Thermodynamic Equilibrium Calculations on Cd Transformation during Sewage Sludge Incineration.

PubMed

Liu, Jing-yong; Huang, Limao; Sun, Shuiyu; Ning, Xun'an; Kuo, Jiahong; Sun, Jian; Wang, Yujie; Xie, Wuming

2016-06-01

Thermodynamic equilibrium calculations were performed to reveal the distribution of cadmium during the sewage sludge incineration process. During sludge incineration in the presence of major minerals, such as SiO2, Al2O3 and CaO, the strongest effect was exerted by SiO2 on the Cd transformation compared with the effect of others. The stable solid product of CdSiO3 was formed easily with the reaction between Cd and SiO2, which can restrain the emissions of gaseous Cd pollutants. CdCl2 was formed more easily in the presence of chloride during incineration, thus, the volatilization of Cd was advanced by increasing chlorine content. At low temperatures, the volatilization of Cd was restrained due to the formation of the refractory solid metal sulfate. At high temperatures, the speciation of Cd was not affected by the presence of sulfur, but sulfur could affect the formation temperature of gaseous metals.

User's guide to PHREEQC, a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, D.L.

1995-01-01

PHREEQC is a computer program written in the C pwgranuning language that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations, (2) reaction-path and advective-transport calculations involving specified irreversible reactions, mixing of solutions, mineral and gas equilibria surface-complex-ation reactions, and ion-exchange reactions, and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for composition differences between waters, within specified compositional uncertainties. PHREEQC is derived from the Fortran program PHREEQE, but it has been completely rewritten in C with the addition many new capabilities. New features include the capabilities to use redox couples to distribute redox elements among their valence states in speciation calculations; to model ion-exchange and surface-compiexation reactions; to model reactions with a fixed-pressure, multicomponent gas phase (that is, a gas bubble); to calculate the mass of water in the aqueous phase during reaction and transport calculations; to keep track of the moles of minerals present in the solid phases and determine antomaticaHy the thermodynamically stable phase assemblage; to simulate advective transport in combination with PHREEQC's reaction-modeling capability; and to make inverse modeling calculations that allow for uncertainties in the analytical data. The user interface is improved through the use of a simplified approach to redox reactions, which includes explicit mole-balance equations for hydrogen and oxygen; the use of a revised input that is modular and completely free format; and the use of mineral names and standard chemical symbolism rather than index numbers. The use of (2 eliminates nearly all limitations on army sizes, including numbers of elements, aqueous species, solutions, phases, and lengths of character strings. A new equation solver that optimizes a set of equalities subject to both equality and inequality constraints is used to determine the thermodynamically stable set of phases in equilibrium with a solution. A more complete Newton-Raphson formulation, master-species switching, and scaling of the algebraic equations reduce the number of failures of the nunmrical method in PHREEQC relative to PHREEQE. This report presents the equations that are the basis for chemical equilibrium and inverse-modeling calculations in PHREEQC, describes the input for the program, and presents twelve examples that demonstrate most of the program's capabilities.

Metal speciation in landfill leachates with a focus on the influence of organic matter

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

Claret, Francis, E-mail: f.claret@brgm.fr; Tournassat, Christophe; Crouzet, Catherine

Highlights: > This study characterises the heavy-metal content in leachates collected from eight landfills in France. > Most of the metals are concentrated in the <30 kDa fraction, while Pb, Cu and Cd are associated with larger particles. > Metal complexation with OM is not sufficient to explain apparent supersaturation of metals with sulphide minerals. - Abstract: This study characterises the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmospheremore » to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.« less

Fate of heavy metals during municipal solid waste incineration.

