaneous reductive dissolution of manganite coupled with the oxidation of Cr IIIaq to highly toxic Cr VIaq. Cr III-hydroxy hydrate was shown to precipitate on the manganite surface while still undersaturated in bulk solution. The rate of manganite dissolution increased with decreasing pH due both to acid-promoted and Mn-reduction-promoted dissolution. Cr oxidation also increased in the lower pH range, this as a result of its direct redox coupling with Mn reduction. Neither Mn II nor Cr VI were ever detected on manganite surfaces, even at the maximum rate of their generation. At the highest pHs of this study, Cr IIIaq was effectively removed from solution to form Cr III-hydroxy hydrate on manganite surfaces and in the bulk solution, and manganite dissolution and Cr VIaq generation were minimized. All interface reactions described above were heterogeneous across the manganite surfaces. This heterogeneity is a direct result of the heterogeneous semiconducting nature of natural manganite crystals and is also an expression of the proximity effect, whereby redox processes on semiconducting surfaces are not limited to next nearest neighbor sites.

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.

Clinopyroxene dissolution in basaltic melt

NASA Astrophysics Data System (ADS)

Chen, Yang; Zhang, Youxue

2009-10-01

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

An experimental and modeling study of grain-scale uranium desorption from field-contaminated sediments and the potential influence of microporosity on mass-transfer

NASA Astrophysics Data System (ADS)

Stoliker, D.; Liu, C.; Kent, D. B.; Zachara, J. M.

2012-12-01

The aquifer below the 300-Area of the Hanford site (Richland, WA, USA) is plagued by a persistent plume of dissolved uranium (U(VI)) in excess of the Environmental Protection Agency drinking water maximum contamination level even after the removal of highly contaminated sediments. The aquifer sediments in the seasonally saturated lower vadose zone act as both a source and sink for uranium during stage changes in the nearby Columbia River. Diffusion limitation of uranium mass-transfer within these sediments has been cited as a potential cause of the plume's persistence. Equilibrium U(VI) sorption is a strong function of variable chemical conditions, especially carbonate, hydrogen, and uranyl ion activities. Field-contaminated sediments from the site require up to 1,000 hours to reach equilibrium in static batch reactors. Increases in U(VI) concentrations over longer time-scales result from changes in chemical conditions, which drive reactions with sediments that favor U(VI) desorption. Grain-scale U(VI) sorption/desorption rates are slow, likely owing to diffusion of U(VI) and other solutes through intra-granular pore domains. In order to improve understanding of the impact of intra-granular diffusion and chemical reactions controlling grain-scale U(VI) release, experiments were conducted on individual particle size fractions of a <8 mm composite of field-contaminated, lower vadose zone sediments. For each size fraction, equilibrium U(VI) sorption/desorption in static batch reactors was well-described by surface complexation models over a range of chemical conditions applicable to the field site. Desorption rates from individual size fractions in flow-through batch reactors, examined under a single set of constant chemical conditions with multiple stop-flow events, were similar for all size fractions <2 mm. Kinetic U(VI) desorption in flow-through batch reactors was modeled using a multi-rate surface complexation approach, where sorption/desorption rates were assumed to be proportional to the displacement from equilibrium and multiple diffusion domains were described with a two-parameter lognormal distribution of mass-transfer rate coefficients. Parameters describing mass transfer were the same for all size fractions <2 mm but differed for the largest (2-8 mm) size fraction. The evolution of pH, along with dissolved cation and carbonate concentrations, was modeled using equilibrium cation exchange, rate-limited calcite dissolution, aerobic respiration, and silica dissolution. Desorption and chemical reaction models calibrated with individual size fractions predicted U(VI) and chemical composition as a function of time for the bulk sediment sample. Volumes of pores less than 2.4 nm, quantified using nitrogen adsorption-desorption isotherms, were the same for all size fractions < 2 mm, nearly double that of the 2-8 mm size fraction. Similarity in the observed pore volumes and multi-rate mass-transfer parameters across all size fractions <2 mm suggest the importance of pores in this size class in controlling slow grain-scale U(VI) desorption rates. Models like these provide a means for testing the influence of grain-scale mass-transfer on the persistence of U(VI) plume at the site.

BIOLAB experiment development status 2005

NASA Astrophysics Data System (ADS)

Brinckmann, Enno; Manieri, Pierfilippo

2005-08-01

BIOLAB, ESA's major facility for biological Space research on the International Space Station (ISS), will accommodate the first two batches of experiments after its launch with the "Columbus" Laboratory (spring 2007). Seven experiments have been selected for development: three of the first batch have concluded Phase A/B with the testing of the breadboards, in which the main functions of the scientific studies can be simulated and defined for further inputs to the final design of the experiment hardware. The biological specimens of the first batch are scorpions, plant seedlings, bacteria suspensions and cell cultures of mammalian and invertebrate origin. The experiment protocols request demanding resources ranging from life support for the entire mission (90 days) to skilled crew operations and transport/storage in deep freezers. Even more sophisticated experiments are in preparation for the second batch, dealing with various cell culture systems. This presentation gives an overview about the experiment development status, whilst the science background and breadboard test results will be presented by the respective experiment teams.

Linking soil chemistry, treeline shifts and climate change: scenario modeling using an experimental approach

NASA Astrophysics Data System (ADS)

Mavris, Christian; Furrer, Gerhard; Anderson, Susanne; Blum, Alex; Wells, Aaron; Dahms, Dennis; Egli, Markus

2014-05-01

Climate change and global warming have a strong influence on the landscape development. As cold areas become warmer, both flora and fauna must adapt to new conditions (a). It is widely accepted that climate changes deeply influence the treeline shifts. In addition to that, wildfires, plant diseases and insect infestation (i.e. mountain pine beetle) can promote a selective replacement of plants, inhibiting some and favoring others, thus modifying the ecosystem in diverse ways. There is little knowledge on the behavior of soil chemistry when such changes occur. Will elemental availability become a crucial factor as a function of climate changes? The Sinks Canyon and Stough Basin - SE flank of the Wind River Range, Wyoming, USA - offer an ideal case study. Conceptually, the areas were divided into three main subsets: tundra, forest and a subarid environment. All soils were developed on granitoid moraines (b, c). From each subset, a liquid topsoil extract was produced and mixed with the solid subsoil samples in batch reactors at 50 °C. The batch experiments were carried out over 1800 h, and the progress of the dissolution was regularly monitored by analyzing liquid aliquots using IC and ICP-OES. The nutrients were mostly released within the first hours of the experiment. Silicon and Al were continuously released into the solution, while some alkali elements - i.e. Na - showed a more complex trend. Organic acids (acetic, citric) and other ligands produced during biodegradation played an active role in mineral dissolution and nutrient release. The mineral colloids detected in the extract (X-ray diffraction) can significantly control surface reactions (adsorption/desorption) and contributed to specific cationic concentrations. The experimental set up was then compared to a computed dissolution model using SerialSTEADYQL software (d, e). Decoding the mechanisms driving mineral weathering is the key to understand the main geochemical aspects of adaptation during climate changing conditions. Our findings suggest that one of the controlling factors in nutrient release is the capacity of ion diffusion, mostly given by the activity of clay minerals and organic matter. (a) Burga, C., Krüsi, B., Egli, M., Wernli, M., Elsener, S., Ziefle, M., Fischer, T., Mavris, C.. Plant succession and soil development on the foreland of the Morteratsch glacier (Pontresina, Switzerland): Straight forward or chaotic? Flora 205 (2010) 561-576 (b) Dahms, D. Relative and Numeric Age Data for Pleistocene Glacial Deposits and Diamictons in and near Sinks Canyon, Wind River Range, Wyoming, U.S.A. AAAR 36, 1 (2004) 59-77 (c) Egli, M., Dahms, D., Norton, K. Soil formation rates on silicate parent material in alpine environments: Different approaches-different results? Geoderma 213 (2014) 320-333 (d) Furrer, G., von Gunten, U., Zobrist, J. Steady-state modelling of biogeochemical processes in columns with aquifer material: 1. Speciation and mass balances. Chemical Geology 133 (1996) 15-28 (e) von Gunten, U, Furrer, G. Steady-state modelling of biogeochemical processes in columns with aquifer material: 2. Dynamics of iron-sulfur interactions. Chemical Geology 167 (2000) 271-284

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.

In Vitro and In Vivo Characterization of Drug Nanoparticles Prepared Using PureNano™ Continuous Crystallizer to Improve the Bioavailability of Poorly Water Soluble Drugs.

PubMed

Tahara, Kohei; Nishikawa, Masahiro; Matsui, Ko; Hisazumi, Koji; Onodera, Risako; Tozuka, Yuichi; Takeuchi, Hirofumi

2016-09-01

The aim of this study was to enhance the dissolution and oral absorption of poorly water-soluble active pharmaceutical ingredients (APIs) using nanoparticle suspensions prepared with a PureNano™ continuous crystallizer (PCC). Nanoparticle suspensions were prepared with a PCC, which is based on microfluidics reaction technology and solvent-antisolvent crystallization. Phenytoin, bezafibrate, flurbiprofen, and miconazole were used as model APIs. These APIs were dissolved in ethanol and precipitated by the addition of water and polyvinyl alcohol. Batch crystallization (BC) using a beaker was also performed to prepare the suspensions. Both PCC and BC formulations were freeze-dried before being characterized in vitro and in vivo. The particle sizes of the nanoparticle suspensions prepared with the PCC were smaller than those prepared by BC. The dissolution rate of each API in vitro significantly increased after crystallization. Reducing the particle size of either the BC or PCC formulation led to increased API flux across Caco-2 cell monolayers. PCC preparations showed higher plasma concentrations after oral administration, demonstrating the advantages of a fast dissolution rate and increased interaction with the gastrointestinal tract owing to the smaller particle size. PCC can continuously produce nanoparticle APIs and is an efficient approach for improving their oral bioavailability.

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.

Dynamic three-dimensional pore-scale imaging of reaction in a carbonate at reservoir conditions.

PubMed

Menke, Hannah P; Bijeljic, Branko; Andrew, Matthew G; Blunt, Martin J

2015-04-07

Quantifying CO2 transport and average effective reaction rates in the subsurface is essential to assess the risks associated with underground carbon capture and storage. We use X-ray microtomography to investigate dynamic pore structure evolution in situ at temperatures and pressures representative of underground reservoirs and aquifers. A 4 mm diameter Ketton carbonate core is injected with CO2-saturated brine at 50 °C and 10 MPa while tomographic images are taken at 15 min intervals with a 3.8 μm spatial resolution over a period of 2(1/2) h. An approximate doubling of porosity with only a 3.6% increase in surface area to volume ratio is measured from the images. Pore-scale direct simulation and network modeling on the images quantify an order of magnitude increase in permeability and an appreciable alteration of the velocity field. We study the uniform reaction regime, with dissolution throughout the core. However, at the pore scale, we see variations in the degree of dissolution with an overall reaction rate which is approximately 14 times lower than estimated from batch measurements. This work implies that in heterogeneous rocks, pore-scale transport of reactants limits dissolution and can reduce the average effective reaction rate by an order of magnitude.

Reaction mechanism for the aqueous-phase mineral carbonation of heat-activated serpentine at low temperatures and pressures in flue gas conditions.

PubMed

Pasquier, Louis-César; Mercier, Guy; Blais, Jean-François; Cecchi, Emmanuelle; Kentish, Sandra

2014-05-06

Mineral carbonation is known as one of the safest ways to sequester CO2. Nevertheless, the slow kinetics and low carbonation rates constitute a major barrier for any possible industrial application. To date, no studies have focused on reacting serpentinite with a relatively low partial pressure of CO2 (pCO2) close to flue gas conditions. In this work, finely ground and heat-treated serpentinite [Mg3Si2O5(OH)4] extracted from mining residues was reacted with a 18.2 vol % CO2 gas stream at moderate global pressures to investigate the effect on CO2 solubility and Mg leaching. Serpentinite dissolution rates were also measured to define the rate-limiting step. Successive batches of gas were contacted with the same serpentinite to identify surface-limiting factors using scanning electron microscopy (SEM) analysis. Investigation of the serpentinite carbonation reaction mechanisms under conditions close to a direct flue gas treatment showed that increased dissolution rates could be achieved relative to prior work, with an average Mg dissolution rate of 3.55 × 10(-11) mol cm(-2) s(-1). This study provides another perspective of the feasibility of applying a mineral carbonation process to reduce industrial greenhouse gas (GHG) emissions from large emission sources.

Anaerobic co-digestion of waste activated sludge and greasy sludge from flotation process: batch versus CSTR experiments to investigate optimal design.

PubMed

Girault, R; Bridoux, G; Nauleau, F; Poullain, C; Buffet, J; Peu, P; Sadowski, A G; Béline, F

2012-02-01

In this study, the maximum ratio of greasy sludge to incorporate with waste activated sludge was investigated in batch and CSTR experiments. In batch experiments, inhibition occurred with a greasy sludge ratio of more than 20-30% of the feed COD. In CSTR experiments, the optimal greasy sludge ratio was 60% of the feed COD and inhibition occurred above a ratio of 80%. Hence, batch experiments can predict the CSTR yield when the degradation phenomenon are additive but cannot be used to determine the maximum ratio to be used in a CSTR configuration. Additionally, when the ratio of greasy sludge increased from 0% to 60% of the feed COD, CSTR methane production increased by more than 60%. When the greasy sludge ratio increased from 60% to 90% of the feed COD, the reactor yield decreased by 75%. Copyright © 2011 Elsevier Ltd. All rights reserved.

Laboratory-scale experiments and numerical modeling of cosolvent flushing of multi-component NAPLs in saturated porous media.

PubMed

Agaoglu, Berken; Scheytt, Traugott; Copty, Nadim K

2012-10-01

This study examines the mechanistic processes governing multiphase flow of a water-cosolvent-NAPL system in saturated porous media. Laboratory batch and column flushing experiments were conducted to determine the equilibrium properties of pure NAPL and synthetically prepared NAPL mixtures as well as NAPL recovery mechanisms for different water-ethanol contents. The effect of contact time was investigated by considering different steady and intermittent flow velocities. A modified version of multiphase flow simulator (UTCHEM) was used to compare the multiphase model simulations with the column experiment results. The effect of employing different grid geometries (1D, 2D, 3D), heterogeneity and different initial NAPL saturation configurations was also examined in the model. It is shown that the change in velocity affects the mass transfer rate between phases as well as the ultimate NAPL recovery percentage. The experiments with low flow rate flushing of pure NAPL and the 3D UTCHEM simulations gave similar effluent concentrations and NAPL cumulative recoveries. Model simulations over-estimated NAPL recovery for high specific discharges and rate-limited mass transfer, suggesting a constant mass transfer coefficient for the entire flushing experiment may not be valid. When multi-component NAPLs are present, the dissolution rate of individual organic compounds (namely, toluene and benzene) into the ethanol-water flushing solution is found not to correlate with their equilibrium solubility values. Copyright © 2012 Elsevier B.V. All rights reserved.

BATCH-GE: Batch analysis of Next-Generation Sequencing data for genome editing assessment

PubMed Central

Boel, Annekatrien; Steyaert, Woutert; De Rocker, Nina; Menten, Björn; Callewaert, Bert; De Paepe, Anne; Coucke, Paul; Willaert, Andy

2016-01-01

Targeted mutagenesis by the CRISPR/Cas9 system is currently revolutionizing genetics. The ease of this technique has enabled genome engineering in-vitro and in a range of model organisms and has pushed experimental dimensions to unprecedented proportions. Due to its tremendous progress in terms of speed, read length, throughput and cost, Next-Generation Sequencing (NGS) has been increasingly used for the analysis of CRISPR/Cas9 genome editing experiments. However, the current tools for genome editing assessment lack flexibility and fall short in the analysis of large amounts of NGS data. Therefore, we designed BATCH-GE, an easy-to-use bioinformatics tool for batch analysis of NGS-generated genome editing data, available from https://github.com/WouterSteyaert/BATCH-GE.git. BATCH-GE detects and reports indel mutations and other precise genome editing events and calculates the corresponding mutagenesis efficiencies for a large number of samples in parallel. Furthermore, this new tool provides flexibility by allowing the user to adapt a number of input variables. The performance of BATCH-GE was evaluated in two genome editing experiments, aiming to generate knock-out and knock-in zebrafish mutants. This tool will not only contribute to the evaluation of CRISPR/Cas9-based experiments, but will be of use in any genome editing experiment and has the ability to analyze data from every organism with a sequenced genome. PMID:27461955

An Experiment with Manifold Purposes: The Chemical Reactivity of Crystal Defects upon Crystal Dissolution.

ERIC Educational Resources Information Center

Lazzarini, Annaluisa Fantola; Lazzarini, Ennio

1983-01-01

Background information and procedures are provided for an experiment designed to introduce (1) crystal defects and their reactivity upon crystal dissolution; (2) hydrates electron and its reactivity; (3) application of radiochemical method of analysis; and (4) the technique of competitive kinetics. Suggested readings and additional experiments are…

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.

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

EGS rock reactions with Supercritical CO2 saturated with water and water saturated with Supercritical CO2

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

Earl D. Mattson; Travis L. McLing; William Smith

2013-02-01

EGS using CO2 as a working fluid will likely involve hydro-shearing low-permeability hot rock reservoirs with a water solution. After that process, the fractures will be flushed with CO2 that is maintained under supercritical conditions (> 70 bars). Much of the injected water in the main fracture will be flushed out with the initial CO2 injection; however side fractures, micro fractures, and the lower portion of the fracture will contain connate water that will interact with the rock and the injected CO2. Dissolution/precipitation reactions in the resulting scCO2/brine/rock systems have the potential to significantly alter reservoir permeability, so it ismore » important to understand where these precipitates form and how are they related to the evolving ‘free’ connate water in the system. To examine dissolution / precipitation behavior in such systems over time, we have conducted non-stirred batch experiments in the laboratory with pure minerals, sandstone, and basalt coupons with brine solution spiked with MnCl2 and scCO2. The coupons are exposed to liquid water saturated with scCO2 and extend above the water surface allowing the upper portion of the coupons to be exposed to scCO2 saturated with water. The coupons were subsequently analyzed using SEM to determine the location of reactions in both in and out of the liquid water. Results of these will be summarized with regard to significance for EGS with CO2 as a working fluid.« less

Establishing column batch repeatability according to Quality by Design (QbD) principles using modeling software.

PubMed

Rácz, Norbert; Kormány, Róbert; Fekete, Jenő; Molnár, Imre

2015-04-10

Column technology needs further improvement even today. To get information of batch-to-batch repeatability, intelligent modeling software was applied. Twelve columns from the same production process, but from different batches were compared in this work. In this paper, the retention parameters of these columns with real life sample solutes were studied. The following parameters were selected for measurements: gradient time, temperature and pH. Based on calculated results, batch-to-batch repeatability of BEH columns was evaluated. Two parallel measurements on two columns from the same batch were performed to obtain information about the quality of packing. Calculating the average of individual working points at the highest critical resolution (R(s,crit)) it was found that the robustness, calculated with a newly released robustness module, had a success rate >98% among the predicted 3(6) = 729 experiments for all 12 columns. With the help of retention modeling all substances could be separated independently from the batch and/or packing, using the same conditions, having high robustness of the experiments. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Understanding and predicting the impact of critical dissolution variables for nifedipine immediate release capsules by multivariate data analysis.

PubMed

Mercuri, A; Pagliari, M; Baxevanis, F; Fares, R; Fotaki, N

2017-02-25

In this study the selection of in vivo predictive in vitro dissolution experimental set-ups using a multivariate analysis approach, in line with the Quality by Design (QbD) principles, is explored. The dissolution variables selected using a design of experiments (DoE) were the dissolution apparatus [USP1 apparatus (basket) and USP2 apparatus (paddle)], the rotational speed of the basket/or paddle, the operator conditions (dissolution apparatus brand and operator), the volume, the pH, and the ethanol content of the dissolution medium. The dissolution profiles of two nifedipine capsules (poorly soluble compound), under conditions mimicking the intake of the capsules with i. water, ii. orange juice and iii. an alcoholic drink (orange juice and ethanol) were analysed using multiple linear regression (MLR). Optimised dissolution set-ups, generated based on the mathematical model obtained via MLR, were used to build predicted in vitro-in vivo correlations (IVIVC). IVIVC could be achieved using physiologically relevant in vitro conditions mimicking the intake of the capsules with an alcoholic drink (orange juice and ethanol). The multivariate analysis revealed that the concentration of ethanol used in the in vitro dissolution experiments (47% v/v) can be lowered to less than 20% v/v, reflecting recently found physiological conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Kinetic modelling of anaerobic hydrolysis of solid wastes, including disintegration processes

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

García-Gen, Santiago; Sousbie, Philippe; Rangaraj, Ganesh

2015-01-15

Highlights: • Fractionation of solid wastes into readily and slowly biodegradable fractions. • Kinetic coefficients estimation from mono-digestion batch assays. • Validation of kinetic coefficients with a co-digestion continuous experiment. • Simulation of batch and continuous experiments with an ADM1-based model. - Abstract: A methodology to estimate disintegration and hydrolysis kinetic parameters of solid wastes and validate an ADM1-based anaerobic co-digestion model is presented. Kinetic parameters of the model were calibrated from batch reactor experiments treating individually fruit and vegetable wastes (among other residues) following a new protocol for batch tests. In addition, decoupled disintegration kinetics for readily and slowlymore » biodegradable fractions of solid wastes was considered. Calibrated parameters from batch assays of individual substrates were used to validate the model for a semi-continuous co-digestion operation treating simultaneously 5 fruit and vegetable wastes. The semi-continuous experiment was carried out in a lab-scale CSTR reactor for 15 weeks at organic loading rate ranging between 2.0 and 4.7 g VS/L d. The model (built in Matlab/Simulink) fit to a large extent the experimental results in both batch and semi-continuous mode and served as a powerful tool to simulate the digestion or co-digestion of solid wastes.« less

Development of interactive graphic user interfaces for modeling reaction-based biogeochemical processes in batch systems with BIOGEOCHEM

NASA Astrophysics Data System (ADS)

Chang, C.; Li, M.; Yeh, G.

2010-12-01

The BIOGEOCHEM numerical model (Yeh and Fang, 2002; Fang et al., 2003) was developed with FORTRAN for simulating reaction-based geochemical and biochemical processes with mixed equilibrium and kinetic reactions in batch systems. A complete suite of reactions including aqueous complexation, adsorption/desorption, ion-exchange, redox, precipitation/dissolution, acid-base reactions, and microbial mediated reactions were embodied in this unique modeling tool. Any reaction can be treated as fast/equilibrium or slow/kinetic reaction. An equilibrium reaction is modeled with an implicit finite rate governed by a mass action equilibrium equation or by a user-specified algebraic equation. A kinetic reaction is modeled with an explicit finite rate with an elementary rate, microbial mediated enzymatic kinetics, or a user-specified rate equation. None of the existing models has encompassed this wide array of scopes. To ease the input/output learning curve using the unique feature of BIOGEOCHEM, an interactive graphic user interface was developed with the Microsoft Visual Studio and .Net tools. Several user-friendly features, such as pop-up help windows, typo warning messages, and on-screen input hints, were implemented, which are robust. All input data can be real-time viewed and automated to conform with the input file format of BIOGEOCHEM. A post-processor for graphic visualizations of simulated results was also embedded for immediate demonstrations. By following data input windows step by step, errorless BIOGEOCHEM input files can be created even if users have little prior experiences in FORTRAN. With this user-friendly interface, the time effort to conduct simulations with BIOGEOCHEM can be greatly reduced.

Coupled Geochemical Impacts of Leaking CO2 and Contaminants from Subsurface Storage Reservoirs on Groundwater Quality

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

Shao, Hongbo; Qafoku, Nikolla; Lawter, Amanda R.

2015-07-07

The leakage of CO2 and the concomitant saline solutions from deep storage reservoirs to overlying groundwater aquifers is considered one of the major potential risks associated with geologic CO2 sequestration (GCS). Batch and column experiments were conducted to determine the fate of trace metals in groundwater in the scenarios of CO2 and metal contaminated brine leakage. The sediments used in this work were collected from an unconsolidated sand and gravel aquifer in Kansas, and contained 0-4 wt% carbonates. Cd and As were spiked into the reaction system to represent potential contaminants from the reservoir brine that could intrude into groundwatermore » aquifers with leaking CO2 at initial concentrations of 114 and 40 ppb, respectively. Through this research we demonstrated that Cd and As were adsorbed on the sediments, in spite of the lowered pH due to CO2 dissolution in the groundwater. Cd concentrations were well below its MCL in both batch and column studies, even for sediment samples without detectable carbonate to buffer the pH. Arsenic concentrations in the effluent were also significantly lower than influent concentration, suggesting that the sediments tested have the capacity to mitigate the coupled adverse effects of CO2 leakage and brine intrusion. However, the mitigation capacity of sediment is a function of its geochemical properties [e.g., the calcite content; the presence of adsorbed As(III); and the presence of P in the natural sediment]. The competitive adsorption between phosphate and arsenate may result in higher concentrations of As in the aqueous phase.« less

Effects of Aging Quartz Sand and Hanford Site Sediment with Sodium Hydroxide on Radionuclide Sorption Coefficients and Sediment Physical and Hydrologic Properties: Final Report for Subtask 2a

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

DI Kaplan; JC Ritter; KE Parker

1998-12-04

Column and batch experiments were conducted in fiscal year 1998 at Pacific Northwest National Laboratory to evaluate the effect of varying concentrations of NaOH on the sorptive, physical, and hydraulic properties of two media, a quartz sand and a composite subsurface sediment from the 200-East Area of the Hanford Site. The NaOH solutions were used as a simplified effluent from a low-activity glass waste form. These experiments were conducted over a limited (O-to 10-month) contact time, with respect to the 10,000-to 100,000-year scenarios described in the Immobilized Low-Activity Waste- Performance Assessment (ILAW-PA). Wheq these two solids were put in contactmore » with the NaOH solutions, dissolution was evident by a substantial increase in dissolved Si concentrations in the leachates. Incremental increases in NaOH con- centrations, resulted in corresponding increases in Si concentrations. A number of physical and hydraulic properties also changed as the NaOH concentrations were changed. It was observed that quartz sand was less reactive than the composite sediment. Further, moisture- retention measurements were made on the quartz sand and composite sedimen$ which showed that the NaOH-treated solids retained more water than the non-NaOH-treated solids. Because the other chemical, physical, and hydraulic measurements did not change dramatically after the high-NaOH treatments, the greater moisture retention of the high-NaOH treatments was attributed to a "salt effect" and not to the formation of small particles during the dissolution (weathering). The distribution coefficients (IQ) for Cs and Sr were measured on the NaOH-treated sediments, with decreases from -3,000 to 1,000 and 1,300 to 300 mL/g noted, respectively, at the 0.01-to 1.O-M NaOH levels. There was no apparent trend for the Sr & values with contact time. The lack of such a trend sug- gests that dissolution of sediment particles is not controlling the drop in IQ rather, it is the competition of the added Na in the various treatment solutions. It is clear from these experiments that the background chemistry of the waste-glass Ieachate is likely to have a significant effect on the hydrology and radionuclide geochemistry in the near-field environment of the ILAW.' These experiments provided an important f~st approximation of several chemical and physical processes. Future research, together with the data presented in this repo~ will provide important guidance for the selection of near-field hydraulic and geochemical input data for the ILAW-PA.« less

A direct comparison of U.S. Environmental Protection Agency's method 304B and batch tests for determining activated-sludge biodegradation rate constants for volatile organic compounds

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

Cano, M.L.; Wilcox, M.E.; Compernolle, R. van

Biodegradation rate constants for volatile organic compounds (VOCs) in activated-sludge systems are needed to quantify emissions. One current US environmental Protection Agency method for determining a biodegradation rate constant is Method 304B. In this approach, a specific activated-sludge unit is simulated by a continuous biological treatment system with a sealed headspace. Batch experiments, however, can be alternatives to Method 304B. Two of these batch methods are the batch test that uses oxygen addition (BOX) and the serum bottle test (SBT). In this study, Method 304B was directly compared to BOX and SBT experiments. A pilot-scale laboratory reactor was constructed tomore » serve as the Method 304B unit. Biomass from the unit was also used to conduct BOX and modified SBT experiments (modification involved use of a sealed draft-tube reactor with a headspace recirculation pump instead of a serum bottle) for 1,2-dichloroethane, diisopropyl ether, methyl tertiary butyl ether, and toluene. Three experimental runs--each consisting of one Method 304B experiment, one BOX experiment, and one modified SBT experiment--were completed. The BOX and SBT data for each run were analyzed using a Monod model, and best-fit biodegradation kinetic parameters were determined for each experiment, including a first-order biodegradation rate constant (K{sub 1}). Experimental results suggest that for readily biodegradable VOCs the two batch techniques can provide improved means of determining biodegradation rate constants compared with Method 304B. In particular, these batch techniques avoid the Method 304B problem associated with steady-state effluent concentrations below analytical detection limits. However, experimental results also suggest that the two batch techniques should not be used to determine biodegradation rate constants for slowly degraded VOCs (i.e., K{sub 1} {lt} 0.1 L/g VSS-h).« less

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

[Heavy metals removal and its kinetics in contaminated soil under effects of EDTA washing].

PubMed

Ke, Xin; Li, Pei-Jun; Zhang, Yun; Sun, Tie-Heng

2007-03-01

In this paper, batch experiments were made to examine the effects of different EDTA concentrations, pH, and washing duration of EDTA on the removal of heavy metals from contaminated soil. An empirical model was employed to describe the kinetics of heavy metals dissolution and desorption, and the form changes of test heavy metals were determined before and after EDTA washing. The results showed that EDTA was effective to the removal of heavy-metals from contaminated soil. At 0.1 mol x L(-1) and pH 7 of EDTA and within 24 h, the removal rate of test heavy metals was the maximum, being 89.14% for Cd, 34.78% for Pb, 14.96% for Cu, and 45.14% for Zn. The mass transfer coefficient was in the order of Cd > Zn > Pb > Cu. Sequential fractionations of treated and untreated soil samples showed that EDTA was effective in removing the exchangeable, carbonate and oxide forms of Cd, Pb, Zn and Cu, but ineffective for the organic and residual forms of test heavy metals.

Methanogenesis-induced pH–Eh shifts drives aqueous metal(loid) mobility in sulfide mineral systems under CO2 enriched conditions

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

Harvey, Omar R.; Qafoku, Nikolla; Cantrell, Kirk J.

2016-01-15

Accounting for microbially-mediated CO2 transformation is pivotal to assessing geochemical implications for elevated CO2 in subsurface environments. A series of batch-reactor experiments were conducted to decipher links between autotrophic methanogenesis, CO2 dynamics and aqueous Fe, As and Pb concentrations in the presence of sulfide minerals. Microbially-mediated solubility-trapping followed by pseudo-first order reduction of HCO3- to CH4 (k’ = 0.28-0.59 d-1) accounted for 95% of the CO2 loss from methanogenic experiments. Bicarbonate-to-methane reduction was pivotal in the mitigation of CO2-induced acidity (~1 pH unit) and enhancement of reducing conditions (Eh change from -0.215 to -0.332V ). Methanogenesis-associated shifts in pH-Eh valuesmore » showed no significant effect on aqueous Pb but favored, 1) increased aqueous As as a result of microbially-mediated dissolution of arsenopyrite and 2) decreased aqueous Fe due to mineral-trapping of CO2-mobilized Fe as Fe-carbonate. Its order of occurrence (and magnitude), relative to solubility- and mineral-trapping, highlighted the potential for autotrophic methanogenesis to modulate both carbon sequestration and contaminant mobility in CO2-impacted subsurface environments.« less

Competitive adsorption and selectivity sequence of heavy metals by chicken bone-derived biochar: Batch and column experiment.

PubMed

Park, Jong-Hwan; Cho, Ju-Sik; Ok, Yong Sik; Kim, Seong-Heon; Kang, Se-Won; Choi, Ik-Won; Heo, Jong-Soo; DeLaune, Ronald D; Seo, Dong-Cheol

2015-01-01

The objective of this research was to evaluate adsorption of heavy metals in single- and ternary-metal forms onto chicken bone biochar (CBB). Competitive sorption of heavy metals by CBB has never been reported previously. The maximum adsorption capacities of metals by CBB were in the order of Cu (130 mg g(-1)) > Cd (109 mg g(-1)) > Zn (93 mg g(-1)) in the single-metal adsorption isotherm and Cu (108 mg g(-1)) > Cd (54 mg g(-1)) ≥ Zn (44 mg g(-1)) in the ternary-metal adsorption isotherm. Cu was the most retained cation, whereas Zn could be easily exchanged and substituted by Cu. Batch experimental data best fit the Langmuir model rather than the Freundlich isotherms. In the column experiments, the total adsorbed amounts of the metals were in the following order of Cu (210 mg g(-1)) > Cd (192 mg g(-1)) > Zn (178) in single-metal conditions, and Cu (156) > Cd (123) > Zn (92) in ternary-metal conditions. Results from both the batch and column experiments indicate that competitive adsorption among metals increases the mobility of these metals. Especially, Zn in single-metal conditions lost it adsorption capacity most significantly. Based on the 3D simulation graphs of heavy metals, adsorption patterns under single adsorption condition were different than under competitive adsorption condition. Results from both the batch and column experiments show that competitive adsorption among metals increases the mobility of these metals. The maximum metal adsorption capacity of the metals in the column experiments was higher than that in the batch experiment indicating other metal retention mechanisms rather than adsorption may be involved. Therefore, both column and batch experiments are needed for estimating retention capacities and removal efficiencies of metals in CBB.

Development and optimization of locust bean gum and sodium alginate interpenetrating polymeric network of capecitabine.

PubMed

Upadhyay, Mansi; Adena, Sandeep Kumar Reddy; Vardhan, Harsh; Pandey, Sureshwar; Mishra, Brahmeshwar

2018-03-01

The objective of the study was to develop interpenetrating polymeric network (IPN) of capecitabine (CAP) using natural polymers locust bean gum (LBG) and sodium alginate (NaAlg). The IPN microbeads were optimized by Box-Behnken Design (BBD) to provide anticipated particle size with good drug entrapment efficiency. The comparative dissolution profile of IPN microbeads of CAP with the marketed preparation proved an excellent sustained drug delivery vehicle. Ionotropic gelation method utilizing metal ion calcium (Ca 2+ ) as a cross-linker was used to prepare IPN microbeads. The optimization study was done by response surface methodology based Box-Behnken Design. The effect of the factors on the responses of optimized batch was exhibited through response surface and contour plots. The optimized batch was analyzed for particle size, % drug entrapment, pharmacokinetic study, in vitro drug release study and further characterized by FTIR, XRD, and SEM. To study the water uptake capacity and hydrodynamic activity of the polymers, swelling studies and viscosity measurement were performed, respectively. The particle size and % drug entrapment of the optimized batch was 494.37 ± 1.4 µm and 81.39 ± 2.9%, respectively, closer to the value predicted by Minitab 17 software. The in vitro drug release study showed sustained release of 92% for 12 h and followed anomalous drug release pattern. The derived pharmacokinetic parameters of optimized batch showed improved results than pure CAP. Thus, the formed IPN microbeads of CAP proved to be an effective extended drug delivery vehicle for the water soluble antineoplastic drug.

Experimental investigation of the Heletz shale caprocks sealing capacity: implication for CO2 geological storage integrity

NASA Astrophysics Data System (ADS)

Abdoulghafour, Halidi; Gouze, Philippe; Luquot, Linda; Arif, Mohamed; Iglauer, Stefan

2017-04-01

Using a combination of core flooding experiments and wettability measurements, we evaluate the sealing efficiency of Heletz caprock under CO2 sequestration conditions. The flow through experiments consisted of flowing CO2 enriched fluid into two micro-fractured cylindrical cores (15 mm length - 9 mm diameter, with hydraulic aperture: 2.7 µm for the sample named H18A and 13 µm for sample named H18B) and monitoring the permeability changes, the evolution of the chemistry from the inlet and outlet fluid. The changes in microstructures and mineralogy were also studied using an environmental scanning electrons microscope (ESEM) and X-ray micro-tomography (XRMT) images. The fracture permeability was found to decrease significantly in the two experiments from 14.1×10-12 m2 to 5.0×10-12 m2 for experiment H18B and from 6.5×10-13 m2 to 2.8×10-13 m2 for experiment H18A. Calcite dissolution and reconversion of k-feldspar to illite and kaolinite were the main reaction on sample H18B while "calcite precipitation" in batch condition was the dominant reaction on sample H18A. Accordingly, the decrease in permeability was induced by the dispersion of dissolution products and the re-organization of clay particles within the fracture for sample H18B as shown by micro-tomography and ESEM images. The fracture healing due to the calcite and clay mineral precipitation along the fracture was attested by ESEM image for sample H18A. The results of capillary pressure breakthrough calculated by applying the Washburn equation and the reservoir scaling method from intrusion of mercury are approximately 380 kPa and 310 kPa for H18B and H18A respectively. Although, these values are sensibly different but close to each other and in good agreement to indicate the weak storage capacity of the heletz caprock. Subsequently less than 90 m of CO2 column height can be efficiently stored in the Heletz reservoir. Thus the self-mitigation of the CO2 leakage is expected only when few quantity of CO2 will be injected.

Optimization of the Ussing chamber setup with excised rat intestinal segments for dissolution/permeation experiments of poorly soluble drugs.

PubMed

Forner, Kristin; Roos, Carl; Dahlgren, David; Kesisoglou, Filippos; Konerding, Moritz A; Mazur, Johanna; Lennernäs, Hans; Langguth, Peter

2017-02-01

Prediction of the in vivo absorption of poorly soluble drugs may require simultaneous dissolution/permeation experiments. In vivo predictive media have been modified for permeation experiments with Caco-2 cells, but not for excised rat intestinal segments. The present study aimed at improving the setup of dissolution/permeation experiments with excised rat intestinal segments by assessing suitable donor and receiver media. The regional compatibility of rat intestine in Ussing chambers with modified Fasted and Fed State Simulated Intestinal Fluids (Fa/FeSSIF mod ) as donor media was evaluated via several parameters that reflect the viability of the excised intestinal segments. Receiver media that establish sink conditions were investigated for their foaming potential and toxicity. Dissolution/permeation experiments with the optimized conditions were then tested for two particle sizes of the BCS class II drug aprepitant. Fa/FeSSIF mod were toxic for excised rat ileal sheets but not duodenal sheets, the compatibility with jejunal segments depended on the bile salt concentration. A non-foaming receiver medium containing bovine serum albumin (BSA) and Antifoam B was nontoxic. With these conditions, the permeation of nanosized aprepitant was higher than of the unmilled drug formulations. The compatibility of Fa/FeSSIF mod depends on the excised intestinal region. The chosen conditions enable dissolution/permeation experiments with excised rat duodenal segments. The experiments correctly predicted the superior permeation of nanosized over unmilled aprepitant that is observed in vivo. The optimized setup uses FaSSIF mod as donor medium, excised rat duodenal sheets as permeation membrane and a receiver medium containing BSA and Antifoam B.

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.

The effects of physicochemical properties of CeO2 nanoparticles on toxicity to soil denitrification processes

NASA Astrophysics Data System (ADS)

Dahle, Jessica Teague

The studies presented in this thesis identify the impact of NP CeO 2 on soil denitrifying microbial communities and reveal that physical and chemical characteristics including particle size, speciation, concentration, pH, and presence of ligands are key to predicting environmental fate and reactivity of NP CeO2 in the soil. A review of the literature in Chapter 1 revealed a widespread lack of toxicological information for soil exposures to NP CeO2. Soil denitrifying bacteria are a keystone species because they serve an important role in the global nitrogen cycle controlling the atmospheric nitrogen input. Soil denitrifiers are important to this study because the reducing conditions during denitrification could induce phase transformation of Ce(IV) to Ce(III), potentially influencing the toxicity of Ce. Cerium is well known for being the only lanthanide that is thermodynamically stable in both the trivalent and tetravalent state in low temperature geochemical environments. Using well characterized NP Ce(IV)O 2 as well as bulk soluble Ce(III), batch denitrification experiments were conducted to evaluate the toxicity of Ce species to the denitrifying community in a Toccoa sandy loam soil. The statistical analysis on the antimicrobial effect on soil denitrifiers was conducted using both steady-state evaluation and zero-order kinetic models in order to compare the toxicity of the Ce(III) species to the NPs. These studies, presented in Chapter 3, show that soluble Ce(III) is far more toxic than Ce(IV)O2 NPs when an equal total concentration of Ce is used, though both species exhibit toxicity to the denitrifiers via statistically significant inhibition of soil denitrification processes. Particle-size dependent toxicity, species-dependent toxicity, and concentration-dependent toxicity were all observed in this study for both the steady-state and the kinetic evaluations. The possibility of toxicity enhancement and diminishment via dissolution and ligand complexation pathways was investigated thoroughly in Chapter 2. In addition to the equilibrium and kinetic-based toxicological assessments presented in Chapter 1, dissolution and sorption experiments were performed to gain an overall understanding of Ce biogeochemistry in the terrestrial environment post-release and reveal possible geochemical controls on toxicity. It was shown that dissolution of bioavailable Ce is pH-dependent; dissolution is only detectable at acidic pH values (< pH 5) and increases with increasing acidity. Dissolution of Ce from NP CeO2 was identified to be almost 100% Ce(III). It was also demonstrated that this dissolution is suppressed by the addition of phosphate ligand, which is largely bioavailable in soils, especially in agricultural lands. This suppression was explained by the strong sorption of phosphate ligand to NP CeO2. The elimination of bioavailable Ce(III) release from NP CeO2 by phosphate ligand is likely one of the most important controls on toxicity effects and should be a large consideration in determining the fate and transport of NP CeO2 in the aquatic and terrestrial environment. It was also demonstrated that both Ce(III) and NP CeO2 have extremely strong affinity for sorption to soil matter, which could serve as another controlling pathway. Experiments indicated that factors such as reductive transformation of NP CeO2 in soils and exchangeable Ce(III) impurity in the NPs could contribute to controls on toxicity as well. In conclusion, the studies presented in this thesis indicate that the toxicity effects of the studied Ce species to soil denitrifiers are strongly affected by physical and chemical characteristics such as speciation, pH, and bioavailable ligands. As the global market for nanomaterials rapidly expands, so does the need of the scientific community for an understanding of how these influences in environmental fate and reactivity may be key in assessing toxicological risks associated with environmental exposures to NP CeO2 as well as other engineered metal oxide nanoparticles. (Abstract shortened by UMI.)

Continuous production of fenofibrate solid lipid nanoparticles by hot-melt extrusion technology: a systematic study based on a quality by design approach.

PubMed

Patil, Hemlata; Feng, Xin; Ye, Xingyou; Majumdar, Soumyajit; Repka, Michael A

2015-01-01

This contribution describes a continuous process for the production of solid lipid nanoparticles (SLN) as drug-carrier systems via hot-melt extrusion (HME). Presently, HME technology has not been used for the manufacturing of SLN. Generally, SLN are prepared as a batch process, which is time consuming and may result in variability of end-product quality attributes. In this study, using Quality by Design (QbD) principles, we were able to achieve continuous production of SLN by combining two processes: HME technology for melt-emulsification and high-pressure homogenization (HPH) for size reduction. Fenofibrate (FBT), a poorly water-soluble model drug, was incorporated into SLN using HME-HPH methods. The developed novel platform demonstrated better process control and size reduction compared to the conventional process of hot homogenization (batch process). Varying the process parameters enabled the production of SLN below 200 nm. The dissolution profile of the FBT SLN prepared by the novel HME-HPH method was faster than that of the crude FBT and a micronized marketed FBT formulation. At the end of a 5-h in vitro dissolution study, a SLN formulation released 92-93% of drug, whereas drug release was approximately 65 and 45% for the marketed micronized formulation and crude drug, respectively. Also, pharmacokinetic study results demonstrated a statistical increase in Cmax, Tmax, and AUC0-24 h in the rate of drug absorption from SLN formulations as compared to the crude drug and marketed micronized formulation. In summary, the present study demonstrated the potential use of hot-melt extrusion technology for continuous and large-scale production of SLN.

User's guide to PHREEQC (Version 2) : a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, David L.; Appelo, C.A.J.

1999-01-01

PHREEQC version 2 is a computer program written in the C programming language that is designed to perform a wide variety of low-temperature aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations; (2) batch-reaction and one-dimensional (1D) transport calculations involving reversible reactions, which include aqueous, mineral, gas, solid-solution, surface-complexation, and ion-exchange equilibria, and irreversible reactions, which include specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and temperature changes; and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for differences in composition between waters, within specified compositional uncertainty limits.New features in PHREEQC version 2 relative to version 1 include capabilities to simulate dispersion (or diffusion) and stagnant zones in 1D-transport calculations, to model kinetic reactions with user-defined rate expressions, to model the formation or dissolution of ideal, multicomponent or nonideal, binary solid solutions, to model fixed-volume gas phases in addition to fixed-pressure gas phases, to allow the number of surface or exchange sites to vary with the dissolution or precipitation of minerals or kinetic reactants, to include isotope mole balances in inverse modeling calculations, to automatically use multiple sets of convergence parameters, to print user-defined quantities to the primary output file and (or) to a file suitable for importation into a spreadsheet, and to define solution compositions in a format more compatible with spreadsheet programs. This report presents the equations that are the basis for chemical equilibrium, kinetic, transport, and inverse-modeling calculations in PHREEQC; describes the input for the program; and presents examples that demonstrate most of the program's capabilities.

Quantification of rapid environmental redox processes with quick-scanning x-ray absorption spectroscopy (Q-XAS)

PubMed Central

Ginder-Vogel, Matthew; Landrot, Gautier; Fischel, Jason S.; Sparks, Donald L.

2009-01-01

Quantification of the initial rates of environmental reactions at the mineral/water interface is a fundamental prerequisite to determining reaction mechanisms and contaminant transport modeling and predicting environmental risk. Until recently, experimental techniques with adequate time resolution and elemental sensitivity to measure initial rates of the wide variety of environmental reactions were quite limited. Techniques such as electron paramagnetic resonance and Fourier transform infrared spectroscopies suffer from limited elemental specificity and poor sensitivity to inorganic elements, respectively. Ex situ analysis of batch and stirred-flow systems provides high elemental sensitivity; however, their time resolution is inadequate to characterize rapid environmental reactions. Here we apply quick-scanning x-ray absorption spectroscopy (Q-XAS), at sub-second time-scales, to measure the initial oxidation rate of As(III) to As(V) by hydrous manganese(IV) oxide. Using Q-XAS, As(III) and As(V) concentrations were determined every 0.98 s in batch reactions. The initial apparent As(III) depletion rate constants (t < 30 s) measured with Q-XAS are nearly twice as large as rate constants measured with traditional analytical techniques. Our results demonstrate the importance of developing analytical techniques capable of analyzing environmental reactions on the same time scale as they occur. Given the high sensitivity, elemental specificity, and time resolution of Q-XAS, it has many potential applications. They could include measuring not only redox reactions but also dissolution/precipitation reactions, such as the formation and/or reductive dissolution of Fe(III) (hydr)oxides, solid-phase transformations (i.e., formation of layered-double hydroxide minerals), or almost any other reaction occurring in aqueous media that can be measured using x-ray absorption spectroscopy. PMID:19805269

A novel determination of calcite dissolution kinetics in seawater

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Mechanistic study of lead desorption during the leaching process of ion-absorbed rare earths: pH effect and the column experiment.

PubMed

Tang, Jie; Xue, Qiang; Chen, Honghan; Li, Wenting

2017-05-01

High concentrations of ammonium sulfate, often used in the in situ mining process, can result in a decrease of pH in the environment and dissolution of rare earth metals. Ammonium sulfate can also cause desorption of toxic heavy metals, leading to environmental and human health implications. In this study, the desorption behavior and fraction changes of lead in the ion-absorbed rare earth ore were studied using batch desorption experiments and column leaching tests. Results from batch desorption experiments showed that the desorption process of lead included fast and slow stages and followed an Elovich model well. The desorption rate and the proportion of lead content in the solution to the total lead in the soil were observed to increase with a decrease in the initial pH of the ammonium sulfate solution. The lead in soil included an acid-extractable fraction, reducible fraction, oxidizable fraction, and a residual fraction, with the predominant fractions being the reducible and acid-extractable fractions. Ninety-six percent of the extractable fraction in soil was desorbed into solution at pH = 3.0, and the content of the reducible fraction was observed to initially increase (when pH >4.0) and then decrease (when pH <4.0) with a decrease in pH. Column leaching tests indicated that the content of lead in the different fractions of soil followed the trend of reducible fraction > oxidizable fraction > acid-extractable fraction > residual fraction after the simulating leaching mining process. The change in pH was also found to have a larger influence on the acid-extractable and reducible fractions than the other two fractions. The proportion of the extractable fraction being leached was ca. 86%, and the reducible fraction was enriched along the migration direction of the leaching liquid. These results suggest that certain lead fractions may desorb again and contaminate the environment via acid rain, which provides significant information for environmental assessment and remediation after mining process. Graphical abstract ᅟ.

Psychedelics, Personality and Political Perspectives.

PubMed

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

2017-01-01

The psychedelic experience (including psychedelic-induced ego dissolution) can effect lasting change in a person's attitudes and beliefs. Here, we aimed to investigate the association between naturalistic psychedelic use and personality, political perspectives, and nature relatedness using an anonymous internet survey. Participants (N = 893) provided information about their naturalistic psychedelic, cocaine, and alcohol use, and answered questions relating to personality traits of openness and conscientiousness (Ten-Item Personality Inventory), nature relatedness (Nature-Relatedness Scale), and political attitudes (one-item liberalism-conservatism measure and five-item libertarian-authoritarian measure). Participants also rated the degree of ego dissolution experienced during their "most intense" recalled psychedelic experience (Ego-Dissolution Inventory). Multivariate linear regression analysis indicated that lifetime psychedelic use (but not lifetime cocaine use or weekly alcohol consumption) positively predicted liberal political views, openness and nature relatedness, and negatively predicted authoritarian political views, after accounting for potential confounding variables. Ego dissolution experienced during a participant's "most intense" psychedelic experience positively predicted liberal political views, openness and nature relatedness, and negatively predicted authoritarian political views. Further work is needed to investigate the nature of the relationship between the peak psychedelic experience and openness to new experiences, egalitarian political views, and concern for the environment.

Income and Independence Effects on Marital Dissolution: Results from the Seattle and Denver Income-Maintenance Experiments.

ERIC Educational Resources Information Center

Hannan, Michael T.; And Others

1978-01-01

Discusses effects of income and income fluctuation on marital dissolution. Data are based on a model of nonlinear income and independence effects. Findings indicated that effects of an income maintenance program on marital dissolution depend upon the payment a couple receives, income before the program, level of the wife's independence, and…

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.

Determination of the dissolution slowness surface by study of etched shapes I. Morphology of the dissolution slowness surface and theoretical etched shapes

NASA Astrophysics Data System (ADS)

Leblois, T.; Tellier, C. R.

1992-07-01

We propose a theoretical model for the anisotropic etching of crystals, in order to be applied in the micromachining. The originality of the model is due to the introduction of dissolution tensors to express the representative surface of the dissolution slowness. The knowledge of the equation of the slowness surface allows us to determine the trajectories of all the elements which compose the starting surface. It is then possible to construct the final etched shape by numerical simulation. Several examples are given in this paper which show that the final etched shapes are correlated to the extrema of the dissolution slowness. Since the slowness surface must be determined from experiments, emphasis is placed on difficulties encountered when we correlate theory to experiments. Nous avons modélisé le processus de dissolution anisotrope des cristaux en vue d'une application à la simulation des formes obtenues par photolithogravure chimique. La principale originalité de ce modèle tient à l'introduction de tenseurs de dissolution pour exprimer la surface représentative de la lenteur de dissolution. La connaissance de l'équation de la lenteur de dissolution permet de calculer les trajectoires des différents éléments constituant la surface de départ puis de reconstituer par simulation la forme dissoute. Les simulations démontrent que les formes limites des cristaux dissous sont corrélées aux extrema de la lenteur de dissolution. La détermination de la surface de la lenteur se faisant à partir de mesures expérimetales, nous nous sommes efforcés de montrer toutes les difficultés attachées à cette analyse.

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.

Decreased Dissolution of ZnO by Iron Doping Yields Nanoparticles with Reduced Toxicity in the Rodent Lung and Zebrafish Embryos

PubMed Central

Xia, Tian; Zhao, Yan; Sager, Tina; George, Saji; Pokhrel, Suman; Li, Ning; Schoenfeld, David; Meng, Huan; Lin, Sijie; Wang, Xiang; Wang, Meiying; Ji, Zhaoxia; Zink, Jeffrey I.; Mädler, Lutz; Castranova, Vincent; Lin, Shuo; Nel, Andre E.

2014-01-01

We have recently shown that the dissolution of ZnO nanoparticles and Zn2+ shedding leads to a series of sub-lethal and lethal toxicological responses at cellular level that can be alleviated by iron-doping. Iron-doping changes the particle matrix and slows the rate of particle dissolution. To determine whether iron doping of ZnO also leads to lesser toxic effects in vivo, toxicity studies were performed in rodent and zebrafish models. First, we synthesized a fresh batch of ZnO nanoparticles doped with 1–10 wt % of Fe. These particles were extensively characterized to confirm their doping status, reduced rate of dissolution in an exposure medium and reduced toxicity in a cellular screen. Subsequent studies compared the effects of undoped to doped particles in the rat lung, mouse lung and the zebrafish embryo. The zebrafish studies looked at embryo hatching and mortality rates as well as the generation of morphological defects, while the endpoints in the rodent lung included an assessment of inflammatory cell infiltrates, LDH release and cytokine levels in the bronchoalveolar lavage fluid. Iron doping, similar to the effect of the metal chelator, DTPA, interfered in the inhibitory effects of Zn2+ on zebrafish hatching. In the oropharyngeal aspiration model in the mouse, iron doping was associated with decreased polymorphonuclear cell counts and IL-6 mRNA production. Doped particles also elicited decreased heme oxygenase 1 expression in the murine lung. In the intratracheal instillation studies in the rat, Fe-doping was associated with decreased polymorphonuclear cell counts, LDH and albumin levels. All considered, the above data show that Fe-doping is a possible safe design strategy for preventing ZnO toxicity in animals and the environment. PMID:21250651

Mechanism of Phase Formation in the Batch Mixtures for Slag-Bearing Glass Ceramics - 12207

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

Stefanovsky, Sergey V.; Stefanovsky, Olga I.; Malinina, Galina A.

2012-07-01

Slag surrogate was produced from chemicals by heating to 900 deg. C and keeping at this temperature for 1 hr. The product obtained was intermixed with either sodium di-silicate (75 wt.% waste loading) or borax (85 wt.% slag loading). The mixtures were heat-treated within a temperature range of 25 to 1300 deg. C. The products were examined by X-ray diffraction and infrared spectroscopy. The products prepared at temperatures of up to 1000 deg. C contained both phase typical of the source slag and intermediate phases as well as phases typical of the materials melted at 1350 deg. C such asmore » nepheline, britholite, magnetite and matrix vitreous phase. Vitrification process in batch mixtures consisting of slag surrogate and either sodium di-silicate or sodium tetraborate runs through formation of intermediate phases mainly silico-phosphates capable to incorporate Sm as trivalent actinides surrogate. Reactions in the batch mixtures are in the whole completed by ∼1000 deg. C but higher temperatures are required to homogenize the products. If in the borate-based system the mechanism is close to simple dissolution of slag constituents in the low viscous borate melt, then in the silicate-based system the mechanism was found to be much complicated and includes re-crystallization during melting with segregation of newly-formed nepheline type phase. (authors)« less

Simplified formulations with high drug loads for continuous twin-screw granulation.

PubMed

Meier, R; Thommes, M; Rasenack, N; Krumme, M; Moll, K-P; Kleinebudde, P

2015-12-30

As different batches of the same excipients will be intermixed during continuous processes, the traceability of batches is complicated. Simplified formulations may help to reduce problems related to batch intermixing and traceability. Twin-screw granulation with subsequent tableting was used to produce granules and tablets, containing drug, disintegrant and binder (binary and ternary mixtures), only. Drug loads up to 90% were achieved and five different disintegrants were screened for keeping their disintegration suitability after wetting. Granule size distributions were consistently mono-modal and narrow. Granule strength reached higher values, using ternary mixtures. Tablets containing croscarmellose-Na as disintegrant displayed tensile strengths up to 3.1MPa and disintegration times from 400 to 466s, resulting in the most robust disintegrant. Dissolution was overall complete and above 96% within 30 min. Na-starch glycolate offers tensile strengths up to 2.8MPa at disintegration times from 25s to 1031s, providing the broadest application window, as it corresponds in some parts to different definitions of orodispersible tablets. Tablets containing micronized crospovidone are not suitable for immediate release, but showed possibilities to produce highly drug loaded, prolonged release tablets. Tablets and granules from simplified formulations offer great opportunities to improve continuous processes, present performances comparable to more complicated formulations and are able to correspond to requirements of the authorities. Copyright © 2015 Elsevier B.V. All rights reserved.

Leaching Behavior Of Mineral Processing Waste: Comparison Of Batch And Column Investigations

EPA Science Inventory

In this study, a comparison of laboratory batch and column experiments on metal release profile from a mineral processing waste (MPW) is presented. Batch (equilibrium) and column (dynamic) leaching tests were conducted on ground MPW at different liquid–solid ratios (LS) to determ...

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

In vitro-in vivo correlation strategy applied to an immediate-release solid oral dosage form with a biopharmaceutical classification system IV compound case study.

PubMed

Bredael, Gerard M; Bowers, Niya; Boulineau, Fabien; Hahn, David

2014-07-01

The ability to predict in vivo response of an oral dosage form based on an in vitro technique has been a sought after goal of the pharmaceutical scientist. Dissolution testing that demonstrates discrimination to various critical formulations or process attributes provides a sensitive quality check that may be representative or may be overpredictive of potential in vivo changes. Dissolution methodology with an established in vitro-in vivo relationship or correlation may provide the desired in vivo predictability. To establish this in vitro-in vivo link, a clinical study must be performed. In this article, recommendations are given in the selection of batches for the clinical study followed by potential outcome scenarios. The investigation of a Level C in vitro-in vivo correlation (IVIVC), which is the most common correlation for immediate-release oral dosage forms, is presented. Lastly, an IVIVC case study involving a biopharmaceutical classification system class IV compound is presented encompassing this strategy and techniques. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Simultaneous heterotrophic and sulfur-oxidizing autotrophic denitrification process for drinking water treatment: control of sulfate production.

PubMed

Sahinkaya, Erkan; Dursun, Nesrin; Kilic, Adem; Demirel, Sevgi; Uyanik, Sinan; Cinar, Ozer

2011-12-15

A long-term performance of a packed-bed bioreactor containing sulfur and limestone was evaluated for the denitrification of drinking water. Autotrophic denitrification rate was limited by the slow dissolution rate of sulfur and limestone. Dissolution of limestone for alkalinity supplementation increased hardness due to release of Ca(2+). Sulfate production is the main disadvantage of the sulfur autotrophic denitrification process. The effluent sulfate concentration was reduced to values below drinking water guidelines by stimulating the simultaneous heterotrophic and autotrophic denitrification with methanol supplementation. Complete removal of 75 mg/L NO(3)-N with effluent sulfate concentration of around 225 mg/L was achieved when methanol was supplemented at methanol/NO(3)-N ratio of 1.67 (mg/mg), which was much lower than the theoretical value of 2.47 for heterotrophic denitrification. Batch studies showed that sulfur-based autotrophic NO(2)-N reduction rate was around three times lower than the reduction rate of NO(3)-N, which led to NO(2)-N accumulation at high loadings. Copyright © 2011 Elsevier Ltd. All rights reserved.

Preparation and physicochemical characterization of 5 niclosamide solvates and 1 hemisolvate.

PubMed

van Tonder, Elsa C; Mahlatji, Mabatane D; Malan, Sarel F; Liebenberg, Wilna; Caira, Mino R; Song, Mingna; de Villiers, Melgardt M

2004-02-23

The purpose of the study was to characterize the physicochemical, structural, and spectral properties of the 1:1 niclosamide and methanol, diethyl ether, dimethyl sulfoxide, N,N' dimethylformamide, and tetrahydrofuran solvates and the 2:1 niclosamide and tetraethylene glycol hemisolvate prepared by recrystallization from these organic solvents. Structural, spectral, and thermal analysis results confirmed the presence of the solvents and differences in the structural properties of these solvates. In addition, differences in the activation energy of desolvation, batch solution calorimetry, and the aqueous solubility at 25 degrees C, 24 hours, showed the stability of the solvates to be in the order: anhydrate > diethyl ether solvate > tetraethylene glycol hemisolvate > methanol solvate > dimethyl sulfoxide solvate > N,N' dimethylformamide solvate. The intrinsic and powder dissolution rates of the solvates were in the order: anhydrate > diethyl ether solvate > tetraethylene glycol hemisolvate > N,N' dimethylformamide solvate > methanol solvate > dimethyl sulfoxide solvate. Although these nonaqueous solvates had higher solubility and dissolution rates than the monohydrous forms, they were unstable in aqueous media and rapidly transformed to one of the monohydrous forms.

Factor analysis in optimization of formulation of high content uniformity tablets containing low dose active substance.

PubMed

Lukášová, Ivana; Muselík, Jan; Franc, Aleš; Goněc, Roman; Mika, Filip; Vetchý, David

2017-11-15

Warfarin is intensively discussed drug with narrow therapeutic range. There have been cases of bleeding attributed to varying content or altered quality of the active substance. Factor analysis is useful for finding suitable technological parameters leading to high content uniformity of tablets containing low amount of active substance. The composition of tabletting blend and technological procedure were set with respect to factor analysis of previously published results. The correctness of set parameters was checked by manufacturing and evaluation of tablets containing 1-10mg of warfarin sodium. The robustness of suggested technology was checked by using "worst case scenario" and statistical evaluation of European Pharmacopoeia (EP) content uniformity limits with respect to Bergum division and process capability index (Cpk). To evaluate the quality of active substance and tablets, dissolution method was developed (water; EP apparatus II; 25rpm), allowing for statistical comparison of dissolution profiles. Obtained results prove the suitability of factor analysis to optimize the composition with respect to batches manufactured previously and thus the use of metaanalysis under industrial conditions is feasible. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Earl D Mattson; Ghanashyam Neupane; Mitchell Plummer

Long-term sustainability of fracture conductivity is critical for commercial success of engineered geothermal system (EGS) and hydrogeothermal field sites. The injection of proppants has been suggested as a means to enhance the conductivity in these systems. Several studies have examined the chemical behavior of proppants that are not at chemical equilibrium with the reservoir rock and water. These studies have suggested that in geothermal systems, geochemical reactions can lead to enhance proppant dissolution and deposition alteration minerals. We hypothesize that proppant dissolution will decrease the strength of the proppant and can potentially reduce the conductivity of the fracture. To examinemore » the geomechanical strength of proppants, we have performed modified crushing tests of proppants and reservoir rock material that was subjected to geothermal reservoir temperature conditions. The batch reactor experiments heated crushed quartz monzonite rock material, proppants (either quartz sand, sintered bauxite or kryptospheres) with Raft River geothermal water to 250 ºC for a period of 2 months. Solid and liquid samples were shipped to University of Utah for chemical characterization with ICP-OES, ICP-MS, and SEM. A separate portion of the rock/proppant material was subjected to a modified American Petroleum Institute ISO 13503-2 proppant crushing test. This test is typically used to determine the maximum stress level that can be applied to a proppant pack without the occurrence of unacceptable proppant crushing. We will use the test results to examine potential changes in proppant/reservoir rock geomechanical properties as compared to samples that have not been subjected to geothermal conditions. These preliminary results will be used to screen the proppants for long term use in EGS and hot hydrogeothermal systems.« less

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.

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.

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.

Dissolution without disappearing: multicomponent gas exchange for CO2 bubbles in a microfluidic channel.

PubMed

Shim, Suin; Wan, Jiandi; Hilgenfeldt, Sascha; Panchal, Prathamesh D; Stone, Howard A

2014-07-21

We studied the dissolution dynamics of CO2 gas bubbles in a microfluidic channel, both experimentally and theoretically. In the experiments, spherical CO2 bubbles in a flow of a solution of sodium dodecyl sulfate (SDS) first shrink rapidly before attaining an equilibrium size. In the rapid dissolution regime, the time to obtain a new equilibrium is 30 ms regardless of SDS concentration, and the equilibrium radius achieved varies with the SDS concentration. To explain the lack of complete dissolution, we interpret the results by considering the effects of other gases (O2, N2) that are already dissolved in the aqueous phase, and we develop a multicomponent dissolution model that includes the effect of surface tension and the liquid pressure drop along the channel. Solutions of the model for a stationary gas bubble show good agreement with the experimental results, which lead to our conclusion that the equilibrium regime is obtained by gas exchange between the bubbles and liquid phase. Also, our observations from experiments and model calculations suggest that SDS molecules on the gas-liquid interface form a diffusion barrier, which controls the dissolution behaviour and the eventual equilibrium radius of the bubble.

Modulation of venlafaxine hydrochloride release from press coated matrix tablet.

PubMed

Gohel, M C; Soni, C D; Nagori, S A; Sarvaiya, K G

2008-01-01

The aim of present study was to prepare novel modified release press coated tablets of venlafaxine hydrochloride. Hydroxypropylmethylcellulose K4M and hydroxypropylmethylcellulose K100M were used as release modifier in core and coat, respectively. A 3(2) full factorial design was adopted in the optimization study. The drug to polymer ratio in core and coat were chosen as independent variables. The drug release in the first hour and drug release rate between 1 and 12 h were chosen as dependent variables. The tablets were characterized for dimension analysis, crushing strength, friability and in vitro drug release. A check point batch, containing 1:2.6 and 1:5.4 drug to polymer in core and coat respectively, was prepared. The tablets of check point batch were subjected to in vitro drug release in dissolution media with pH 5, 7.2 and distilled water. The kinetics of drug release was best explained by Korsmeyer and Peppas model (anomalous non-Fickian diffusion). The systematic formulation approach enabled us to develop modified release venlafaxine hydrochloride tablets.

Comparative studies of binding potential of Prunus armeniaca and Prunus domestica gums in tablets formulations.

PubMed

Rahim, Haroon; Khan, Mir Azam; Sadiq, Abdul; Khan, Shahzeb; Chishti, Kamran Ahmad; Rahman, Inayat U

2015-05-01

The current study was undertaken to compare the binding potential of Prunus armeniaca L. and Prunus domestica L. gums in tablets' formulations. Tablet batches (F-1 to F-9) were prepared Diclofenac sodium as model drug using 5%, 7.5% and 10% of each Prunus armeniaca L., Prunus domestica L. gums as binder. PVP K30 was used as a standard binder. Magnesium stearate was used as lubricant. Flow properties of granules (like bulk density, tapped density, Carr's index, Hausner's ratio, angle of repose) as well as the physical parameters of compressed tablets including hardness, friability, thickness and disintegration time were determined. Flow parameters of granules of all the batches were found good. Physical parameters (drug content, weight variation, thickness, hardness, friability, disintegration time) of formulated tablets were found within limit when tested. The dissolution studies showed that tablets formulations containing each Prunus domestica showed better binding capacity compared to Prunus armeniaca gum. The binding potential increased as the concentration of gums increased. The FTIR spectroscopic investigation showed that the formulations containing plant gum are compatible with the drug and other excipients used.

Quantification of concentrated Chinese medicine granules by quantitative polymerase chain reaction.

PubMed

Lo, Yat-Tung; Shaw, Pang-Chui

2017-10-25

Determination of the amount of constituent in a multi-herb product is important for quality control. In concentrated Chinese medicine granules (CCMG), no dregs are left after dissolution of the CCMG. This study is the first to examine the feasibility of using quantitative polymerase chain reaction (qPCR) to find the amount of CCMG in solution form. DNA was extracted from Hirudo and Zaocys CCMG mixed at different ratios and amplified in qPCR using species-specific primers. The threshold cycle (C T ) obtained was compared with the respective standard curves. Results showed that reproducible quantification results could be obtained (1) for 5-50mg CCMG using a modified DNA extraction protocol, (2) amongst DNA extracted from the same batch of CCMG and (3) amongst different batches of CCMG from the same company. This study demonstrated the constitute amount of CCMG in a mixture could be determined using qPCR. This work has extended the application of DNA techniques for the quantification of herbal products and this approach may be developed for quality assurance in the CCMG industry. Copyright © 2017 Elsevier B.V. All rights reserved.

Mineralogical determination and geo-chemical modeling of chromium release from AOD slag: Distribution and leachability aspects.

PubMed

Li, Junguo; Liu, Bao; Zeng, Yanan; Wang, Ziming

2017-01-01

AOD (argon oxygen decarburization) slag, which is the by-product of the stainless steel refining process, is a recyclable slag because of its high content of calcium and silicon. The leaching toxicity cannot be ignored in the recycling process because the slag contains a certain amount of Cr. In this study, the mineral analysis, batch leaching tests and thermodynamic and kinetic modeling by PHREEQC combined with FactSage software were performed to explore the influence of the dissolution of primary minerals and the precipitation of secondary minerals on the elution of Cr from AOD slag. The results indicated that the main minerals in the original AOD slag are larnite, merwinite, pyroxene and periclase. Cr was dispersed in the mineral phases mentioned above. The simulation of Cr leaching controlled by Cr(III)-hydroxide corresponded better to the batch leaching tests, while the Cr leaching controlled by chromite or double control was underestimated. Increasing the L/S ratio enhances the pH of the leachate and restrains the elution of Cr from the AOD slag. Copyright © 2016 Elsevier Ltd. All rights reserved.

MODELING HEXAVALENT CHROMIUM REDUCTION IN GROUND- WATER IN FIELD-SCALE TRANSPORT AND LABORATORY BATCH EXPERIMENTS

EPA Science Inventory

A plausible and consistent model is developed to obtain a quantitative description of the gradual disappearance of hexavalent chromium (Cr(VI)) from groundwater in a small-scale field tracer test and in batch kinetic experiments using aquifer sediments under similar chemical cond...

Experience with a UNIX based batch computing facility for H1

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

Gerhards, R.; Kruener-Marquis, U.; Szkutnik, Z.

1994-12-31

A UNIX based batch computing facility for the H1 experiment at DESY is described. The ultimate goal is to replace the DESY IBM mainframe by a multiprocessor SGI Challenge series computer, using the UNIX operating system, for most of the computing tasks in H1.

Arsenic release from shallow aquifers of the Hetao basin, Inner Mongolia: evidence from bacterial community in aquifer sediments and groundwater.

PubMed

Li, Yuan; Guo, Huaming; Hao, Chunbo

2014-12-01

Indigenous microbes play crucial roles in arsenic mobilization in high arsenic groundwater systems. Databases concerning the presence and the activity of microbial communities are very useful in evaluating the potential of microbe-mediated arsenic mobilization in shallow aquifers hosting high arsenic groundwater. This study characterized microbial communities in groundwaters at different depths with different arsenic concentrations by DGGE and one sediment by 16S rRNA gene clone library, and evaluated arsenic mobilization in microcosm batches with the presence of indigenous bacteria. DGGE fingerprints revealed that the community structure changed substantially with depth at the same location. It indicated that a relatively higher bacterial diversity was present in the groundwater sample with lower arsenic concentration. Sequence analysis of 16S rRNA gene demonstrated that the sediment bacteria mainly belonged to Pseudomonas, Dietzia and Rhodococcus, which have been widely found in aquifer systems. Additionally, NO3(-)-reducing bacteria Pseudomonas sp. was the largest group, followed by Fe(III)-reducing, SO4(2-)-reducing and As(V)-reducing bacteria in the sediment sample. These anaerobic bacteria used the specific oxyanions as electron acceptor and played a significant role in reductive dissolution of Fe oxide minerals, reduction of As(V), and release of arsenic from sediments into groundwater. Microcosm experiments, using intact aquifer sediments, showed that arsenic release and Fe(III) reduction were microbially mediated in the presence of indigenous bacteria. High arsenic concentration was also observed in the batch without amendment of organic carbon, demonstrating that the natural organic matter in sediments was the potential electron donor for microbially mediated arsenic release from these aquifer sediments.

Volcanic ash leaching as a means of tracing the environmental impact of the 2011 Grímsvötn eruption, Iceland.

PubMed

Cabré, J; Aulinas, M; Rejas, M; Fernandez-Turiel, J L

2016-07-01

The Grímsvötn volcanic eruption, from 21 to 28 May, 2011, was the largest eruption of the Grímsvötn Volcanic System since 1873, with a Volcanic Explosivity Index (VEI) of magnitude 4. The main geochemical features of the potential environmental impact of the volcanic ash-water interaction were determined using two different leaching methods as proxies (batch and vertical flow-through column experiments). Ash consists of glass with minor amounts of plagioclase, clinopyroxene, diopside, olivine and iron sulphide; this latter mineral phase is very rare in juvenile ash. Ash grain morphology and size reflect the intense interaction of magma and water during eruption. Batch and column leaching tests in deionised water indicate that Na, K, Ca, Mg, Si, Cl, S and F had the highest potential geochemical fluxes to the environment. Release of various elements from volcanic ash took place immediately through dissolution of soluble salts from the ash surface. Element solubilities of Grímsvötn ash regarding bulk ash composition were <1 %. Combining the element solubilities and the total estimated mass of tephra (7.29 × 10(14) g), the total inputs of environmentally important elements were estimated to be 8.91 × 10(9) g Ca, 7.02 × 10(9) g S, 1.10 × 10(9) g Cl, 9.91 × 10(8) g Mg, 9.91 × 10(8) g Fe and 1.45 × 10(8) g P The potential environmental problems were mainly associated with the release of F (5.19 × 10(9) g).

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.

Dissolution of Platinum in the Operational Range of Fuel Cells

PubMed Central

Keeley, Gareth P.; Geiger, Simon; Zeradjanin, Aleksandar R.; Hodnik, Nejc; Kulyk, Nadiia

2015-01-01

Abstract One of the most important practical issues in low‐temperature fuel‐cell catalyst degradation is platinum dissolution. According to the literature, it initiates at 0.6–0.9 VRHE, whereas previous time‐ and potential‐resolved inductively coupled plasma mass spectrometry (ICP–MS) experiments, however, revealed dissolution onset at only 1.05 VRHE. In this manuscript, the apparent discrepancy is addressed by investigating bulk and nanoparticulated catalysts. It is shown that, given enough time for accumulation, traces of platinum can be detected at potentials as low as 0.85 VRHE. At these low potentials, anodic dissolution is the dominant process, whereas, at more positive potentials, more platinum dissolves during the oxide reduction after accumulation. Interestingly, the potential and time dissolution dependence is similar for both types of electrode. Dissolution processes are discussed with relevance to fuel‐cell operation and plausible dissolution mechanisms are considered. PMID:27525206

In Silico Modeling Approach for the Evaluation of Gastrointestinal Dissolution, Supersaturation, and Precipitation of Posaconazole.

PubMed

Hens, Bart; Pathak, Shriram M; Mitra, Amitava; Patel, Nikunjkumar; Liu, Bo; Patel, Sanjaykumar; Jamei, Masoud; Brouwers, Joachim; Augustijns, Patrick; Turner, David B

2017-12-04

The aim of this study was to evaluate gastrointestinal (GI) dissolution, supersaturation, and precipitation of posaconazole, formulated as an acidified (pH 1.6) and neutral (pH 7.1) suspension. A physiologically based pharmacokinetic (PBPK) modeling and simulation tool was applied to simulate GI and systemic concentration-time profiles of posaconazole, which were directly compared with intraluminal and systemic data measured in humans. The Advanced Dissolution Absorption and Metabolism (ADAM) model of the Simcyp Simulator correctly simulated incomplete gastric dissolution and saturated duodenal concentrations of posaconazole in the duodenal fluids following administration of the neutral suspension. In contrast, gastric dissolution was approximately 2-fold higher after administration of the acidified suspension, which resulted in supersaturated concentrations of posaconazole upon transfer to the upper small intestine. The precipitation kinetics of posaconazole were described by two precipitation rate constants, extracted by semimechanistic modeling of a two-stage medium change in vitro dissolution test. The 2-fold difference in exposure in the duodenal compartment for the two formulations corresponded with a 2-fold difference in systemic exposure. This study demonstrated for the first time predictive in silico simulations of GI dissolution, supersaturation, and precipitation for a weakly basic compound in part informed by modeling of in vitro dissolution experiments and validated via clinical measurements in both GI fluids and plasma. Sensitivity analysis with the PBPK model indicated that the critical supersaturation ratio (CSR) and second precipitation rate constant (sPRC) are important parameters of the model. Due to the limitations of the two-stage medium change experiment the CSR was extracted directly from the clinical data. However, in vitro experiments with the BioGIT transfer system performed after completion of the in silico modeling provided an almost identical CSR to the clinical study value; this had no significant impact on the PBPK model predictions.

Monitoring carbonate dissolution using spatially resolved under-sampled NMR propagators and MRI

NASA Astrophysics Data System (ADS)

Sederman, A. J.; Colbourne, A.; Mantle, M. D.; Gladden, L. F.; Oliveira, R.; Bijeljic, B.; Blunt, M. J.

2017-12-01

The dissolution of a porous rock matrix by an acidic flow causes a change in the pore structure and consequently the pattern of fluid flow and rock permeability. This process is relevant to many areas of practical relevance such as enhanced oil recovery, water contaminant migration and sequestration of supercritical CO2. The most important governing factors for the type of change in the pore space are related by the Péclet (Pe) and Damköhler (Da) dimensionless numbers; these compare the transport properties of the fluid in the porous medium with the reactive properties of the solid matrix and the incident fluid respectively. Variation in Pe and Da can cause very different evolution regimes of the pore space and flow can occur, ranging from a uniform dissolution through different "wormholing" regimes (shown on the left hand side of figure 1) to face dissolution. NMR has a unique capability of measuring both the flow and structural changes during such dissolution whilst the characteristics of flow in the highly heterogeneous matrix that is formed can be predicted by the CTRW modelling approach. Here, NMR measurements of displacement probability distributions, or propagators, have been used to monitor the evolution of fluid flow during a reactive dissolution rock core floods. Developments in the NMR method by undersampling the acquisition data enable spatially resolved measurements of the propagators to be done at sufficient displacement resolution and in a timescale that is short enough to capture the changes in structure and flow. The highly under-sampled (4%) data, which typically reduces the acquisition time from 2 hours to 6 minutes, has been shown to produce equivalent propagator results to the fully sampled experiment. Combining these propagator measurements with quantitative and fast imaging techniques a full time-resolved picture of the dissolution reaction is built up. Experiments have been done for both Ketton and Estaillades carbonate rock cores, which exhibit very different dissolution behaviours, and for which experiments and model comparisons will be shown.

Simultaneously bio treatment of textiles and food industries effluent at difference ratios with the aid of e-beam radiation

NASA Astrophysics Data System (ADS)

Bakar, Khomsaton Abu; Selambakkannu, Sarala; Ting, Teo Ming; Shariff, Jamaliah

2012-09-01

The combination of irradiation and biological technique was used to study COD, BOD5 and colour removal of textiles effluent in the presence of food industry wastewater at two different ratios. Two biological treatment system, the first consisting a mix of unirradiated textile and food industry wastewater and the second a mix of irradiated textile wastewater and food industry wastewater were operated in parallel. The experiment was conducted by batch. For the first batch the ratio was use for textile wastewater and food industry wastewater in biological treatment was 1:1. Meanwhile, for the second batch the ratio used for textile wastewater and food industry wastewater in biological treatment was 1:2. The results obtained for the first and second batch varies from each other. After irradiation, COD reduce in textile wastewater for the both batches are roughly 29% - 33% from the unirradiated wastewater. But after undergoing the biological treatment the percentage of COD reduction for first batch and second batch was 62.1% and 80.7% respectively. After irradiation the BOD5 of textile wastewater reduced by 22.2% for the first batch and 55.1% for the second batch. But after biological treatment, the BOD5 value for the first batch was same as its initial, 36mg/l and 40.4mg/l for the second batch. Colour had decreased from 899.5 ADMI to 379.3 ADMI after irradiation and decrease to 109.3 after undergoes biological treatment for the first batch. Meantime for the batch two, colour had decreased from 1000.44 ADMI to 363.40 ADMI after irradiation and dropped to 79.20 ADMI after biological treatment. The experiment show that 1:2 ratio show better reduction on COD, BOD5 and colour, compared to the ratio of 1:1.

Geochemical modelling of worst-case leakage scenarios at potential CO2-storage sites - CO2 and saline water contamination of drinking water aquifers

NASA Astrophysics Data System (ADS)

Szabó, Zsuzsanna; Edit Gál, Nóra; Kun, Éva; Szőcs, Teodóra; Falus, György

2017-04-01

Carbon Capture and Storage is a transitional technology to reduce greenhouse gas emissions and to mitigate climate change. Following the implementation and enforcement of the 2009/31/EC Directive in the Hungarian legislation, the Geological and Geophysical Institute of Hungary is required to evaluate the potential CO2 geological storage structures of the country. Basic assessment of these saline water formations has been already performed and the present goal is to extend the studies to the whole of the storage complex and consider the protection of fresh water aquifers of the neighbouring area even in unlikely scenarios when CO2 injection has a much more regional effect than planned. In this work, worst-case scenarios are modelled to understand the effects of CO2 or saline water leaks into drinking water aquifers. The dissolution of CO2 may significantly change the pH of fresh water which induces mineral dissolution and precipitation in the aquifer and therefore, changes in solution composition and even rock porosity. Mobilization of heavy metals may also be of concern. Brine migration from CO2 reservoir and replacement of fresh water in the shallower aquifer may happen due to pressure increase as a consequence of CO2 injection. The saline water causes changes in solution composition which may also induce mineral reactions. The modelling of the above scenarios has happened at several methodological levels such as equilibrium batch, kinetic batch and kinetic reactive transport simulations. All of these have been performed by PHREEQC using the PHREEQC.DAT thermodynamic database. Kinetic models use equations and kinetic rate parameters from the USGS report of Palandri and Kharaka (2004). Reactive transport modelling also considers estimated fluid flow and dispersivity of the studied formation. Further input parameters are the rock and the original ground water compositions of the aquifers and a range of gas-phase CO2 or brine replacement ratios. Worst-case scenarios at seven potential CO2-storage areas have been modelled. The visualization of results has been automatized by R programming. The three types of models (equilibrium, kinetic batch and reactive transport) provide different type but overlapping information. All modelling output of both scenarios (CO2/brine) indicate the increase of ion-concentrations in the fresh water, which might exceed drinking water limit values. Transport models provide a possibility to identify the most suitable chemical parameter in the fresh water for leakage monitoring. This indicator parameter may show detectable and early changes even far away from the contamination source. In the CO2 models potassium concentration increase is significant and runs ahead of the other parameters. In the rock, the models indicate feldspar, montmorillonite, dolomite and illite dissolution whereas calcite, chlorite, kaolinite and silica precipitates, and in the case of CO2-inflow models, dawsonite traps a part of the leaking gas.

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.

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

In vitro growth of Curcuma longa L. in response to five mineral elements and plant density in fed-batch culture systems.

PubMed

El-Hawaz, Rabia F; Bridges, William C; Adelberg, Jeffrey W

2015-01-01

Plant density was varied with P, Ca, Mg, and KNO3 in a multifactor experiment to improve Curcuma longa L. micropropagation, biomass and microrhizome development in fed-batch liquid culture. The experiment had two paired D-optimal designs, testing sucrose fed-batch and nutrient sucrose fed-batch techniques. When sucrose became depleted, volume was restored to 5% m/v sucrose in 200 ml of modified liquid MS medium by adding sucrose solutions. Similarly, nutrient sucrose fed-batch was restored to set points with double concentration of treatments' macronutrient and MS micronutrient solutions, along with sucrose solutions. Changes in the amounts of water and sucrose supplementations were driven by the interaction of P and KNO3 concentrations. Increasing P from 1.25 to 6.25 mM increased both multiplication and biomass. The multiplication ratio was greatest in the nutrient sucrose fed-batch technique with the highest level of P, 6 buds/vessel, and the lowest level of Ca and KNO3. The highest density (18 buds/vessel) produced the highest fresh biomass at the highest concentrations of KNO3 and P with nutrient sucrose fed-batch, and moderate Ca and Mg concentrations. However, maximal rhizome dry biomass required highest P, sucrose fed-batch, and a moderate plant density. Different media formulations and fed-batch techniques were identified to maximize the propagation and storage organ responses. A single experimental design was used to optimize these dual purposes.

In Vitro Growth of Curcuma longa L. in Response to Five Mineral Elements and Plant Density in Fed-Batch Culture Systems

PubMed Central

El-Hawaz, Rabia F.; Bridges, William C.; Adelberg, Jeffrey W.