PubMed

Abanades, S; Flamant, G; Gagnepain, B; Gauthier, D

2002-02-01

A thermodynamic analysis was performed to determine whether it is suitable to predict the heavy metal (HM) speciation during the Municipal Solid Waste Incineration process. The fate of several selected metals (Cd, Pb, Zn, Cr, Hg, As, Cu, Co, Ni) during incineration was theoretically investigated. The equilibrium analysis predicted the metal partitioning during incineration and determined the impact of operating conditions (temperature and gas composition) on their speciation. The study of the gas composition influence was based on the effects of the contents of oxygen (reducing or oxidising conditions) and chlorine on the HM partitioning. The theoretical HM speciation which was calculated in a complex system representing a burning sample of Municipal Solid Waste can explain the real partitioning (obtained from literature results) of all metals among the various ashes except for Pb. Then, the results of the thermodynamic study were compared with those of characterisation of real incinerator residues, using complementary techniques (chemical extraction series and X-ray micro-analyses). These analysis were performed to determine experimentally the speciation of the three representative metals Cr, Pb, and Zn. The agreement is good for Cr and Zn but not for Pb again, which mainly shows unleachable chemical speciations in the residues. Pb tends to remain in the bottom ash whereas thermodynamics often predicts its complete volatilisation under chlorides, and thus its presence exclusively in fly ash.

Chemical behavior of Cu, Zn, Cd, and Pb in a eutrophic reservoir: speciation and complexation capacity.

PubMed

Tonietto, Alessandra Emanuele; Lombardi, Ana Teresa; Choueri, Rodrigo Brasil; Vieira, Armando Augusto Henriques

2015-10-01

This research aimed at evaluating cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) speciation in water samples as well as determining water quality parameters (alkalinity, chlorophyll a, chloride, conductivity, dissolved organic carbon, dissolved oxygen, inorganic carbon, nitrate, pH, total suspended solids, and water temperature) in a eutrophic reservoir. This was performed through calculation of free metal ions using the chemical equilibrium software MINEQL+ 4.61, determination of labile, dissolved, and total metal concentrations via differential pulse anodic stripping voltammetry, and determination of complexed metal by the difference between the total concentration of dissolved and labile metal. Additionally, ligand complexation capacities (CC), such as the strength of the association of metals-ligands (logK'ML) and ligand concentrations (C L) were calculated via Ruzic's linearization method. Water samples were taken in winter and summer, and the results showed that for total and dissolved metals, Zn > Cu > Pb > Cd concentration. In general, higher concentrations of Cu and Zn remained complexed with the dissolved fraction, while Pb was mostly complexed with particulate materials. Chemical equilibrium modeling (MINEQL+) showed that Zn(2+) and Cd(2+) dominated the labile species, while Cu and Pb were complexed with carbonates. Zinc was a unique metal for which a direct relation between dissolved species with labile and complexed forms was obtained. The CC for ligands indicated a higher C L for Cu, followed by Pb, Zn, and Cd in decreasing amounts. Nevertheless, the strength of the association of all metals and their respective ligands was similar. Factor analysis with principal component analysis as the extraction procedure confirmed seasonal effects on water quality parameters and metal speciation. Total, dissolved, and complexed Cu and total, dissolved, complexed, and labile Pb species were all higher in winter, whereas in summer, Zn was mostly present in the complexed form. A high degree of deterioration of the reservoir was confirmed by the results of this study.

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

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

Robinson, Troy A

2011-08-01

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd 3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22Na and 13C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd 3+, Na +,more » lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP) 2] x; (with x > 1). By substituting lanthanum (La 3+) for Nd 3+ in this system, NMR scoping experiments using 23Na, 31P nuclei and 13C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu 3+) and 8-hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu 3+) and 8-hydroxyquinoline speciation. Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8-hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu 3+ led to lower stability hydrolysis complexes in the mixed solvent than in water. Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explored systems, but more work is required to produce a comprehensive understanding of the speciation involved.« less

Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

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

Moffat, Harry K.; Jove-Colon, Carlos F.