2015-01-01

Plant density was varied with P, Ca, Mg, and KNO3 in a multifactor experiment to improve Curcuma longa L. micropropagation, biomass and microrhizome development in fed-batch liquid culture. The experiment had two paired D-optimal designs, testing sucrose fed-batch and nutrient sucrose fed-batch techniques. When sucrose became depleted, volume was restored to 5% m/v sucrose in 200 ml of modified liquid MS medium by adding sucrose solutions. Similarly, nutrient sucrose fed-batch was restored to set points with double concentration of treatments’ macronutrient and MS micronutrient solutions, along with sucrose solutions. Changes in the amounts of water and sucrose supplementations were driven by the interaction of P and KNO3 concentrations. Increasing P from 1.25 to 6.25 mM increased both multiplication and biomass. The multiplication ratio was greatest in the nutrient sucrose fed-batch technique with the highest level of P, 6 buds/vessel, and the lowest level of Ca and KNO3. The highest density (18 buds/vessel) produced the highest fresh biomass at the highest concentrations of KNO3 and P with nutrient sucrose fed-batch, and moderate Ca and Mg concentrations. However, maximal rhizome dry biomass required highest P, sucrose fed-batch, and a moderate plant density. Different media formulations and fed-batch techniques were identified to maximize the propagation and storage organ responses. A single experimental design was used to optimize these dual purposes. PMID:25830292

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

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.

Experiments and modeling of variably permeable carbonate reservoir samples in contact with CO₂-acidified brines

DOE PAGES

Smith, Megan M.; Hao, Yue; Mason, Harris E.; ...

2014-12-31

Reactive experiments were performed to expose sample cores from the Arbuckle carbonate reservoir to CO₂-acidified brine under reservoir temperature and pressure conditions. The samples consisted of dolomite with varying quantities of calcite and silica/chert. The timescales of monitored pressure decline across each sample in response to CO₂ exposure, as well as the amount of and nature of dissolution features, varied widely among these three experiments. For all samples cores, the experimentally measured initial permeability was at least one order of magnitude or more lower than the values estimated from downhole methods. Nondestructive X-ray computed tomography (XRCT) imaging revealed dissolution featuresmore » including “wormholes,” removal of fracture-filling crystals, and widening of pre-existing pore spaces. In the injection zone sample, multiple fractures may have contributed to the high initial permeability of this core and restricted the distribution of CO₂-induced mineral dissolution. In contrast, the pre-existing porosity of the baffle zone sample was much lower and less connected, leading to a lower initial permeability and contributing to the development of a single dissolution channel. While calcite may make up only a small percentage of the overall sample composition, its location and the effects of its dissolution have an outsized effect on permeability responses to CO₂ exposure. The XRCT data presented here are informative for building the model domain for numerical simulations of these experiments but require calibration by higher resolution means to confidently evaluate different porosity-permeability relationships.« less

Biodegradation, sorption, and transport of 2,4-dichlorophenoxyacetic acid in saturated and unsaturated soils.

PubMed Central

Estrella, M R; Brusseau, M L; Maier, R S; Pepper, I L; Wierenga, P J; Miller, R M

1993-01-01

The fate of an organic contaminant in soil depends on many factors, including sorption, biodegradation, and transport. The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model compound to illustrate the impact of these interacting factors on the fate of an organic contaminant. Batch and column experiments performed with a sandy loam soil mixture under saturated and unsaturated conditions were used to determine the effects of sorption and biodegradation on the fate and transport of 2,4-D. Sorption of 2,4-D was found to have a slight but significant effect on transport of 2,4-D under saturated conditions (retardation factor, 1.8) and unsaturated conditions (retardation factor, 3.4). Biodegradation of 2,4-D was extensive under both batch and column conditions and was found to have a significant impact on 2,4-D transport in column experiments. In batch experiments, complete mineralization of 2,4-D (100 mg kg-1) occurred over a 4-day period following a 3-day lag phase under both saturated and unsaturated conditions. The biodegradation rate parameters calculated for batch experiments were found to be significantly different from those estimated for column experiments. PMID:8285717

Development and optimization of press coated tablets of release engineered valsartan for pulsatile delivery.

PubMed

Shah, Sunny; Patel, Romik; Soniwala, Moinuddin; Chavda, Jayant

2015-01-01

The present work is aimed to develop and optimize pulsatile delivery during dissolution of an improved formulation of valsartan to coordinate the drug release with circadian rhythm. Preliminary studies suggested that β cyclodextrin could improve the solubility of valsartan and showed AL type solubility curve. A 1:1 stoichiometric ratio of valsartan to β cyclodextrin was revealed from phase solubility studies and Job's plot. The prepared complex showed significantly better dissolution efficiency (p < 0.05) compared to pure drug, which could be due to the formation of inclusion complex as revealed from FTIR and DSC studies. Continuous dissolution-absorption studies revealed that absorption of drug from valsartan β cyclodextrin complex was significantly higher (p < 0.05) compared to pure drug, in second part press-coated tablets of valsartan β cyclodextrin complex were subsequently prepared and application of the Plackett-Burman screening design revealed that HPMC K4M and EC showed significant effect on lag time. A 3(2) full factorial design was used to measure the response of HPMC K4M and EC on lag time and time taken for 90% drug release (T90). The optimized batch prepared according to the levels obtained from the desirability function had a lag time of 6 h and consisted of HPMC K4M:ethylcellulose in a 1:1.5 ratio with 180 mg of coating and revealed a close agreement between observed and predicted value (R(2 )= 0.9694).

Effects of Bacterial Siderophore and Biofilm Synthesis on Silicate Mineral Dissolution Kinetics: Results from Experiments with Targeted Mutants

NASA Astrophysics Data System (ADS)

Van Den Berghe, M. D.; West, A. J.; Nealson, K. H.

2018-05-01

This project aims to characterize and quantify the specific microbial mechanisms and metabolic pathways responsible for silicate mineral dissolution and micronutrient acquisition directly from mineral phases.

Mass Transport Phenomena Between Bubbles and Dissolved Gases in Liquids Under Reduced Gravity Conditions

NASA Technical Reports Server (NTRS)

Dewitt, K. J.; Brockwell, J. L.

1985-01-01

The long term objective of the experiment is to observe the dissolution of isolated, immobile gas bubbles of specified size and composition in a solvent liquid of known concentration in the reduced gravity environment of earth orbit. Preliminary bubble dissolution experiment conducted both in the NASA Lewis 2.2 sec drop tower and in normal gravity using SO2 - Toluene system were not completely successful in their objective. The method of gas injection and lack of bubble interface stabiliy experienced due to the extreme solubility of SO in Toluene has the effects of changing the problem from that of bubble dissolution to one of bubble formation stability and subsequent dissolution in a liquid of unknown initial solute concentration. Current work involves further experimentation in order to refine the bubble injection system and to investigate the concept of having a bubble with a critical radius in a state of unstable equilibrium.

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.

Assessing soil and groundwater contamination from biofuel spills.

PubMed

Chen, Colin S; Shu, Youn-Yuen; Wu, Suh-Huey; Tien, Chien-Jung

2015-03-01

Future modifications of fuels should include evaluation of the proposed constituents for their potential to damage environmental resources such as the subsurface environment. Batch and column experiments were designed to simulate biofuel spills in the subsurface environment and to evaluate the sorption and desorption behavior of target fuel constituents (i.e., monoaromatic and polyaromatic hydrocarbons) in soil. The extent and reversibility of the sorption of aromatic biofuel constituents onto soil were determined. When the ethanol content in ethanol-blended gasoline exceeded 25%, enhanced desorption of the aromatic constituents to water was observed. However, when biodiesel was added to diesel fuel, the sorption of target compounds was not affected. In addition, when the organic carbon content of the soil was higher, the desorption of target compounds into water was lower. The empirical relationships between the organic-carbon normalized sorption coefficient (Koc) and water solubility and between Koc and the octanol-water partition coefficient (Kow) were established. Column experiments were carried out for the comparison of column effluent concentration/mass from biofuel-contaminated soil. The dissolution of target components depended on chemical properties such as the hydrophobicity and total mass of biofuel. This study provides a basis for predicting the fate and transport of hydrophobic organic compounds in the event of a biofuel spill. The spill scenarios generated can assist in the assessment of biofuel-contaminated sites.

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.

Facilitating Conceptual Understanding of Gas-Liquid Mass Transfer Coefficient through a Simple Experiment Involving Dissolution of Carbon Dioxide in Water in a Surface Aeration Reactor

ERIC Educational Resources Information Center

Utgikar, Vivek P.; MacPherson, David

2016-01-01

Students in the undergraduate "transport phenomena" courses typically have a greater difficulty in understanding the theoretical concepts underlying the mass transport phenomena as compared to the concepts of momentum and energy transport. An experiment based on dissolution of carbon dioxide in water was added to the course syllabus to…

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.

Cadmium removal using Cladophora in batch, semi-batch and flow reactors.

PubMed

Sternberg, Steven P K; Dorn, Ryan W

2002-02-01

This study presents the results of using viable algae to remove cadmium from a synthetic wastewater. In batch and semi-batch tests, a local strain of Cladophora algae removed 80-94% of the cadmium introduced. The flow experiments that followed were conducted using non-local Cladophora parriaudii. Results showed that the alga removed only 12.7(+/-6.4)% of the cadmium introduced into the reactor. Limited removal was the result of insufficient algal quantities and poor contact between the algae and cadmium solution.

Uncertainty and variability in laboratory derived sorption parameters of sediments from a uranium in situ recovery site

NASA Astrophysics Data System (ADS)

Dangelmayr, Martin A.; Reimus, Paul W.; Johnson, Raymond H.; Clay, James T.; Stone, James J.

2018-06-01

This research assesses the ability of a GC SCM to simulate uranium transport under variable geochemical conditions typically encountered at uranium in-situ recovery (ISR) sites. Sediment was taken from a monitoring well at the SRH site at depths 192 and 193 m below ground and characterized by XRD, XRF, TOC, and BET. Duplicate column studies on the different sediment depths, were flushed with synthesized restoration waters at two different alkalinities (160 mg/l CaCO3 and 360 mg/l CaCO3) to study the effect of alkalinity on uranium mobility. Uranium breakthrough occurred 25% - 30% earlier in columns with 360 mg/l CaCO3 over columns fed with 160 mg/l CaCO3 influent water. A parameter estimation program (PEST) was coupled to PHREEQC to derive site densities from experimental data. Significant parameter fittings were produced for all models, demonstrating that the GC SCM approach can model the impact of carbonate on uranium in flow systems. Derived site densities for the two sediment depths were between 141 and 178 μmol-sites/kg-soil, demonstrating similar sorption capacities despite heterogeneity in sediment mineralogy. Model sensitivity to alkalinity and pH was shown to be moderate compared to fitted site densities, when calcite saturation was allowed to equilibrate. Calcite kinetics emerged as a potential source of error when fitting parameters in flow conditions. Fitted results were compared to data from previous batch and column studies completed on sediments from the Smith-Ranch Highland (SRH) site, to assess variability in derived parameters. Parameters from batch experiments were lower by a factor of 1.1 to 3.4 compared to column studies completed on the same sediments. The difference was attributed to errors in solid-solution ratios and the impact of calcite dissolution in batch experiments. Column studies conducted at two different laboratories showed almost an order of magnitude difference in fitted site densities suggesting that experimental methodology may play a bigger role in column sorption behavior than actual sediment heterogeneity. Our results demonstrate the necessity for ISR sites to remove residual pCO2 and equilibrate restoration water with background geochemistry to reduce uranium mobility. In addition, the observed variability between fitted parameters on the same sediments highlights the need to provide standardized guidelines and methodology for regulators and industry when the GC SCM approach is used for ISR risk assessments.

Uncertainty and variability in laboratory derived sorption parameters of sediments from a uranium in situ recovery site.

PubMed

Dangelmayr, Martin A; Reimus, Paul W; Johnson, Raymond H; Clay, James T; Stone, James J

2018-06-01

This research assesses the ability of a GC SCM to simulate uranium transport under variable geochemical conditions typically encountered at uranium in-situ recovery (ISR) sites. Sediment was taken from a monitoring well at the SRH site at depths 192 and 193 m below ground and characterized by XRD, XRF, TOC, and BET. Duplicate column studies on the different sediment depths, were flushed with synthesized restoration waters at two different alkalinities (160 mg/l CaCO 3 and 360 mg/l CaCO 3 ) to study the effect of alkalinity on uranium mobility. Uranium breakthrough occurred 25% - 30% earlier in columns with 360 mg/l CaCO 3 over columns fed with 160 mg/l CaCO 3 influent water. A parameter estimation program (PEST) was coupled to PHREEQC to derive site densities from experimental data. Significant parameter fittings were produced for all models, demonstrating that the GC SCM approach can model the impact of carbonate on uranium in flow systems. Derived site densities for the two sediment depths were between 141 and 178 μmol-sites/kg-soil, demonstrating similar sorption capacities despite heterogeneity in sediment mineralogy. Model sensitivity to alkalinity and pH was shown to be moderate compared to fitted site densities, when calcite saturation was allowed to equilibrate. Calcite kinetics emerged as a potential source of error when fitting parameters in flow conditions. Fitted results were compared to data from previous batch and column studies completed on sediments from the Smith-Ranch Highland (SRH) site, to assess variability in derived parameters. Parameters from batch experiments were lower by a factor of 1.1 to 3.4 compared to column studies completed on the same sediments. The difference was attributed to errors in solid-solution ratios and the impact of calcite dissolution in batch experiments. Column studies conducted at two different laboratories showed almost an order of magnitude difference in fitted site densities suggesting that experimental methodology may play a bigger role in column sorption behavior than actual sediment heterogeneity. Our results demonstrate the necessity for ISR sites to remove residual pCO2 and equilibrate restoration water with background geochemistry to reduce uranium mobility. In addition, the observed variability between fitted parameters on the same sediments highlights the need to provide standardized guidelines and methodology for regulators and industry when the GC SCM approach is used for ISR risk assessments. Copyright © 2018 Elsevier B.V. All rights reserved.

Kinetic modeling of multi-feed simultaneous saccharification and co-fermentation of pretreated birch to ethanol.

PubMed

Wang, Ruifei; Koppram, Rakesh; Olsson, Lisbeth; Franzén, Carl Johan

2014-11-01

Fed-batch simultaneous saccharification and fermentation (SSF) is a feasible option for bioethanol production from lignocellulosic raw materials at high substrate concentrations. In this work, a segregated kinetic model was developed for simulation of fed-batch simultaneous saccharification and co-fermentation (SSCF) of steam-pretreated birch, using substrate, enzymes and cell feeds. The model takes into account the dynamics of the cellulase-cellulose system and the cell population during SSCF, and the effects of pre-cultivation of yeast cells on fermentation performance. The model was cross-validated against experiments using different feed schemes. It could predict fermentation performance and explain observed differences between measured total yeast cells and dividing cells very well. The reproducibility of the experiments and the cell viability were significantly better in fed-batch than in batch SSCF at 15% and 20% total WIS contents. The model can be used for simulation of fed-batch SSCF and optimization of feed profiles. Copyright © 2014 Elsevier Ltd. All rights reserved.

Remediation of cadmium-contaminated soil by extraction with para-sulphonato-thiacalix[4]arene, a novel supramolecular receptor.

PubMed

Li, Yushuang; Hu, Xiaojun; Song, Xueying; Sun, Tieheng

2012-08-01

Batch extractions were conducted to evaluate the performance of para-sulphonato-thiacalix[4]arene (STC[4]A), a novel supramolecular receptor, for removing cadmium (Cd) from soil. The extraction mechanism was investigated by determination of the conditional stability constants (log K) of the STC[4]A-Cd complex. The influences of various variables were examined, including pH, contact time, and extractant concentration. The Cd extraction efficiency increased with increasing pH, reaching the maximum at pH 11 and then declining at higher pH values. This pH dependence was explained by the variation in the log K value of the STC[4]A-Cd complex along with pH change. When the STC[4]A dose was increased to an STC[4]A:Cd molar ratio of 2.5:1, Cd was exhaustively removed (up to 96.8%). The comparison experiment revealed that the Cd extraction performance of STC[4]A was almost equivalent to that of EDTA and significantly better than that of natural organic acids. STC[4]A extraction could efficiently prevent co-dissolution of soil minerals. Copyright © 2012 Elsevier Ltd. All rights reserved.

Flow-Through Leaching of Marine Barite: New Insights on its Composition and Diagenesis

NASA Astrophysics Data System (ADS)

Hsieh, C.; Torres, M. E.; Ungerer, A.; Klinkhammer, G. P.

2007-12-01

The distribution of stable mineral barite (BaSO4) in marine sediments has long been studied as a proxy for paleoproductivity. It is important to investigate the variation in Sr/Ba ratios of crystal barite, as it has a great influence on barite solubility and its early diagenetic processes. In addition, the role of alternative barium carriers to the sediments (e.g. aluminum silicates and oxyhydroxides) and their contributions to overall barium budget and burial efficiency need to be resolved. The techniques currently used to describe and quantify barium phases are all based on batch leaching techniques that define barium phases operationally, not chemically. Because during batch analyses each phase is characterized by a single-point measurement, variations due to phase heterogeneities cannot be resolved; nor can the results of these experiments be related in any systematic way to what happens in nature. To overcome this problem, we are developing a flow-through method that makes use of automated chromatographic techniques, which allows complete monitoring of the dissolution of barite samples with time-resolved analysis (TRA) as each phase is sequentially leached using different reagents. We have analyzed a barite sample recovered from seeps along the San Clemente escarpment, and show that we can attain complete dissolution of the sample (>85%) in 2 hours, using DTPA at 80°C. Approximately 100 μg of barite are first leached with distilled water (pH 5) for 30 minutes. During this step ~2% of the barite is removed. This highly soluble phase has Sr/Ba ratios that range from 30 to 120 mmol/mol. Acid leaching of the samples with 10 mM HNO3 removes an additional 4~8% of the barite, and this phase has Sr/Ba ratios ranging from 13 to 35 mmol/mol. Higher acid concentration (100 mM HNO3) dissolves up to 40% of the barite. These results are consistent with electron microprobe data that show clear oscillatory zoning of the (Ba,Sr)SO4. Unlike the barite sample, sediment samples collected at the base of the escarpment did not show a Ba release in the water leach. We might speculate that the highly susceptible Sr-rich barium phase present in the barite sample, dissolved during transport from a seep site leaving a barite with a lower Sr/Ba ratio, as found in the sediment samples. Our analytical approach has the potential to further address a variety of outstanding questions on the complex geochemical cycle of barium and its applications to climate change, upper ocean fertility and ocean circulation through time.

Modeling hexavalent chromium reduction in groundwater in field-scale transport and laboratory batch experiments

USGS Publications Warehouse

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

1995-01-01

A plausible and consistent model is developed to obtain a quantitative description of the gradual disappearance of hexavalent chromium (Cr(VI)) from groundwater in a small-scale field tracer test and in batch kinetic experiments using aquifer sediments under similar chemical conditions. The data exhibit three distinct timescales. Fast reduction occurs in well-stirred batch reactors in times much less than 1 hour and is followed by slow reduction over a timescale of the order of 2 days. In the field, reduction occurs on a timescale of the order of 8 days. The model is based on the following hypotheses. The chemical reduction reaction occurs very fast, and the longer timescales are caused by diffusion resistance. Diffusion into the secondary porosity of grains causes the apparent slow reduction rate in batch experiments. In the model of the field experiments, the reducing agent, heavy Fe(II)-bearing minerals, is heterogeneously distributed in thin strata located between larger nonreducing sand lenses that comprise the bulk of the aquifer solids. It is found that reducing strata of the order of centimeters thick are sufficient to contribute enough diffusion resistance to cause the observed longest timescale in the field. A one-dimensional advection/dispersion model is formulated that describes the major experimental trends. Diffusion rates are estimated in terms of an elementary physical picture of flow through a stratified medium containing identically sized spherical grains. Both reduction and sorption reactions are included. Batch simulation results are sensitive to the fraction of reductant located at or near the surface of grains, which controls the amount of rapid reduction, and the secondary porosity, which controls the rate of slow reduction observed in batch experiments. Results of Cr(VI) transport simulations are sensitive to the thickness and relative size of the reducing stratum. Transport simulation results suggest that nearly all of the reductant must be located in the reducing stratum. Within this context and as long as there is adequate reductive capacity present, the transport simulation results are insensitive to the parameters important for the batch simulations. The results illustrate how a combination of field measurements and batch laboratory studies can be used to improve predictive modeling of contaminant transport.

Formulation, development and characterization of mucoadhesive film for treatment of vaginal candidiasis.

PubMed

Mishra, Renuka; Joshi, Priyanka; Mehta, Tejal

2016-01-01

The objective of the present investigation was formulation, optimization and characterization of mucoadhesive film of clotrimazole (CT) which is patient-convenient and provides an effective alternative for the treatment of vaginal candidiasis. CT is an antimycotic drug applied locally for the treatment of vaginal candidiasis. Mucoadhesive vaginal films were prepared by solvent casting technique using hydroxyl propylcellulose and sodium alginate as polymers. Propylene glycol and polyethylene glycol-400 were evaluated as plasticizers. The mucoadhesive vaginal films were evaluated for percentage elongation, tensile strength, folding endurance, drug content, in vitro disintegration time, in vitro dissolution study, swelling index, bioadhesive strength, and diffusion study. Among various permeation enhancers used, isopropyl myristate was found to be suitable. To evaluate the role of the concentration of permeation enhancer and concentration of polymers in the optimization of mucoadhesive vaginal film, 3(2) full factorial design was employed. Optimized batch showed in vitro disintegration time, 18 min; drug content, 99.83%; and tensile strength, 502.1 g/mm(2). In vitro diffusion study showed that 77% drug diffusion occurred in 6 h. This batch was further evaluated by scanning electron microscopy indicating uniformity of the film. In vitro Lactobacillus inhibition and in vitro antifungal activity of optimized batch showed an inhibitory effect against Candida albicans and no effect on Lactobacillus, which is a normal component of vaginal flora. Mucoadhesive vaginal film of CT is an effective dosage form for the treatment of vaginal candidiasis.

Novel method for screening of enteric film coatings properties with magnetic resonance imaging.

PubMed

Dorożyński, Przemysław; Jamróz, Witold; Niwiński, Krzysztof; Kurek, Mateusz; Węglarz, Władysław P; Jachowicz, Renata; Kulinowski, Piotr

2013-11-18

The aim of the study is to present the concept of novel method for fast screening of enteric coating compositions properties without the need of preparation of tablets batches for fluid bed coating. Proposed method involves evaluation of enteric coated model tablets in specially designed testing cell with application of MRI technique. The results obtained in the testing cell were compared with results of dissolution studies of mini-tablets coated in fluid bed apparatus. The method could be useful in early stage of formulation development for screening of film coating properties that will shorten and simplify the development works. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Effects of dissolved CO2 on Shallow Freshwater Microbial Communities simulating a CO2 Leakage Scenario

NASA Astrophysics Data System (ADS)

Gulliver, D. M.; Lowry, G. V.; Gregory, K.

2013-12-01

Geological carbon sequestration is likely to be part of a comprehensive strategy to minimize the atmospheric release of greenhouse gasses, establishing a concern of sequestered CO2 leakage into overlying potable aquifers. Leaking CO2 may affect existing biogeochemical processes and therefore water quality. There is a critical need to understand the evolution of CO2 exposed microbial communities that influence the biogeochemistry in these freshwater aquifers. The evolution of microbial ecology for different CO2 exposure concentrations was investigated using fluid-slurry samples obtained from a shallow freshwater aquifer (55 m depth, 0.5 MPa, 22 °C, Escatawpa, MS). The microbial community of well samples upstream and downstream of CO2 injection was characterized. In addition, batch vessel experiments were conducted with the upstream aquifer samples exposed to varying pCO2 from 0% to 100% under reservoir temperature and pressure for up to 56 days. The microbial community of the in situ experiment and the batch reactor experiment were analyzed with 16S rRNA clone libraries and qPCR. In both the in situ experiment and the batch reactor experiment, DNA concentration did not correlate with CO2 exposure. Both the in situ experiment and the batch reactors displayed a changing microbial community with increased CO2 exposure. The well water isolate, Curvibacter, appeared to be the most tolerant genus to high CO2 concentrations in the in situ experiments and to mid-CO2 concentrations in the batch reactors. In batch reactors with pCO2 concentrations higher than experienced in situ (pCO2 = 0.5 MPa), Pseudomonas appeared to be the most tolerant genus. Findings provide insight into a dynamic biogeochemical system that will alter with CO2 exposure. Adapted microbial populations will eventually give rise to the community that will impact the metal mobility and water quality. Knowledge of the surviving microbial populations will enable improved models for predicting the fate of CO2 following leakage and lead to better strategies for ensuring the quality of potable aquifer water.

Correcting for intra-experiment variation in Illumina BeadChip data is necessary to generate robust gene-expression profiles.

PubMed

Kitchen, Robert R; Sabine, Vicky S; Sims, Andrew H; Macaskill, E Jane; Renshaw, Lorna; Thomas, Jeremy S; van Hemert, Jano I; Dixon, J Michael; Bartlett, John M S

2010-02-24

Microarray technology is a popular means of producing whole genome transcriptional profiles, however high cost and scarcity of mRNA has led many studies to be conducted based on the analysis of single samples. We exploit the design of the Illumina platform, specifically multiple arrays on each chip, to evaluate intra-experiment technical variation using repeated hybridisations of universal human reference RNA (UHRR) and duplicate hybridisations of primary breast tumour samples from a clinical study. A clear batch-specific bias was detected in the measured expressions of both the UHRR and clinical samples. This bias was found to persist following standard microarray normalisation techniques. However, when mean-centering or empirical Bayes batch-correction methods (ComBat) were applied to the data, inter-batch variation in the UHRR and clinical samples were greatly reduced. Correlation between replicate UHRR samples improved by two orders of magnitude following batch-correction using ComBat (ranging from 0.9833-0.9991 to 0.9997-0.9999) and increased the consistency of the gene-lists from the duplicate clinical samples, from 11.6% in quantile normalised data to 66.4% in batch-corrected data. The use of UHRR as an inter-batch calibrator provided a small additional benefit when used in conjunction with ComBat, further increasing the agreement between the two gene-lists, up to 74.1%. In the interests of practicalities and cost, these results suggest that single samples can generate reliable data, but only after careful compensation for technical bias in the experiment. We recommend that investigators appreciate the propensity for such variation in the design stages of a microarray experiment and that the use of suitable correction methods become routine during the statistical analysis of the data.

Correcting for intra-experiment variation in Illumina BeadChip data is necessary to generate robust gene-expression profiles

PubMed Central

2010-01-01

Background Microarray technology is a popular means of producing whole genome transcriptional profiles, however high cost and scarcity of mRNA has led many studies to be conducted based on the analysis of single samples. We exploit the design of the Illumina platform, specifically multiple arrays on each chip, to evaluate intra-experiment technical variation using repeated hybridisations of universal human reference RNA (UHRR) and duplicate hybridisations of primary breast tumour samples from a clinical study. Results A clear batch-specific bias was detected in the measured expressions of both the UHRR and clinical samples. This bias was found to persist following standard microarray normalisation techniques. However, when mean-centering or empirical Bayes batch-correction methods (ComBat) were applied to the data, inter-batch variation in the UHRR and clinical samples were greatly reduced. Correlation between replicate UHRR samples improved by two orders of magnitude following batch-correction using ComBat (ranging from 0.9833-0.9991 to 0.9997-0.9999) and increased the consistency of the gene-lists from the duplicate clinical samples, from 11.6% in quantile normalised data to 66.4% in batch-corrected data. The use of UHRR as an inter-batch calibrator provided a small additional benefit when used in conjunction with ComBat, further increasing the agreement between the two gene-lists, up to 74.1%. Conclusion In the interests of practicalities and cost, these results suggest that single samples can generate reliable data, but only after careful compensation for technical bias in the experiment. We recommend that investigators appreciate the propensity for such variation in the design stages of a microarray experiment and that the use of suitable correction methods become routine during the statistical analysis of the data. PMID:20181233

Cognitive processing in the aftermath of relationship dissolution: Associations with concurrent and prospective distress and posttraumatic growth.

PubMed

Del Palacio-González, Adriana; Clark, David A; O'Sullivan, Lucia F

2017-12-01

Non-marital romantic relationship dissolution is amongst the most stressful life events experienced by young adults. Yet, some individuals experience posttraumatic growth following relationship dissolution. Little is known about the specific and differential contribution of trait-like and event-specific cognitive processing styles to each of these outcomes. A longitudinal design was employed in which trait-like (brooding and reflection) and dissolution-specific (intrusive and deliberate) cognitive processing was examined as predictors of growth (Posttraumatic Growth Inventory) and distress (Breakup Distress Scale) following a recent relationship dissolution. Initially, 148 participants completed measures of trait-like and dissolution-specific cognitive processing, growth, and distress (T1). A subsample completed a seven-month follow-up (T2). Higher frequency of relationship-dissolution intrusive thoughts predicted concurrent distress after accounting for brooding and relationship characteristics. Further, higher brooding and lower reflection predicted higher distress prospectively. Concurrent growth was predicted by both higher brooding and more deliberate relationship-dissolution thoughts. Prospectively, T1 dissolution intrusive thoughts predicted higher T2 deliberate thoughts, and the interaction between these two constructs predicted higher T2 growth. Therefore, deliberately thinking of the dissolution was related to positive psychological outcomes. In contrast, intrusive dissolution cognitions and a tendency for brooding had a mixed (paradoxical) association with psychological adjustment. Copyright © 2016 John Wiley & Sons, Ltd.

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.

Solution-mediated phase transformation of haloperidol mesylate in the presence of sodium lauryl sulfate.

PubMed

Greco, Kristyn; Bogner, Robin

2011-09-01

Forming a salt is a common way to increase the solubility of a poorly soluble compound. However, the solubility enhancement gained by salt formation may be lost due to solution-mediated phase transformation (SMPT) during dissolution. The SMPT of a salt can occur due to a supersaturated solution near the dissolving surface caused by pH or other solution conditions. In addition to changes in pH, surfactants are also known to affect SMPT. In this study, SMPT of a highly soluble salt, haloperidol mesylate, at pH 7 in the presence of a commonly used surfactant, sodium lauryl sulfate (SLS), was investigated. Dissolution experiments were performed using a flow-through dissolution apparatus with solutions containing various concentrations of SLS. Compacts of haloperidol mesylate were observed during dissolution in the flow-through apparatus using a stereomicroscope. Raman microscopy was used to characterize solids. The dissolution of haloperidol mesylate was significantly influenced by the addition of sodium lauryl sulfate. In conditions where SMPT was expected, the addition of SLS at low concentrations (0.1-0.2 mM) reduced the dissolution of haloperidol mesylate. In solutions containing concentrations of SLS above the critical micelle concentration (CMC) (10-15 mM), the dissolution of haloperidol mesylate increased compared to below the CMC. The solids recovered from solubility experiments of haloperidol mesylate indicated that haloperidol free base precipitated at all concentrations of SLS. Above 5 mM of SLS, Raman microscopy suggested a new form, perhaps the estolate salt. The addition of surfactant in solids that undergo solution-mediated phase transformation can add complexity to the dissolution profiles and conversion.

Solutal Convection in Porous Media

NASA Astrophysics Data System (ADS)

Liang, Y.; Wen, B.; DiCarlo, D. A.; Hesse, M. A.

2017-12-01

Atmospheric CO2 is one important component of greenhouse gases, which can greatly affect the temperature of the Earth. There are four trapping mechanisms for CO2sequestration, including structural & stratigraphic trapping, residual trapping, dissolution trapping and mineral trapping. Leakage potential is a serious problem for its storage efficiency, and dissolution trapping is a method that can prevent such leakages effectively. Convective dissolution trapping process can be simplified to an interesting physical problem: in porous media, dissolution can initiate convection, and then its dynamics can be affected by the continuous convection conversely. However, it is difficult to detect whether the convective dissolution may take place, as well as how fast and in what pattern it may take place. Previous studies have established a model and related scaling (Rayleigh number and Sherwood number) to describe this physical problem. To testify this model with a large range of Rayleigh numbers, we conducted a series of convective dissolution experiments in porous media. In addition, this large experimental assembly can allow us to quantify relation between wavenumber of the convective motion and the controlling factors of the system for the first time. The result of our laboratory experiments are revolutionary: On one hand, it shows that previous scaling of the convective dissolution becomes invalid once the permeability is large enough; On the other hand, the relation between wavenumber and Rayleigh number demonstrates an opposite trend against the classic model. According to our experimental results, we propose a new model to describe the solutal convection in porous media, and our model can describe and explain our experimental observations. Also, simulation work has been conducted to confirm our model. In the future, our model and relevant knowledge can be unscaled to industrial applications which are relevant to convective dissolution process.

Influence of pH, particle size and crystal form on dissolution behaviour of engineered nanomaterials.

PubMed

Avramescu, M-L; Rasmussen, P E; Chénier, M; Gardner, H D

2017-01-01

Solubility is a critical component of physicochemical characterisation of engineered nanomaterials (ENMs) and an important parameter in their risk assessments. Standard testing methodologies are needed to estimate the dissolution behaviour and biodurability (half-life) of ENMs in biological fluids. The effect of pH, particle size and crystal form on dissolution behaviour of zinc metal, ZnO and TiO 2 was investigated using a simple 2 h solubility assay at body temperature (37 °C) and two pH conditions (1.5 and 7) to approximately frame the pH range found in human body fluids. Time series dissolution experiments were then conducted to determine rate constants and half-lives. Dissolution characteristics of investigated ENMs were compared with those of their bulk analogues for both pH conditions. Two crystal forms of TiO 2 were considered: anatase and rutile. For all compounds studied, and at both pH conditions, the short solubility assays and the time series experiments consistently showed that biodurability of the bulk analogues was equal to or greater than biodurability of the corresponding nanomaterials. The results showed that particle size and crystal form of inorganic ENMs were important properties that influenced dissolution behaviour and biodurability. All ENMs and bulk analogues displayed significantly higher solubility at low pH than at neutral pH. In the context of classification and read-across approaches, the pH of the dissolution medium was the key parameter. The main implication is that pH and temperature should be specified in solubility testing when evaluating ENM dissolution in human body fluids, even for preliminary (tier 1) screening.

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.

Adaptation to high throughput batch chromatography enhances multivariate screening.

PubMed

Barker, Gregory A; Calzada, Joseph; Herzer, Sibylle; Rieble, Siegfried

2015-09-01

High throughput process development offers unique approaches to explore complex process design spaces with relatively low material consumption. Batch chromatography is one technique that can be used to screen chromatographic conditions in a 96-well plate. Typical batch chromatography workflows examine variations in buffer conditions or comparison of multiple resins in a given process, as opposed to the assessment of protein loading conditions in combination with other factors. A modification to the batch chromatography paradigm is described here where experimental planning, programming, and a staggered loading approach increase the multivariate space that can be explored with a liquid handling system. The iterative batch chromatography (IBC) approach is described, which treats every well in a 96-well plate as an individual experiment, wherein protein loading conditions can be varied alongside other factors such as wash and elution buffer conditions. As all of these factors are explored in the same experiment, the interactions between them are characterized and the number of follow-up confirmatory experiments is reduced. This in turn improves statistical power and throughput. Two examples of the IBC method are shown and the impact of the load conditions are assessed in combination with the other factors explored. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Looking for the Self: Phenomenology, Neurophysiology and Philosophical Significance of Drug-induced Ego Dissolution.

PubMed

Millière, Raphaël

2017-01-01

There is converging evidence that high doses of hallucinogenic drugs can produce significant alterations of self-experience, described as the dissolution of the sense of self and the loss of boundaries between self and world. This article discusses the relevance of this phenomenon, known as "drug-induced ego dissolution (DIED)", for cognitive neuroscience, psychology and philosophy of mind. Data from self-report questionnaires suggest that three neuropharmacological classes of drugs can induce ego dissolution: classical psychedelics, dissociative anesthetics and agonists of the kappa opioid receptor (KOR). While these substances act on different neurotransmitter receptors, they all produce strong subjective effects that can be compared to the symptoms of acute psychosis, including ego dissolution. It has been suggested that neuroimaging of DIED can indirectly shed light on the neural correlates of the self. While this line of inquiry is promising, its results must be interpreted with caution. First, neural correlates of ego dissolution might reveal the necessary neurophysiological conditions for the maintenance of the sense of self, but it is more doubtful that this method can reveal its minimally sufficient conditions. Second, it is necessary to define the relevant notion of self at play in the phenomenon of DIED. This article suggests that DIED consists in the disruption of subpersonal processes underlying the "minimal" or "embodied" self, i.e., the basic experience of being a self rooted in multimodal integration of self-related stimuli. This hypothesis is consistent with Bayesian models of phenomenal selfhood, according to which the subjective structure of conscious experience ultimately results from the optimization of predictions in perception and action. Finally, it is argued that DIED is also of particular interest for philosophy of mind. On the one hand, it challenges theories according to which consciousness always involves self-awareness. On the other hand, it suggests that ordinary conscious experience might involve a minimal kind of self-awareness rooted in multisensory processing, which is what appears to fade away during DIED.

Influence of soil moisture on sunflower oil extraction of polycyclic aromatic hydrocarbons from a manufactured gas plant soil.

PubMed

Gong, Zongqiang; Wilke, B-M; Alef, Kassem; Li, Peijun

2005-05-01

The influence of soil moisture on efficiency of sunflower oil extraction of polycyclic aromatic hydrocarbons (PAHs) from contaminated soil was investigated. The PAH-contaminated soil was collected from a manufactured gas plant (MGP) site in Berlin, Germany. Half of the soil was air-dried, and the other half was kept as field-moist soil. Batch experiments were performed using air-dried and field-moist soils, and sunflower oil was used as extractant at oil/soil ratios of 2:1 and 1:1 (v/m). The experimental data were fitted to a first-order empirical model to describe mass-transfer profiles of the PAHs. Column extraction experiments were also conducted. Field-moist and air-dried soils in the column were extracted using sunflower oil at an oil/soil ratio of 2:1. In the batch experiments, PAHs were more rapidly extracted from air-dried soil than from field-moist soil. Removal rate of total PAH increased 23% at oil/soil ratio of 1:1 and 15.5% at oil/soil ratio of 2:1 after the soil was air dried. The most favorable conditions for batch extraction were air-dried soil, with an oil/soil ratio of 2:1. In the column experiments, the removal rate of total PAH from air-dried soil was 30.7% higher than that from field-moist soil. For field-moist soil, extraction efficiencies of the batch extraction (67.2% and 81.5%) were better than that for column extraction (65.6%). However, this difference between the two methods became less significant for the air-dried soil, with a total removal rate of 96.3% for column extraction and 90.2% and 97% for batch extractions. A mass-balance test was carried out for analytical quality assurance. The results of both batch and column experiments indicated that drying the soil increased efficiency of extraction of PAHs from the MGP soil.

Determination of the long-term release of metal(loid)s from construction materials using DGTs.

PubMed

Schmukat, A; Duester, L; Ecker, D; Heininger, P; Ternes, T A

2013-09-15

Long-term leaching experiments are crucial to estimate the potential release of dangerous substances from construction materials. The application of Diffuse Gradients in Thin film (DGT) in static-batch experiments was tested to study the long-term release of metal(loid)s from construction materials for hydraulic engineering, for half a year. Long-term release experiments are essential to improve calculations of the life-time release for this materials. DGTs in batch experiments were found to be a space and labour efficient application, which enabled (i) to study, in a non-invasive manner, the total release of nine metal(loid)s for half a year, (ii) to differentiate between release mechanisms and (iii) to study mechanisms which were contrary to the release or caused experimental artefacts in the batch experiments. For copper slag (test material) it was found that eight metal(loid)s were released over the whole time period of 184 d. Cu, Ni and Pb were found to be released, predominantly caused by (the) weathering of sulphide minerals. Only for Zn a surface depletion mechanism was identified. The results from the long-term batch experiments deliver new information on the release of metal(loid)s during the life cycle of construction materials with regard to river basin management objectives. Copyright © 2013 Elsevier B.V. All rights reserved.

Development of modified release diltiazem HCl tablets using composite index to identify optimal formulation.

PubMed

Gohel, M C; Patel, M M; Amin, A F

2003-05-01

This article reports the preparation of tartaric acid treated ispaghula husk powder for the development of modified release tablets of diltiazem HCl by adopting direct compression technique and a 32 full factorial design. The modified ispaghula husk powder showed superior swelling and gelling as compared to untreated powder. Addition of compaction augmenting agent such as dicalcium phosphate was found to be essential for obtaining tablets with adequate crushing strength. In order to improve the crushing strength of diltiazem HCl tablets, to modulate drug release pattern, and to obtain similarity of dissolution profiles in distilled water and simulated gastric fluid (pH 1.2), modified guar gum was used along with modified ispaghula husk powder and tartaric acid. A novel composite index, which considers a positive or a negative deviation from an ideal value, was calculated considering percentage drug release in 60, 300, and 540 min as dependent variables for the selection of a most appropriate batch. Polynomial equation and contour plots are presented. The concept of similarity factor (f2) was used to prove similarity of dissolution in water and simulated gastric fluid (pH 1.2).

Production and Application of Olivine Nano-Silica in Concrete

NASA Astrophysics Data System (ADS)

Mardiana, Oesman; Haryadi

2017-05-01

The aim of this research was to produce nano silica by synthesis of nano silica through extraction and dissolution of ground olivine rock, and applied the nano silica in the design concrete mix. The producing process of amorphous silica used sulfuric acid as the dissolution reagent. The separation of ground olivine rock occurred when the rock was heated in a batch reactor containing sulfuric acid. The results showed that the optimum mole ratio of olivine- acid was 1: 8 wherein the weight ratio of the highest nano silica generated. The heating temperature and acid concentration influenced the mass of silica produced, that was at temperature of 90 °C and 3 M acid giving the highest yield of 44.90%. Characterization using Fourier Transform Infrared (FTIR ) concluded that amorphous silica at a wavenumber of 1089 cm-1 indicated the presence of siloxane, Si-O-Si, stretching bond. Characterization using Scanning Electron Microscope - Energy Dispersive Spectroscopy (SEM-EDS) showed the surface and the size of the silica particles. The average size of silica particles was between 1-10 μm due to the rapid aggregation of the growing particles of nano silica into microparticles, caused of the pH control was not fully achieved.

Innovative Approach for Interstitial Cystitis: Vaginal Pessaries Loaded Diazepam—A Preliminary Study

PubMed Central

Capra, P.; Perugini, P.; Bleve, M.; Pavanetto, P.; Musitelli, G.; Rovereto, B.; Porru, D.