2009-06-01

In this report, we summarize our work on developing a production level capability for modeling brine thermodynamic properties using the open-source code Cantera. This implementation into Cantera allows for the application of chemical thermodynamics to describe the interactions between a solid and an electrolyte solution at chemical equilibrium. The formulations to evaluate the thermodynamic properties of electrolytes are based on Pitzer's model to calculate molality-based activity coefficients using a real equation-of-state (EoS) for water. In addition, the thermodynamic properties of solutes at elevated temperature and pressures are computed using the revised Helgeson-Kirkham-Flowers (HKF) EoS for ionic and neutral aqueous species.more » The thermodynamic data parameters for the Pitzer formulation and HKF EoS are from the thermodynamic database compilation developed for the Yucca Mountain Project (YMP) used with the computer code EQ3/6. We describe the adopted equations and their implementation within Cantera and also provide several validated examples relevant to the calculations of extensive properties of electrolyte solutions.« less

GEOSURF: a computer program for modeling adsorption on mineral surfaces from aqueous solution

NASA Astrophysics Data System (ADS)

Sahai, Nita; Sverjensky, Dimitri A.

1998-11-01

A new program, GEOSURF, has been developed for calculating aqueous and surface speciation consistent with the triple-layer model of surface complexation. GEOSURF is an extension of the original programs MINEQL, MICROQL and HYDRAQL. We present, here, the basic algorithm of GEOSURF along with a description of the new features implemented. GEOSURF is linked to internally consistent data bases for surface species (SURFK.DAT) and for aqueous species (AQSOL.DAT). SURFK.DAT contains properties of minerals such as site densities, and equilibrium constants for adsorption of aqueous protons and electrolyte ions on a variety of oxides and hydroxides. The Helgeson, Kirkham and Flowers version of the extended Debye-Huckel Equation for 1:1 electrolytes is implemented for calculating aqueous activity coefficients. This permits the calculation of speciation at ionic strengths greater than 0.5 M. The activity of water is computed explicitly from the osmotic coefficient of the solution, and the total amount of electrolyte cation (or anion) is adjusted to satisfy the electroneutrality condition. Finally, the use of standard symbols for chemical species rather than species identification numbers is included to facilitate use of the program. One of the main limitations of GEOSURF is that aqueous and surface speciation can only be calculated at fixed pH and at fixed concentration of total adsorbate. Thus, the program cannot perform reaction-path calculations: it cannot determine whether or not a solution is over- or under-saturated with respect to one or more solid phases. To check the proper running of GEOSURF, we have compared results generated by GEOSURF with those from two other programs, HYDRAQL and EQ3. The Davies equation and the "bdot" equation, respectively, are used in the latter two programs for calculating aqueous activity coefficients. An example of the model fit to experimental data for rutile in 0.001 M-2.0 M NaNO 3 is included.

Mussel-inspired histidine-based transient network metal coordination hydrogels

PubMed Central

Fullenkamp, Dominic E.; He, Lihong; Barrett, Devin G.; Burghardt, Wesley R.; Messersmith, Phillip B.

2013-01-01

Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants. PMID:23441102

EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 3

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

Wolery, T.J.

1992-09-14

EQ3NR is an aqueous solution speciation-solubility modeling code. It is part of the EQ3/6 software package for geochemical modeling. It computes the thermodynamic state of an aqueous solution by determining the distribution of chemical species, including simple ions, ion pairs, and complexes, using standard state thermodynamic data and various equations which describe the thermodynamic activity coefficients of these species. The input to the code describes the aqueous solution in terms of analytical data, including total (analytical) concentrations of dissolved components and such other parameters as the pH, pHCl, Eh, pe, and oxygen fugacity. The input may also include a desiredmore » electrical balancing adjustment and various constraints which impose equilibrium with special pure minerals, solid solution end-member components (of specified mole fractions), and gases (of specified fugacities). The code evaluates the degree of disequilibrium in terms of the saturation index (SI = 1og Q/K) and the thermodynamic affinity (A = {minus}2.303 RT log Q/K) for various reactions, such as mineral dissolution or oxidation-reduction in the aqueous solution itself. Individual values of Eh, pe, oxygen fugacity, and Ah (redox affinity) are computed for aqueous redox couples. Equilibrium fugacities are computed for gas species. The code is highly flexible in dealing with various parameters as either model inputs or outputs. The user can specify modification or substitution of equilibrium constants at run time by using options on the input file.« less