2013-01-01

Bladder pain is a characteristic disorder of interstitial cystitis. Diazepam is well known for its antispasmodic activity in the treatment of muscular hypertonus. The aim of this work was to develop and characterize vaginal pessaries as an intravaginal delivery system of diazepam for the treatment of interstitial cystitis. In particular, the performance of two types of formulations, with and without beta-glucan, was compared. In particular, the preparation of pessaries, according to the modified Pharmacopeia protocol, the setup of the analytical method to determine diazepam, pH evaluation, dissolution profile, and photostability assay were reported. Results showed that the modified protocol permitted obtaining optimal vaginal pessaries, without air bubbles, with good consistency and handling and with good pH profiles. In order to determine the diazepam amount, calibration curves with good correlation coefficients were obtained, by the spectrophotometric method, using placebo pessaries as matrix with the addition of diazepam standard solution. This method was demonstrated sensible and accurate to determine the amount of drug in batches. Dissolution profiles showed a complete diazepam release just after 15 minutes, even if beta-glucan pessaries released drug more gradually. Finally, a possible drug photodegradation after exacerbated UV-visible exposition was evaluated. PMID:26555976

Aerobic biodegradability of methyldiethanolamine (MDEA) used in natural gas sweetening plants in batch tests and continuous flow experiments.

PubMed

Fürhacker, M; Pressl, A; Allabashi, R

2003-09-01

Mixtures of different amines including tertiary amines (methyldiethanolamine, MDEA) are commonly used for the removal of CO2 from gas mixtures or in gas sweetening processes for the extraction of CO2 and H2S. The absorber solutions used can be released into the industrial waste water due to continuous substitution of degraded MDEA, periodically cleaning processes or an accidental spill. In this study, the aerobic biodegradability of MDEA was investigated in a standardised batch test and a continuous flow experiment (40 l/d). The results of the batch test indicated that the MDEA-solution was non-biodegradable during the test period of 28 days, whereas the continuous flow experiments showed biodegradation of more than 96% based on TOC-measurements. This was probably due to the adaptation of the microorganisms to this particular waste water contamination during continuous flow experiment.

An Integer Batch Scheduling Model for a Single Machine with Simultaneous Learning and Deterioration Effects to Minimize Total Actual Flow Time

NASA Astrophysics Data System (ADS)

Yusriski, R.; Sukoyo; Samadhi, T. M. A. A.; Halim, A. H.

2016-02-01

In the manufacturing industry, several identical parts can be processed in batches, and setup time is needed between two consecutive batches. Since the processing times of batches are not always fixed during a scheduling period due to learning and deterioration effects, this research deals with batch scheduling problems with simultaneous learning and deterioration effects. The objective is to minimize total actual flow time, defined as a time interval between the arrival of all parts at the shop and their common due date. The decision variables are the number of batches, integer batch sizes, and the sequence of the resulting batches. This research proposes a heuristic algorithm based on the Lagrange Relaxation. The effectiveness of the proposed algorithm is determined by comparing the resulting solutions of the algorithm to the respective optimal solution obtained from the enumeration method. Numerical experience results show that the average of difference among the solutions is 0.05%.

Impact of Elevated CO2 on Trace Element Release from Aquifer Sediments of the San Joaquin Valley, CA

NASA Astrophysics Data System (ADS)

Fox, P. M.; Nico, P. S.; Davis, J. A.; Spycher, N.

2014-12-01

Carbon capture and storage (CCS) is a promising technique for mitigating climate change by storing large volumes of carbon dioxide in deep saline aquifers. In California, the thick marine sediments of the Central and Salinas Valleys have been identified as prime targets for future CO2 storage. However, the potential impacts on water quality of overlying drinking-water aquifers must be studied before CCS can be implemented. In this study, we compare trace element release from San Joaquin Valley aquifer sediments with a wide range of textural and redox properties. Kinetic batch experiments were performed with artificial groundwater continuously equilibrated under CO2-saturated (at 1 atm) and background CO2 (0.002-0.006 atm) conditions, resulting in a shift of nearly 3 pH units. In addition, the reversibility of trace element release was studied by sequentially lowering the CO2 from 1.0 atm to 0.5 atm to background concentrations (0.002-0.006 atm) for CO2-saturated systems in order to mimic the dissipation of a CO2 plume in the aquifer. During exposure to high CO2, a number of elements displayed enhanced release compared to background CO2 experiments (Ca, Mg, Li, Si, B, As, Sr, Ni, Fe, Mn, V, Ti, and Co) with concentrations of As, Fe, and Mn exceeding EPA maximum contaminant levels in some cases. On the other hand, Mo and U showed suppressed release. Most intriguing, many of the elements showing enhanced release displayed at least some degree of irreversibility when CO2 concentrations were decreased to background levels. In fact, in some cases (i.e., for V), an element showed further release when CO2 concentrations were decreased. These results suggest that there may be longer-term effects on groundwater quality that persist even after the CO2 plume has dissipated. Several different mechanisms of trace element release including ion exchange, desorption, and carbonate mineral dissolution are explored. Preliminary modeling results suggest that carbonate mineral dissolution can play a key role in driving trace element release even in sediments where carbonates are in low abundance.

Transport and Application of Heat-Activated Persulfate for In-situ Chemical Oxidation of Residual Trichloroethylene

NASA Astrophysics Data System (ADS)

Quig, L.; Johnson, G. R.

2015-12-01

Persulfate ISCO has been shown to treat a wide range of contaminants. While persulfate ISCO can be tailored to site and pollutant specific characteristics (e.g., activation via energy or catalysis), thermal activation of persulfate is particularly promising as it can be easily controlled and requires no additional reagents. A mechanistic study of the physical and chemical processes controlling the effectiveness of this remedial approach is not well documented in the literature with much therein focused on reactions in batch systems. The purpose of this research was twofold. Initial studies characterized the overall transport behavior of unactivated and thermally-activated persulfate (20, 60, and 90°C) in one-dimensional soil column systems. Finally, experiments were conducted to investigate persulfate ISCO as a remedial approach for residual-phase trichloroethylene (TCE). At all activation temperatures investigated, persulfate exhibited ideal transport behavior in miscible displacement experiments. Moment analysis of persulfate ion breakthrough curves indicated negligible interaction of persulfate with the natural sandy material. Persulfate ISCO for residual-phase TCE was characterized at two flow rates, 0.2 mL/min and 0.5 mL/min, resulting in two degrees of persulfate activation, 39.5% and 24.6%, respectively. Both ISCO soil column systems showed an initial, long-term plateau in effluent TCE concentrations indicating steady-state dissolution of pure phase TCE. Observed effluent concentrations decreased after 75 and 100 pore volumes (normalized for the measured residual NAPL fraction) compared to 110 pore volumes in the control study. Pseudo first-order reaction rate constants for the decreasing TCE concentrations equaled 0.063/hr and 0.083/hr, respectively, compared to 0.041/hr for the control. Moment analysis of the complete dissolution of TCE in the persulfate/activated persulfate remediation systems indicated approximately 33% oxidation of TCE mass present. By characterizing the overall transport behavior and application of persulfate/heat-activated persulfate in a natural porous media for the ISCO of residual nonaqueous phase liquid, this work aids in improving the implementation of persulfate ISCO systems.

Size-dependent reactivity of magnetite nanoparticles: a field-laboratory comparison

USGS Publications Warehouse

Swindle, Andrew L.; Elwood Madden, Andrew S.; Cozzarelli, Isabelle M.; Benamara, Mourad

2014-01-01

Logistic challenges make direct comparisons between laboratory- and field-based investigations into the size-dependent reactivity of nanomaterials difficult. This investigation sought to compare the size-dependent reactivity of nanoparticles in a field setting to a laboratory analog using the specific example of magnetite dissolution. Synthetic magnetite nanoparticles of three size intervals, ∼6 nm, ∼44 nm, and ∼90 nm were emplaced in the subsurface of the USGS research site at the Norman Landfill for up to 30 days using custom-made subsurface nanoparticle holders. Laboratory analog dissolution experiments were conducted using synthetic groundwater. Reaction products were analyzed via TEM and SEM and compared to initial particle characterizations. Field results indicated that an organic coating developed on the particle surfaces largely inhibiting reactivity. Limited dissolution occurred, with the amount of dissolution decreasing as particle size decreased. Conversely, the laboratory analogs without organics revealed greater dissolution of the smaller particles. These results showed that the presence of dissolved organics led to a nearly complete reversal in the size-dependent reactivity trends displayed between the field and laboratory experiments indicating that size-dependent trends observed in laboratory investigations may not be relevant in organic-rich natural systems.

Comparison of neptunium sorption results using batch and column techniques

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

Triay, I.R.; Furlano, A.C.; Weaver, S.C.

1996-08-01

We used crushed-rock columns to study the sorption retardation of neptunium by zeolitic, devitrified, and vitric tuffs typical of those at the site of the potential high-level nuclear waste repository at Yucca Mountain, Nevada. We used two sodium bicarbonate waters (groundwater from Well J-13 at the site and water prepared to simulate groundwater from Well UE-25p No. 1) under oxidizing conditions. It was found that values of the sorption distribution coefficient, Kd, obtained from these column experiments under flowing conditions, regardless of the water or the water velocity used, agreed well with those obtained earlier from batch sorption experiments undermore » static conditions. The batch sorption distribution coefficient can be used to predict the arrival time for neptunium eluted through the columns. On the other hand, the elution curves showed dispersivity, which implies that neptunium sorption in these tuffs may be nonlinear, irreversible, or noninstantaneous. As a result, use of a batch sorption distribution coefficient to calculate neptunium transport through Yucca Mountain tuffs would yield conservative values for neptunium release from the site. We also noted that neptunium (present as the anionic neptunyl carbonate complex) never eluted prior to tritiated water, which implies that charge exclusion does not appear to exclude neptunium from the tuff pores. The column experiments corroborated the trends observed in batch sorption experiments: neptunium sorption onto devitrified and vitric tuffs is minimal and sorption onto zeolitic tuffs decreases as the amount of sodium and bicarbonate/carbonate in the water increases.« less

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

Cloud iron speciation: Experimental simulations

NASA Astrophysics Data System (ADS)

Sofikitis, A. M.; Colin, J. L.; Desboeufs, K. V.; Losno, R.

2003-04-01

The aim of our contribution is to identify major processes controlling iron speciation in the atmospheric aqueous phase. Fe is known to participate in a variety of redox reactions in cloud chemistry, as well as controlling free radical production in the troposphere. Iron cycling is slower than cycles with other catalytic transition metals (Cu, Mn). The residence time of each iron species is around ten minutes, this allows analytical separation and determination of each iron redox species and therefore its ratio. As the only source of trace metals in aqueous atmospheric phase is due to the solubilization of aerosols, we present here dissolution rate measurements obtained by laboratory experiments with an open flow reactor. This reactor enables us to reproduce the dissolution of a particle in aqueous atmospheric water. The dissolution rate and the speciation of iron are dependent on the mineralogy of the solid phase. Our experiments included Goethite, hematite and vermiculite, which are typical mineral constituents of dust particles. Comparisons were made with natural loess which is a blend of various crystalline and amorphous phases. We will present results of crustal origin particles dissolution experiments where kinetic parameters are determined, including iron speciation. Major functions of variation are pH and photochemistry in the aqueous weathering solution.

Bio-processing of copper from combined smelter dust and flotation concentrate: a comparative study on the stirred tank and airlift reactors.

PubMed

Vakylabad, Ali Behrad; Schaffie, Mahin; Ranjbar, Mohammad; Manafi, Zahra; Darezereshki, Esmaeel

2012-11-30

To scrutinize the influence of the design and type of the bioreactors on the bioleaching efficiency, the bioleaching were evaluated in a batch airlift and a batch stirred tank bioreactors with mixed mesophilic and mixed moderately thermophilic bacteria. According to the results, maximum copper recoveries were achieved using the cultures in the stirred tank bioreactors. It is worth noting that the main phase of the flotation concentrate was chalcopyrite (as a primary sulphide), but the smelter dust mainly contained secondary copper sulphides such as Cu(2)S, CuS, and Cu(5)FeS(4).Under optimum conditions, copper dissolution from the combined flotation concentrate and smelter dust (as an environmental hazard) reached 94.50% in the STR, and 88.02% in the airlift reactor with moderately thermophilic, after 23 days. Also, copper extractions calculated for the bioleaching using mesophilic bacteria were 48.73% and 37.19% in the STR (stirred tank reactor) and the airlift bioreactor, respectively. In addition, the SEM/EDS, XRD, chemical, and mineralogical analyses and studies confirmed the above results. Copyright © 2012 Elsevier B.V. All rights reserved.

Kinetics of steel slag leaching: Batch tests and modeling

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

De Windt, Laurent, E-mail: laurent.dewindt@mines-paristech.fr; Chaurand, Perrine; Rose, Jerome

2011-02-15

Reusing steel slag as an aggregate for road construction requires to characterize the leaching kinetics and metal releases. In this study, basic oxygen furnace (BOF) steel slag were subjected to batch leaching tests at liquid to solid ratios (L/S) of 10 and 100 over 30 days; the leachate chemistry being regularly sampled in time. A geochemical model of the steel slag is developed and validated from experimental data, particularly the evolution with leaching of mineralogical composition of the slag and trace element speciation. Kinetics is necessary for modeling the primary phase leaching, whereas a simple thermodynamic equilibrium approach can bemore » used for secondary phase precipitation. The proposed model simulates the kinetically-controlled dissolution (hydrolysis) of primary phases, the precipitation of secondary phases (C-S-H, hydroxide and spinel), the pH and redox conditions, and the progressive release of major elements as well as the metals Cr and V. Modeling indicates that the dilution effect of the L/S ratio is often coupled to solubility-controlled processes, which are sensitive to both the pH and the redox potential. A sensitivity analysis of kinetic uncertainties on the modeling of element releases is performed.« less

Removing tannins from medicinal plant extracts using an alkaline ethanol precipitation process: a case study of Danshen injection.

PubMed

Gong, Xingchu; Li, Yao; Qu, Haibin

2014-11-14

The alkaline ethanol precipitation process is investigated as an example of a technique for the removal of tannins extracted from Salviae miltiorrhizae Radix et Rhizoma for the manufacture of Danshen injection. More than 90% of the tannins can be removed. However, the recoveries of danshensu, rosmarinic acid, and salvianolic acid B were less than 60%. Total tannin removal increased as the refrigeration temperature decreased or the amount of NaOH solution added increased. Phenolic compound recoveries increased as refrigeration temperature increased or the amount of NaOH solution added decreased. When operated at a low refrigeration temperature, a relative high separation selectivity can be realized. Phenolic compound losses and tannin removal were mainly caused by precipitation. The formation of phenol salts, whose solubility is small in the mixture of ethanol and water used, is probably the reason for the precipitation. A model considering dissociation equilibrium and dissolution equilibrium was established. Satisfactory correlation results were obtained for phenolic compound recoveries and total tannin removal. Two important parameters in the model, which are the water content and pH value of alkaline supernatant, are suggested to be monitored and controlled to obtain high batch-to-batch consistency.

A Tiered Analytical Approach for Investigating Poor Quality Emergency Contraceptives

PubMed Central

Monge, María Eugenia; Dwivedi, Prabha; Zhou, Manshui; Payne, Michael; Harris, Chris; House, Blaine; Juggins, Yvonne; Cizmarik, Peter; Newton, Paul N.; Fernández, Facundo M.; Jenkins, David

2014-01-01

Reproductive health has been deleteriously affected by poor quality medicines. Emergency contraceptive pills (ECPs) are an important birth control method that women can use after unprotected coitus for reducing the risk of pregnancy. In response to the detection of poor quality ECPs commercially available in the Peruvian market we developed a tiered multi-platform analytical strategy. In a survey to assess ECP medicine quality in Peru, 7 out of 25 different batches showed inadequate release of levonorgestrel by dissolution testing or improper amounts of active ingredient. One batch was found to contain a wrong active ingredient, with no detectable levonorgestrel. By combining ultrahigh performance liquid chromatography-ion mobility spectrometry-mass spectrometry (UHPLC-IMS-MS) and direct analysis in real time MS (DART-MS) the unknown compound was identified as the antibiotic sulfamethoxazole. Quantitation by UHPLC-triple quadrupole tandem MS (QqQ-MS/MS) indicated that the wrong ingredient was present in the ECP sample at levels which could have significant physiological effects. Further chemical characterization of the poor quality ECP samples included the identification of the excipients by 2D Diffusion-Ordered Nuclear Magnetic Resonance Spectroscopy (DOSY 1H NMR) indicating the presence of lactose and magnesium stearate. PMID:24748219

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.

Competitive interactions and controlled release of a natural antioxidant from halloysite nanotubes.

PubMed

Hári, József; Gyürki, Ádám; Sárközi, Márk; Földes, Enikő; Pukánszky, Béla

2016-01-15

Halloysite nanotubes used as potential carrier material for a controlled release stabilizer in polyethylene were thoroughly characterized with several techniques including the measurement of specific surface area, pore volume and surface energy. The high surface energy of the halloysite results in the strong bonding of the additive to the surface. Dissolution experiments carried out with eight different solvents for the determination of the effect of solvent characteristics on the amount of irreversibly bonded quercetin proved that adsorption and dissolution depend on competitive interactions prevailing in the system. Solvents with low polarity dissolve only surplus quercetin adsorbed in multilayers. Polyethylene is a very apolar polymer forming weak interactions with every substance; quercetin dissolves into it from the halloysite surface only above a critical surface coverage. Stabilization experiments confirmed that strong adhesion prevents dissolution and results in limited stabilization efficiency. At larger adsorbed amounts better stability and extended effect were measured indicating dissolution and controlled release. Copyright © 2015 Elsevier Inc. All rights reserved.

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

PubMed

Nyström, C; Westerberg, M

1986-03-01

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

Dissolution of uranophane: An AFM, XPS, SEM and ICP study

NASA Astrophysics Data System (ADS)

Schindler, Michael; Freund, Michael; Hawthorne, Frank C.; Burns, Peter C.; Maurice, Patricia A.

2009-05-01

Dissolution experiments on single crystals of uranophane and uranophane-β, Ca(H 2O) 5[(UO 2)(SiO 3(OH)] 2, from the Shinkolobwe mine of the Democratic Republic of Congo, were done in an aqueous HCl solution of pH 3.5 for 3 h, in HCl solutions of pH 2 for 5, 10 and 30 min, and in Pb 2+-, Ba-, Sr-, Ca- and Mg-HCl solutions of pH 2 for 30 min. The basal surfaces of the treated uranophane crystals were examined using atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Solutions after dissolution experiments on single crystals and synthetic powders were analysed with inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectroscopy (ICP-MS). The morphology of the observed etch pits (measured by AFM) were compared to the morphology, predicted on the basis of the bond-valence deficiency of polyhedron chains along the edges of the basal surface. Etch pits form in HCl solutions of pH 2. Their decrease in depth with the duration of the dissolution experiment is explained with the stepwave dissolution model, which describes the lowering of the surrounding area of an etch pit with continuous waves of steps emanated from the etch pit into the rest of the crystal surface. Hillocks form in an HCl solution of pH 3.5, and the chemical composition of the surface (as indicated by XPS) shows that these hillocks are the result of the precipitation of a uranyl-hydroxy-hydrate phase. Well-orientated hillocks form on the surface of uranophane in a SrCl 2-HCl solution of pH 2. They are part of an aged silica coating of composition Si 2O 2(OH) 4(H 2O) n. An amorphous layer forms on the surface of uranophane in a MgCl 2-HCl solution of pH 2, which has a composition and structure similar to silicic acid. Small crystallites of uranyl-hydroxy-hydrate phases form on the surface of uranophane after treatment in Pb(NO 3) 2-HCl and BaCl 2-HCl solutions of pH 2. Dissolution experiments on synthetic uranophane powders show that in the early stage of the experiments, the dissolution rate of uranophane increase in the sequence Pb(NO 3) 2-HCl < BaCl 2-HCl < CaCl 2-HCl < HCl < SrCl 2-HCl < MgCl 2-HCl, indicating that the dissolution of uranophane is more enhanced in solutions containing divalent cations of small ionic radii and high Lewis acidity (Mg, MgCl +).

Disintegration of highly soluble immediate release tablets: a surrogate for dissolution.

PubMed

Gupta, Abhay; Hunt, Robert L; Shah, Rakhi B; Sayeed, Vilayat A; Khan, Mansoor A

2009-01-01

The purpose of the work was to investigate correlation between disintegration and dissolution for immediate release tablets containing a high solubility drug and to identify formulations where disintegration test, instead of the dissolution test, may be used as the acceptance criteria based on International Conference on Harmonization Q6A guidelines. A statistical design of experiments was used to study the effect of filler, binder, disintegrating agent, and tablet hardness on the disintegration and dissolution of verapamil hydrochloride tablets. All formulation variables, i.e., filler, binder, and disintegrating agent, were found to influence tablet dissolution and disintegration, with the filler and disintegrating agent exerting the most significant influence. Slower dissolution was observed with increasing disintegration time when either the filler or the disintegrating agent was kept constant. However, no direct corelationship was observed between the disintegration and dissolution across all formulations due to the interactions between different formulation components. Although all tablets containing sodium carboxymethyl cellulose as the disintegrating agent, disintegrated in less than 3 min, half of them failed to meet the US Pharmacopeia 30 dissolution criteria for the verapamil hydrochloride tablets highlighting the dependence of dissolution process on the formulation components other than the disintegrating agent. The results identified only one formulation as suitable for using the disintegration test, instead of the dissolution test, as drug product acceptance criteria and highlight the need for systematic studies before using the disintegration test, instead of the dissolution test as the drug acceptance criteria.

The long-term dissolution characteristics of a residually trapped BTX mixture in soil

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

Rixey, W.G.

1996-12-31

A mass transfer limited model is presented to describe the long-term dissolution of organic compounds from a benzene, toluene, and xylenes (BTX) mixture residually trapped in a sandy soil. The model is an extension of a previously presented equilibrium dissolution model which takes into consideration mass transfer limitations that develop later in the leaching process and is similar to that presented by Borden and Kao for modeling BTX dissolution from residually trapped gasoline. The residual nonaqueous phase liquid (NAPL) is divided into multiple regions: one region which undergoes equilibrium dissolution and additional regions in which mass transfer is progressively limited.more » Application of the model to BTX column effluent data indicates that the initial dissolution (exponential decay region) of BTX can be effectively described by equilibrium dissolution. When applied to later dissolution times (Asymptotic region) a multiple-region model is required to rationalize the data for all three components. This explanation of the observed tailing in leaching experiments form residually trapped hydrocarbons if offered as an alternative to the explanation of tailing due to rate-limited desorption from soils. 16 refs., 5 figs., 2 tabs.« less

The impact of posttraumatic stress symptoms, posttraumatic stress cognitions and interpersonal dependency on psychological co-morbidities following relationship dissolution among college students.

PubMed

Fang, Siqi; Chung, Man Cheung; Watson, Clare

2018-02-13

Relationship dissolution is a distressing experience which can result in the emergence of posttraumatic stress (i.e. post-dissolution PTSS) and other psychological symptoms among college students. Little is known, however, whether posttraumatic stress cognitions and interpersonal dependency may influence the severity of these distress outcomes. This study examined the interrelationship between posttraumatic stress symptoms (PTSS), posttraumatic stress cognitions, interpersonal dependency and psychological co-morbidities following relationship dissolution. One hundred and eighty college students (M = 69, F = 111) who had experienced relationship dissolution completed the Posttraumatic Stress Diagnostic Scale, Posttraumatic Stress Cognition Inventory, Interpersonal Dependency Inventory and General Health Questionnaire-28. Posttraumatic stress symptoms following relationship dissolution (post-dissolution PTSS) were associated with increased psychological co-morbidities. Negative view of oneself and self-blame mediated between PTSS and psychological co-morbidities. Assertion of autonomy moderated the mediational effects of negative cognitions on psychological co-morbidities. People can develop PTSSs and other psychological symptoms following the dissolution of a romantic relationship. Their concept of self and tendency to seek independence and control played a key role in determining the severity of distress symptoms.

Dynamic reservoir-condition microtomography of reactive transport in complex carbonates: Effect of initial pore structure and initial brine pH

NASA Astrophysics Data System (ADS)

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

2017-05-01

We study the impact of brine acidity and initial pore structure on the dynamics of fluid/solid reaction at high Péclet numbers and low Damköhler numbers. A laboratory μ-CT scanner was used to image the dissolution of Ketton, Estaillades, and Portland limestones in the presence of CO2-acidified brine at reservoir conditions (10 MPa and 50 °C) at two injected acid strengths for a period of 4 h. Each sample was scanned between 6 and 10 times at ∼4 μm resolution and multiple effluent samples were extracted. The images were used as inputs into flow simulations, and analysed for dynamic changes in porosity, permeability, and reaction rate. Additionally, the effluent samples were used to verify the image-measured porosity changes. We find that initial brine acidity and pore structure determine the type of dissolution. Dissolution is either uniform where the porosity increases evenly both spatially and temporally, or occurs as channelling where the porosity increase is concentrated in preferential flow paths. Ketton, which has a relatively homogeneous pore structure, dissolved uniformly at pH = 3.6 but showed more channelized flow at pH = 3.1. In Estaillades and Portland, increasingly complex carbonates, channelized flow was observed at both acidities with the channel forming faster at lower pH. It was found that the effluent pH, which is higher than that injected, is a reasonably good indicator of effective reaction rate during uniform dissolution, but a poor indicator during channelling. The overall effective reaction rate was up to 18 times lower than the batch reaction rate measured on a flat surface at the effluent pH, with the lowest reaction rates in the samples with the most channelized flow, confirming that transport limitations are the dominant mechanism in determining reaction dynamics at the fluid/solid boundary.

Identification of formulation and manufacturing variables that influence in vitro dissolution and in vivo bioavailability of propranolol hydrochloride tablets.

PubMed

Eddington, N D; Ashraf, M; Augsburger, L L; Leslie, J L; Fossler, M J; Lesko, L J; Shah, V P; Rekhi, G S

1998-11-01

The purpose of this study was to evaluate the effect of formulation and processing changes on the dissolution and bioavailability of propranolol hydrochloride tablets. Directly compressed blends of 6 kg (20,000 units) were prepared by mixing in a 16-qt V blender and tablets were compressed on an instrumented Manesty D3B tablet press. A half-factorial (2(5-1), Resolution V) design was used to study the following variables: filler ratio (lactose/dicalcium phosphate), sodium starch glycolate level, magnesium stearate level, lubricant blend time, and compression force. The levels and ranges of the excipients and processing changes studied represented level 2 or greater changes as indicated by the Scale-up and Post Approval Changes (SUPAC-IR) Guidance. Changes in filler ratio, disintegrant level, and compression force were significant in affecting percent drug released (Q) in 5 min (Q5) and Q10. However, changes in magnesium stearate level and lubricant blend time did not influence Q5 and Q10. Hardness was found to be affected by changes in all of the variables studied. Some interaction effects between the variables studied were also found to be significant. To examine the impact of formulation and processing variables on in vivo absorption, three batches were selected for a bioavailability study based on their dissolution profiles. Thirteen subjects received four propranolol treatments (slow-, medium-, and fast-dissolving formulations and Inderal 80 mg) separated by 1 week washout according to a randomized crossover design. The formulations were found to be bioequivalent with respect to the log Cmax and log AUC0-infinity. The results of this study suggest that (i) bioavailability/bioequivalency studies may not be necessary for propranolol and perhaps other class 1 drugs after level 2 type changes, and (ii) in vitro dissolution tests may be used to show bioequivalence of propranolol formulations with processing or formulation changes within the specified level 2 ranges examined.

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.

Wildfires and water chemistry: effect of metals associated with wood ash.

PubMed

Cerrato, José M; Blake, Johanna M; Hirani, Chris; Clark, Alexander L; Ali, Abdul-Mehdi S; Artyushkova, Kateryna; Peterson, Eric; Bixby, Rebecca J

2016-08-10

The reactivity of metals associated with ash from wood collected from the Valles Caldera National Preserve, Jemez Mountains, New Mexico, was assessed through a series of laboratory experiments. Microscopy, spectroscopy, diffraction, and aqueous chemistry measurements were integrated to determine the chemical composition of wood ash and its effect on water chemistry. Climate change has caused dramatic impacts and stresses that have resulted in large-scale increases in wildfire activity in semi-arid areas of the world. Metals and other constituents associated with wildfire ash can be transported by storm event runoff and negatively affect the water quality in streams and rivers. Differences among ash from six tree species based on total concentrations of metals such as Ca, Al, Mg, Fe, and Mn were identified using non-metric multidimensional analysis. Metal-bearing carbonate and oxide phases were quantified by X-ray diffraction analyses and X-ray spectroscopy analyses. These metal-bearing carbonate phases were readily dissolved in the first 30 minutes of reaction with 18 MΩ water and 10 mM HCO3(-) in laboratory batch experiments which resulted in the release of metals and carbonates in the ash, causing water alkalinity to increase. However, metal concentrations decreased over the course of the experiment, suggesting that metals re-adsorb to ash. Our results suggest that the dissolution of metal-bearing carbonate and oxide phases in ash and metal re-adsorption to ash are relevant processes affecting water chemistry after wildfire events. These results have important implications to better understand the impact of wildfire events on water quality.

Leaching potential of pervious concrete and immobilization of Cu, Pb and Zn using pervious concrete.

PubMed

Solpuker, U; Sheets, J; Kim, Y; Schwartz, F W

2014-06-01

This paper investigates the leaching potential of pervious concrete and its capacity for immobilizing Cu, Pb and Zn, which are common contaminants in urban runoff. Batch experiments showed that the leachability of Cu, Pb and Zn increased when pH<8. According to PHREEQC equilibrium modeling, the leaching of major ions and trace metals was mainly controlled by the dissolution/precipitation and surface complexation reactions, respectively. A 1-D reactive transport experiment was undertaken to better understand how pervious concrete might function to attenuate contaminant migration. A porous concrete block was sprayed with low pH water (pH=4.3±0.1) for 190 h. The effluent was highly alkaline (pH~10 to 12). In the first 50 h, specific conductance and trace-metal were high but declined towards steady state values. PHREEQC modeling showed that mixing of interstitial alkaline matrix waters with capillary pore water was required in order to produce the observed water chemistry. The interstitial pore solutions seem responsible for the high pH values and relatively high concentrations of trace metals and major cations in the early stages of the experiment. Finally, pervious concrete was sprayed with a synthetic contaminated urban runoff (10 ppb Cu, Pb and Zn) with a pH of 4.3±0.1 for 135 h. It was found that Pb immobilization was greater than either Cu or Zn. Zn is the most mobile among three and also has the highest variation in the observed degree of immobilization. Copyright © 2014 Elsevier B.V. All rights reserved.

Dissolution and sorption of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues from detonated mineral surfaces.

PubMed

Jaramillo, Ashley M; Douglas, Thomas A; Walsh, Marianne E; Trainor, Thomas P

2011-08-01

Composition B (Comp B) is a commonly used military formulation composed of the toxic explosive compounds 2,4,6-trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Numerous studies of the temporal fate of explosive compounds in soils, surface water and laboratory batch reactors have been conducted. However, most of these investigations relied on the application of explosive compounds to the media via aqueous addition and thus these studies do not provide information on the real world loading of explosive residues during detonation events. To address this we investigated the dissolution and sorption of TNT and RDX from Comp B residues loaded to pure mineral phases through controlled detonation. Mineral phases included nontronite, vermiculite, biotite and Ottawa sand (quartz with minor calcite). High Performance Liquid Chromatography and Attenuated Total Reflectance Fourier Transform Infrared spectroscopy were used to investigate the dissolution and sorption of TNT and RDX residues loaded onto the mineral surfaces. Detonation resulted in heterogeneous loading of TNT and RDX onto the mineral surfaces. Explosive compound residues dissolved rapidly (within 9 h) in all samples but maximum concentrations for TNT and RDX were not consistent over time due to precipitation from solution, sorption onto mineral surfaces, and/or chemical reactions between explosive compounds and mineral surfaces. We provide a conceptual model of the physical and chemical processes governing the fate of explosive compound residues in soil minerals controlled by sorption-desorption processes. Published by Elsevier Ltd.

A mathematical analysis of drug dissolution in the USP flow through apparatus

NASA Astrophysics Data System (ADS)

McDonnell, David; D'Arcy, D. M.; Crane, L. J.; Redmond, Brendan

2018-03-01

This paper applies boundary layer theory to the process of drug dissolution in the USP (United States Pharmacopeia) Flow Through Apparatus. The mass transfer rate from the vertical planar surface of a compact within the device is examined. The theoretical results obtained are then compared with those of experiment. The paper also examines the effect on the dissolution process caused by the interaction between natural and forced convection within the apparatus and the introduction of additional boundaries.

Mobilization of soil-borne arsenic by three common organic acids: Dosage and time effects.

PubMed

Onireti, Olaronke O; Lin, Chuxia

2016-03-01

A batch experiment was conducted to investigate the mobilization of soil-borne arsenic by three common low-molecular-weight organic acids with a focus on dosage and time effects. The results show that oxalic acid behaved differently from citric acid and malic acid in terms of mobilizing As that was bound to iron compounds. At an equivalent molar concentration, reactions between oxalic acid and soil-borne Fe were kinetically more favourable, as compared to those between either citric acid or malic acid and the soil-borne Fe. It was found that reductive dissolution of soil-borne Fe played a more important role in liberating As, as compared to non-reductive reactions. Prior to the 7th day of the experiment, As mobility increased with increasing dose of oxalic acid while there was no significant difference (P > 0.05) in mobilized As among the treatments with different doses of citric acid or malic acid. The dosage effect on soil-borne As mobilization in the citric acid and malic acid treatments became clear only after the 7th day of the experiment. Soluble Ca present in the soils could cause re-immobilization of As by competing with solution-borne Fe for available organic ligands to form practically insoluble organic compounds of calcium (i.e. calcium oxalate). This resulted in transformation of highly soluble organic complexes of iron (i.e. iron oxalate complexes) into slightly soluble organic compounds of iron (i.e. iron oxalate) or free ferric ion, which then reacted with the solution-borne arsenate ions to form practically insoluble iron arsenates in the latter part of the experiment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Brokenhearts: Dissolution of Romantic Relationships.

ERIC Educational Resources Information Center

Meeker, F. B.; La Fong, Carl

Results of an investigation examining the dissolution of romantic relationships are analyzed. Men and women (N=105) who had ended romantic relationships were surveyed in structured individual interviews. Commonalities and differences in respondents' perceptions of the experience were examined. Specific tests were made of a corollary to Waller's…

Abiotic, biotic and photolytic degradation affinity of 14 antibiotics and one metabolite - batch experiments and a model framework.

PubMed

Kaeseberg, Thomas; Zhang, Jin; Schubert, Sara; Oertel, Reinhard; Krebs, Peter

2018-05-26

In this study, degradation affinities of 14 antibiotics and one metabolite were determined in batch experiments. A modelling framework was applied to decrypt potential ranges of abiotic, biotic and photolytic degradation coefficients. In detail, we performed batch experiments with three different sewages in the dark at 7 °C and 22 °C. Additionally, we conducted further batch experiments with artificial irradiation and different dilutions of the sewage at 30 °C - de novo three different sewages were used. The batch experiments were initially spiked with a stock solution with 14 antibiotics and one metabolite to increase background concentrations by 1 μg L -1 for each compound. The final antibiotic concentrations were sub-inhibitory with regard to sewage bacteria. The here presented modelling framework based on the Activated Sludge Model No. 3 in combination with adsorption and desorption processes. The model was calibrated with monitored standard sewage compounds before antibiotic degradation rates were quantified. The model decrypted ranges of abiotic, biotic and photolytic degradation coefficients. In detail, six antibiotics were not abiotic degradable at 7 °C, five antibiotics not at 22 °C and only 2 antibiotics at 30 °C. Finally, nine antibiotics were not significantly biodegradable at 7 °C and 22 °C. The model determined the link between adsorption characteristics and biodegradation rates. In detail, the rate was significantly affected by the bio-solid partition coefficient and the duration until adsorption was balanced. All antibiotics and the metabolite were photolytic degradable. In general, photolytic degradation was the most efficient elimination pathway of presented antibiotics except for the given metabolite and penicillin antibiotics. Copyright © 2018 Elsevier Ltd. All rights reserved.

Monochloramine Cometabolism by Mixed-Culture Nitrifiers under Drinking Water Conditions

EPA Science Inventory

The current research investigated monochloramine cometabolism by nitrifying mixed cultures grown under drinking water relevant conditions and harvested from sand-packed reactors before conducting suspended growth batch kinetic experiments. Three batch reactors were used in each ...

CALIBRATION OF SUBSURFACE BATCH AND REACTIVE-TRANSPORT MODELS INVOLVING COMPLEX BIOGEOCHEMICAL PROCESSES

EPA Science Inventory

In this study, the calibration of subsurface batch and reactive-transport models involving complex biogeochemical processes was systematically evaluated. Two hypothetical nitrate biodegradation scenarios were developed and simulated in numerical experiments to evaluate the perfor...

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.

Modeling of the pyruvate production with Escherichia coli: comparison of mechanistic and neural networks-based models.

PubMed

Zelić, B; Bolf, N; Vasić-Racki, D

2006-06-01

Three different models: the unstructured mechanistic black-box model, the input-output neural network-based model and the externally recurrent neural network model were used to describe the pyruvate production process from glucose and acetate using the genetically modified Escherichia coli YYC202 ldhA::Kan strain. The experimental data were used from the recently described batch and fed-batch experiments [ Zelić B, Study of the process development for Escherichia coli-based pyruvate production. PhD Thesis, University of Zagreb, Faculty of Chemical Engineering and Technology, Zagreb, Croatia, July 2003. (In English); Zelić et al. Bioproc Biosyst Eng 26:249-258 (2004); Zelić et al. Eng Life Sci 3:299-305 (2003); Zelić et al Biotechnol Bioeng 85:638-646 (2004)]. The neural networks were built out of the experimental data obtained in the fed-batch pyruvate production experiments with the constant glucose feed rate. The model validation was performed using the experimental results obtained from the batch and fed-batch pyruvate production experiments with the constant acetate feed rate. Dynamics of the substrate and product concentration changes was estimated using two neural network-based models for biomass and pyruvate. It was shown that neural networks could be used for the modeling of complex microbial fermentation processes, even in conditions in which mechanistic unstructured models cannot be applied.

Dissolution of Used Nuclear Fuel Using a TBP/N-Paraffin Solvent

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

Rudisill, T. S.; Shehee, T. C.; Jones, D. H.

2017-10-02

The dissolution of unirradiated used nuclear fuel (UNF) pellets pretreated for tritium removal was demonstrated using a tributly phosphate (TBP) solvent. Dissolution of pretreated fuel in TBP could potentially combine dissolution with two cycle of solvent extraction required for separating the actinides and lanthanides from other fission products. Dissolutions were performed using UNF surrogates prepared from both uranyl nitrate and uranium trioxide produced from the pretreatment process by adding selected actinide and stable fission product elements. In laboratory-scale experiments, the U dissolution efficiency ranged from 80-99+% for both the nitrate and oxide surrogate fuels. On average, 80% of the Pumore » and 50% of the Np and Am in the nitrate surrogate dissolved; however, little of the transuranic elements dissolved in the oxide form. The majority of the 3+ lanthanide elements dissolved. Only small amounts of Sr (0-1.6%) and Mo (0.1-1.7%) and essentially no Cs, Ru, Zr, or Pd dissolved.« less

Adolescents' Explanations for Romantic Dissolutions: A Developmental Perspective

ERIC Educational Resources Information Center

Connolly, Jennifer; McIsaac, Caroline

2009-01-01

Our objective was to examine the prevalence and developmental significance of romantic break-ups in adolescence, a relatively unexplored area of study. We examined their occurrence in a sample of 910 adolescents, first noting the frequency of these events across age, gender, and romantic experience, and then analyzing the dissolution explanations…

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

A new nanospray drying method for the preparation of nicergoline pure nanoparticles

NASA Astrophysics Data System (ADS)

Martena, Valentina; Censi, Roberta; Hoti, Ela; Malaj, Ledjan; Di Martino, Piera

2012-06-01

Three different batches of pure nanoparticles (NPs) of nicergoline (NIC) were prepared by spray drying a water:ethanol solution by a new Nano Spray Dryer Büchi B-90. Spherical pure NPs were obtained, and several analytical techniques such as differential scanning calorimetry and X-ray powder diffractometry permitted to assess their amorphous character. A comparison of the solubility, intrinsic dissolution, and drug release of original particles and pure amorphous NPs were determined, revealing an interesting improvement of biopharmaceutical properties of amorphous NPs, due to both amorphous properties and nanosize dimensions. Since in a previous work, the high-thermodynamic stability of amorphous NIC was demonstrated, this study is addressed toward the formulation of NIC as pure amorphous NPs.

Carbonate ions and arsenic dissolution by groundwater

USGS Publications Warehouse

Kim, M.-J.; Nriagu, J.; Haack, S.

2000-01-01

Samples of Marshall Sandstone, a major source of groundwater with elevated arsenic levels in southeast Michigan, were exposed to bicarbonate ion under controlled chemical conditions. In particular, effects of pH and redox conditions on arsenic release were evaluated. The release of arsenic from the aquifer rock was strongly related to the bicarbonate concentration in the leaching solution. The results obtained suggest that the carbonation of arsenic sulfide minerals, including orpiment (As2S3) and realgar (As2S2), is an important process in leaching arsenic into groundwater under anaerobic conditions. The arseno-carbonate complexes formed, believed to be As(CO3)2-, As(CO3)(OH)2-, and AsCO3+, are stable in groundwater. The reaction of ferrous ion with the thioarsenite from carbonation process can result in the formation of arsenopyrite which is a common mineral in arsenic-rich aquifers.Samples of Marshall Sandstone, a major source of groundwater with elevated arsenic levels in southeast Michigan, were exposed to bicarbonate ion under controlled chemical conditions. In particular, effects of pH and redox conditions on arsenic release were evaluated. The release of arsenic from the aquifer rock was strongly related to the bicarbonate concentration in the leaching solution. The results obtained suggest that the carbonation of arsenic sulfide minerals, including orpiment (As2S3) and realgar (As2S2), is an important process in leaching arsenic into groundwater under anaerobic conditions. The arseno-carbonate complexes formed, believed to be As(CO3)2-, As(CO3)(OH)2-, and AsCO3+, are stable in groundwater. The reaction of ferrous ion with the thioarsenite from carbonation process can result in the formation of arsenopyrite which is a common mineral in arsenic-rich aquifers.The role of bicarbonate in leaching arsenic into groundwater was investigated by conducting batch experiments using core samples of Marshall Sandstone from southeast Michigan and different bicarbonate solutions. The effects of pH and redox conditions on As dissolution were examined. Results showed that As was not leached significantly out of the Marshall Sandstone samples after 3 d using either deionized water or groundwater, but As was leached efficiently by sodium bicarbonate, potassium bicarbonate, and ferric chloride solutions. The leaching rate with sodium bicarbonate was about 25% higher than that with potassium bicarbonate. The data indicated that bicarbonate ion was involved primarily in As dissolution and that hydroxyl radical ion did not affect As dissolution to any significant degree. The amount of As leached was dependent upon the sodium bicarbonate concentration, increasing with reaction time for each concentration. Significant As leaching was found in the extreme pH ranges of <1.9 and 8.0-10.4. The resulting arseno-carbonate complexes formed were stable in groundwater.