Non-equilibrium dynamics and floral trait interactions shape extant angiosperm diversity

PubMed Central

O'Meara, Brian C.; Smith, Stacey D.; Armbruster, W. Scott; Harder, Lawrence D.; Hardy, Christopher R.; Hileman, Lena C.; Hufford, Larry; Litt, Amy; Magallón, Susana; Smith, Stephen A.; Stevens, Peter F.; Fenster, Charles B.; Diggle, Pamela K.

2016-01-01

Why are some traits and trait combinations exceptionally common across the tree of life, whereas others are vanishingly rare? The distribution of trait diversity across a clade at any time depends on the ancestral state of the clade, the rate at which new phenotypes evolve, the differences in speciation and extinction rates across lineages, and whether an equilibrium has been reached. Here we examine the role of transition rates, differential diversification (speciation minus extinction) and non-equilibrium dynamics on the evolutionary history of angiosperms, a clade well known for the abundance of some trait combinations and the rarity of others. Our analysis reveals that three character states (corolla present, bilateral symmetry, reduced stamen number) act synergistically as a key innovation, doubling diversification rates for lineages in which this combination occurs. However, this combination is currently less common than predicted at equilibrium because the individual characters evolve infrequently. Simulations suggest that angiosperms will remain far from the equilibrium frequencies of character states well into the future. Such non-equilibrium dynamics may be common when major innovations evolve rarely, allowing lineages with ancestral forms to persist, and even outnumber those with diversification-enhancing states, for tens of millions of years. PMID:27147092

Non-equilibrium dynamics and floral trait interactions shape extant angiosperm diversity.

PubMed

O'Meara, Brian C; Smith, Stacey D; Armbruster, W Scott; Harder, Lawrence D; Hardy, Christopher R; Hileman, Lena C; Hufford, Larry; Litt, Amy; Magallón, Susana; Smith, Stephen A; Stevens, Peter F; Fenster, Charles B; Diggle, Pamela K

2016-05-11

Why are some traits and trait combinations exceptionally common across the tree of life, whereas others are vanishingly rare? The distribution of trait diversity across a clade at any time depends on the ancestral state of the clade, the rate at which new phenotypes evolve, the differences in speciation and extinction rates across lineages, and whether an equilibrium has been reached. Here we examine the role of transition rates, differential diversification (speciation minus extinction) and non-equilibrium dynamics on the evolutionary history of angiosperms, a clade well known for the abundance of some trait combinations and the rarity of others. Our analysis reveals that three character states (corolla present, bilateral symmetry, reduced stamen number) act synergistically as a key innovation, doubling diversification rates for lineages in which this combination occurs. However, this combination is currently less common than predicted at equilibrium because the individual characters evolve infrequently. Simulations suggest that angiosperms will remain far from the equilibrium frequencies of character states well into the future. Such non-equilibrium dynamics may be common when major innovations evolve rarely, allowing lineages with ancestral forms to persist, and even outnumber those with diversification-enhancing states, for tens of millions of years. © 2016 The Author(s).

Using Visible Spectrophotometers and pH Measurements to Study Speciation in a Guided-Inquiry Laboratory

ERIC Educational Resources Information Center

Otto, William H.; Larive, Cynthia K.; Mason, Susan L.; Robinson, Janet B.; Heppert Joseph A.; Ellis, James D.

2005-01-01

An experiment to perform a simple initial investigation that illustrates concepts of speciation and equilibrium, using the instrument and chemical resources in the laboratory is presented. The investigation showed that the presence of multiple chemical species in a reaction mixture (phenol red solution) reflects the acid and base conditions…

Evaluation of trace metals bioavailability in Japanese river waters using DGT and a chemical equilibrium model.

PubMed

Han, Shuping; Naito, Wataru; Hanai, Yoshimichi; Masunaga, Shigeki

2013-09-15

To develop efficient and effective methods of assessing and managing the risk posed by metals to aquatic life, it is important to determine the effects of water chemistry on the bioavailability of metals in surface water. In this study, we employed the diffusive gradients in thin-films (DGT) to determine the bioavailability of metals (Ni, Cu, Zn, and Pb) in Japanese water systems. The DGT results were compared with a chemical equilibrium model (WHAM 7.0) calculation to examine its robustness and utility to predict dynamic metal speciation. The DGT measurements showed that biologically available fractions of metals in the rivers impacted by mine drainage and metal industries were relatively high compared with those in urban rivers. Comparison between the DGT results and the model calculation indicated good agreement for Zn. The model calculation concentrations for Ni and Cu were higher than the DGT concentrations at most sites. As for Pb, the model calculation depended on whether the precipitated iron(III) hydroxide or precipitated aluminum(III) hydroxide was assumed to have an active surface. Our results suggest that the use of WHAM 7.0 combined with the DGT method can predict bioavailable concentrations of most metals (except for Pb) with reasonable accuracy. Copyright © 2013. Published by Elsevier Ltd.

Biological signatures of dynamic river networks from a coupled landscape evolution and neutral community model

NASA Astrophysics Data System (ADS)

Stokes, M.; Perron, J. T.

2017-12-01

Freshwater systems host exceptionally species-rich communities whose spatial structure is dictated by the topology of the river networks they inhabit. Over geologic time, river networks are dynamic; drainage basins shrink and grow, and river capture establishes new connections between previously separated regions. It has been hypothesized that these changes in river network structure influence the evolution of life by exchanging and isolating species, perhaps boosting biodiversity in the process. However, no general model exists to predict the evolutionary consequences of landscape change. We couple a neutral community model of freshwater organisms to a landscape evolution model in which the river network undergoes drainage divide migration and repeated river capture. Neutral community models are macro-ecological models that include stochastic speciation and dispersal to produce realistic patterns of biodiversity. We explore the consequences of three modes of speciation - point mutation, time-protracted, and vicariant (geographic) speciation - by tracking patterns of diversity in time and comparing the final result to an equilibrium solution of the neutral model on the final landscape. Under point mutation, a simple model of stochastic and instantaneous speciation, the results are identical to the equilibrium solution and indicate the dominance of the species-area relationship in forming patterns of diversity. The number of species in a basin is proportional to its area, and regional species richness reaches its maximum when drainage area is evenly distributed among sub-basins. Time-protracted speciation is also modeled as a stochastic process, but in order to produce more realistic rates of diversification, speciation is not assumed to be instantaneous. Rather, each new species must persist for a certain amount of time before it is considered to be established. When vicariance (geographic speciation) is included, there is a transient signature of increased regional diversity after river capture. The results indicate that the mode of speciation and the rate of speciation relative to the rate of divide migration determine the evolutionary signature of river capture.

Interactions between hydrated cement paste and organic acids: Thermodynamic data and speciation modeling

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

De Windt, Laurent, E-mail: laurent.dewindt@mines-paristech.fr; Bertron, Alexandra; Larreur-Cayol, Steeves