Deep learning classifier with optical coherence tomography images for early dental caries detection

NASA Astrophysics Data System (ADS)

Karimian, Nima; Salehi, Hassan S.; Mahdian, Mina; Alnajjar, Hisham; Tadinada, Aditya

2018-02-01

Dental caries is a microbial disease that results in localized dissolution of the mineral content of dental tissue. Despite considerable decline in the incidence of dental caries, it remains a major health problem in many societies. Early detection of incipient lesions at initial stages of demineralization can result in the implementation of non-surgical preventive approaches to reverse the demineralization process. In this paper, we present a novel approach combining deep convolutional neural networks (CNN) and optical coherence tomography (OCT) imaging modality for classification of human oral tissues to detect early dental caries. OCT images of oral tissues with various densities were input to a CNN classifier to determine variations in tissue densities resembling the demineralization process. The CNN automatically learns a hierarchy of increasingly complex features and a related classifier directly from training data sets. The initial CNN layer parameters were randomly selected. The training set is split into minibatches, with 10 OCT images per batch. Given a batch of training patches, the CNN employs two convolutional and pooling layers to extract features and then classify each patch based on the probabilities from the SoftMax classification layer (output-layer). Afterward, the CNN calculates the error between the classification result and the reference label, and then utilizes the backpropagation process to fine-tune all the layer parameters to minimize this error using batch gradient descent algorithm. We validated our proposed technique on ex-vivo OCT images of human oral tissues (enamel, cortical-bone, trabecular-bone, muscular-tissue, and fatty-tissue), which attested to effectiveness of our proposed method.

Kinetics of carbonate dissolution in CO2-saturated aqueous system at reservoir conditions

NASA Astrophysics Data System (ADS)

Peng, Cheng; Crawshaw, John P.; Maitland, Geoffrey; Trusler, J. P. Martin

2014-05-01

In recent years, carbon capture and storage (CCS) has emerged as a key technology for limiting anthropogenic CO2 emissions while allowing the continued utilisation of fossil fuels. The most promising geological storage sites are deep saline aquifers because the capacity, integrity and injection economics are most favourable, and the environmental impact can be minimal. Many rock-fluid chemical reactions are known to occur both during and after CO2 injection in saline aquifers. The importance of rock-fluid reactions in the (CO2 + H2O) system can be understood in terms of their impact on the integrity and stability of both the formation rocks and cap rocks. The chemical interactions between CO2-acidified brines and the reservoir minerals can influence the porosity and permeability of the formations, resulting in changes in the transport processes occurring during CO2 storage. Since carbonate minerals are abundant in sedimentary rocks, one of the requirements to safely implement CO2 storage in saline aquifers is to characterise the reactivity of carbonate minerals in aqueous solutions at reservoir conditions. In this work, we reported measurements of the intrinsic rate of carbonate dissolution in CO2-saturated water under high-temperature high-pressure reservoir conditions extending up to 373 K and 14 MPa. The rate of carbonate dissolution in CO2-free HCl(aq) was also measured at ambient pressure at temperatures up to 353 K. Various pure minerals and reservoir rocks were investigated in this study, including single-crystals of calcite and magnesite, and samples of dolomite, chalks and sandstones. A specially-designed batch reactor system, implementing the rotating disc technique, was used to obtain the intrinsic reaction rate at the solid/liquid interface, free of mass transfer effects. The effective area and mineralogy of the exposed surface was determined by a combination of surface characterisation techniques including XRD, SEM, EDX and optical microscopy. The results of the study indicate that the rotating disc technique can allow accurate measurement of the carbonate dissolution rate under surface-reaction-controlled conditions, and that the carbonate dissolution rate typically increases with the increase of temperature, CO2 partial pressure and solution acidity. The study shows that the dissolution of carbonate in CO2-free acidic solutions can be described as a first order heterogeneous reaction; however, this model is not sufficient to describe the reaction kinetics of carbonate minerals in the (CO2 + H2O) system, particularly for high reactivity carbonates, such as calcite, at reservoir conditions. For these systems, both pH and the activity of CO2(aq) influence the dissolution rate. Based on the experimental results, kinetic models have been developed and parameterised to describe the dissolution of different carbonate minerals. The results of this study should facilitate more rigorous modelling of mineral dissolution in deep saline aquifers used for CO2 storage. We gratefully acknowledge the funding of QCCSRC provided jointly by Qatar Petroleum, Shell, and the Qatar Science & Technology Park. Keywords: Carbon Dioxide, Carbonate, High Pressure, High Temperature, Reaction Kinetics.

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

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.

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.

Impact of vibration and agitation speed on dissolution of USP prednisone tablets RS and various IR tablet formulations.

PubMed

Seeger, Nicole; Lange, Sigrid; Klein, Sandra

2015-08-01

Dissolution testing is an in vitro procedure which is widely used in quality control (QC) of solid oral dosage forms and, given that real biorelevant test conditions are applied, can also be used as a predictive tool for the in vivo performance of such formulations. However, if a dissolution method is intended to be used for such purposes, it has to deliver results that are only determined by the quality of the test product, but not by other variables. In the recent past, more and more questions were arising on how to address the effects of vibration on dissolution test results. The present study was performed to screen for the correlation of prednisone dissolution of USP Prednisone Tablets RS with vibration caused by a commercially available vibration source as well as to investigate how drug release from a range of immediate release formulations containing class 1-4 drugs of the biopharmaceutical classification scheme is affected by vibration when performing dissolution experiments at different agitation rates. Results of the present study show that the dissolution process of oral drug formulations can be affected by vibration. However, it also becomes clear that the degree of which a certain level of vibration impacts dissolution is strongly dependent on several factors such as drug properties, formulation parameters, and the design of the dissolution method. To ensure the establishment of robust and predictive dissolution test methods, the impact of variation should thus be considered in method design and validation.

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.

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

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.

Acid dissolution experiments - Carbonates and the 6.8-micrometer bands in interplanetary dust particles

NASA Technical Reports Server (NTRS)

Sandford, S. A.

1986-01-01

A chemical dissolution experiment on an interplanetary dust particle (IDP) showed that carbonates, not acid-insoluble organic compounds, were responsible for virtually all the absorption at 6.8 micrometers seen in the infrared spectra of this particle. The IDP examined had an infrared spectrum characteristic of layer-lattice silicates and belongs to a class of IDP's whose spectra resemble those of protostellar objects like W33 A, which also exhibit a band at 6.8 micrometers.

Uptake Mechanisms of Eu(III) on Hydroxyapatite: A Potential Permeable Reactive Barrier Backfill Material for Trapping Trivalent Minor Actinides.

PubMed

Xu, Lin; Zheng, Tao; Yang, Shitong; Zhang, Linjuan; Wang, Jianqiang; Liu, Wei; Chen, Lanhua; Diwu, Juan; Chai, Zhifang; Wang, Shuao

2016-04-05

The permeable reactive barrier (PRB) technique has attracted an increasing level of attention for the in situ remediation of contaminated groundwater. In this study, the macroscopic uptake behaviors and microscopic speciation of Eu(III) on hydroxyapatite (HAP) were investigated by a combination of theoretical modeling, batch experiments, powder X-ray diffraction (PXRD) fitting, and X-ray absorption spectroscopy (XAS). The underlying removal mechanisms were identified to further assess the application potential of HAP as an effective PRB backfill material. The macroscopic analysis revealed that nearly all dissolved Eu(III) in solution was removed at pH 6.5 within an extremely short reaction time of 5 min. In addition, the thermodynamic calculations, desorption experiments, and PXRD and XAS analyses definitely confirmed the formation of the EuPO4·H2O(s) phase during the process of uptake of dissolved Eu(III) by HAP via the dissolution-precipitation mechanism. A detailed comparison of the present experimental findings and related HAP-metal systems suggests that the relative contribution of precipitation to the total Eu(III) removal increases as the P:Eu ratio decreases. The dosage of HAP-based PRB for the remediation of groundwater polluted by Eu(III) and analogous trivalent actinides [e.g., Am(III) and Cm(III)] should be strictly controlled depending on the dissolved Eu(III) concentration to obtain an optimal P:M (M represents Eu, Am, or Cm) ratio and treatment efficiency.

Leaching of copper and nickel in soil-water systems contaminated by bauxite residue (red mud) from Ajka, Hungary: the importance of soil organic matter.

PubMed

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

2015-07-01

Red mud is a highly alkaline (pH >12) waste product from bauxite ore processing. The red mud spill at Ajka, Hungary, in 2010 released 1 million m(3) of caustic red mud into the surrounding area with devastating results. Aerobic and anaerobic batch experiments and solid phase extraction techniques were used to assess the impact of red mud addition on the mobility of Cu and Ni in soils from near the Ajka spill site. Red mud addition increases aqueous dissolved organic carbon (DOC) concentrations due to soil alkalisation, and this led to increased mobility of Cu and Ni complexed to organic matter. With Ajka soils, more Cu was mobilised by contact with red mud than Ni, despite a higher overall Ni concentration in the solid phase. This is most probably because Cu has a higher affinity to form complexes with organic matter than Ni. In aerobic experiments, contact with the atmosphere reduced soil pH via carbonation reactions, and this reduced organic matter dissolution and thereby lowered Cu/Ni mobility. These data show that the mixing of red mud into organic rich soils is an area of concern, as there is a potential to mobilise Cu and Ni as organically bound complexes, via soil alkalisation. This could be especially problematic in locations where anaerobic conditions can prevail, such as wetland areas contaminated by the spill.

Colloid-Facilitated Transport of 137Cs in Fracture-Fill Material. Experiments and Modeling

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

Dittrich, Timothy M.; Reimus, Paul William

2015-10-29

In this study, we demonstrate how a combination of batch sorption/desorption experiments and column transport experiments were used to effectively parameterize a model describing the colloid-facilitated transport of Cs in the Grimsel granodiorite/FFM system. Cs partition coefficient estimates onto both the colloids and the stationary media obtained from the batch experiments were used as initial estimates of partition coefficients in the column experiments, and then the column experiment results were used to obtain refined estimates of the number of different sorption sites and the adsorption and desorption rate constants of the sites. The desorption portion of the column breakthrough curvesmore » highlighted the importance of accounting for adsorption-desorption hysteresis (or a very nonlinear adsorption isotherm) of the Cs on the FFM in the model, and this portion of the breakthrough curves also dictated that there be at least two different types of sorption sites on the FFM. In the end, the two-site model parameters estimated from the column experiments provided excellent matches to the batch adsorption/desorption data, which provided a measure of assurance in the validity of the model.« less

Microbially mediated barite dissolution in anoxic brines

USGS Publications Warehouse

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

2017-01-01

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

Salt dissolution and sinkhole formation: Results of laboratory experiments

NASA Astrophysics Data System (ADS)

Oz, Imri; Eyal, Shalev; Yoseph, Yechieli; Ittai, Gavrieli; Elad, Levanon; Haim, Gvirtzman

2016-10-01

The accepted mechanism for the formation of thousands of sinkholes along the coast of the Dead Sea suggests that their primary cause is dissolution of a salt layer by groundwater undersaturated with respect to halite. This is related to the drop in the Dead Sea level, which caused a corresponding drop of the freshwater-saltwater interface, resulting in fresher groundwater replacing the brines that were in contact with the salt layer. In this study we used physical laboratory experiments to examine the validity of this mechanism by reproducing the full dynamic natural process and to examine the impact of different hydrogeological characteristics on this process. The experimental results show surface subsidence and sinkhole formation. The stratigraphic configurations of the aquifer, together with the mechanical properties of the salt layer, determine the dynamic patterns of the sinkhole formation (instantaneous versus gradual formation). Laboratory experiments were also used to study the potential impact of future stratification in the Dead Sea, if and when the "Red Sea-Dead Sea Canal" project is carried out, and the Dead Sea level remains stable. The results show that the dissolution rates are slower by 1 order of magnitude in comparison with a nonstratified saltwater body, and therefore, the processes of salt dissolution and sinkhole formation will be relatively restrained under these conditions.

Experimental Fluidic Investigation of Degradation of Pico-liter Oil Droplets by Physical and Biological Processes

NASA Astrophysics Data System (ADS)

Jalali, Maryam; Sheng, Jian

2016-11-01

This study used laboratory experiments to assess degradation of crude oil by physical and biological processes including dissolution and consumption. To perform this study, we have developed a bioassay that consists of a flow chamber with a bottom glass substrate printed with an array of pico-liter oil droplets using micro-Transfer Printing. The technique allows the printing of highly homogeneous pico-liter droplet array with different dimensions and shapes that can be maintained for weeks. Since the droplets are pinned and stationary on the bottom substrate, the key processes can be evaluated by measuring the change of shape and volume using Atomic Force Microscopy. Parallel microfluidic bioassays are established at the beginning, exposed to abiotic/biotic solutions, and scarified for characterization at given time intervals for each experiment. Two processes, dissolution and consumption, are investigated. In addition, the effects of dispersant on these processes are also studied. The results show that the amount of oil degraded by bacteria accounts for almost 50% of the total volume in comparison to 25% via dissolution. Although dispersant has a subtle effect on dissolution, the effect on rates of consumption and its asymptotic behavior are substantial. Experiments involving different bacterial strains, dispersant concentration, and flow shear rate are on-going.

High-solid mesophilic methane fermentation of food waste with an emphasis on Iron, Cobalt, and Nickel requirements.

PubMed

Qiang, Hong; Lang, Dong-Li; Li, Yu-You

2012-01-01

The effect of trace metals on the mesophilic methane fermentation of high-solid food waste was investigated using both batch and continuous experiments. The continuous experiment was conducted by using a CSTR-type reactor with three run. During the first run, the HRT of the reactor was stepwise decreased from 100 days to 30 days. From operation day 50, the reactor efficiency deteriorated due to the lack of trace metals. The batch experiment showed that iron, cobalt, and nickel combinations had a significant effect on food waste. According to the results of the batch experiment, a combination of iron, cobalt, and nickel was added into the CSTR reactor by two different methods at run II, and III. Based on experimental results and theoretical calculations, the most suitable values of Fe/COD, Co/COD, and Ni/COD in the substrate were identified as 200, 6.0, and 5.7 mg/kg COD, respectively. Copyright © 2011 Elsevier Ltd. All rights reserved.

Evaluation of pretreatment methods on mixed inoculum for both batch and continuous thermophilic biohydrogen production from cassava stillage.

PubMed

Luo, Gang; Xie, Li; Zou, Zhonghai; Wang, Wen; Zhou, Qi

2010-02-01

Anaerobic sludges, pretreated by chloroform, base, acid, heat and loading-shock, as well as untreated sludge were evaluated for their thermophilic fermentative hydrogen-producing characters from cassava stillage in both batch and continuous experiments. Results showed that the highest hydrogen production was obtained by untreated sludge and there were significant differences (p<0.05) in hydrogen yields (varied from 32.9 to 65.3mlH(2)/gVS) among the tested pretreatment methods in batch experiments. However, the differences in hydrogen yields disappeared in continuous experiments, which indicated the pretreatment methods had only short-term effects on the hydrogen production. Further study showed that alkalinity was a crucial parameter influencing the fermentation process. When the influent was adjusted to pH 6 by NaHCO(3) instead of NaOH, the hydrogen yield increased from about 40 to 52mlH(2)/gVS in all the experiments. Therefore, pretreatment of anaerobic sludge is unnecessary for practical thermophilic fermentative hydrogen production from cassava stillage.

Miniaturized INtrinsic DISsolution Screening (MINDISS) assay for preformulation.

PubMed

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

2016-05-25

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

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

PubMed

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

2018-05-04

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

NIGHTHAWK - A Program for Modeling Saturated Batch and Column Experiments Incorporating Equilibrium and Kinetic Biogeochemistry

EPA Science Inventory

NIGHTHAWK simulates the fate and transport of biogeochemically reactive contaminants in the saturated subsurface. Version 1.2 supports batch and one- dimensional advective-dispersive-reactive transport involving a number of biogeochemical processes, including: microbially-mediate...

Coupled multiphase reactive flow and mineral dissolution-precipitation kinetics: Examples of long-term CO2 sequestration in Utsira Sand, Norway and Mt. Simon Formation, Midwest USA

NASA Astrophysics Data System (ADS)

Zhang, Y.; Zhang, G.; Lu, P.; Hu, B.; Zhu, C.

2017-12-01

The extent of CO2 mineralization after CO2 injection into deep saline aquifers is a result of the complex coupling of multiphase fluid flow, mass transport, and brine-mineral reactions. The effects of dissolution rate laws and groundwater flow on the long-term fate of CO2 have been seriously overlooked. To investigate these effects, we conducted multiphase (CO2 and brine) coupled reactive transport modeling of CO2 storage in two sandy formations (Utsira Sand, Norway1,2 and Mt. Simon formation, USA 3) using ToughReact and simulated a series of scenarios. The results indicated that: (1) Different dissolution rate laws for feldspars can significantly affect the amount of CO2 mineralization. Increased feldspar dissolution will promote CO2 mineral trapping through the coupling between feldspar dissolution and carbonate mineral precipitation at raised pH. The predicted amount of CO2 mineral trapping when using the principle of detailed balancing-based rate law for feldspar dissolution is about twice as much as that when using sigmoidal rate laws in the literature. (2) Mineral trapping is twice as much when regional groundwater flow is taken into consideration in long-term simulations (e.g., 10,000 years) whereas most modeling studies neglected the regional groundwater flow back and effectively simulated a batch reactor process. Under the influence of regional groundwater flow, the fresh brine from upstream continuously dissolves CO2 at the tail of CO2 plume, generating a large acidified area where large amount of CO2 mineralization takes place. The upstream replenishment of groundwater results in ˜22% mineral trapping at year 10,000, compared to ˜4% when this effect is ignored. Refs: 1Zhang, G., Lu, P., Wei, X., Zhu, C. (2016). Impacts of Mineral Reaction Kinetics and Regional Groundwater Flow on Long-Term CO2 Fate at Sleipner. Energy & Fuels, 30(5), 4159-4180. 2Zhu, C., Zhang, G., Lu, P., Meng, L., Ji, X. (2015). Benchmark modeling of the Sleipner CO2 plume: Calibration to seismic data for the uppermost layer and model sensitivity analysis. International Journal of Greenhouse Gas Control, 43, 233-246. 3Zhang, G., Lu, P., Zhang, Y., Wei, X., Zhu, C. (2015). Effects of rate law formulation on predicting CO2 sequestration in sandstone formations. International Journal of Energy Research, 39(14), 1890-1908.

Pore-scale supercritical CO 2 dissolution and mass transfer under drainage conditions

DOE PAGES

Chang, Chun; Zhou, Quanlin; Oostrom, Mart; ...

2016-12-05

Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO 2 (scCO 2) and a prolonged depletion of residual scCO 2. In this paper, pore-scale scCO 2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO 2 into the sandstone-analogue pore network initially saturated by water without dissolved CO 2 (dsCO 2). During the experiments, time-lapse images of dye intensity, reflecting water pH,more » were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO 2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO 2 dissolution and phase equilibrium occurs when scCO 2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO 2 dissolution at phase interfaces and diffusion of dsCO 2 at the pore scale (10–100 µm) observed after scCO 2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO 2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. Finally, this finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO 2 at narrow pore throats.« less

Quantifying the Movement and Dissolution of Fugitive Methane in Shallow Aquifers: Visualization Experiments

NASA Astrophysics Data System (ADS)

Van De Ven, C. J. C.; Mumford, K. G.

2016-12-01

The environmental impact and potential human health implications, specifically from the contamination of groundwater sources, has sparked controversy around shale gas extraction in North America. It is clear that understanding the effects of hydraulic fracturing on shallow fresh water aquifers is of great importance, including the threat of stray gas (also referred to as fugitive methane) on groundwater quality. Faulty wells provide a preferential pathway for free gas phase (mostly methane) to migrate from deeper gas-bearing formations of natural gas to shallow aquifers, followed by its dissolution into the surrounding groundwater. An increased understanding of the fate of fugitive methane in shallow aquifers is required to assess the potential risks associated with current and future operations, as well as to better link gas migration, dissolution and the deterioration of groundwater quality. In this study, a series of laboratory experiments were performed using carbon dioxide (CO2) gas as a surrogate for methane to improve our understanding of gas dissolution in groundwater systems. Using CO2, a novel laboratory technique was developed that allows the measurement of dissolved CO2 concentrations using image analysis alongside visualization of free gas mobilization. The technique is based on the acidification of water during CO2 dissolution, which causes a colour change in an indicator dye. The colour change is recorded using a visual light transmission technique, in which digital images are used to track dissolved concentrations at high spatial (1 mm) and temporal (5 s) resolutions in a two-dimensional (25 × 25 × 1 cm3) flow cell. The experiments were completed in both homogeneous sand packs and sand packs containing layered heterogeneities to investigate the dissolution of both gas fingers and gas pools. The results demonstrate the potential of this novel technique for investigating gas dissolution, and showed significant tailing of dissolved CO2 and persistence of other gas phase components. This technique will aid in the development of conceptual models to link fugitive methane to groundwater contamination and provide detailed data required for the validation of numerical models that account for gas-water mass transfer; both of which are required for the development of sound monitoring techniques.

Pore-scale supercritical CO 2 dissolution and mass transfer under drainage conditions

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

Chang, Chun; Zhou, Quanlin; Oostrom, Mart

Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO 2 (scCO 2) and a prolonged depletion of residual scCO 2. In this paper, pore-scale scCO 2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO 2 into the sandstone-analogue pore network initially saturated by water without dissolved CO 2 (dsCO 2). During the experiments, time-lapse images of dye intensity, reflecting water pH,more » were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO 2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO 2 dissolution and phase equilibrium occurs when scCO 2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO 2 dissolution at phase interfaces and diffusion of dsCO 2 at the pore scale (10–100 µm) observed after scCO 2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO 2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. Finally, this finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO 2 at narrow pore throats.« less

Pore-scale supercritical CO 2 dissolution and mass transfer under drainage conditions

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

Chang, Chun; Zhou, Quanlin; Oostrom, Mart

Abstract: Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO 2 (scCO 2) and a prolonged depletion of residual scCO 2. In this study, pore-scale scCO 2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO 2 into the sandstone-analogue pore network initially saturated by water without dissolved CO 2 (dsCO 2). During the experiments, time-lapse images of dye intensity, reflecting watermore » pH, were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO 2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO 2 dissolution and phase equilibrium occurs when scCO 2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO 2 dissolution at phase interfaces and diffusion of dsCO 2 at the pore scale (10-100 µm) observed after scCO 2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO 2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. This finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO 2 at narrow pore throats.« less

Ion exchange of several radionuclides on the hydrous crystalline silicotitanate, UOP IONSIV IE-911

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

Huckman, M.E.; Latheef, I.M.; Anthony, R.G.

1999-04-01

The crystalline silicotitanate, UOP IONSIV IE-911, is a proven material for removing radionuclides from a wide variety of waste streams. It is superior for removing several radionuclides from the highly alkaline solutions typical of DOE wastes. This laboratory previously developed an equilibrium model applicable to complex solutions for IE-910 (the power form of the granular IE-911), and more recently, the authors have developed several single component ion-exchange kinetic models for predicting column breakthrough curves and batch reactor concentration histories. In this paper, the authors model ion-exchange column performance using effective diffusivities determined from batch kinetic experiments. This technique is preferablemore » because the batch experiments are easier, faster, and cheaper to perform than column experiments. They also extend these ideas to multicomponent systems. Finally, they evaluate the ability of the equilibrium model to predict data for IE-911.« less

Experimental and numerical simulation of dissolution and precipitation: implications for fracture sealing at Yucca Mountain, Nevada

NASA Astrophysics Data System (ADS)

Dobson, Patrick F.; Kneafsey, Timothy J.; Sonnenthal, Eric L.; Spycher, Nicolas; Apps, John A.

2003-05-01

Plugging of flow paths caused by mineral precipitation in fractures above the potential repository at Yucca Mountain, Nevada could reduce the probability of water seeping into the repository. As part of an ongoing effort to evaluate thermal-hydrological-chemical (THC) effects on flow in fractured media, we performed a laboratory experiment and numerical simulations to investigate mineral dissolution and precipitation under anticipated temperature and pressure conditions in the repository. To replicate mineral dissolution by vapor condensate in fractured tuff, water was flowed through crushed Yucca Mountain tuff at 94 °C. The resulting steady-state fluid composition had a total dissolved solids content of about 140 mg/l; silica was the dominant dissolved constituent. A portion of the steady-state mineralized water was flowed into a vertically oriented planar fracture in a block of welded Topopah Spring Tuff that was maintained at 80 °C at the top and 130 °C at the bottom. The fracture began to seal with amorphous silica within 5 days. A 1-D plug-flow numerical model was used to simulate mineral dissolution, and a similar model was developed to simulate the flow of mineralized water through a planar fracture, where boiling conditions led to mineral precipitation. Predicted concentrations of the major dissolved constituents for the tuff dissolution were within a factor of 2 of the measured average steady-state compositions. The mineral precipitation simulations predicted the precipitation of amorphous silica at the base of the boiling front, leading to a greater than 50-fold decrease in fracture permeability in 5 days, consistent with the laboratory experiment. These results help validate the use of a numerical model to simulate THC processes at Yucca Mountain. The experiment and simulations indicated that boiling and concomitant precipitation of amorphous silica could cause significant reductions in fracture porosity and permeability on a local scale. However, differences in fluid flow rates and thermal gradients between the experimental setup and anticipated conditions at Yucca Mountain need to be factored into scaling the results of the dissolution/precipitation experiments and associated simulations to THC models for the potential Yucca Mountain repository.

Looking for the Self: Phenomenology, Neurophysiology and Philosophical Significance of Drug-induced Ego Dissolution

PubMed Central

Millière, Raphaël

2017-01-01

There is converging evidence that high doses of hallucinogenic drugs can produce significant alterations of self-experience, described as the dissolution of the sense of self and the loss of boundaries between self and world. This article discusses the relevance of this phenomenon, known as “drug-induced ego dissolution (DIED)”, for cognitive neuroscience, psychology and philosophy of mind. Data from self-report questionnaires suggest that three neuropharmacological classes of drugs can induce ego dissolution: classical psychedelics, dissociative anesthetics and agonists of the kappa opioid receptor (KOR). While these substances act on different neurotransmitter receptors, they all produce strong subjective effects that can be compared to the symptoms of acute psychosis, including ego dissolution. It has been suggested that neuroimaging of DIED can indirectly shed light on the neural correlates of the self. While this line of inquiry is promising, its results must be interpreted with caution. First, neural correlates of ego dissolution might reveal the necessary neurophysiological conditions for the maintenance of the sense of self, but it is more doubtful that this method can reveal its minimally sufficient conditions. Second, it is necessary to define the relevant notion of self at play in the phenomenon of DIED. This article suggests that DIED consists in the disruption of subpersonal processes underlying the “minimal” or “embodied” self, i.e., the basic experience of being a self rooted in multimodal integration of self-related stimuli. This hypothesis is consistent with Bayesian models of phenomenal selfhood, according to which the subjective structure of conscious experience ultimately results from the optimization of predictions in perception and action. Finally, it is argued that DIED is also of particular interest for philosophy of mind. On the one hand, it challenges theories according to which consciousness always involves self-awareness. On the other hand, it suggests that ordinary conscious experience might involve a minimal kind of self-awareness rooted in multisensory processing, which is what appears to fade away during DIED. PMID:28588463

A high-throughput media design approach for high performance mammalian fed-batch cultures

PubMed Central

Rouiller, Yolande; Périlleux, Arnaud; Collet, Natacha; Jordan, Martin; Stettler, Matthieu; Broly, Hervé

2013-01-01

An innovative high-throughput medium development method based on media blending was successfully used to improve the performance of a Chinese hamster ovary fed-batch medium in shaking 96-deepwell plates. Starting from a proprietary chemically-defined medium, 16 formulations testing 43 of 47 components at 3 different levels were designed. Media blending was performed following a custom-made mixture design of experiments considering binary blends, resulting in 376 different blends that were tested during both cell expansion and fed-batch production phases in one single experiment. Three approaches were chosen to provide the best output of the large amount of data obtained. A simple ranking of conditions was first used as a quick approach to select new formulations with promising features. Then, prediction of the best mixes was done to maximize both growth and titer using the Design Expert software. Finally, a multivariate analysis enabled identification of individual potential critical components for further optimization. Applying this high-throughput method on a fed-batch, rather than on a simple batch, process opens new perspectives for medium and feed development that enables identification of an optimized process in a short time frame. PMID:23563583

Improving tablet coating robustness by selecting critical process parameters from retrospective data.

PubMed

Galí, A; García-Montoya, E; Ascaso, M; Pérez-Lozano, P; Ticó, J R; Miñarro, M; Suñé-Negre, J M

2016-09-01

Although tablet coating processes are widely used in the pharmaceutical industry, they often lack adequate robustness. Up-scaling can be challenging as minor changes in parameters can lead to varying quality results. To select critical process parameters (CPP) using retrospective data of a commercial product and to establish a design of experiments (DoE) that would improve the robustness of the coating process. A retrospective analysis of data from 36 commercial batches. Batches were selected based on the quality results generated during batch release, some of which revealed quality deviations concerning the appearance of the coated tablets. The product is already marketed and belongs to the portfolio of a multinational pharmaceutical company. The Statgraphics 5.1 software was used for data processing to determine critical process parameters in order to propose new working ranges. This study confirms that it is possible to determine the critical process parameters and create design spaces based on retrospective data of commercial batches. This type of analysis is thus converted into a tool to optimize the robustness of existing processes. Our results show that a design space can be established with minimum investment in experiments, since current commercial batch data are processed statistically.

Leaching of TCIPP from furniture foam is rapid and substantial.

PubMed

Stubbings, William A; Harrad, Stuart

2018-02-01

A series of laboratory experiments were conducted, in which waste furniture polyurethane foam samples containing tris (1-chloro-2-propyl) phosphate (TCIPP) were contacted with a range of leaching fluids, formulated to simulate the composition of landfill leachate. Leaching was examined under a number of different scenarios, such as: dissolved humic matter concentration, pH, and temperature, as well as the effect of agitation, and waste:leaching fluid contact duration. In addition to single batch (no replenishment of leaching fluid), serial batch (draining of leachate and replenishment with fresh leaching fluid at various time intervals) experiments were conducted. Leaching of TCIPP from PUF appears to be a first order process. Concentrations of TCIPP in leachate generated by the experiments in this study ranged from 13 mg L -1 to 130 mg L -1 . In serial batch leaching experiments, >95% of TCIPP was depleted from PUF after 168 h total contact with leaching fluid. Our experiments indicate leaching is potentially a very significant pathway of TCIPP emissions to the environment. Copyright © 2017. Published by Elsevier Ltd.

Spousal Dissimilarity, Race, and Marital Dissolution

ERIC Educational Resources Information Center

Clarkwest, Andrew

2007-01-01

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

Investigating Dissolution and Precipitation Phenomena with a Smartphone Microscope

ERIC Educational Resources Information Center

Lumetta, Gregg J.; Arcia, Edgar

2016-01-01

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…

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

Wang, Li-Fang; Ou, Chin-Ching; Striebel, Kathryn A.

The goal of this research was to measure Mn dissolution from a thin porous spinel LiMn{sub 2}O{sub 4} electrode by rotating ring-disk collection experiments. The amount of Mn dissolution from the spinel LiMn{sub 2}O{sub 4} electrode under various conditions was detected by potential step chronoamperometry. The concentration of dissolved Mn was found to increase with increasing cycle numbers and elevated temperature. The dissolved Mn was not dependent on disk rotation speed, which indicated that the Mn dissolution from the disk was under reaction control. The in situ monitoring of Mn dissolution from the spinel was carried out under various conditions.more » The ring currents exhibited maxima corresponding to the end-of-charge (EOC) and end-of-discharge (EOD), with the largest peak at EOC. The results suggest that the dissolution of Mn from spinel LiMn{sub 2}O{sub 4} occurs during charge/discharge cycling, especially in a charged state (at >4.1 V) and in a discharged state (at <3.1 V). The largest peak at EOC demonstrated that Mn dissolution took place mainly at the top of charge. At elevated temperatures, the ring cathodic currents were larger due to the increase of Mn dissolution rate.« less

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.

Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

USGS Publications Warehouse

Ravichandran, Mahalingam; Aiken, George R.; Reddy, Michael M.; Ryan, Joseph N.

1998-01-01

Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 μM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca2+. Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nM) dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates (determined by 13C NMR) correlated positively with enhanced cinnabar dissolution. ζ-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar (pHpzc = 4.0) at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

The ubiquitous nature of accessory calcite in granitoid rocks: Implications for weathering, solute evolution, and petrogenesis

USGS Publications Warehouse

White, A.F.; Schulz, M.S.; Lowenstern, J. B.; Vivit, D.V.; Bullen, T.D.

2005-01-01

Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg-1 (mean = 2.52 g kg-1). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and 87Sr/86Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO2 in DI water for 75 d at 25??C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and 87Sr/ 86Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and 87Sr/86Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO2 fugacities, calcite is a stable phase at temperatures of 400 to 700??C. Copyright ?? 2005 Elsevier Ltd.

Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

NASA Astrophysics Data System (ADS)

Migeon, Valérie; Bourdon, Bernard; Pili, Eric; Fitoussi, Caroline

2018-06-01

As an attempt to prevent illicit trafficking of nuclear materials, it is critical to identify the origin and transformation of uranium materials from the nuclear fuel cycle based on chemical and isotope tracers. The potential of molybdenum (Mo) isotopes as tracers is considered in this study. We focused on leaching, the first industrial process used to release uranium from ores, which is also known to extract Mo depending on chemical conditions. Batch experiments were performed in the laboratory with pH ranging from 0.3 to 5.5 in sulfuric acid. In order to span a large range in uranium and molybdenum yields, oxidizers such as nitric acid, hydrogen peroxide and manganese dioxide were also added. An enrichment in heavy Mo isotopes is produced in the solution during leaching of a granitic uranium ore, when Mo recovery is not quantitative. At least two Mo reservoirs were identified in the ore: ∼40% as Mo oxides soluble in water or sulfuric acid, and ∼40% of Mo hosted in sulfides soluble in nitric acid or hydrogen peroxide. At pH > 1.8, adsorption and/or precipitation processes induce a decrease in Mo yields with time correlated with large Mo isotope fractionations. Quantitative models were used to evaluate the relative importance of the processes involved in Mo isotope fractionation: dissolution, adsorption, desorption, precipitation, polymerization and depolymerization. Model best fits are obtained when combining the effects of dissolution/precipitation, and adsorption/desorption onto secondary minerals. These processes are inferred to produce an equilibrium isotope fractionation, with an enrichment in heavy Mo isotopes in the liquid phase and in light isotopes in the solid phase. Quantification of Mo isotope fractionation resulting from uranium leaching is thus a promising tool to trace the origin and transformation of nuclear materials. Our observations of Mo leaching are also consistent with observations of natural Mo isotope fractionation taking place during chemical weathering in terrestrial environments where the role of secondary processes such as adsorption is significant.

Analysis and interpretation of the leaching behaviour of waste thermal treatment bottom ash by batch and column tests.

PubMed

Di Gianfilippo, Martina; Costa, Giulia; Verginelli, Iason; Gavasci, Renato; Lombardi, Francesco

2016-10-01

This paper investigates the leaching behaviour of specific types of waste thermal treatment bottom ash (BA) as a function of both pH and the liquid-to-solid ratio (L/S). Specifically, column percolation tests and different types of batch tests (including pH-dependence) were applied to BA produced by hospital waste incineration (HW-I), Refuse Derived Fuel (RDF) gasification (RDF-G) and RDF incineration (RDF-I). The results of these tests were interpreted applying an integrated graphical and modelling approach aimed at identifying the main mechanisms (solubility, availability or time-controlled dissolution and diffusion) governing the release of specific constituents from each type of BA. The final aim of this work was in fact to gain insight on the information that can be provided by the leaching tests applied, and hence on which ones may be more suitable to apply for assessing the leaching concentrations expected in the field. The results of the leaching tests showed that the three samples of analysed BA presented differences of orders of magnitude in their leaching behaviour, especially as a function of pH, but also in terms of the L/S. These were mainly related to the differences in mineralogy of the samples. In addition, for the same type of bottom ash, the comparison between the results of batch and percolation column tests, expressed in terms of cumulative release, showed that for some constituents (e.g. Mg for HW-I BA and Cu for RDF-G BA) differences of over one order of magnitude were obtained due to variations in pH and DOC release. Similarly, the eluate concentrations observed in the percolation tests, for most of the investigated elements, were not directly comparable with the results of the pH-dependence tests. In particular, in some cases the percolation test results showed eluate concentrations of some constituents (e.g. K and Ca in HW-I BA) of up to one order of magnitude higher than the values obtained from the pH-dependence experiments at the same pH value. This was attributed to a rapid washout from the column of the soluble phases present in the BA. In contrast, for other constituents (e.g. Mg and Ba for the RDF-G BA), especially at high L/S ratios, the concentrations in the column tests were of up to one order of magnitude lower than the solubility value, indicating release under non-equilibrium conditions. In these cases, batch pH-dependence tests should be preferred, since column tests results could underestimate the concentrations expected in the field. Copyright © 2016 Elsevier Ltd. All rights reserved.

Simulated Batch Production of Penicillin

ERIC Educational Resources Information Center

Whitaker, A.; Walker, J. D.

1973-01-01

Describes a program in applied biology in which the simulation of the production of penicillin in a batch fermentor is used as a teaching technique to give students experience before handling a genuine industrial fermentation process. Details are given for the calculation of minimum production cost. (JR)

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.

Process performance of high-solids batch anaerobic digestion of sewage sludge.

PubMed

Liao, Xiaocong; Li, Huan; Cheng, Yingchao; Chen, Nan; Li, Chenchen; Yang, Yuning

2014-01-01

The characteristics of high-solids anaerobic digestion (AD) of sewage sludge were investigated by comparison with conventional low-solids processes. A series of batch experiments were conducted under mesophilic condition and the initial solid contents were controlled at four levels of 1.79%, 4.47%, 10.28% and 15.67%. During these experiments, biogas production, organic degradation and intermediate products were monitored. The results verified that high-solids batch AD of sewage sludge was feasible. Compared with the low-solids AD with solid contents of 1.79% or 4.47%, the high-solids processes decreased the specific biogas yield per gram of sludge volatile solids slightly, achieved the same organic degradation rate of about 40% within extended degradation time, but increased the volumetric biogas production rate and the treatment capability of digesters significantly. The blocked mass and energy transfer, the low substrate to inoculum rate and the excessive cumulative free ammonia were the main factors impacting the performance of high-solids batch AD.

Kinetic modelling of anaerobic hydrolysis of solid wastes, including disintegration processes.

PubMed

García-Gen, Santiago; Sousbie, Philippe; Rangaraj, Ganesh; Lema, Juan M; Rodríguez, Jorge; Steyer, Jean-Philippe; Torrijos, Michel

2015-01-01

A methodology to estimate disintegration and hydrolysis kinetic parameters of solid wastes and validate an ADM1-based anaerobic co-digestion model is presented. Kinetic parameters of the model were calibrated from batch reactor experiments treating individually fruit and vegetable wastes (among other residues) following a new protocol for batch tests. In addition, decoupled disintegration kinetics for readily and slowly biodegradable fractions of solid wastes was considered. Calibrated parameters from batch assays of individual substrates were used to validate the model for a semi-continuous co-digestion operation treating simultaneously 5 fruit and vegetable wastes. The semi-continuous experiment was carried out in a lab-scale CSTR reactor for 15 weeks at organic loading rate ranging between 2.0 and 4.7 gVS/Ld. The model (built in Matlab/Simulink) fit to a large extent the experimental results in both batch and semi-continuous mode and served as a powerful tool to simulate the digestion or co-digestion of solid wastes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of ZnO nanoparticles on wastewater biological nitrogen and phosphorus removal.

PubMed

Zheng, Xiong; Wu, Rui; Chen, Yinguang

2011-04-01

With the increasing utilization of nanomaterials, zinc oxide nanoparticles (ZnO NPs) have been reported to induce adverse effects on human health and aquatic organisms. However, the potential impacts of ZnO NPs on wastewater nitrogen and phosphorus removal with an activated sludge process are unknown. In this paper, short-term exposure experiments were conducted to determine whether ZnO NPs caused adverse impacts on biological nitrogen and phosphorus removal in the unacclimated anaerobic-low dissolved oxygen sequencing batch reactor. Compared with the absence of ZnO NPs, the presence of 10 and 50 mg/L of ZnO NPs decreased total nitrogen removal efficiencies from 81.5% to 75.6% and 70.8%, respectively. The corresponding effluent phosphorus concentrations increased from nondetectable to 10.3 and 16.5 mg/L, respectively, which were higher than the influent phosphorus (9.8 mg/L), suggesting that higher concentration of ZnO NPs induced the loss of normal phosphorus removal. It was found that the inhibition of nitrogen and phosphorus removal induced by higher concentrations of ZnO NPs was due to the release of zinc ions from ZnO NPs dissolution and increase of reactive oxygen species (ROS) production, which caused inhibitory effect on polyphosphate-accumulating organisms and decreased nitrate reductase, exopolyphosphatase, and polyphosphate kinase activities.

Combined effects of low-molecular-weight organic acids on mobilization of arsenic and lead from multi-contaminated soils.

PubMed

Onireti, Olaronke O; Lin, Chuxia; Qin, Junhao

2017-03-01

A batch experiment was conducted to examine the combined effects of three common low-molecular-weight organic acids (LMWOAs) on the mobilization of arsenic and lead in different types of multi-contaminated soils. The capacity of individual LMWOAs (at a same molar concentration) to mobilize soil-borne As and Pb varied significantly. The combination of the organic acids did not make a marked "additive" effect on the mobilization of the investigated three elements. An "antagonistic" effect on element mobilization was clear in the treatments involving oxalic acid for some soils. The acid strength of a LMWOA did not play an important role in controlling the mobilization of elements. While the mobilization of As and Pb was closely associated with the dissolution of soil-borne Fe, soil properties such as original soil pH, organic matter contents and the total amount of the element relative to the total Fe markedly complicated the mobility of that element. Aging led to continual consumption of proton introduced from addition of LMWOAs and consequently caused dramatic changes in solution-borne Fe, which in turn resulted in change in As and Pb in the soil solution though different elements behaved differently. Copyright © 2016 Elsevier Ltd. All rights reserved.

Processes of zinc attenuation by biogenic manganese oxides forming in the hyporheic zone of Pinal Creek, Arizona

USGS Publications Warehouse

Fuller, Christopher C.; Bargar, John R.

2014-01-01

The distribution and speciation of Zn sorbed to biogenic Mn oxides forming in the hyporheic zone of Pinal Creek, AZ, was investigated using extended X-ray absorption fine structure (EXAFS) and microfocused synchrotron X-ray fluorescence (μSXRF) mapping, and chemical extraction. μSXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and microfocused EXAFS spectra of Zn in the biogenic Mn oxide coating are indicative of Zn forming triple-corner-sharing inner-sphere complexes over octahedral vacancies in the Mn oxide sheet structure. Zn desorbed in response to the decrease in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in the solid/solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating that desorption is not controlled by dissolution of secondary Zn phases. In summary, these findings support the idea that Zn attenuation in Pinal Creek is largely controlled by sorption to microbial Mn oxides forming in the streambed during hyporheic exchange. Sorption to biogenic Mn oxides is likely an important process of Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present.

Vertical movement of iron-cyanide complexes in soils of a former Manufactured Gas Plant site

NASA Astrophysics Data System (ADS)

Sut, Magdalena; Repmann, Frank; Raab, Thomas

2015-04-01

In Germany, soil and groundwater at more than a thousand sites are contaminated with iron-cyanide complexes. These contaminations originate from the gas purification process that was conducted in Manufactured Gas Plants (MGP). The phenomenon of iron-cyanide complexes mobility in soil, according to the literature, is mainly governed by the dissolution and precipitation of ferric ferrocyanide, which is only slightly soluble (< 1 mg L-1) under acidic conditions. This study suggests vertical transport of a colloidal ferric ferrocyanide, in the excess of iron and circum-neutral pH conditions, as an alternative process that influences the retardation of the pollutant movement through the soil profile. Preliminary in situ investigations of the two boreholes implied transport of ferric ferricyanide from the initial deposition in the wastes layer towards the sandy loam material (secondary accumulation), which possibly retarded the mobility of cyanide (CN). The acidic character of the wastes and the accumulation of the blue patches suggested the potential filter function of a sandy loam material due to colloidal transport of the ferric ferricyanide. Series of batch and column experiments, using sandy loam soil, revealed reduction of CN concentration due to mechanical filtration of precipitated solid iron-cyanide complexes and due to the formation of potassium manganese iron-cyanide (K2Mn[Fe(CN)6]).

Surfactant mediated enhanced biodegradation of hexachlorocyclohexane (HCH) isomers by Sphingomonas sp. NM05.

PubMed

Manickam, Natesan; Bajaj, Abhay; Saini, Harvinder S; Shanker, Rishi

2012-09-01

Environmental biodegradation of several chlorinated pesticides is limited by their low solubility and sorption to soil surfaces. To mitigate this problem we quantified the effect of three biosurfactant viz., rhamnolipid, sophorolipid and trehalose-containing lipid on the dissolution, bioavailability, and biodegradation of HCH-isomers in liquid culture and in contaminated soil. The effect of biosurfactants was evaluated through the critical micelle concentration (CMC) value as determined for each isomer. The surfactant increased the solubilization of HCH isomers by 3-9 folds with rhamnolipid and sophorolipid being more effective and showing maximum solubilization of HCH isomers at 40 μg/mL, compared to trehalose-containing lipid showing peak solubilization at 60 μg/mL. The degradation of HCH isomers by Sphingomonas sp. NM05 in surfactant-amended liquid mineral salts medium showed 30% enhancement in 2 days as compared to degradation in 10 days in the absence of surfactant. HCH-spiked soil slurry incubated with surfactant also showed around 30-50% enhanced degradation of HCH which was comparable to the corresponding batch culture experiments. Among the three surfactants, sophorolipid offered highest solubilization and enhanced degradation of HCH isomers both in liquid medium and soil culture. The results of this study suggest the effectiveness of surfactants in improving HCH degradation by increased bioaccessibility.

Reactive Transport at the Pore Scale with Applications to the Dissolution of Carbonate Rocks for CO2 Sequestration Operations

NASA Astrophysics Data System (ADS)

Boek, E.; Gray, F.; Welch, N.; Shah, S.; Crawshaw, J.

2014-12-01

In CO2 sequestration operations, CO2 injected into a brine aquifer dissolves in the liquid to create an acidic solution. This may result in dissolution of the mineral grains in the porous medium. Experimentally, it is hard to investigate this process at the pore scale. Therefore we develop a new hybrid particle simulation algorithm to study the dissolution of solid objects in a laminar flow field, as encountered in porous media flow situations. First, we calculate the flow field using a multi-relaxation-time lattice Boltzmann (LB) algorithm implemented on GPUs, which demonstrates a very efficient use of the GPU device and a considerable performance increase over CPU calculations. Second, using a stochastic particle approach, we solve the advection-diffusion equation for a single reactive species and dissolve solid voxels according to our reaction model. To validate our simulation, we first calculate the dissolution of a solid sphere as a function of time under quiescent conditions. We compare with the analytical solution for this problem [1] and find good agreement. Then we consider the dissolution of a solid sphere in a laminar flow field and observe a significant change in the sphericity with time due to the coupled dissolution - flow process. Second, we calculate the dissolution of a cylinder in channel flow in direct comparison with corresponding dissolution experiments. We discuss the evolution of the shape and dissolution rate. Finally, we calculate the dissolution of carbonate rock samples at the pore scale in direct comparison with micro-CT experiments. This work builds on our recent research on calculation of multi-phase flow [2], [3] and hydrodynamic dispersion and molecular propagator distributions for solute transport in homogeneous and heterogeneous porous media using LB simulations [4]. It turns out that the hybrid simulation model is a suitable tool to study reactive flow processes at the pore scale. This is of great importance for CO2 storage and Enhanced Oil Recovery applications. References[1] Rice, R. G. and Do, D.D., Chem. Eng. Sci., 61, 775-778 (2006)[2] Boek, E.S. and Venturoli, M., Comp. and Maths with Appl. 59, 2305-2314 (2010)[3] Yang, J. and Boek, E.S., Comp. and Maths with Appl. 65, 882-890 (2013)[4] Yang, J. Crawshaw, J. and Boek, E.S., Water Resources Research 49, 8531-8538 (2013)

NaK pool-boiler solar receiver durability bench test. Volume 2: Metallurgical analysis

NASA Astrophysics Data System (ADS)

Goods, S. H.; Bradshaw, R. W.

1995-01-01

The principal materials used in the construction of a NaK based pool-boiler were analyzed. The device, operated for 7500 hours, accumulated 1000 thermal cycles to a peak temperature of 750 C. Haynes 230, used to fabricate the pool-boiler vessel, was found to perform satisfactorily. Air-side corrosion of the pool-boiler vessel was insignificant. Internal surface of the alloy exhibited some NaK-induced elemental dissolution; this dissolution was somewhat more extensive where the alloy was exposed to the liquid metal compared to regions exposed only to NaK vapor; however, the corresponding metal loss in all regions was inconsequential, never exceeding more than a few microns. Autogenous seam welds of the alloy responded in a similar fashion, exhibiting only minimal metal loss over the course of the experiment. While there was 50% loss in ductility of the alloy there remained adequate ductility for the anticipated operating environment. An enhanced boiling nucleation surface comprised of stainless steel powder brazed to the vessel ID showed no change in its structure. It remained intact, showing no cracking after repeated thermal cycling. Other materials used in the experiment showed more extensive degradation after exposure to the NaK. IN 600, used to fabricate thermowells, exhibited extensive surface and intergranular dissolution. Grain boundary dissolution was sufficiently severe in one of the thermowells to cause an air leak, resulting in experiment termination. BNi-3, a brazing alloy used to join the pool-boiler vessel, endcaps and thermowells, showed some dissolution where it was exposed to the NaK as well as thermal aging effects. However, all brazes remained structurally sound. A nickel metal ribbon showed catastrophic dissolution, resulting in the formation of deep (greater than 30 (mu)m) pits and cavities. A zirconium metal foil used to getter oxygen from the NaK became extremely brittle.

Experimental study on anomalous neutron production in deuterium/solid system

NASA Astrophysics Data System (ADS)

He, Jianyu; Zhu, Rongbao; Wang, Xiaozhong; Lu, Feng; Luo, Longjun; Liu, Hengjun; Jiang, Jincai; Tian, Baosheng; Chen, Guoan; Yuan, Yuan; Dong, Baiting; Yang, Liucheng; Qiao, Shengzhong; Yi, Guoan; Guo, Hua; Ding, Dazhao; Menlove, H. O.

1991-05-01

A series of experiments on both D2O electrolysis and thermal cycle of deuterium absorbed Ti Turnings has been designed to examine the anomalous phenomena in Deuterium/Solid System. A neutron detector containing 16 BF3 tubes with a detection limit of 0.38 n/s for two hour counting was used for electrolysis experiments. No neutron counting rate statistically higher than detection limit was observed from Fleischmann & Pons type experiments. An HLNCC neutron detector equipped with 18 3He tubes and a JSR-11 shift register unit with a detection limit of 0.20 n/s for a two hour run was employed to study the neutron signals in D2 gas experiments. Different material pretreatments were selected to review the changes in frequency and size of the neutron burst production. Experiment sequence was deliberately designed to distinguish the neutron burst from fake signals, e.g. electronic noise pickup, the cosmic rays and other sources of environmental background. Ten batches of dry fusion samples were tested, among them, seven batches with neutron burst signals occurred roughly at the temperature from -100 degree centigrade to near room temperature. In the first four runs of a typical sample batch, seven neutron bursts were observed with neutron numbers from 15 to 482, which are 3 and 75 times, respectively, higher than the uncertainty of background. However, no bursts happened for H2 dummy samples running in-between and afterwards and for sample batch after certain runs.

Phosphate-Induced Immobilization of Uranium in Hanford Sediments.

PubMed

Pan, Zezhen; Giammar, Daniel E; Mehta, Vrajesh; Troyer, Lyndsay D; Catalano, Jeffrey G; Wang, Zheming

2016-12-20

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred only at high initial U(VI) (>25 μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.

Phosphate-Induced Immobilization of Uranium in Hanford Sediments

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

Pan, Zezhen; Giammar, Daniel E.; Mehta, Vrajesh

2016-12-20

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred onlymore » at high initial U(VI) (>25 μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.« less

Phosphate-Induced Immobilization of Uranium in Hanford Sediments

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

Pan, Zezhen; Giammar, Daniel E.; Mehta, Vrajesh

2016-12-20

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred onlymore » at high initial U(VI) (>25μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.« less

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Autotrophic denitrification supported by biotite dissolution in crystalline aquifers: (2) transient mixing and denitrification dynamic during long-term pumping.

PubMed

Roques, Clément; Aquilina, Luc; Boisson, Alexandre; Vergnaud-Ayraud, Virginie; Labasque, Thierry; Longuevergne, Laurent; Laurencelle, Marc; Dufresne, Alexis; de Dreuzy, Jean-Raynald; Pauwels, Hélène; Bour, Olivier

2018-04-01

We investigated the mixing and dynamic of denitrification processes induced by long-term pumping in the crystalline aquifer of Ploemeur (Brittany, France). Hydrological and geochemical parameters have been continuously recorded over 15 boreholes in 5km 2 on a 25-year period. This extensive spatial and temporal monitoring of conservative as well as reactive compounds is a key opportunity to identify aquifer-scale transport and reactive processes in crystalline aquifers. Time series analysis of the conservative elements recorded at the pumped well were used to determine mixing fractions from different compartments of the aquifer on the basis of a Principal Component Analysis approach coupled with an end-member mixing analysis. We could reveal that pumping thus induces a thorough reorganization of fluxes known as capture, favoring infiltration and vertical fluxes in the recharge zone, and upwelling of deep and distant water at long-term time scales. These mixing fractions were then used to quantify the extent of denitrification linked to pumping. Based on the results from batch experiments described in a companion paper, our computations revealed that i) autotrophic denitrification processes are dominant in this context where carbon sources are limited, that ii) nitrate reduction does not only come from the oxidation of pyrite as classically described in previous studies analyzing denitrification processes in similar contexts, and that iii) biotite plays a critical role in sustaining the nitrate reduction process. Both nitrate reduction, sulfate production as well as fluor release ratios support the hypothesis that biotite plays a key role of electron donor in this context. The batch-to-site similarities support biotite availability and the role by bacterial communities as key controls of nitrate removal in such crystalline aquifers. However, the long term data monitoring also indicates that mixing and reactive processes evolve extremely slowly at the scale of the decade. Copyright © 2017 Elsevier B.V. All rights reserved.

Porous Chromatographic Materials as Substrates for Preparing Synthetic Nuclear Explosion Debris Particles

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

Harvey, Scott D.; Liezers, Martin; Antolick, Kathryn C.

2013-06-13

In this study, we investigated several porous chromatographic materials as synthetic substrates for preparing surrogate nuclear explosion debris particles. The resulting synthetic debris materials are of interest for use in developing analytical methods. Eighteen metals, including some of forensic interest, were loaded onto materials by immersing them in metal solutions (556 mg/L of each metal) to fill the pores, applying gentle heat (110°C) to drive off water, and then treating them at high temperatures (up to 800°C) in air to form less soluble metal species. High-boiling-point metals were uniformly loaded on spherical controlled-pore glass to emulate early fallout, whereas low-boiling-pointmore » metals were loaded on core-shell silica to represent coated particles formed later in the nuclear fallout-formation process. Analytical studies were applied to characterize solubility, material balance, and formation of recalcitrant species. Dissolution experiments indicated loading was 1.5 to 3 times higher than expected from the pore volume alone, a result attributed to surface coating. Analysis of load solutions before and after filling the material pores revealed that most metals were passively loaded; that is, solutions filled the pores without active metal discrimination. However, niobium and tin concentrations were lower in solutions after pore filling, and were found in elevated concentrations in the final products, indicating some metals were selectively loaded. High-temperature treatments caused reduced solubility of several metal species, and loss of some metals (rhenium and tellurium) because volatile species were formed. Sample preparation reproducibility was high (the inter-batch relative standard deviation was 7.8%, and the intra-batch relative standard deviation was 0.84%) indicating that this material is suitable for use as a working standard for analytical methods development. We anticipate future standardized radionuclide-loaded materials will find use in radioanalytical methods development and/or serve as a starting material for the synthesis of more complex forms of nuclear explosion debris (e.g., Trinitite).« less

Arsenic occurrence, mobility, and retardation in sandstone and dolomite formations of the Fox River Valley, Eastern Wisconsin.

PubMed

Thornburg, Katie; Sahai, Nita

2004-10-01

Elevated levels of groundwater arsenic (approximately 100 microg L(-1) = 1.3 x 10(-6) M) are found in the Fox River Valley, eastern Wisconsin. The goals of this study were to identifythe sources of As contamination and to determine the reactions responsible for As mobilization and retardation in areas lacking a discrete zone of As-enriched sulfides, shown previouslyto cause elevated arsenic in groundwater. Detailed mineralogical and chemical analyses were conducted on samples from the Sinnipee Group dolomite and St. Peter sandstone in eastern Wisconsin. Solution chemistry was monitored in batch reactions of dolomite, quartz, and sulfide mineral fractions with a 0.01 M CsCl solution at pH 7 for 3 weeks in air. Results indicate that arsenic is present in isomorphous substitution with pyrite/marcasite (FeS2), which occurs as disseminated veins, grains, and nodules in the dolomite and sandstone. The released As subsequently sorbs on the ferric oxyhydroxides formed or coprecipitates in a scorodite-like phase. Significantly, oxidative dissolution of the disseminated As-rich FeS2 grains and nodules is sufficient to explain the elevated As levels observed in eastern Wisconsin groundwater. Although complete uptake of As is observed in the batch experiments, persistent elevated As levels with spatial and temporal variations in regional groundwaters are attributed to differences in the type of sulfide occurrence (discrete horizon vs dispersed grains, veins, and nodules), variations in the dissolved oxygen content of the groundwater, and variable (limited) buildup of reacted surface layers on sulfide grains in the natural flow-through system. Discrete nanoparticulate As phases, As surface precipitates on sulfides, and sorbed As on dolomite and quartz are eliminated as major sources, and sorption of arsenic on dolomite and quartz is deemed less important than association with ferric oxyhydroxides for retardation in the regional system.

UPTAKE OF HEAVY METALS IN BATCH SYSTEMS BY A RECYCLED IRON-BEARING MATERIAL

EPA Science Inventory

An iron-bearing material deriving from surface finishing operations in the manufacturing of cast-iron components demonstrates potential for removal of heavy metals from aqueous waste streams. Batch isotherm and rate experiments were conducted for uptake of cadmium, zinc, and lead...

Finding the self by losing the self: Neural correlates of ego-dissolution under psilocybin.

PubMed

Lebedev, Alexander V; Lövdén, Martin; Rosenthal, Gidon; Feilding, Amanda; Nutt, David J; Carhart-Harris, Robin L

2015-08-01

Ego-disturbances have been a topic in schizophrenia research since the earliest clinical descriptions of the disorder. Manifesting as a feeling that one's "self," "ego," or "I" is disintegrating or that the border between one's self and the external world is dissolving, "ego-disintegration" or "dissolution" is also an important feature of the psychedelic experience, such as is produced by psilocybin (a compound found in "magic mushrooms"). Fifteen healthy subjects took part in this placebo-controlled study. Twelve-minute functional MRI scans were acquired on two occasions: subjects received an intravenous infusion of saline on one occasion (placebo) and 2 mg psilocybin on the other. Twenty-two visual analogue scale ratings were completed soon after scanning and the first principal component of these, dominated by items referring to "ego-dissolution", was used as a primary measure of interest in subsequent analyses. Employing methods of connectivity analysis and graph theory, an association was found between psilocybin-induced ego-dissolution and decreased functional connectivity between the medial temporal lobe and high-level cortical regions. Ego-dissolution was also associated with a "disintegration" of the salience network and reduced interhemispheric communication. Addressing baseline brain dynamics as a predictor of drug-response, individuals with lower diversity of executive network nodes were more likely to experience ego-dissolution under psilocybin. These results implicate MTL-cortical decoupling, decreased salience network integrity, and reduced inter-hemispheric communication in psilocybin-induced ego disturbance and suggest that the maintenance of "self"or "ego," as a perceptual phenomenon, may rest on the normal functioning of these systems. © 2015 Wiley Periodicals, Inc.

Biopharmaceutical characterisation of ciprofloxacin-metallic ion interactions: comparative study into the effect of aluminium, calcium, zinc and iron on drug solubility and dissolution.

PubMed

Stojković, Aleksandra; Tajber, Lidia; Paluch, Krzysztof J; Djurić, Zorica; Parojčić, Jelena; Corrigan, Owen I

2014-03-01

Ciprofloxacin bioavailability may be reduced when ciprofloxacin is co-administered with metallic ion containing preparations. In our previous study, physicochemical interaction between ciprofloxacin and ferrous sulphate was successfully simulated in vitro. In the present work, comparative in vitro ciprofloxacin solubility and dissolution studies were performed in the reactive media containing aluminium hydroxide, calcium carbonate or zinc sulphate. Solid phases collected from the dissolution vessel with aluminium hydroxide, calcium carbonate and zinc sulphate were investigated for their properties. The results obtained indicate that different types of adducts may form and retard ciprofloxacin solubility and dissolution. In the case of aluminium, no phase changes were observed. The solid phase generated in the presence of calcium carbonate was identified as hydrated ciprofloxacin base. Similarly to iron, a new complex consistent with Zn(SO4)2(Cl)2(ciprofloxacin)2 × nH2O stoichiometry was generated in the presence of relatively high concentrations of ciprofloxacin hydrochloride and zinc sulphate, indicating that small volume dissolution experiments can be useful for biorelevant dissolution tests.

Design, development, and optimization of polymeric based-colonic drug delivery system of naproxen.

PubMed

Sharma, Pooja; Chawla, Anuj; Pawar, Pravin

2013-01-01

The aim of present investigation deals with the development of time-dependent and pH sensitive press-coated tablets for colon specific drug delivery of naproxen. The core tablets were prepared by wet granulation method then press coated with hydroxypropyl cellulose (HPC) or Eudragit RSPO : RLPO mixture and further coated with Eudragit S-100 by dip immerse method. The in vitro drug release study was conducted in different dissolution media such as pH 1.2, 6.8, and 7.4 with or without rat caecal content to simulate GIT conditions. Surface morphology and cross-sectional view of the tablets were visualized by scanning electron microscopy (SEM). All prepared batches were in compliance with the pharmacopoeial standards. The tablets which are compression coated with HPC followed by Eudragit S-100 coated showed highest in vitro drug release of 98.10% in presence of rat caecal content. The SEM of tablets suggested that the number of pores got increased in pH 7.4 medium followed by dissolution of coating layer. The tablets coat erosion study suggested that the lag time depends upon the coating concentrations of polymers. A time-dependent hydrophilic polymer and pH sensitive polymer based press-coated tablets of naproxen were promising delivery for colon targeting.

Design, Development, and Optimization of Polymeric Based-Colonic Drug Delivery System of Naproxen

PubMed Central

Sharma, Pooja; Chawla, Anuj; Pawar, Pravin

2013-01-01

The aim of present investigation deals with the development of time-dependent and pH sensitive press-coated tablets for colon specific drug delivery of naproxen. The core tablets were prepared by wet granulation method then press coated with hydroxypropyl cellulose (HPC) or Eudragit RSPO : RLPO mixture and further coated with Eudragit S-100 by dip immerse method. The in vitro drug release study was conducted in different dissolution media such as pH 1.2, 6.8, and 7.4 with or without rat caecal content to simulate GIT conditions. Surface morphology and cross-sectional view of the tablets were visualized by scanning electron microscopy (SEM). All prepared batches were in compliance with the pharmacopoeial standards. The tablets which are compression coated with HPC followed by Eudragit S-100 coated showed highest in vitro drug release of 98.10% in presence of rat caecal content. The SEM of tablets suggested that the number of pores got increased in pH 7.4 medium followed by dissolution of coating layer. The tablets coat erosion study suggested that the lag time depends upon the coating concentrations of polymers. A time-dependent hydrophilic polymer and pH sensitive polymer based press-coated tablets of naproxen were promising delivery for colon targeting. PMID:24198725

Dissolution testing and potentiometric determination of famciclovir in pure, dosage forms and biological fluids.

PubMed

Rezk, Mohamed S; El Nashar, Rasha M

2013-02-01

The performance characteristics of two new plastic membrane ion selective electrodes (ISEs) used for the determination of famciclovir (Fcv) based on the ion associate of Fcv with phosphotungstic acid (PTA) or phosphomolybdic acid (PMA) are described. Different experimental conditions as type of plasticizer to be incorporated in the membrane, life span, effect of soaking, pH, temperature, and interferences were studied. Both electrodes showed similar performance under these conditions, exhibiting Nernstian slopes of S (Fcv-PTA)=58.60±0.84 mV/decade and S (Fcv-PMA)=58.77±0.68 mV/decade within a usable concentration range of 10⁻⁵-10⁻² [Fcv/M] at 298/K. Famciclovir was assayed potentiometrically in its pure solution, pharmaceutical preparations and biological fluids (urine and plasma) using proposed electrodes under batch and flow injection analysis (FIA) conditions with a recovery % ranging between 96.76% and 102.83% having RSD of 0.66%-1.81%. The electrodes were also successfully applied in the determination of the dissolution profile of Fcv tablets and the results came in agreement with the validated results of the HPLC method obtained from the quality control unit of the company producing the tablets. Copyright © 2012 Elsevier B.V. All rights reserved.

Biodegradation of pharmaceuticals in hospital wastewater by staged Moving Bed Biofilm Reactors (MBBR).

PubMed

Casas, Mònica Escolà; Chhetri, Ravi Kumar; Ooi, Gordon; Hansen, Kamilla M S; Litty, Klaus; Christensson, Magnus; Kragelund, Caroline; Andersen, Henrik R; Bester, Kai

2015-10-15

Hospital wastewater represents a significant input of pharmaceuticals into municipal wastewater. As Moving Bed Biofilm Reactors (MBBRs) appear to remove organic micro-pollutants, hospital wastewater was treated with a pilot plant consisting of three MBBRs in series. The removal of pharmaceuticals was studied in two experiments: 1) A batch experiment where pharmaceuticals were spiked to each reactor and 2) a continuous flow experiment at native concentrations. DOC removal, nitrification as well as removal of pharmaceuticals (including X-ray contrast media, β-blockers, analgesics and antibiotics) occurred mainly in the first reactor. In the batch experiment most of the compounds followed a single first-order kinetics degradation function, giving degradation rate constants ranged from 5.77 × 10(-3) to 4.07 h(-1), from -5.53 × 10(-3) to 9.24 × 10(-1) h(-1) and from 1.83 × 10(-3) to 2.42 × 10(-1) h(-1) for first, second and third reactor respectively. Generally, the highest removal rate constants were found in the first reactor while the lowest were found in the third one. This order was inverted for most compounds, when the removal rate constants were normalized to biomass, indicating that the last tank had the most effective biofilms. In the batch experiment, 21 out of 26 compounds were assessed to be degraded with more than 20% within the MBBR train. In the continuous flow experiment the measured removal rates were lower than those estimated from the batch experiments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Deposition and transport of Pseudomonas aeruginosa in porous media: lab-scale experiments and model analysis.

PubMed

Kwon, Kyu-Sang; Kim, Song-Bae; Choi, Nag-Choul; Kim, Dong-Ju; Lee, Soonjae; Lee, Sang-Hyup; Choi, Jae-Woo

2013-01-01

In this study, the deposition and transport of Pseudomonas aeruginosa on sandy porous materials have been investigated under static and dynamic flow conditions. For the static experiments, both equilibrium and kinetic batch tests were performed at a 1:3 and 3:1 soil:solution ratio. The batch data were analysed to quantify the deposition parameters under static conditions. Column tests were performed for dynamic flow experiments with KCl solution and bacteria suspended in (1) deionized water, (2) mineral salt medium (MSM) and (3) surfactant + MSM. The equilibrium distribution coefficient (K(d)) was larger at a 1:3 (2.43 mL g(-1)) than that at a 3:1 (0.28 mL g(-1)) soil:solution ratio. Kinetic batch experiments showed that the reversible deposition rate coefficient (k(att)) and the release rate coefficient (k(det)) at a soil:solution ratio of 3:1 were larger than those at a 1:3 ratio. Column experiments showed that an increase in ionic strength resulted in a decrease in peak concentration of bacteria, mass recovery and tailing of the bacterial breakthrough curve (BTC) and that the presence of surfactant enhanced the movement of bacteria through quartz sand, giving increased mass recovery and tailing. Deposition parameters under dynamic condition were determined by fitting BTCs to four different transport models, (1) kinetic reversible, (2) two-site, (3) kinetic irreversible and (4) kinetic reversible and irreversible models. Among these models, Model 4 was more suitable than the others since it includes the irreversible sorption term directly related to the mass loss of bacteria observed in the column experiment. Applicability of the parameters obtained from the batch experiments to simulate the column breakthrough data is evaluated.

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

PubMed

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

2017-11-01

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

Repartnering and (Re)employment: Strategies to Cope with the Economic Consequences of Partnership Dissolution

ERIC Educational Resources Information Center

Jansen, Mieke; Mortelmans, Dimitri; Snoeckx, Laurent

2009-01-01

The economic consequences of a partnership dissolution have been described consistently in the research literature. For women all studies indicate severe financial losses, whereas men do not experience income decreases to the same extent. This article focuses on the 2 main strategies to cope with the economic consequences of a separation:…

Comparative study of the influence of natural convection on directional solidification of Al 3.5 wt% Ni and Al 7 wt% Si alloys

NASA Astrophysics Data System (ADS)

Zhou, B. H.; Jung, H.; Mangelinck-Noël, N.; Nguyen-Thi, H.; Billia, B.; Liu, Q. S.; Lan, C. W.

We present numerical simulations of thermosolutal convection for directional solidification of Al 3.5 wt% Ni and Al 7 wt% Si. Numerical results predict that fragmentation of dendrite arms resulting from dissolution could be favored in Al 7 wt% Si, but not in Al 3.5 wt% Ni. Corresponding experiments are in qualitative agreement with the numerical predictions. Distinguishing the two fragmentation mechanisms, namely dissolution and remelting, is critical during experiments on earth, when fluid flow is dominant.

Mixture experiment methods in the development and optimization of microemulsion formulations

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

Furlanetto, Sandra; Cirri, Marzia; Piepel, Gregory F.

2011-06-25

Microemulsion formulations represent an interesting delivery vehicle for lipophilic drugs, allowing for improving their solubility and dissolution properties. This work developed effective microemulsion formulations using glyburide (a very poorly-water-soluble hypoglycaemic agent) as a model drug. First, the area of stable microemulsion (ME) formations was identified using a new approach based on mixture experiment methods. A 13-run mixture design was carried out in an experimental region defined by constraints on three components: aqueous, oil, and surfactant/cosurfactant. The transmittance percentage (at 550 nm) of ME formulations (indicative of their transparency and thus of their stability) was chosen as the response variable. Themore » results obtained using the mixture experiment approach corresponded well with those obtained using the traditional approach based on pseudo-ternary phase diagrams. However, the mixture experiment approach required far less experimental effort than the traditional approach. A subsequent 13-run mixture experiment, in the region of stable MEs, was then performed to identify the optimal formulation (i.e., having the best glyburide dissolution properties). Percent drug dissolved and dissolution efficiency were selected as the responses to be maximized. The ME formulation optimized via the mixture experiment approach consisted of 78% surfactant/cosurfacant (a mixture of Tween 20 and Transcutol, 1:1 v/v), 5% oil (Labrafac Hydro) and 17% aqueous (water). The stable region of MEs was identified using mixture experiment methods for the first time.« less

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.

Impact of dissolution and carbonate precipitation on carbon storage in basalt

NASA Astrophysics Data System (ADS)

Wells, R. K.; Xiong, W.; Tadeoye, J.; Menefee, A.; Ellis, B. R.; Skemer, P. A.; Giammar, D.

2016-12-01

The spatial evolution of silicate mineral dissolution, carbonate precipitation, and the transport of fluids influence the viability of carbon storage in basalt reservoirs. Dissolution of natural basalt and subsequent carbonate precipitation in systems with different transport processes operating were characterized using static and flow-through (5 mL/hr) experiments at 50, 100, and 150 °C, and 100 bar CO2. Intact samples and cores with milled pathways that simulate fractures were tested. Spatial and mineralogical patterns in dissolution and precipitation were analyzed using optical and electron microscopy, microCT scanning, and surface roughness data. Precipitates and fluid chemistry were analyzed using Raman spectroscopy, SEM-EDS, and ICP-MS. Analysis of the bulk solution and surface topography suggests dissolution of olivine and pyroxene grains begins within hours of the start of the experiments. In flow-through experiments, total effluent cation concentrations reach a peak concentration within a few hours then drop towards a steady state within a few days. In static experiments, the initial rate of cation release is faster than it is after several weeks. In both cases Ca2+, Mg2+, and Fe2+ are the dominant cations in solution in the initial stages of reaction. Lower concentrations of Na2+, K+, and Al3+, and the preservation of feldspar and matrix grains after several weeks of reaction indicate the slow reactivity of these minerals. As the reaction progresses, the surface roughness increases steadily with cavities developing at the sites of olivine and pyroxene grains. Post-reaction analysis of basalt samples reacted at static conditions with milled pathways reveals that both siderite and amorphous silica precipitated within diffusion-limited zones as early as 4-6 weeks. Siderite abundance varies with distance along the pathway with the highest concentration of carbonates 1-2 cm below the fracture opening. Siderite precipitates are large enough to fill fracture opening 100 μm wide within 4-6 weeks.

Photometric determination of phosphorus in mineralized biodiesel using a micro-flow-batch analyzer with solenoid micro-pumps.

PubMed

Lima, Marcelo B; Barreto, Inakã S; Andrade, Stéfani Iury E; Neta, Maria S S; Almeida, Luciano F; Araújo, Mário C U

2012-08-30

A method for the determination of phosphorus in mineralized biodiesel using a micro-flow-batch analyzer (μFBA) with solenoid micro-pumps was proposed. The samples were mineralized using an ashing procedure at 550 °C followed by dissolution of the residue. The determination of phosphorus was performed by employing the well-known molybdenum blue method. The measures of the absorbance were performed at 850 nm using an InfraRed LED integrated into the μFBA. Comparing with the reference method, no statistically significant differences were observed when applying the paired t-test at a 95% confidence level. Recovery study shows results between 97.9% and 105.8%. The proposed microsystem using solenoid micro-pumps presented satisfactory robustness and high sampling rate (190 h(-1)), with satisfactory reproducibility (relative standard deviation <4.5%, n=3), low reagents consumption (32 μL per analysis) and cost to build the device. Moreover, μFBA presents limit of detection (0.014 mg Kg(-1)), precision and accuracy compatible with the biodiesel regulations that establish a maximum concentration of 10 mg Kg(-1) (Brazil, USA, EU), suggesting that it is a good alternative for the determination of phosphorus in biodiesel. Copyright © 2012 Elsevier B.V. All rights reserved.

Sludge granulation and performance of a low superficial gas velocity sequencing batch reactor (SBR) in the treatment of prepared sanitary wastewater.

PubMed

Ji, Guodong; Zhai, Fengmin; Wang, Rongjing; Ni, Jinren

2010-12-01

A sequencing batch reactor (SBR) employing a low superficial gas velocity was used to produce aerobic granular sludge for wastewater treatment. At a gas velocity of 0.0056 m s(-1) sludge containing a mixture of light yellow and black granules with similar functional groups was quickly formed. The black granules contained crystals of CaCO(3), FeS, and Fe(2)O(3) as well as filamentous bacteria that strengthened the particles and reduced the mass transfer resistance. No inorganic crystals were detected in the yellow sludge granules, and their structure was maintained through cohesion mediated by extracellular polymeric substances (EPS). The light yellow granules were denser and offered better settling performance than the black granules, enhancing the settling properties of the mixed sludge. During a 12-h cycle, the maximum reductions in chemical oxygen demand (COD), NH(3)-N, and total nitrogen (TN) occurred at 240, 480, and 360 min with removal efficiencies of 90%, 90%, and 54%. When the cycle time was limited to 480 min, self-dissolution of the granules was avoided while sill maintaining removal efficiencies for COD, NH(3)-N, and TN of 88%, 90%, and 53%. 2010 Elsevier Ltd. All rights reserved.

Impact of microbial communities from tropical soils on the mobilization of trace metals during dissolution of cinnabar ore.

PubMed

Balland-Bolou-Bi, Clarisse; Turc, Benjamin; Alphonse, Vanessa; Bousserrhine, Noureddine

2017-06-01

Biodissolution experiments on cinnabar ore (mercury sulphide and other sulphide minerals, such as pyrite) were performed with microorganisms extracted directly from soil. These experiments were carried out in closed systems under aerobic and anaerobic conditions with 2 different soils sampled in French Guyana. The two main objectives of this study were (1) to quantify the ability of microorganisms to mobilize metals (Fe, Al, Hg) during the dissolution of cinnabar ore, and (2) to identify the links between the type and chemical properties of soils, environmental parameters such as season and the strategies developed by indigenous microorganisms extracted from tropical natural soils to mobilize metals. Results indicate that microbial communities extracted directly from various soils are able to (1) survive in the presence of cinnabar ore, as indicated by consumption of carbon sources and, (2) leach Hg from cinnabar in oxic and anoxic dissolution experiments via the acidification of the medium and the production of low molecular mass organic acids (LMMOAs). The dissolution rate of cinnabar in aerobic conditions with microbial communities ranged from 4.8×10 -4 to 2.6×10 -3 μmol/m 2 /day and was independent of the metabolites released by the microorganisms. In addition, these results suggest an indirect action by the microorganisms in the cinnabar dissolution. Additionally, because iron is a key element in the dynamics of Hg, microbes were stimulated by the presence of this metal, and microbes released LMMOAs that leached iron from iron-bearing minerals, such as pyrite and oxy-hydroxide of iron, in the mixed cinnabar ore. Copyright © 2016. Published by Elsevier B.V.

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.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

The release of nutritive elements through apatite dissolution represents the main source of phosphorus, calcium, and several micronutrients (e.g., Zn, Cu) for organisms in non-fertilized forest ecosystems. The aim of this study was to quantify, for the first time, the dissolution rate of apatite grains by tree roots that were or were not associated with a mineral weathering bacterial strain, and by various acids known to be produced by tree roots and soil bacterial strains in open-system flow microcosms. In addition, we explored whether the mobilization of trace elements (including rare earth elements) upon apatite dissolution was affected by the presence of trees and associated microorganisms. The dissolution rate of apatite by Scots pine plants that were or were not inoculated with the strain Burkholderia glathei PML1(12)Rp, and by inorganic (nitric) and organic (citric, oxalic and gluconic) acids at pH 5.5, 4.8, 3.8, 3.5, 3.0, and 2.0 was monitored in two controlled experiments: "plant-bacteria interaction" and "inorganic and organic acids". Analyses of the outlet solutions in the "plant-bacteria interaction" experiment showed that Scots pine roots and B. glathei PML1(12)Rp produced protons and organic acids such as gluconate, oxalate, acetate, and lactate. The weathering budget calculation revealed that Scots pines (with or without PML1(12)Rp) significantly increased (factor > 10) the release of Ca, P, As, Sr, Zn, U, Y, and rare earth elements such as Ce, La, Nd from apatite, compared to control abiotic treatment. Scanning electron microscopy observation confirmed traces of apatite dissolution in contact of roots. Most dissolved elements were taken up by Scots pine roots, i.e., approximately 50% of Ca, 70% of P, 30% of As, 70% of Sr, 90% of Zn, and 100% of U, Y, and rare earth elements. Interestingly, no significant additional effect due to the bacterial strain PML1(12)Rp on apatite dissolution and Scots pine nutrition and growth was observed. The "inorganic and organic acids" experiment demonstrated that the apatite dissolution efficacy of organic acids was higher than for the inorganic acid and varied in function of the acids: oxalic acid > citric acid > gluconic acid > nitric acid for pH ⩽3.5. In addition, apatite dissolution increased with increasing acidity for each acid. Only oxalic acid generated non-stoichiometric release of calcium and phosphorus from apatite in the solution at pH ⩽3.5, due to the precipitation of Ca-oxalate crystals at apatite surfaces. Comparison of the experiments revealed that the apatite dissolution rate by Scots pines supplied with nutritive solution at pH 5.5 reached 2.0 × 10-13 mol cm-2 s-1 and was equivalent to rates with nitric acid at pH 3.2, gluconic acid at pH 3.5, citric acid at pH 3.7, and oxalic acid at pH 3.8. Altogether our results highlight that, through the production of weathering agents, notably protons and organic acids, tree roots and root-associated microorganisms are able to significantly increase the release of macro- and micro-nutrients from apatite, thus maintaining high-nutrient conditions to support their growth.

Observations of magnetite dissolution in poorly drained soils

USGS Publications Warehouse

Grimley, D.A.; Arruda, N.K.

2007-01-01

Dissolution of strongly magnetic minerals is a common and relatively rapid phenomenon in poorly drained soils of the central United States, resulting in low magnetic susceptibility (MS). Low Eh reducing conditions are primarily responsible for magnetic mineral dissolution; a process likely mediated by iron-reducing bacteria in the presence of soil organic matter. Based on transects across drainage sequences from nine sites, natural magnetic minerals (>5 ??m) extracted from surface soil consist of 54% ?? 18% magnetite, 21% ?? 11% titanomagnetite, and 17% ?? 14% ilmenite. Magnetite and titanomagnetite dissolution, assessed by scanning electron microscopy on a 0-to-3 scale, inversely correlates with surface soil MS (r = 0.53), a proxy for soil drainage at studied transects. Altered magnetite typically displays etch pits 5 ??m) include 26% ?? 18% anthropogenic fly ash that also exhibits greater dissolution in low MS soils (r = 0.38), indicating detectable alteration can occur within 150 years in low Eh soils. Laboratory induced reduction of magnetite, titanomagnetite, and magnetic fly ash, with a citrate-bicarbonate- dithionite solution, resulted in dissolution textures similar to those of in situ soil particles. Although experiments indicate that reductive dissolution of magnetite can occur abiotically under extreme conditions, bacteria likely play an important role in the natural environment. ?? 2007 Lippincott Williams & Wilkins, Inc.

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.

In-syringe extraction using dissolvable layered double hydroxide-polymer sponges templated from hierarchically porous coordination polymers.

PubMed

Ghani, Milad; Frizzarin, Rejane M; Maya, Fernando; Cerdà, Víctor

2016-07-01

Herein we report the use of cobalt porous coordination polymers (PCP) as intermediates to prepare advanced extraction media based on layered double hydroxides (LDH) supported on melamine polymer foam. The obtained dissolvable Ni-Co LDH composite sponges can be molded and used as sorbent for the in-syringe solid-phase extraction (SPE) of phenolic acids from fruit juices. The proposed sorbent is obtained due to the surfactant-assisted self-assembly of Co(II)/imidazolate PCPs on commercially available melamine foam, followed by the in situ conversion of the PCP into the final dissolvable LDH coating. Advantageous features for SPE are obtained by using PCPs with hierarchical porosity (HPCPs). The LDH-sponge prepared using intermediate HPCPs (HLDH-sponge) is placed in the headspace of a glass syringe, enabling flow-through extraction followed by analyte elution by the dissolution of the LDH coating in acidic conditions. Three phenolic acids (gallic acid, p-hydroxybenzoic acid and caffeic acid) were extracted and quantified using high performance liquid chromatography. Using a 5mL sample volume, the obtained detection limits were 0.15-0.35μgL(-1). The proposed method for the preparation of HLDH-sponges showed a good reproducibility as observed from the intra- and inter-day RSD's, which were <10% for all analytes. The batch-to-batch reproducibility for three different batches of HLDH-sponges was 10.6-11.2%. Enrichment factors of 15-21 were obtained. The HLDH-sponges were applied satisfactorily to the determination of phenolic acids in natural and commercial fruit juices, obtaining relative recoveries among 89.7-95.3%. Copyright © 2016 Elsevier B.V. All rights reserved.

Numerical Simulation of Tuff Dissolution and Precipitation Experiments: Validation of Thermal-Hydrologic-Chemical (THC) Coupled-Process Modeling

NASA Astrophysics Data System (ADS)

Dobson, P. F.; Kneafsey, T. J.

2001-12-01

As part of an ongoing effort to evaluate THC effects on flow in fractured media, we performed a laboratory experiment and numerical simulations to investigate mineral dissolution and precipitation. To replicate mineral dissolution by condensate in fractured tuff, deionized water equilibrated with carbon dioxide was flowed for 1,500 hours through crushed Yucca Mountain tuff at 94° C. The reacted water was collected and sampled for major dissolved species, total alkalinity, electrical conductivity, and pH. The resulting steady-state fluid composition had a total dissolved solids content of about 140 mg/L; silica was the dominant dissolved constituent. A portion of the steady-state reacted water was flowed at 10.8 mL/hr into a 31.7-cm tall, 16.2-cm wide vertically oriented planar fracture with a hydraulic aperture of 31 microns in a block of welded Topopah Spring tuff that was maintained at 80° C at the top and 130° C at the bottom. The fracture began to seal within five days. A 1-D plug-flow model using the TOUGHREACT code developed at Berkeley Lab was used to simulate mineral dissolution, and a 2-D model was developed to simulate the flow of mineralized water through a planar fracture, where boiling conditions led to mineral precipitation. Predicted concentrations of the major dissolved constituents for the tuff dissolution were within a factor of 2 of the measured average steady-state compositions. The fracture-plugging simulations result in the precipitation of amorphous silica at the base of the boiling front, leading to a hundred-fold decrease in fracture permeability in less than 6 days, consistent with the laboratory experiment. These results help validate the use of the TOUGHREACT code for THC modeling of the Yucca Mountain system. The experiment and simulations indicate that boiling and concomitant precipitation of amorphous silica could cause significant reductions in fracture porosity and permeability on a local scale. The TOUGHREACT code will be used to evaluate larger-scale silica sealing observed in a portion of the Yellowstone geothermal system, a natural analog for the precipitation-experiment processes.

VERIFICATION OF THE DEFENSE WASTE PROCESSING FACILITY PROCESS DIGESTION METHOD FOR THE SLUDGE BATCH 6 QUALIFICATION SAMPLE

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

Click, D.; Jones, M.; Edwards, T.

2010-06-09

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) confirms applicability of the digestion method to be used by the DWPF lab for elemental analysis of Sludge Receipt and Adjustment Tank (SRAT) receipt samples and SRAT product process control samples.1 DWPF SRAT samples are typically dissolved using a room temperature HF-HNO3 acid dissolution (i.e., DWPF Cold Chem (CC) Method, see DWPF Procedure SW4-15.201) and then analyzed by inductively coupled plasma - atomic emission spectroscopy (ICPAES). In addition to the CC method confirmation, the DWPF lab's mercury (Hg) digestion methodmore » was also evaluated for applicability to SB6 (see DWPF procedure 'Mercury System Operating Manual', Manual: SW4-15.204. Section 6.1, Revision 5, Effective date: 12-04-03). This report contains the results and comparison of data generated from performing the Aqua Regia (AR), Sodium Peroxide/Hydroxide Fusion (PF) and DWPF Cold Chem (CC) method digestion of Sludge Batch 6 (SB6) SRAT Receipt and SB6 SRAT Product samples. For validation of the DWPF lab's Hg method, only SRAT receipt material was used and compared to AR digestion results. The SB6 SRAT Receipt and SB6 SRAT Product samples were prepared in the SRNL Shielded Cells, and the SRAT Receipt material is representative of the sludge that constitutes the SB6 Batch or qualification composition. This is the sludge in Tank 51 that is to be transferred into Tank 40, which will contain the heel of Sludge Batch 5 (SB5), to form the SB6 Blend composition. In addition to the 16 elements currently measured by the DWPF, this report includes Hg and thorium (Th) data (Th comprising {approx}2.5 - 3 Wt% of the total solids in SRAT Receipt and SRAT Product, respectively) and provides specific details of ICP-AES analysis of Th. Thorium was found to interfere with the U 367.007 nm emission line, and an inter-element correction (IEC) had to be applied to U data, which is also discussed. The results for any one particular element should not be used in any way to identify the form or speciation of a particular element without support from XRD analysis or used to estimate ratios of compounds in the sludge.« less

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

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.

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.

Determination of oxidant exposure during ozonation of secondary effluent to predict contaminant removal.

PubMed

Zucker, Ines; Avisar, Dror; Mamane, Hadas; Jekel, Martin; Hübner, Uwe

2016-09-01

The use of kinetic models to predict oxidation performance in wastewater is limited due to fast ozone depletion during the first milliseconds of the reaction. This paper introduces the Quench Flow Module (QFM), a bench-scale experimental technique developed to measure the first 5-500 milliseconds of ozone depletion for accurate determination of ozone exposure in wastewater-ozonation processes. Calculated ozone exposure in QFM experiments was up to 24% lower than in standard batch experiments, strongly depending on the initial sampling point for measurement in batch experiments. However, oxidation rates of slowly- and moderately-reacting trace organic compounds (TrOCs) were accurately predicted from batch experiments based on integration of ozone depletion and removal of an ozone-resistant probe compound to calculate oxidant exposures. An alternative concept, where ozone and hydroxyl radical exposures are back-calculated from the removal of two probe compounds, was tested as well. Although the QFM was suggested to be an efficient mixing reactor, ozone exposure ranged over three orders of magnitude when different probe compounds reacting moderately with ozone were used for the calculation. These effects were beyond uncertainty ranges for apparent second order rate constants and consistently observed with different ozone-injection techniques, i.e. QFM, batch experiments, bubble columns and venturi injection. This indicates that previously suggested mixing effects are not responsible for the difference and other still unknown factors might be relevant. Results furthermore suggest that ozone exposure calculations from the relative residual concentration of a probe compound are not a promising option for evaluation of ozonation of secondary effluents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Growth of Coccolithophores Controlled by Internal Nutrient Stores in Light- and Nutrient-Limited Batch Reactors: Relevance for the BIOSOPE Deep Ecological Niche of Coccolithophores.

NASA Astrophysics Data System (ADS)

Laura, P.; Probert, I.; Langer, G.; Aloisi, G.

2016-02-01

Coccolithophores are unicellular, calcifying marine algae that play a fundamental role in the oceanic carbon cycle. Recent research has focused on investigating the effect of ocean acidification on cellular calcification. However, the success of this important phytoplankton group in the future ocean will depend on how cellular growth reacts to changes in a combination of environmental variables. We carried out batch culture experiments in conditions of light- and nutrient- (nitrate and phosphate) limitation that reproduce the in situ conditions of a deep ecological niche of coccolithophores in the South Pacific Gyre (BIOSOPE cruise, 2004). We modelled nutrient acquisition and cellular growth in our batch experiments using a Droop internal-stores model. We show that nutrient acquisition and growth are decoupled in coccolithophores; this ability may be key in making life possible in oligotrophic conditions such as the deep BIOSOPE biological niche. Combining the results of our culture experiments with those of Langer et al. (2013), we used the model to obtain estimates of fundamental physiological parameters such as the Monod constant for nutrient uptake, the maximum growth rate and the minimum cellular nutrient quota. These parameters are characteristic of different phytoplankton groups and are needed to simulate phytoplankton growth in biogeochemical models. Our results suggest that growth of coccolithophores in the BIOSOPE deep ecological niche is light-limited rather than nutrient-limited. Our work also shows that simple batch experiments and straightforward numerical modelling are capable of providing estimates of physiological parameters usually obtained in more costly and complicated chemostat experiments.

Fluoride and phosphate release from carbonate-rich fluorapatite during managed aquifer recharge

NASA Astrophysics Data System (ADS)

Schafer, David; Donn, Michael; Atteia, Olivier; Sun, Jing; MacRae, Colin; Raven, Mark; Pejcic, Bobby; Prommer, Henning

2018-07-01

Managed aquifer recharge (MAR) is increasingly used as a water management tool to enhance water availability and to improve water quality. Until now, however, the risk of fluoride release during MAR with low ionic strength injectate has not been recognised or examined. In this study we analyse and report the mobilisation of fluoride (up to 58 μM) and filterable reactive phosphorus (FRP) (up to 55 μM) during a field groundwater replenishment experiment in which highly treated, deionised wastewater (average TDS 33 mg/L) was injected into a siliciclastic Cretaceous aquifer. In the field experiment, maximum concentrations, which coincided with a rise in pH, exceeded background groundwater concentrations by an average factor of 3.6 for fluoride and 24 for FRP. The combined results from the field experiment, a detailed mineralogical characterisation and geochemical modelling suggested carbonate-rich fluorapatite (CFA: Ca10(PO4)5(CO3,F)F2) to be the most likely source of fluoride and phosphate release. An anoxic batch experiment with powdered CFA-rich nodules sourced from the target aquifer and aqueous solutions of successively decreasing ionic strength closely replicated the field-observed fluoride and phosphate behaviour. Based on the laboratory experiment and geochemical modelling, we hypothesise that the release of fluoride and phosphate results from the incongruent dissolution of CFA and the simultaneous formation of a depleted layer that has hydrated di-basic calcium phosphate (CaHPO4·nH2O) composition at the CFA-water interface. Disequilibrium caused by calcium removal following breakthrough of the deionised injectate triggered the release of fluoride and phosphate. Given the increasing use of highly treated, deionised water for MAR and the ubiquitous presence of CFA and fluorapatite (Ca10(PO4)6F2) in aquifer settings worldwide, the risk of fluoride and phosphate release needs to be considered in the MAR design process.

Lifetime and dissolution kinetics of zinc oxide nanoparticles in aqueous media

NASA Astrophysics Data System (ADS)

Wang, Ning; Tong, Tiezheng; Xie, Minwei; Gaillard, Jean-François

2016-08-01

We have assessed the persistence and lifetime of ZnO nanoparticles (ZnO-NPs) by performing dissolution experiments in three different aqueous media. These experiments were performed at ZnO-NP concentration levels close to the solubility of zincite (˜8 μM or 650 μg l-1 of ZnO)—a concentration that is orders of magnitude higher than current estimated relevant environmental concentrations. The kinetics were followed by voltammetry, while maintaining the pH at about 7.5 using a CO2/N2 gas mixture to remove di-oxygen interference. Our results show that, under these conditions, ZnO-NPs readily dissolve with a lifetime expectancy that does not exceed 90 min. Water chemistry, especially the presence of dissolved organic matter (DOM), plays an important role in ZnO-NP dissolution. Dissolution rates significantly increase in the presence of strong chelating agents, EDTA and L-cysteine, while the addition of polymeric DOM, such as sodium alginate, has the opposite effect. Our results suggest that ZnO-NPs are unlikely to persist in natural aqueous media and that the toxicity should be primarily related to the released Zn2+ ions rather than effects commonly associated to the presence of nanoparticles.

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.

Preparation, characterization, and scale-up of ketoconazole with enhanced dissolution and bioavailability.

PubMed

Elder, Edmund J; Evans, Jonathan C; Scherzer, Brian D; Hitt, James E; Kupperblatt, Gary B; Saghir, Shakil A; Markham, Dan A

2007-07-01

Many new molecular entities targeted for pharmaceutical applications face serious development challenges because of poor water solubility. Although particle engineering technologies such as controlled precipitation have been shown to enhance aqueous dissolution and bioavailability of poorly water soluble active pharmaceutical ingredients, the data available are the results of laboratory-scale experiments. These technologies must be evaluated at larger scale to ensure that the property enhancement is scalable and that the modified drugs can be processed on conventional equipment. In experiments using ketoconazole as the model drug, the controlled precipitation process was shown to produce kg-scale modified drug powder with enhanced dissolution comparable to that of lab-scale powder. Ketoconazole was demonstrated to be stable throughout the controlled precipitation process, with a residual methanol level below the ICH limit. The modified crystalline powder can be formulated, and then compressed using conventional high-speed tableting equipment, and the resulting tablets showed bioavailability more than double that of commercial tablets. When appropriately protected from moisture, both the modified powder and tablets prepared from the modified powder showed no change in dissolution performance for at least 6 months following storage at accelerated conditions and for at least 18 months following storage at room temperature.

Surfactant-enhanced remediation of a trichloroethene-contaminated aquifer. 1. Transport of triton X-100

USGS Publications Warehouse

Smith, J.A.; Sahoo, D.; Mclellan, H.M.; Imbrigiotta, T.E.

1997-01-01

Transport of a nonionic surfactant (Triton X-100) at aqueous concentrations less than 400 mg/L through a trichloroethene-contaminated sand-and-gravel aquifer at Picatinny Arsenal, NJ, has been studied through a series of laboratory and field experiments. In the laboratory, batch and column experiments were conducted to quantify the rate and amount of Triton X-100 sorption to the aquifer sediments. In the field, a 400 mg/L aqueous Triton X-100 solution was injected into the aquifer at a rate of 26.5 L/min for a 35-d period. The transport of Triton X-100 was monitored by sampling and analysis of groundwater at six locations surrounding the injection well. Equilibrium batch sorption experiments showed that Triton X-100 sorbs strongly and nonlinearly to the field soil with the sharpest inflection point of the isotherm occurring at an equilibrium aqueous Triton X-100 concentration close to critical micelle concentration. Batch, soil column, and field experimental data were analyzed with zero-, one-, and two- dimensional (respectively) transient solute transport models with either equilibrium or rate-limited sorption. These analyses reveal that Triton X- 100 sorption to the aquifer solids is slow relative to advective and dispersive transport and that an equilibrium sorption model cannot simulate accurately the observed soil column and field data. Comparison of kinetic sorption parameters from batch, column, and field transport data indicate that both physical heterogeneities and Triton X-100 mass transfer between water and soil contribute to the kinetic transport effects.Transport of a nonionic surfactant (Triton X-100) at aqueous concentrations less than 400 mg/L through a trichloroethene-contaminated sand-and-gravel aquifer was studied. Equilibrium batch sorption experiments showed that Triton X-100 sorbs strongly and nonlinearly to the field soil with the sharpest inflection point of the isotherm occurring at an equilibrium aqueous Triton X-100 concentration close to critical micelle concentration. Batch, soil column, and field experimental data were analyzed with zero-, one-, and two-dimensional transient solute transport models with either equilibrium or rate-limited sorption. These analyses revealed that Triton X-100 sorption to the aquifer solids was slow relative to advective and dispersive transport.

"Batch" kinetics in flow: online IR analysis and continuous control.

PubMed

Moore, Jason S; Jensen, Klavs F

2014-01-07

Currently, kinetic data is either collected under steady-state conditions in flow or by generating time-series data in batch. Batch experiments are generally considered to be more suitable for the generation of kinetic data because of the ability to collect data from many time points in a single experiment. Now, a method that rapidly generates time-series reaction data from flow reactors by continuously manipulating the flow rate and reaction temperature has been developed. This approach makes use of inline IR analysis and an automated microreactor system, which allowed for rapid and tight control of the operating conditions. The conversion/residence time profiles at several temperatures were used to fit parameters to a kinetic model. This method requires significantly less time and a smaller amount of starting material compared to one-at-a-time flow experiments, and thus allows for the rapid generation of kinetic data. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using SEM Analysis on Ion-Milled Shale Surface to Determine Shale-Fracturing Fluid Interaction

NASA Astrophysics Data System (ADS)

Lu, J.; Mickler, P. J.; Nicot, J. P.

2014-12-01

It is important to document and assess shale-fluid interaction during hydraulic fracturing (HF) in order to understand its impact on flowback water chemistry and rock property. A series of autoclave experiments were conducted to react shale samples from major oil and gas shales with synthetic HF containing various additives. To better determine mineral dissolution and precipitation at the rock-fluid interface, ion-milling technique was applied to create extremely flat rock surfaces that were examined before and after the autoclave experiments using a scanning electron microscope (SEM) coupled with energy dispersive spectroscopy (EDS) detectors. This method is able to reveal a level of detail not observable on broken surface or mechanically polished surface. It allows direct comparison of the same mineral and organic matter particles before and after the reaction experiments. Minerals undergone dissolution and newly precipitated materials are readily determined by comparing to the exact locations before reaction. The dissolution porosity and the thickness of precipitates can be quantified by tracing and measuring the geometry of the pores and precipitates. Changes in porosity and permeability were confirmed by mercury intrusion capillary tests.

INTERACTIONS BETWEEN OCEAN ACIDIFICATION AND WARMING ON THE MORTALITY AND DISSOLUTION OF CORALLINE ALGAE(1).

PubMed

Diaz-Pulido, Guillermo; Anthony, Kenneth R N; Kline, David I; Dove, Sophie; Hoegh-Guldberg, Ove

2012-02-01

Coralline algae are among the most sensitive calcifying organisms to ocean acidification as a result of increased atmospheric carbon dioxide (pCO2 ). Little is known, however, about the combined impacts of increased pCO2 , ocean acidification, and sea surface temperature on tissue mortality and skeletal dissolution of coralline algae. To address this issue, we conducted factorial manipulative experiments of elevated CO2 and temperature and examined the consequences on tissue survival and skeletal dissolution of the crustose coralline alga (CCA) Porolithon (=Hydrolithon) onkodes (Heydr.) Foslie (Corallinaceae, Rhodophyta) on the southern Great Barrier Reef (GBR), Australia. We observed that warming amplified the negative effects of high pCO2 on the health of the algae: rates of advanced partial mortality of CCA increased from <1% to 9% under high CO2 (from 400 to 1,100 ppm) and exacerbated to 15% under warming conditions (from 26°C to 29°C). Furthermore, the effect of pCO2 on skeletal dissolution strongly depended on temperature. Dissolution of P. onkodes only occurred in the high-pCO2 treatment and was greater in the warm treatment. Enhanced skeletal dissolution was also associated with a significant increase in the abundance of endolithic algae. Our results demonstrate that P. onkodes is particularly sensitive to ocean acidification under warm conditions, suggesting that previous experiments focused on ocean acidification alone have underestimated the impact of future conditions on coralline algae. Given the central role that coralline algae play within coral reefs, these conclusions have serious ramifications for the integrity of coral-reef ecosystems. © 2011 Phycological Society of America.

Dynamics of basaltic glass dissolution - Capturing microscopic effects in continuum scale models

NASA Astrophysics Data System (ADS)

Aradóttir, E. S. P.; Sigfússon, B.; Sonnenthal, E. L.; Björnsson, G.; Jónsson, H.

2013-11-01

The method of 'multiple interacting continua' (MINC) was applied to include microscopic rate-limiting processes in continuum scale reactive transport models of basaltic glass dissolution. The MINC method involves dividing the system up to ambient fluid and grains, using a specific surface area to describe the interface between the two. The various grains and regions within grains can then be described by dividing them into continua separated by dividing surfaces. Millions of grains can thus be considered within the method without the need to explicity discretizing them. Four continua were used for describing a dissolving basaltic glass grain; the first one describes the ambient fluid around the grain, while the second, third and fourth continuum refer to a diffusive leached layer, the dissolving part of the grain and the inert part of the grain, respectively. The model was validated using the TOUGHREACT simulator and data from column flow through experiments of basaltic glass dissolution at low, neutral and high pH values. Successful reactive transport simulations of the experiments and overall adequate agreement between measured and simulated values provides validation that the MINC approach can be applied for incorporating microscopic effects in continuum scale basaltic glass dissolution models. Equivalent models can be used when simulating dissolution and alteration of other minerals. The study provides an example of how numerical modeling and experimental work can be combined to enhance understanding of mechanisms associated with basaltic glass dissolution. Column outlet concentrations indicated basaltic glass to dissolve stoichiometrically at pH 3. Predictive simulations with the developed MINC model indicated significant precipitation of secondary minerals within the column at neutral and high pH, explaining observed non-stoichiometric outlet concentrations at these pH levels. Clay, zeolite and hydroxide precipitation was predicted to be most abundant within the column.

Role of bacterial adhesion in the microbial ecology of biofilms in cooling tower systems.

PubMed

Liu, Yang; Zhang, Wei; Sileika, Tadas; Warta, Richard; Cianciotto, Nicholas P; Packman, Aaron

2009-01-01

The fate of the three heterotrophic biofilm forming bacteria, Pseudomonas aeruginosa, Klebsiella pneumoniae and Flavobacterium sp. in pilot scale cooling towers was evaluated both by observing the persistence of each species in the recirculating water and the formation of biofilms on steel coupons placed in each cooling tower water reservoir. Two different cooling tower experiments were performed: a short-term study (6 days) to observe the initial bacterial colonization of the cooling tower, and a long-term study (3 months) to observe the ecological dynamics with repeated introduction of the test strains. An additional set of batch experiments (6 days) was carried out to evaluate the adhesion of each strain to steel surfaces under similar conditions to those found in the cooling tower experiments. Substantial differences were observed in the microbial communities that developed in the batch systems and cooling towers. P. aeruginosa showed a low degree of adherence to steel surfaces both in batch and in the cooling towers, but grew much faster than K. pneumoniae and Flavobacterium in mixed-species biofilms and ultimately became the dominant organism in the closed batch systems. However, the low degree of adherence caused P. aeruginosa to be rapidly washed out of the open cooling tower systems, and Flavobacterium became the dominant microorganism in the cooling towers in both the short-term and long-term experiments. These results indicate that adhesion, retention and growth on solid surfaces play important roles in the bacterial community that develops in cooling tower systems.

Role of bacterial adhesion in the microbial ecology of biofilms in cooling tower systems

PubMed Central

Liu, Yang; Zhang, Wei; Sileika, Tadas; Warta, Richard; Cianciotto, Nicholas P.; Packman, Aaron

2009-01-01

The fate of the three heterotrophic biofilm forming bacteria, Pseudomonas aeruginosa, Klebsiella pneumoniae and Flavobacterium sp. in pilot scale cooling towers was evaluated both by observing the persistence of each species in the recirculating water and the formation of biofilms on steel coupons placed in each cooling tower water reservoir. Two different cooling tower experiments were performed: a short-term study (6 days) to observe the initial bacterial colonization of the cooling tower, and a long-term study (3 months) to observe the ecological dynamics with repeated introduction of the test strains. An additional set of batch experiments (6 days) was carried out to evaluate the adhesion of each strain to steel surfaces under similar conditions to those found in the cooling tower experiments. Substantial differences were observed in the microbial communities that developed in the batch systems and cooling towers. P. aeruginosa showed a low degree of adherence to steel surfaces both in batch and in the cooling towers, but grew much faster than K. pneumoniae and Flavobacterium in mixed-species biofilms and ultimately became the dominant organism in the closed batch systems. However, the low degree of adherence caused P. aeruginosa to be rapidly washed out of the open cooling tower systems, and Flavobacterium became the dominant microorganism in the cooling towers in both the short-term and long-term experiments. These results indicate that adhesion, retention and growth on solid surfaces play important roles in the bacterial community that develops in cooling tower systems. PMID:19177226

Kinetics of styrene biodegradation by Pseudomonas sp. E-93486.

PubMed

Gąszczak, Agnieszka; Bartelmus, Grażyna; Greń, Izabela

2012-01-01

The research into kinetics of styrene biodegradation by bacterial strain Pseudomonas sp. E-93486 coming from VTT Culture Collection (Finland) was presented in this work. Microbial growth tests in the presence of styrene as the sole carbon and energy source were performed both in batch and continuous cultures. Batch experiments were conducted for initial concentration of styrene in the liquid phase changed in the range of 5-90 g m(-3). The Haldane model was found to be the best to fit the kinetic data, and the estimated constants of the equation were: μ (m) = 0.1188 h(-1), K(S) = 5.984 mg l(-1), and K (i) = 156.6 mg l(-1). The yield coefficient mean value [Formula in text] for the batch culture was 0.72 g(dry cells weight) (g(substrate))(-1). The experiments conducted in a chemostat at various dilution rates (D = 0.035-0.1 h(-1)) made it possible to determine the value of the coefficient for maintenance metabolism m (d) = 0.0165 h(-1) and the maximum yield coefficient value [Formula in text]. Chemostat experiments confirmed the high value of yield coefficient [Formula in text] observed in the batch culture. The conducted experiments showed high activity of the examined strain in the styrene biodegradation process and a relatively low sensitivity to inhibition of its growth at higher concentrations of styrene in the solution. Such exceptional features of Pseudomonas sp. E-93486 make this bacterial strain the perfect candidate for technical applications.

The influence of DOM and microbial processes on arsenic release from karst during ASR operations in the Floridan Aquifer

NASA Astrophysics Data System (ADS)

Jin, J.; Zimmerman, A. R.

2011-12-01

The mobilization of subsurface As poses a serious threat to human health, particularly in a region such as Florida where population is heavily dependent on highly porous karstic aquifers for drinking water. Injection water used in aquifer storage and recovery (ASR) or aquifer recharge (AR) operations is commonly high in dissolved organic matter (DOM) and OM can also be present in the subsurface carbonate rock. Using batch incubation experiments, this study examined the role of core preservation methods, as well as the influence of labile and more refractory DOM on the mobilization of As from carbonate rock. Incubation experiments used sealed reaction vessels with preserved and homogenized core materials collected via coring the Suwannee Formation in southwest Florida and treatment additions consisting of 1) source water (SW) enriched in sterilized soil DOM, 2) SW enriched in soil DOM and microbes, and 3) SW enriched in sodium acetate. During an initial equilibration phase in native groundwater (NGW) with low dissolved oxygen (DO; Phase 1), we found the greatest As release of the whole incubation. In the beginning of Phase 2 (N2 headspace) in which NGW was replaced with treatment solutions, there was little As release except in the vessel with Na-acetate added, which also had the lowest ORP. At the start of Phase 3, when incubations were exposed to air, most vessels saw more ion (including As) release into solution. Vessel with Na-acetate had less As release in Phase 3 than in Phase 2. During all experimental phases, treatments of DOM or microbe additions had no apparent effect on the amount of As release. The core materials was found contain significant amount of indigenous DOM (about 8 g OC/kg core) which was released during the incubation so DOC concentrations displayed no clear pattern among different treatments. At least three abiotic As mobilization mechanisms may play a role in As released during different stages of the experiment. Desorption of As from iron oxyhydroxides may have occurred, particularly at the beginning of each experimental phase. Reductive dissolution and oxidative dissolution likely lead to As release during phase 2 and 3, respectively. While not directly implicated, the presence of labile OM clearly fueled microbial alteration of redox conditions, leading to further As release. Addition of microbes had no effect as indigenous microbes were just as active in untreated cores.

CO2 Extraction from Ambient Air Using Alkali-Metal Hydroxide Solutions Derived from Concrete Waste and Steel Slag

NASA Astrophysics Data System (ADS)

Stolaroff, J. K.; Lowry, G. V.; Keith, D. W.

2003-12-01

To mitigate global climate change, deep reductions in CO2 emissions are required in the coming decades. Carbon sequestration will play a crucial role in this reduction. Early adoption of carbon sequestration in low-cost niche markets will help develop the technology and experience required for large-scale deployment. One such niche may be the use of alkali metals from industrial waste streams to form carbonate minerals, a safe and stable means of sequestering carbon. In this research, the potential of using two industrial waste streams---concrete and steel slag---for sequestering carbon is assessed. The scheme is outlined as follows: Ca and Mg are leached with water from a finely ground bed of steel slag or concrete. The resulting solution is sprayed through air, capturing CO2 and forming solid carbonates, and collected. The feasibility of this scheme is explored with a combination of experiments, theoretical calculations, cost accounting, and literature review. The dissolution kinetics of steel slag and concrete as a function of particle size and pH is examined. In stirred batch reactors, the majority of Ca which dissolved did so within the first hour, yielding between 50 and 250 (mg; Ca)/(g; slag) and between 10 and 30 (mg; Ca)/(g; concrete). The kinetics of dissolution are thus taken to be sufficiently fast to support the type of scheme described above. As proof-of-concept, further experiments were performed where water was dripped slowly through a stagnant column of slag or concrete and collected at the bottom. Leachate Ca concentrations in the range of 15 mM were achieved --- sufficient to support the scheme. Using basic physical principles and numerical methods, the quantity of CO2 captured by falling droplets is estimated. Proportion of water loss and required pumping energy is similarly estimated. The results indicate that sprays are capable of capturing CO2 from the air and that the water and energy requirements are tractable. An example system for enacting the scheme is presented, along with capital and operational cost estimates. The system is found to be profitable for carbon credits above \\5/ton; C. Many findings in this research apply to a more general set of systems which capture CO_2$ from the air for sequestration. The metal-hydroxide solution in these systems is regenerated on site, allowing application of this scheme on as large a scale as needed. Implications of this study's findings for these more general carbon-capture systems is discussed.

Feed additive production by fermentation of herb Polygonum hydropiper L. and cassava pulp with simultaneous flavonoid dissolution.

PubMed

Song, Zhen-Tao; Zhu, Ming-Jun

2017-03-01

Fermentation of herb Polygonum hydropiper L. (PHL) and cassava pulp (CP) for feed additive production with simultaneous flavonoid dissolution was investigated, and a two-stage response surface methodology (RSM) based on Plackett-Burman factorial design (PB design) was used to optimize the flavonoid dissolution and protein content. Using the screening function of PB design, four different significant factors for the two response variables were acquired: factors A (CP) and B (PHL) for the flavonoid dissolution versus factors G (inoculum size) and H (fermentation time) for protein content. Then, two RSMs were used sequentially to improve the values of the two response variables separately. The mutual corroboration of the experimental results in the present study confirmed the validity of the associated experimental design. The validation experiment showed a flavonoid dissolution rate of 94.00%, and a protein content of 18.20%, gaining an increase in 21.20% and 199.10% over the control, respectively. The present study confirms the feasibility of feed additive production by Saccharomyces cerevisiae with CP and PHL and simultaneous optimization of flavonoid dissolution and protein content using a two-stage RSM. © 2016 International Union of Biochemistry and Molecular Biology, Inc.

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

Application of gain scheduling to the control of batch bioreactors

NASA Technical Reports Server (NTRS)

Cardello, Ralph; San, Ka-Yiu

1987-01-01

The implementation of control algorithms to batch bioreactors is often complicated by the inherent variations in process dynamics during the course of fermentation. Such a wide operating range may render the performance of fixed gain PID controllers unsatisfactory. In this work, a detailed study on the control of batch fermentation is performed. Furthermore, a simple batch controller design is proposed which incorporates the concept of gain-scheduling, a subclass of adaptive control, with oxygen uptake rate as an auxiliary variable. The control of oxygen tension in the biorector is used as a vehicle to convey the proposed idea, analysis and results. Simulation experiments indicate significant improvement in controller performance can be achieved by the proposed approach even in the presence of measurement noise.

Consumption and diffusion of dissolved oxygen in sedimentary rocks.

PubMed

Manaka, M; Takeda, M

2016-10-01

Fe(II)-bearing minerals (e.g., biotite, chlorite, and pyrite) are a promising reducing agent for the consumption of atmospheric oxygen in repositories for the geological disposal of high-level radioactive waste. To estimate effective diffusion coefficients (D e , in m 2 s -1 ) for dissolved oxygen (DO) and the reaction rates for the oxidation of Fe(II)-bearing minerals in a repository environment, we conducted diffusion-chemical reaction experiments using intact rock samples of Mizunami sedimentary rock. In addition, we conducted batch experiments on the oxidation of crushed sedimentary rock by DO in a closed system. From the results of the diffusion-chemical reaction experiments, we estimated the values of D e for DO to lie within the range 2.69×10 -11

On the longevity of silicic magma based on multi-isotope investigation of zircons and modeling their survivals destinies

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Wotzlaw, J. F.; Melnik, O. E.

2015-12-01

Large volumes of crystal poor, near-liquidus rhyolites are erupted worldwide as tuffs and lavas in rift and hot spots more common previously on early earth, creating temporally very high magma production rates. In this contribution we combine results of IDTIMS dating of zircons with numerical modeling of zircon crystallization. New investigation of zircons in major Yellowstone tuffs: Huckleberry Ridge (Members A,B,C), Mesa Falls, and Lava Creek (A,B) tuffs was done by a combination of in situ measurements of oxygen isotopes followed by ID-TIMS U-Pb dating, Hf isotopes and trace elemental investigation of single crystals. We discover that nearly all zircons are of eruption age, but display significant isotope (O,Hf) diversity and often show decoupled O and Hf isotope systematics. This record rapid (~103yrs) double or triple remelting and sequestration from diverse Archean crust and hydrothermally altered shallow-crustal rocks from previous eruptive cycles, followed by effective mixing of co-existing magma reservoirs with diverse zircons prior to eruptions. Similar results characterize other studied Snake River Plain rhyolites in pre-Yellowstone Heise complex. These results collectively suggest that zircons crystallize after reheating above saturation rejuvenation in isotopically-diverse areas of the crust in the magma plumbing system. Modeling of zircon and quartz dissolution and crystallization trajectories outline conditions of survival (inheritance) vs complete dissolution on conductive timescales, and when combined with a phase diagram, magma T-t paths can be computed. Zircon rejuvenation requires hot, >770-800°C peak temperatures lasting 10-102yrs. We speculate that near liquidus hot and dry Yellowstone rhyolites are kept alive in a multi-batch state by a series of interconnected pods and sills that can rapidly get thermomechanically assembled into large, shallow and eruptable supervolcanoic magma bodies. We suggest that overpressure and roof dynamics and rheology plays a more important role than magma buyoncy. The runaway batch assembly process creates temporally very high magma production rates, orders of magnitude higher than for arc volcanoes. Such views have implication for the state of the magma chamber under Yellowstone and similar supervolcanoes elsewhere.

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

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

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

McNab, W; Ezzedine, S; Detwiler, R

2007-02-26

Industrial organic solvents such as trichloroethylene (TCE) and tetrachloroethylene (PCE) constitute a principal class of groundwater contaminants. Cleanup of groundwater plume source areas associated with these compounds is problematic, in part, because the compounds often exist in the subsurface as dense nonaqueous phase liquids (DNAPLs). Ganglia (or 'blobs') of DNAPL serve as persistent sources of contaminants that are difficult to locate and remediate (e.g. Fenwick and Blunt, 1998). Current understanding of the physical and chemical processes associated with dissolution of DNAPLs in the subsurface is incomplete and yet is critical for evaluating long-term behavior of contaminant migration, groundwater cleanup, andmore » the efficacy of source area cleanup technologies. As such, a goal of this project has been to contribute to this critical understanding by investigating the multi-phase, multi-component physics of DNAPL dissolution using state-of-the-art experimental and computational techniques. Through this research, we have explored efficient and accurate conceptual and numerical models for source area contaminant transport that can be used to better inform the modeling of source area contaminants, including those at the LLNL Superfund sites, to re-evaluate existing remediation technologies, and to inspire or develop new remediation strategies. The problem of DNAPL dissolution in natural porous media must be viewed in the context of several scales (Khachikian and Harmon, 2000), including the microscopic level at which capillary forces, viscous forces, and gravity/buoyancy forces are manifested at the scale of individual pores (Wilson and Conrad, 1984; Chatzis et al., 1988), the mesoscale where dissolution rates are strongly influenced by the local hydrodynamics, and the field-scale. Historically, the physico-chemical processes associated with DNAPL dissolution have been addressed through the use of lumped mass transfer coefficients which attempt to quantify the dissolution rate in response to local dissolved-phase concentrations distributed across the source area using a volume-averaging approach (Figure 1). The fundamental problem with the lumped mass transfer parameter is that its value is typically derived empirically through column-scale experiments that combine the effects of pore-scale flow, diffusion, and pore-scale geometry in a manner that does not provide a robust theoretical basis for upscaling. In our view, upscaling processes from the pore-scale to the field-scale requires new computational approaches (Held and Celia, 2001) that are directly linked to experimental studies of dissolution at the pore scale. As such, our investigation has been multi-pronged, combining theory, experiments, numerical modeling, new data analysis approaches, and a synthesis of previous studies (e.g. Glass et al, 2001; Keller et al., 2002) aimed at quantifying how the mechanisms controlling dissolution at the pore-scale control the long-term dissolution of source areas at larger scales.« less

Matching phosphate and maleate buffer systems for dissolution of weak acids: Equivalence in terms of buffer capacity of bulk solution or surface pH?

PubMed

Cristofoletti, Rodrigo; Dressman, Jennifer B

2016-06-01

The development of in vitro dissolution tests able to anticipate the in vivo fate of drug products has challenged pharmaceutical scientists over time, especially in the case of ionizable compounds. In the seminal model proposed by Mooney et al. thirty-five years ago, the pH at the solid-liquid interface (pH0) was identified as a key parameter in predicting dissolution rate. In the current work it is demonstrated that the in vitro dissolution of the weak acid ibuprofen in maleate and phosphate buffer systems is a function of the pH0, which in turn is affected by properties of the drug and the medium. The reported pH0 for ibuprofen dissolution in bicarbonate buffer, the predominant buffer species in the human small intestine under fasting conditions, can be achieved by reducing the phosphate buffer concentration to 5.0mM or the maleate buffer concentration to 2.2mM. Using this approach to identify the appropriate buffer/buffer capacity combination for in vitro experiments in FaSSIF-type media, it would be possible to increase the physiological relevance of this important biopharmaceutics tool. However, the necessity of monitoring and adjusting the bulk pH during the experiments carried out in 5.0mM phosphate or 2.2mM maleate buffers must also be taken into consideration. Copyright © 2016 Elsevier B.V. All rights reserved.

Mixture experiment methods in the development and optimization of microemulsion formulations.

PubMed

Furlanetto, S; Cirri, M; Piepel, G; Mennini, N; Mura, P

2011-06-25

Microemulsion formulations represent an interesting delivery vehicle for lipophilic drugs, allowing for improving their solubility and dissolution properties. This work developed effective microemulsion formulations using glyburide (a very poorly-water-soluble hypoglycaemic agent) as a model drug. First, the area of stable microemulsion (ME) formations was identified using a new approach based on mixture experiment methods. A 13-run mixture design was carried out in an experimental region defined by constraints on three components: aqueous, oil and surfactant/cosurfactant. The transmittance percentage (at 550 nm) of ME formulations (indicative of their transparency and thus of their stability) was chosen as the response variable. The results obtained using the mixture experiment approach corresponded well with those obtained using the traditional approach based on pseudo-ternary phase diagrams. However, the mixture experiment approach required far less experimental effort than the traditional approach. A subsequent 13-run mixture experiment, in the region of stable MEs, was then performed to identify the optimal formulation (i.e., having the best glyburide dissolution properties). Percent drug dissolved and dissolution efficiency were selected as the responses to be maximized. The ME formulation optimized via the mixture experiment approach consisted of 78% surfactant/cosurfacant (a mixture of Tween 20 and Transcutol, 1:1, v/v), 5% oil (Labrafac Hydro) and 17% aqueous phase (water). The stable region of MEs was identified using mixture experiment methods for the first time. Copyright © 2011 Elsevier B.V. All rights reserved.

Geochemical Impacts of Leaking CO2 from Subsurface Storage Reservoirs on the Fate of Metal Contaminants in an Overlaying Groundwater Aquifer

NASA Astrophysics Data System (ADS)

Shao, H.; Qafoku, N. P.; Lawter, A.; Bowden, M. E.; Brown, C. F.

2014-12-01

The leakage of CO2 and the concomitant upward transport of brine solutions and contaminants from deep storage reservoirs to overlaying groundwater aquifers is considered one of the major risks associated with geologic carbon sequestration (GCS). A systematic understanding of how such leakage would impact the geochemistry of potable aquifers is crucial to the maintenance of environmental quality and the widespread acceptance of GCS. A series of batch and column experiments studies were conducted to understand the fate (mobilization and immobilization) of trace metals, such as Cd and As in the groundwater aquifer after the intrusion of CO2 gas and CO2-saturated fluids containing leached metals from deep subsurface storage reservoirs. Sediments from the High Plains aquifer in Kansas, United States, were used in this investigation, which is part of the National Risk Assessment Partnership Program sponsored by the US DOE. This aquifer was selected to be representative of consolidated sand and gravel/sandstone aquifers overlying potential CO2 sequestration repositories within the continental US. The experiments were conducted at room temperature and atmospheric pressure. The results demonstrated that Cd and As that intrude into groundwater aquifers with the leaking CO2 at initial concentrations of 40 and 114 mg/L, respectively, will be adsorbed on the sediments, in spite of the acidic pH (between 5 and 6) due to CO2 dissolution in the groundwater. Cd concentrations were well below its MCL in both the aqueous solution of the batch study and the effluent of the column study, even for one of the sediment samples which had undetectable amount of carbonate minerals to buffer the pH. Arsenic concentrations were also significantly lower than that in the influent, suggesting that natural sediments have the capacity to mitigate the adverse effects of the CO2 leakage. However, the mitigation capacity of sediments is influenced by its geochemical properties. When there are anions such as phosphate in the sediment, competitive adsorption may occur and result in higher concentrations of toxic metals in the aqueous phase. Results from these investigations will provide useful information to support site selection, risk assessment, and public education efforts associated with geological CO2 storage and sequestration.

A short term quality control tool for biodegradable microspheres.

PubMed

D'Souza, Susan; Faraj, Jabar A; Dorati, Rossella; DeLuca, Patrick P

2014-06-01

Accelerated in vitro release testing methodology has been developed as an indicator of product performance to be used as a discriminatory quality control (QC) technique for the release of clinical and commercial batches of biodegradable microspheres. While product performance of biodegradable microspheres can be verified by in vivo and/or in vitro experiments, such evaluation can be particularly challenging because of slow polymer degradation, resulting in extended study times, labor, and expense. Three batches of Leuprolide poly(lactic-co-glycolic acid) (PLGA) microspheres having varying morphology (process variants having different particle size and specific surface area) were manufactured by the solvent extraction/evaporation technique. Tests involving in vitro release, polymer degradation and hydration of the microspheres were performed on the three batches at 55°C. In vitro peptide release at 55°C was analyzed using a previously derived modification of the Weibull function termed the modified Weibull equation (MWE). Experimental observations and data analysis confirm excellent reproducibility studies within and between batches of the microsphere formulations demonstrating the predictability of the accelerated experiments at 55°C. The accelerated test method was also successfully able to distinguish the in vitro product performance between the three batches having varying morphology (process variants), indicating that it is a suitable QC tool to discriminate product or process variants in clinical or commercial batches of microspheres. Additionally, data analysis utilized the MWE to further quantify the differences obtained from the accelerated in vitro product performance test between process variants, thereby enhancing the discriminatory power of the accelerated methodology at 55°C.

Effects of plants and essential oils on ruminal in vitro batch culture methane production and fermentation

USDA-ARS?s Scientific Manuscript database

In this study, plants (14) and essential oils (EO; 88) from plants that are naturalized to, or can be successfully grown in North America were evaluated in a batch culture in vitro screening experiments with ruminal fluid as potential anti-methanogenic additives for ruminant diets. Essential oils we...

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.

Coper Isotope Fractionation in Porphyry Copper Deposits: A Controlled Experiment

NASA Astrophysics Data System (ADS)

Ruiz, J.; Mathur, R.; Uhrie, J. L.; Hiskey, B.

2001-12-01

Previous studies have shown that copper is fractionated in the environment. However, the mechanisms for isotope fractionation and the role of organic and inorganic processes in the fractionation are not well understood. Here we used the well controlled experiments used by Phelps Dodge Corporation aimed at leaching copper from their ore deposits to constrain the mechanism of copper isotope fractionation in natural systems. The isotope data were collected on a Micromass Isoprobe. High temperature copper sulfides from ore deposits in Chile and Arizona yield delta 65Cu near 0 permil. The reproducibility of the data is better that 0.1 permil. Controlled experiments consisting of large columns of rocks were fed solutions containing bacteria such as Thiobacillus ferroxidans and Leptospirrilium ferroxidan. Solutions fom the columns were sampled for sixty days and analyzed for copper concentrations, oxidation potential, ferrous/ferric ratios and pH. The results indicate that the bacterially aided dissolution of copper fractionated copper. Preliminary experiments of copper dissolution not using bacteria show no isotope fractionation The original rock in the experiment has a delta 65Cu of -2.1. The first solutions that were collected from the columns had a delta 65Cu of -5.0 per mil. The liquid changed its isotopic composition from -50 to -10 during the sixty days of sampling. The greatest shift in the isotope ratios occurred the first 30 days when the copper recovered was less than 40% and the ferrous/ferric ratios were somewhat constant. At approximately 35 days after the start of the experiments, the copper recovery increases the ferrousferric ratio decreased and the copper isotope ratio of the fluids remained fairly constant. The data suggest that the bacteria are required to effectively fractionate copper isotopes in natural systems and that the mechanisms of bacterial aided copper dissolution may include a direct dissolution of the sulfides by the bacteria. Experiments underway with enzimes without the bacteria may confirm this hypothesis. The data obtained in these experiments will provide some constraints in the use of copper isotopes as proxy for life in the rock record.

Hydrogen production from the dissolution of nano zero valent iron and its effect on anaerobic digestion.

PubMed

Huang, Yu-Xi; Guo, Jialiang; Zhang, Chunyang; Hu, Zhiqiang

2016-01-01

Nano zero valent iron (NZVI) has shown inhibition on methanogenesis in anaerobic digestion due to its reductive decomposition of cell membrane. The inhibition was accompanied by the accumulation of hydrogen gas due to rapid NZVI dissolution. It is not clear whether and how rapid hydrogen release from NZVI dissolution directly affects anaerobic digestion. In this study, the hydrogen release kinetics from NZVI (average size = 55 ± 11 nm) dissolution in deionized water under anaerobic conditions was first evaluated. The first-order NZVI dissolution rate constant was 2.62 ± 0.26 h(-1) with its half-life of 0.26 ± 0.03 h. Two sets of anaerobic digestion experiments (i.e., in the presence of glucose or without any substrate but at different anaerobic sludge concentrations) were performed to study the impact of H2 release from rapid NZVI dissolution, in which H2 was generated in a separate water bottle containing NZVI (i.e., ex situ H2 or externally supplied from NZVI dissolution) before hydrogen gas was introduced to anaerobic digestion. The results showed that the H2 partial pressure in the headspace of the digestion bottle reached as high as 0.27 atm due to rapid NZVI dissolution, resulting in temporary inhibition of methane production. Nevertheless, the 5-d cumulative methane volume in the group with ex situ H2 production due to NZVI dissolution was actually higher than that of control, suggesting NZVI inhibition on methanogenesis is solely due to the reductive decomposition of cell membrane after direct contact with NZVI. Copyright © 2015 Elsevier Ltd. All rights reserved.

Limited Carbonate Dissolution by Boring Microflora at Two Volcanically Acidified Temperate Sites: Ischia (Italy, Mediterranean Sea) and Faial (Azores, NE Atlantic Ocean)

NASA Astrophysics Data System (ADS)

Tribollet, A.; Grange, J. S.; Parra, H.; Rodolfo-Metalpa, R.; Carreiro-Silva, M.

2018-01-01

In situ effects of ocean acidification on carbonate dissolution by microboring flora, also called biogenic dissolution, have only been studied once in tropical environments. Naturally acidified seawaters due to CO2 vents offer a perfect setting to study these effects in temperate systems. Three sites were selected at Ischia (Italy, Mediterranean Sea) with one experiencing ambient pH and the two others a mean pHT of 7.2 and 7.5. At Faial (Azores, NE Atlantic), one site with ambient pH and one acidified site with a mean pHT of 7.4 were selected. Experiments were carried out during 1.5 months and 6 months in Azores and Ischia, respectively, to determine the effects of OA on microboring communities in various carbonate substrates. Low pH influenced negatively boring microflora development by limiting their depth of penetration and abundance in substrates. Biogenic dissolution was thus reduced by a factor 3 to 7 depending on sites and substrate types. At sites with ambient pH in Faial, biogenic dissolution contributed up to 23% to the total weight loss, while it contributed less than 1% to the total weight loss of substrates at the acidified sites. Most of the dissolution at these sites was due to chemical dissolution (often Ω ≤ 1). Such conditions maintained microboring communities at a pioneer stage with a limited depth of penetration in substrates. Our results, together with previous findings that showed an increase of biogenic dissolution at pH > 7.7, suggest that there is a pH tipping point below which microborer development and thus carbonate biogenic dissolution is strongly limited.

ADSORPTION MECHANISMS AND TRANSPORT BEHAVIOR BETWEEN SELENATE AND SELENITE ON DIFFERENT SORBENTS

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

Snyder, Michelle MV; Um, Wooyong

Adsorption of different oxidation species of selenium (Se), selenate (SeO42-) and selenite (SeO32-), with varying pHs (2 - 10) and ionic strengths (I = 0.01 M, 0.1 M and 1.0 M NaNO3) was measured on quartz, aluminum oxide, and synthetic iron oxide (ferrihydrite) using batch reactors to obtain a more detailed understanding of the adsorption mechanisms (e.g., inner- and outer-sphere complex). In addition to the batch experiments with single minerals contained in native Hanford Site sediment, additional batch adsorption studies were conducted with native Hanford Site sediment and groundwater as a function of 1) total Se concentration (from 0.01 tomore » 10 mg L-1) and 2) soil to solution ratios (1:20 and 1:2 grams per mL). Results from these batch studies were compared to a set of saturated column experiments that were conducted with natural Hanford sediment and groundwater spiked with either selenite or selenate to observe the transport behavior of these species. Both batch and column results indicated that selenite adsorption was consistently higher than that of selenate in all experimental conditions used. These different adsorption mechanisms between selenite and selenate result in the varying mobility of Se in the subsurface environment and explain the dependence on the oxidation species.« less

Microfluidic biolector-microfluidic bioprocess control in microtiter plates.

PubMed

Funke, Matthias; Buchenauer, Andreas; Schnakenberg, Uwe; Mokwa, Wilfried; Diederichs, Sylvia; Mertens, Alan; Müller, Carsten; Kensy, Frank; Büchs, Jochen

2010-10-15

In industrial-scale biotechnological processes, the active control of the pH-value combined with the controlled feeding of substrate solutions (fed-batch) is the standard strategy to cultivate both prokaryotic and eukaryotic cells. On the contrary, for small-scale cultivations, much simpler batch experiments with no process control are performed. This lack of process control often hinders researchers to scale-up and scale-down fermentation experiments, because the microbial metabolism and thereby the growth and production kinetics drastically changes depending on the cultivation strategy applied. While small-scale batches are typically performed highly parallel and in high throughput, large-scale cultivations demand sophisticated equipment for process control which is in most cases costly and difficult to handle. Currently, there is no technical system on the market that realizes simple process control in high throughput. The novel concept of a microfermentation system described in this work combines a fiber-optic online-monitoring device for microtiter plates (MTPs)--the BioLector technology--together with microfluidic control of cultivation processes in volumes below 1 mL. In the microfluidic chip, a micropump is integrated to realize distinct substrate flow rates during fed-batch cultivation in microscale. Hence, a cultivation system with several distinct advantages could be established: (1) high information output on a microscale; (2) many experiments can be performed in parallel and be automated using MTPs; (3) this system is user-friendly and can easily be transferred to a disposable single-use system. This article elucidates this new concept and illustrates applications in fermentations of Escherichia coli under pH-controlled and fed-batch conditions in shaken MTPs. Copyright 2010 Wiley Periodicals, Inc.

A comparison of abundance estimates from extended batch-marking and Jolly–Seber-type experiments

PubMed Central

Cowen, Laura L E; Besbeas, Panagiotis; Morgan, Byron J T; Schwarz, Carl J

2014-01-01

Little attention has been paid to the use of multi-sample batch-marking studies, as it is generally assumed that an individual's capture history is necessary for fully efficient estimates. However, recently, Huggins et al. (2010) present a pseudo-likelihood for a multi-sample batch-marking study where they used estimating equations to solve for survival and capture probabilities and then derived abundance estimates using a Horvitz–Thompson-type estimator. We have developed and maximized the likelihood for batch-marking studies. We use data simulated from a Jolly–Seber-type study and convert this to what would have been obtained from an extended batch-marking study. We compare our abundance estimates obtained from the Crosbie–Manly–Arnason–Schwarz (CMAS) model with those of the extended batch-marking model to determine the efficiency of collecting and analyzing batch-marking data. We found that estimates of abundance were similar for all three estimators: CMAS, Huggins, and our likelihood. Gains are made when using unique identifiers and employing the CMAS model in terms of precision; however, the likelihood typically had lower mean square error than the pseudo-likelihood method of Huggins et al. (2010). When faced with designing a batch-marking study, researchers can be confident in obtaining unbiased abundance estimators. Furthermore, they can design studies in order to reduce mean square error by manipulating capture probabilities and sample size. PMID:24558576

Immobilization of Iodate and Iodide using Iron Oxides through Sorption and Co-precipitation at Hanford Site

NASA Astrophysics Data System (ADS)

Wang, G.; Qafoku, N. P.; Truex, M. J.; Strickland, C. E.; Freedman, V. L.

2017-12-01

Isotopes of iodine were generated during plutonium production at the U.S. Department of Energy (DOE) Hanford Site. The long half-life 129I generated during reactor operations has been released into the subsurface, resulting in several large plumes at the Hanford subsurface. We studied the interaction of iodate (IO3-) and iodide (I-) with Fe oxides. A series of batch experiments were conducted to investigate adsorption and co-precipitation of iodine species in the presence of a variety of Fe oxides, such as ferrihydrite, goethite, hematite and magnetite. In the sorption experiments, each Fe oxide was added to an artificial groundwater containing either iodate or iodide, and reacted at room temperature. The sorption batch experiments for each mineral were conducted at varied initial iodate or iodide concentrations under 3 different pH conditions (pH 5, 7, and 9). In the co-precipitation batch experiments, the initial Fe-mineral-forming solutions were prepared in artificial groundwater containing iodate or iodide. Our results indicate that both sorption and co-precipitation are viable mechanisms of the attenuation of the liquid phase iodine. Species Fe oxides could serve as hosts of iodate and iodide that are present at the Hanford subsurface.

Removal of diclofenac from a non-sterile aqueous system using Trametes versicolor with an emphasis on adsorption and biodegradation mechanisms.

PubMed

Stenholm, Åke; Hedeland, Mikael; Arvidsson, Torbjörn; Pettersson, Curt E

2018-03-04

This paper describes the search for procedures through which the xenobiotic pollutant diclofenac can be removed from non-sterile aquatic systems. Specifically, adsorption to solid supports (carriers) in combination with biodegradation by non-immobilized and immobilized white rot fungus Trametes versicolor were investigated. Batch experiments using polyurethane foam (PUF)-carriers resulted in 99.9% diclofenac removal after 4 h, with monolayer adsorption of diclofenac to carrier and glass surfaces accounting for most of the diclofenac decrease. Enzymatic reactions contributed less, accounting for approximately < 0.5% of this decrease. In bioreactor experiments using PUF-carriers, an initial 100% removal was achieved with biodegradation contributing approximately 7%. In batch experiments that utilized polyethylene-carriers with negligible immobilization of Trametes versicolor, a 98% total diclofenac removal was achieved after one week, with a biodegradation contribution of approximately 14%. Five novel enzyme-catalyzed biodegradation products were tentatively identified in the batch-wise and bioreactor experiments using full scan ultra-high-performance liquid chromatography-quadrupole/time of flight mass spectrometry. Both reduction and oxidation products were found, with the contents estimated to be at µg L -1 concentration levels.

Integrated Platform for Expedited Synthesis–Purification–Testing of Small Molecule Libraries

PubMed Central

2017-01-01

The productivity of medicinal chemistry programs can be significantly increased through the introduction of automation, leading to shortened discovery cycle times. Herein, we describe a platform that consolidates synthesis, purification, quantitation, dissolution, and testing of small molecule libraries. The system was validated through the synthesis and testing of two libraries of binders of polycomb protein EED, and excellent correlation of obtained data with results generated through conventional approaches was observed. The fully automated and integrated platform enables batch-supported compound synthesis based on a broad array of chemical transformations with testing in a variety of biochemical assay formats. A library turnaround time of between 24 and 36 h was achieved, and notably, each library synthesis produces sufficient amounts of compounds for further evaluation in secondary assays thereby contributing significantly to the shortening of medicinal chemistry discovery cycles. PMID:28435537

Deoxygenation of waste cooking oil and non-edible oil for the production of liquid hydrocarbon biofuels.

PubMed

Romero, M J A; Pizzi, A; Toscano, G; Busca, G; Bosio, B; Arato, E

2016-01-01

Deoxygenation of waste cooking vegetable oil and Jatropha curcas oil under nitrogen atmosphere was performed in batch and semi-batch experiments using CaO and treated hydrotalcite (MG70) as catalysts at 400 °C. In batch conditions a single liquid fraction (with yields greater than 80 wt.%) was produced containing a high proportion of hydrocarbons (83%). In semi-batch conditions two liquid fractions (separated by a distillation step) were obtained: a light fraction and an intermediate fraction containing amounts of hydrocarbons between 72-80% and 85-88% respectively. In order to assess the possible use of the liquid products as alternative fuels a complete chemical characterization and measurement of their properties were carried out. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of Coformer Stoichiometric Ratio on Pharmaceutical Cocrystal Dissolution: Three Cocrystals of Carbamazepine/4-Aminobenzoic Acid.

PubMed

Li, Zi; Matzger, Adam J

2016-03-07

Cocrystallization is a technique to optimize solid forms that shows great potential to improve the solubility of active pharmaceutical ingredients (APIs). In some systems, an API can form cocrystals in multiple stoichiometries with the same coformer. However, it remains unclear how coformer stoichiometry influences solubility. This paper investigates the pharmaceutical:coformer pair carbamazepine (CBZ)/p-aminobenzoic acid (PABA); both CBZ/PABA 1:1 and 2:1 cocrystals are known, and a novel 4:1 CBZ/PABA cocrystal is reported here. The 4:1 cocrystal is structurally characterized, and phase stability data suggest that it is a thermodynamically unstable form. Dissolution experiments show that there is no correlation between the cocrystal stoichiometry and dissolution rate in this system. On the other hand, with the relatively weak intermolecular interactions, metastable forms can be beneficial to dissolution rate, which suggests that more effort should be devoted to cocrystal production with kinetic growth methods.

Modeling Remineralization of Desalinated Water by Micronized Calcite Dissolution.

PubMed

Hasson, David; Fine, Larissa; Sagiv, Abraham; Semiat, Raphael; Shemer, Hilla

2017-11-07

A widely used process for remineralization of desalinated water consists of dissolution of calcite particles by flow of acidified desalinated water through a bed packed with millimeter-size calcite particles. An alternative process consists of calcite dissolution by slurry flow of micron-size calcite particles with acidified desalinated water. The objective of this investigation is to provide theoretical models enabling design of remineralization by calcite slurry dissolution with carbonic and sulfuric acids. Extensive experimental results are presented displaying the effects of acid concentration, slurry feed concentration, and dissolution contact time. The experimental data are shown to be in agreement within less than 10% with theoretical predictions based on the simplifying assumption that the slurry consists of uniform particles represented by the surface mean diameter of the powder. Agreement between theory and experiment is improved by 1-8% by taking into account the powder size distribution. Apart from the practical value of this work in providing a hitherto lacking design tool for a novel technology. The paper has the merit of being among the very few publications providing experimental confirmation to the theory describing reaction kinetics in a segregated flow system.

Production Experiences with the Cray-Enabled TORQUE Resource Manager

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

Ezell, Matthew A; Maxwell, Don E; Beer, David

High performance computing resources utilize batch systems to manage the user workload. Cray systems are uniquely different from typical clusters due to Cray s Application Level Placement Scheduler (ALPS). ALPS manages binary transfer, job launch and monitoring, and error handling. Batch systems require special support to integrate with ALPS using an XML protocol called BASIL. Previous versions of Adaptive Computing s TORQUE and Moab batch suite integrated with ALPS from within Moab, using PERL scripts to interface with BASIL. This would occasionally lead to problems when all the components would become unsynchronized. Version 4.1 of the TORQUE Resource Manager introducedmore » new features that allow it to directly integrate with ALPS using BASIL. This paper describes production experiences at Oak Ridge National Laboratory using the new TORQUE software versions, as well as ongoing and future work to improve TORQUE.« less

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

Predictors of supportive coparenting after relationship dissolution among at-risk parents.

PubMed

Kamp Dush, Claire M; Kotila, Letitia E; Schoppe-Sullivan, Sarah J

2011-06-01

Supportive coparenting after relationship dissolution is associated with increased father involvement which can buffer against the negative effects of parental relationship dissolution. Low-income, at-risk families are much more likely to experience relationship dissolutions; hence, supportive coparenting after dissolution is particularly important in these families. We examined whether relationship (commitment and quality) and child (difficult temperament and gender) characteristics predicted initial levels of, and change in, supportive coparenting after relationship dissolution in the Fragile Families and Child Wellbeing Study (N = 1,603). We used structural equation modeling of latent growth curves to examine four time points collected at the focal child's birth and first, third, and fifth birthdays. Ninety-percent of the mothers had nonmarital births, and about three-quarters had a high school diploma or less education. Overall, supportive coparenting decreased over time. Mothers in more committed relationships prior to the dissolution initially had significantly lower supportive coparenting. But over time, mothers who had been in more committed relationships increased in supportive coparenting. Mothers who had been in higher quality relationships prior to dissolution initially reported more supportive coparenting. At each time point, if a mother was romantically involved with a new partner, she reported significantly lower supportive coparenting compared to mothers who were single. With regard to child characteristics, mothers who reported their child as more difficult had significantly lower initial supportive coparenting. Similar results for fathers are discussed. Overall, the relationship characteristics of parents were important predictors of supportive coparenting both initially and over time. 2011 APA, all rights reserved

Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants

PubMed Central

Losa-Adams, Elisabeth; F.-Dávila, Alfonso; Gago-Duport, Luis

2014-01-01

Summary The Fenton reaction is the most widely used advanced oxidation process (AOP) for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc) as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2) particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe3+ into Fe2+ and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm) with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L) and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites. PMID:24991522

Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants.

PubMed

Gil-Lozano, Carolina; Losa-Adams, Elisabeth; F-Dávila, Alfonso; Gago-Duport, Luis

2014-01-01

The Fenton reaction is the most widely used advanced oxidation process (AOP) for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc) as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2) particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe(3+) into Fe(2+) and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm) with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L) and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites.

Can a fractured caprock self-heal?

NASA Astrophysics Data System (ADS)

Elkhoury, Jean E.; Detwiler, Russell L.; Ameli, Pasha

2015-05-01

The ability of geologic seals to prevent leakage of fluids injected into the deep subsurface is critical for mitigating risks associated with greenhouse-gas sequestration and natural-gas production. Fractures caused by tectonic or injection-induced stresses create potential leakage pathways that may be further enhanced by mineral dissolution. We present results from reactive-flow experiments in fractured caprock (dolomitic anhydrite), where additional dissolution occurs in the rock matrix adjacent to the fracture surfaces. Preferential dissolution of anhydrite left a compacted layer of dolomite in the fractures. At lower flow rate, rock-fluid reactions proceeded to near equilibrium within the fracture with preferential flow paths persisting over the 6-month duration of the experiment and a negligible change in permeability. At higher flow rate, permeability decreased by a dramatic two orders of magnitude. This laboratory-scale observation of self-healing argues against the likelihood of runaway permeability growth in fractured porous caprock composed of minerals with different solubilities and reaction kinetics. However, scaling arguments suggest that at larger length scales this self-healing process may be offset by the formation of dissolution channels. Our results have relevance beyond the greenhouse-gas sequestration problem. Chemical disequilibrium at waste injection sites and in hydrothermal reservoirs will lead to reactive flows that may also significantly alter formation permeability.

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

PubMed

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

2017-09-15

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

The recovery of zinc from hot galvanizing slag in an anion-exchange membrane electrolysis reactor.

PubMed

Ren, Xiulian; Wei, Qifeng; Hu, Surong; Wei, Sijie

2010-09-15

This paper reports the optimization of the process parameters for recovery of zinc from hot galvanizing slag in an anion-exchange membrane electrolysis reactor. The experiments were carried out in an ammoniacal ammonium chloride system. The influence of composition of electrolytes, pH, stirring rate, current density and temperature, on cathodic current efficiency, specific power consumption and anodic dissolution of Zn were investigated. The results indicate that the cathode current efficiency increases and the hydrogen evolution decreased with increasing the cathode current density. The partial current for electrodeposition of Zn has liner relationship with omega(1/2) (omega: rotation rate). The highest current efficiency for dissolving zinc was obtained when NH(4)Cl concentration was 53.46 g L(-1) and the anodic dissolution of zinc was determined by mass transfer rate at stirring rate 0-300 r min(-1). Increase in temperature benefits to improve CE and dissolution of Zn, and reduce cell voltage. Initial pH of electrolytes plays an important role in the deposition and anodic dissolution of Zn. The results of single factor experiment show that about 50% energy consumption was saved for electrodeposition of Zn in the anion-exchange membrane electrolysis reactor. Copyright 2010 Elsevier B.V. All rights reserved.

Behaviour and occurrence of estrogens in municipal sewage treatment plants--II. Aerobic batch experiments with activated sludge.

PubMed

Ternes, T A; Kreckel, P; Mueller, J

1999-01-12

Aerobic batch experiments containing a diluted slurry of activated sludge from a real sewage treatment plant (STP) near Frankfurt/Main were undertaken, in order to investigate the persistence of natural estrogens and contraceptives under aerobic conditions. The batch experiments showed that while in contact with activated sludge the natural estrogen 17 beta-estradiol was oxidized to estrone, which was further eliminated in the batch experiments in an approximate linear time dependence. Further degradation products of estrone were not observed. 16 alpha-hydroxyestrone was rapidly eliminated, again without detection of further degradation products. The contraceptive 17 alpha-ethinylestradiol was principally persistent under the selected aerobic conditions, whereas mestranol was rapidly eliminated and small portions of 17 alpha-ethinylestradiol were formed by demethylation. Additionally, two glucuronides of 17 beta-estradiol (17 beta-estradiol-17-glucuronide and 17 beta-estradiol-3-glucuronide) were cleaved in contact with the diluted activated sludge solution and thus 17 beta-estradiol was released. The glucuronidase activity of the activated sludge was further confirmed by the cleavage of 4-methylumbelliferyl-beta-D-glucuronide (MUF-beta-glucuronide) in a solution of a activated sludge slurry and Milli-Q-water (1:100, v/v). The turnover rate obtained was approximately steady state, with a turnover rate of 0.1 mumol/l for the released MUF. Hence, it is very likely that the glucuronic acid moiety of 17 beta-estradiol glucuronides and other estrogen glucuronides become cleaved in a real municipal STP, so that the concentrations of the free estrogens increase.

Acceptance Test Data for BWXT Coated Particle Batches 93172B and 93173B—Defective IPyC and Pyrocarbon Anisotropy

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

Hunn, John D.; Helmreich, Grant W.; Dyer, John A.

Coated particle batches J52O-16-93172B and J52O-16-93173B were produced by Babcock and Wilcox Technologies (BWXT) as part of the production campaign for the Advanced Gas Reactor Fuel Development and Qualification (AGR) Program’s AGR-5/6/7 irradiation test in the Idaho National Laboratory (INL) Advanced Test Reactor (ATR), but were not used in the final fuel composite. However, these batches may be used as demonstration production-scale coated particle fuel for other experiments. Each batch was coated in a 150-mm-diameter production-scale fluidized-bed chemical vapor deposition (CVD) furnace. Tristructural isotropic (TRISO) coatings were deposited on 425-μm-nominal-diameter spherical kernels from BWXT lot J52R-16-69317 containing a mixture ofmore » 15.5%-enriched uranium carbide and uranium oxide (UCO). The TRISO coatings consisted of four consecutive CVD layers: a ~50% dense carbon buffer layer with 100-μm-nominal thickness, a dense inner pyrolytic carbon (IPyC) layer with 40-μm-nominal thickness, a silicon carbide (SiC) layer with 35-μm-nominal thickness, and a dense outer pyrolytic carbon (OPyC) layer with 40-μm-nominal thickness. The TRISO-coated particle batches were sieved to upgrade the particles by removing over-sized and under-sized material, and the upgraded batches were designated by appending the letter A to the end of the batch number (e.g., 93172A). Secondary upgrading by sieving was performed on the A-designated batches to remove particles with missing or very-thin buffer layers that were identified during previous analysis of the individual batches for defective IPyC, as reported in the acceptance test data report for the AGR-5/6/7 production batches [Hunn et al. 2017b]. The additionally-upgraded batches were designated by appending the letter B to the end of the batch number (e.g., 93172B).« less

An experiment to assess the effects of diatom dissolution on oxygen isotope ratios.

PubMed

Smith, Andrew C; Leng, Melanie J; Swann, George E A; Barker, Philip A; Mackay, Anson W; Ryves, David B; Sloane, Hilary J; Chenery, Simon R N; Hems, Mike

2016-01-30

Current studies which use the oxygen isotope composition from diatom silica (δ(18) Odiatom ) as a palaeoclimate proxy assume that the δ(18) Odiatom value reflects the isotopic composition of the water in which the diatom formed. However, diatoms dissolve post mortem, preferentially losing less silicified structures in the water column and during/after burial into sediments. The impact of dissolution on δ(18) Odiatom values and potential misinterpretation of the palaeoclimate record are evaluated. Diatom frustules covering a range of ages (6 samples from the Miocene to the Holocene), environments and species were exposed to a weak alkaline solution for 48 days at two temperatures (20 °C and 4 °C), mimicking natural dissolution post mucilage removal. Following treatment, dissolution was assessed using scanning electron microscope images and a qualitative diatom dissolution index. The diatoms were subsequently analysed for their δ(18) O values using step-wise fluorination and isotope ratio mass spectrometry. Variable levels of diatom dissolution were observed between the six samples; in all cases higher temperatures resulted in more frustule degradation. Dissolution was most evident in younger samples, probably as a result of the more porous nature of the silica. The degree of diatom dissolution does not directly equate to changes in the isotope ratios; the δ(18) Odiatom value was, however, lower after dissolution, but in only half the samples was this reduction outside the analytical error (2σ analytical error = 0.46‰). We have shown that dissolution can have a small negative impact on δ(18) Odiatom values, causing reductions of up to 0.59‰ beyond analytical error (0.46‰) at natural environmental temperatures. These findings need to be considered in palaeoenvironmental reconstructions using δ(18) Odiatom values, especially when interpreting variations in these values of <1‰. Copyright © 2015 John Wiley & Sons, Ltd.

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

Evidence of Multiple Sorption Modes in Layered Double Hydroxides Using Mo As Structural Probe.

PubMed

Ma, Bin; Fernandez-Martinez, Alejandro; Grangeon, Sylvain; Tournassat, Christophe; Findling, Nathaniel; Claret, Francis; Koishi, Ayumi; Marty, Nicolas C M; Tisserand, Delphine; Bureau, Sarah; Salas-Colera, Eduardo; Elkaïm, Erik; Marini, Carlo; Charlet, Laurent

2017-05-16

Layered double hydroxides (LDHs) have been considered as effective phases for the remediation of aquatic environments, to remove anionic contaminants mainly through anion exchange mechanisms. Here, a combination of batch isotherm experiments and X-ray techniques was used to examine molybdate (MoO 4 2- ) sorption mechanisms on CaAl LDHs with increasing loadings of molybdate. Advanced modeling of aqueous data shows that the sorption isotherm can be interpreted by three retention mechanisms, including two types of edge sites complexes, interlayer anion exchange, and CaMoO 4 precipitation. Meanwhile, Mo geometry evolves from tetrahedral to octahedral on the edge, and back to tetrahedral coordination at higher Mo loadings, indicated by Mo K-edge X-ray absorption spectra. Moreover, an anion exchange process on both CaAl LDHs was followed by in situ time-resolved synchrotron-based X-ray diffraction, remarkably agreeing with the sorption isotherm. This detailed molecular view shows that different uptake mechanisms-edge sorption, interfacial dissolution-reprecipitation-are at play and control anion uptake under environmentally relevant conditions, which is contrast to the classical view of anion exchange as the primary retention mechanism. This work puts all these mechanisms in perspective, offering a new insight into the complex interplay of anion uptake mechanisms by LDH phases, by using changes in Mo geometry as powerful molecular-scale probe.

Processes of zinc attenuation by biogenic manganese oxides forming in the hyporheic zone of Pinal Creek, Arizona

PubMed Central

Fuller, Christopher C.; Bargar, John R.

2014-01-01

The distribution and speciation of Zn sorbed to biogenic Mn oxides forming in the hyporheic zone of Pinal Creek, AZ, was investigated using micro-focused Extended X-ray Absorption Fine Structure (EXAFS) and X-ray fluorescence (μSXRF) mapping , bulk EXAFS, and chemical extraction. μSXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and micro-focused EXAFS spectra of Zn in the biogenic Mn oxides coating are indicative of Zn forming triple corner sharing inner-sphere complexes over octahedral vacancies in the Mn oxide sheet structure. Zn desorbed in response to decreasing in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in solid to solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating desorption is not controlled by dissolution of secondary Zn phases. In sum, these findings support the idea that Zn attenuation in Pinal Creek is largely controlled by sorption to microbial Mn oxides forming in the streambed during hyporheic exchange. Sorption to biogenic Mn oxides is likely an important process in Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present. PMID:24460038

Remediation of lead-contaminated sediment by biochar-supported nano-chlorapatite: Accompanied with the change of available phosphorus and organic matters.

PubMed

Huang, Danlian; Deng, Rui; Wan, Jia; Zeng, Guangming; Xue, Wenjing; Wen, Xiaofeng; Zhou, Chengyun; Hu, Liang; Liu, Xigui; Xu, Piao; Guo, Xueying; Ren, Xiaoya

2018-04-15

Some rivers in China have been seriously contaminated due to the discharge of lead (Pb) smelting wastewater. In this study, biochar-supported nano-chlorapatite (BC-nClAP) was synthesized to immobilize Pb in contaminated sediment. The remediation effect of BC-nClAP on Pb-contaminated sediment was evaluated through batch experiments and the materials were characterized by x-ray diffraction, scanning electron microscope, Brunner-Emmet-Teller and electronic differential system. It was found that BC-nClAP can transform Pb effectively from labile fraction into stable fraction with a maximum transformation efficiency increasing to 94.1% after 30 days of treatment, and the stabilization efficiency of toxicity characteristic leaching procedure reached 100% only after 16 days of treatment. The content of available phosphorus (AP) in the sediments treated by BC-nClAP was much less than that treated by nClAP, which indicated a lower risk of eutrophication and suggested the dissolution-precipitation mechanism involved in Pb immobilization. BC-nClAP presented the best immobilization efficiency of Pb and the content of organic matters in BC-nClAP treated samples increased the most, thus the OM might play an important role during the Pb immobilization. Copyright © 2018 Elsevier B.V. All rights reserved.

Biochar immobilizes soil-borne arsenic but not cationic metals in the presence of low-molecular-weight organic acids.

PubMed

Alozie, Nneka; Heaney, Natalie; Lin, Chuxia

2018-07-15

A batch experiment was conducted to examine the effects of biochar on the behaviour of soil-borne arsenic and metals that were mobilized by three low-molecular-weight organic acids. In the presence of citric acid, oxalic acid and malic acid at a molar concentration of 0.01M, the surface of biochar was protonated, which disfavours adsorption of the cationic metals released from the soil by organic acid-driven mobilization. In contrast, the oxyanionic As species were re-immobilized by the protonated biochar effectively. Biochar could also immobilize oxyanionic Cr species but not cationic Cr species. The addition of biochar increased the level of metals in the solution due to the release of the biochar-borne metals under attack by LMWOAs via cation exchange. Biochar could also have the potential to enhance reductive dissolution of iron and manganese oxides in the soil, leading to enhanced release of trace elements bound to these oxides. The findings obtained from this study have implications for evaluating the role of biochar in immobilizing trace elements in rhizosphere. Adsorption of cationic heavy metals on biochar in the presence of LMWOAs is unlikely to be a mechanism responsible for the impeded uptake of heavy metals by plants growing in heavy metal-contaminated soils. Copyright © 2018 Elsevier B.V. All rights reserved.

Metal release from sandstones under experimentally and numerically simulated CO2 leakage conditions.

PubMed

Kirsch, Katie; Navarre-Sitchler, Alexis K; Wunsch, Assaf; McCray, John E

2014-01-01

Leakage of CO2 from a deep storage formation into an overlying potable aquifer may adversely impact water quality and human health. Understanding CO2-water-rock interactions is therefore an important step toward the safe implementation of geologic carbon sequestration. This study targeted the geochemical response of siliclastic rock, specifically three sandstones of the Mesaverde Group in northwestern Colorado. To test the hypothesis that carbonate minerals, even when present in very low levels, would be the primary source of metals released into a CO2-impacted aquifer, two batch experiments were conducted. Samples were reacted for 27 days with water and CO2 at partial pressures of 0.01 and 1 bar, representing natural background levels and levels expected in an aquifer impacted by a small leakage, respectively. Concentrations of major (e.g., Ca, Mg) and trace (e.g., As, Ba, Cd, Fe, Mn, Pb, Sr, U) elements increased rapidly after CO2 was introduced into the system, but did not exceed primary Maximum Contaminant Levels set by the U.S. Environmental Protection Agency. Results of sequential extraction suggest that carbonate minerals, although volumetrically insignificant in the sandstone samples, are the dominant source of mobile metals. This interpretation is supported by a simple geochemical model, which could simulate observed changes in fluid composition through CO2-induced calcite and dolomite dissolution.

Silicate minerals for CO2 scavenging from biogas in Autogenerative High Pressure Digestion.

PubMed

Lindeboom, Ralph E F; Ferrer, Ivet; Weijma, Jan; van Lier, Jules B

2013-07-01

Autogenerative High Pressure Digestion (AHPD) is a novel concept that integrates gas upgrading with anaerobic digestion by selective dissolution of CO2 at elevated biogas pressure. However, accumulation of CO2 and fatty acids after anaerobic digestion of glucose resulted in pH 3-5, which is incompatible with the commonly applied high-rate methanogenic processes. Therefore, we studied the use of wollastonite, olivine and anorthosite, with measured composition of CaSi1.05O3.4, Mg2Fe0.2Ni0.01Si1.2O5.3 and Na0.7Ca1K0.1Mg0.1Fe0.15Al3.1Si4O24, respectively, to scavenge CO2 during batch AHPD of glucose. Depending on the glucose to mineral ratio the pH increased to 6.0-7.5. Experiments with wollastonite showed that Ca(2+)-leaching was caused by volatile fatty acid (VFA) production during glucose digestion. At 1, 3 and 9 bar, the CH4 content reached 74%, 86% and 88%, respectively, indicating CO2 scavenging. Fixation of produced CO2 by CaCO3 precipitation in the sludge was confirmed by Fourier Transferred-InfraRed, Combined Field emission Scanning Electron Microscopy-Energy-dispersive X-ray spectroscopy and Thermogravimetric Analysis-Mass Spectroscopy. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

Quality-by-design approach for the development of telmisartan potassium tablets.

PubMed

Oh, Ga-Hui; Park, Jin-Hyun; Shin, Hye-Won; Kim, Joo-Eun; Park, Young-Joon

2018-05-01

A quality-by-design approach was adopted to develop telmisartan potassium (TP) tablets, which were bioequivalent with the commercially available Micardis ® (telmisartan free base) tablets. The dissolution pattern and impurity profile of TP tablets differed from those of Micardis ® tablets because telmisartan free base is poorly soluble in water. After identifying the quality target product profile and critical quality attributes (CQAs), drug dissolution, and impurities were predicted to be risky CQAs. To determine the exact range and cause of risks, we used the risk assessment (RA) tools, preliminary hazard analysis and failure mode and effect analysis to determine the parameters affecting drug dissolution, impurities, and formulation. The range of the design space was optimized using the face-centered central composite design among the design of experiment (DOE) methods. The binder, disintegrant, and kneading time in the wet granulation were identified as X values affecting Y values (disintegration, hardness, friability, dissolution, and impurities). After determining the design space with the desired Y values, the TP tablets were formulated and their dissolution pattern was compared with that of the reference tablet. The selected TP tablet formulated using design space showed a similar dissolution to that of Micardis ® tablets at pH 7.5. The QbD approach TP tablet was bioequivalent to Micardis ® tablets in beagle dogs.

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.

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

Role of fiber dissolution in biological activity in rats.

PubMed

Eastes, W; Hadley, J G

1994-12-01

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

'Own-Label' Versus Branded Commercial Dental Resin Composite Materials: Mechanical And Physical Property Comparisons.

PubMed

Shaw, Kathryn; Martins, Ricardo; Hadis, Mohammed Abdul; Burke, Trevor; Palin, William

2016-09-01

A majority of dental materials are manufactured by companies who have experience in the field. However, a number of "own label" materials have become available, principally marketed by distributors and other companies with little or no experience in the field. These materials are attractive because of their reduced cost, but they may have no research on which clinicians might base their potential performance. It is therefore the purpose of this work to compare the performance of different batches of a number of "own-label" dental materials with a similar number from manufacturers with experience in the field, using a variety of laboratory test regimes which include filler determination, degree of conversion, flexural strength and flexural modulus, in order to evaluate key material properties. The results indicated that own-label dental resin composites produced similar results to materials from established companies in terms of flexural strength characteristics and degree of conversion. However, a greater batch-to-batch variation in several mechanical and physical properties of the own-label materials was noted. Copyright© 2016 Dennis Barber Ltd.

Chemical disinfection of combined sewer overflow waters using performic acid or peracetic acids.

PubMed

Chhetri, Ravi Kumar; Thornberg, Dines; Berner, Jesper; Gramstad, Robin; Öjstedt, Ulrik; Sharma, Anitha Kumari; Andersen, Henrik Rasmus

2014-08-15

We investigated the possibility of applying performic acid (PFA) and peracetic acid (PAA) for disinfection of combined sewer overflow (CSO) in existing CSO management infrastructures. The disinfection power of PFA and PAA towards Escherichia coli (E. coli) and Enterococcus was studied in batch-scale and pre-field experiments. In the batch-scale experiment, 2.5 mg L(-1) PAA removed approximately 4 log unit of E. coli and Enterococcus from CSO with a 360 min contact time. The removal of E. coli and Enterococcus from CSO was always around or above 3 log units using 2-4 mg L(-1) PFA; with a 20 min contact time in both batch-scale and pre-field experiments. There was no toxicological effect measured by Vibrio fischeri when CSO was disinfected with PFA; a slight toxic effect was observed on CSO disinfected with PAA. When the design for PFA based disinfection was applied to CSO collected from an authentic event, the disinfection efficiencies were confirmed and degradation rates were slightly higher than predicted in simulated CSO. Copyright © 2014 Elsevier B.V. All rights reserved.

Elimination of the Reaction Rate "Scale Effect": Application of the Lagrangian Reactive Particle-Tracking Method to Simulate Mixing-Limited, Field-Scale Biodegradation at the Schoolcraft (MI, USA) Site

NASA Astrophysics Data System (ADS)

Ding, Dong; Benson, David A.; Fernández-Garcia, Daniel; Henri, Christopher V.; Hyndman, David W.; Phanikumar, Mantha S.; Bolster, Diogo

2017-12-01

Measured (or empirically fitted) reaction rates at groundwater remediation sites are typically much lower than those found in the same material at the batch or laboratory scale. The reduced rates are commonly attributed to poorer mixing at the larger scales. A variety of methods have been proposed to account for this scaling effect in reactive transport. In this study, we use the Lagrangian particle-tracking and reaction (PTR) method to simulate a field bioremediation experiment at the Schoolcraft, MI site. A denitrifying bacterium, Pseudomonas Stutzeri strain KC (KC), was injected to the aquifer, along with sufficient substrate, to degrade the contaminant, carbon tetrachloride (CT), under anaerobic conditions. The PTR method simulates chemical reactions through probabilistic rules of particle collisions, interactions, and transformations to address the scale effect (lower apparent reaction rates for each level of upscaling, from batch to column to field scale). In contrast to a prior Eulerian reaction model, the PTR method is able to match the field-scale experiment using the rate coefficients obtained from batch experiments.

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.

Leaching of cadmium and tellurium from cadmium telluride (CdTe) thin-film solar panels under simulated landfill conditions

PubMed Central

Ramos-Ruiz, Adriana; Wilkening, Jean V.; Field, James A.; Sierra-Alvarez, Reyes

2017-01-01

A crushed non-encapsulated CdTe thin-film solar cell was subjected to two standardized batch leaching tests (i.e., Toxicity Characteristic Leaching Procedure (TCLP) and California Waste Extraction Test (WET)) and to a continuous-flow column test to assess cadmium (Cd) and tellurium (Te) dissolution under conditions simulating the acidic- and the methanogenic phases of municipal solid waste landfills. Low levels of Cd and Te were solubilized in both batch leaching tests (<8.2% and <3.6% of added Cd and Te, respectively). On the other hand, over the course of 30 days, 73% of the Cd and 21% of the Te were released to the synthetic leachate of a continuous-flow column simulating the acidic landfill phase. The dissolved Cd concentration was 3.24-fold higher than the TCLP limit (1 mg L-1), and 650-fold higher than the maximum contaminant level established by the US-EPA for this metal in drinking water (0.005 mg L-1). In contrast, the release of Cd and Te to the effluent of the continuous-flow column simulating the methanogenic phase of a landfill was negligible. The remarkable difference in the leaching behavior of CdTe in the columns is related to different aqueous pH and redox conditions promoted by the microbial communities in the columns, and is in agreement with thermodynamic predictions. PMID:28472709