2015-03-15

Interactions of short-chain organic acids with hydrated cement phases affect structure durability in the agro-food and nuclear waste industries but can also be used to modify cement properties. Most previous studies have been experimental, performed at fixed concentrations and pH, without quantitatively discriminating among polyacidity effects, or complexation and salt precipitation processes. This paper addresses such issues by thermodynamic equilibrium calculations for acetic, citric, oxalic, succinic acids and a simplified hydrated CEM-I. The thermodynamic constants collected from the literature allow the speciation to be modeled over a wide range of pH and concentrations. Citric and oxalic had a stronger chelatingmore » effect than acetic acid, while succinic acid was intermediate. Similarly, Ca-citrate and Ca-oxalate salts were more insoluble than Ca-acetate and Ca-succinate salts. Regarding aluminium complexation, hydroxyls, sulfates, and acid competition was highlighted. The exploration of acid mixtures showed the preponderant effect of oxalate and citrate over acetate and succinate.« less

Calculation of the relative metastabilities of proteins using the CHNOSZ software package

PubMed Central

Dick, Jeffrey M

2008-01-01

Background Proteins of various compositions are required by organisms inhabiting different environments. The energetic demands for protein formation are a function of the compositions of proteins as well as geochemical variables including temperature, pressure, oxygen fugacity and pH. The purpose of this study was to explore the dependence of metastable equilibrium states of protein systems on changes in the geochemical variables. Results A software package called CHNOSZ implementing the revised Helgeson-Kirkham-Flowers (HKF) equations of state and group additivity for ionized unfolded aqueous proteins was developed. The program can be used to calculate standard molal Gibbs energies and other thermodynamic properties of reactions and to make chemical speciation and predominance diagrams that represent the metastable equilibrium distributions of proteins. The approach takes account of the chemical affinities of reactions in open systems characterized by the chemical potentials of basis species. The thermodynamic database included with the package permits application of the software to mineral and other inorganic systems as well as systems of proteins or other biomolecules. Conclusion Metastable equilibrium activity diagrams were generated for model cell-surface proteins from archaea and bacteria adapted to growth in environments that differ in temperature and chemical conditions. The predicted metastable equilibrium distributions of the proteins can be compared with the optimal growth temperatures of the organisms and with geochemical variables. The results suggest that a thermodynamic assessment of protein metastability may be useful for integrating bio- and geochemical observations. PMID:18834534

Trace metal speciation in natural waters: Computational vs. analytical

USGS Publications Warehouse

Nordstrom, D. Kirk

1996-01-01

Improvements in the field sampling, preservation, and determination of trace metals in natural waters have made many analyses more reliable and less affected by contamination. The speciation of trace metals, however, remains controversial. Chemical model speciation calculations do not necessarily agree with voltammetric, ion exchange, potentiometric, or other analytical speciation techniques. When metal-organic complexes are important, model calculations are not usually helpful and on-site analytical separations are essential. Many analytical speciation techniques have serious interferences and only work well for a limited subset of water types and compositions. A combined approach to the evaluation of speciation could greatly reduce these uncertainties. The approach proposed would be to (1) compare and contrast different analytical techniques with each other and with computed speciation, (2) compare computed trace metal speciation with reliable measurements of solubility, potentiometry, and mean activity coefficients, and (3) compare different model calculations with each other for the same set of water analyses, especially where supplementary data on speciation already exist. A comparison and critique of analytical with chemical model speciation for a range of water samples would delineate the useful range and limitations of these different approaches to speciation. Both model calculations and analytical determinations have useful and different constraints on the range of possible speciation such that they can provide much better insight into speciation when used together. Major discrepancies in the thermodynamic databases of speciation models can be evaluated with the aid of analytical speciation, and when the thermodynamic models are highly consistent and reliable, the sources of error in the analytical speciation can be evaluated. Major thermodynamic discrepancies also can be evaluated by simulating solubility and activity coefficient data and testing various chemical models for their range of applicability. Until a comparative approach such as this is taken, trace metal speciation will remain highly uncertain and controversial.

Understanding how biodiversity unfolds through time under neutral theory.

PubMed

Missa, Olivier; Dytham, Calvin; Morlon, Hélène

2016-04-05

Theoretical predictions for biodiversity patterns are typically derived under the assumption that ecological systems have reached a dynamic equilibrium. Yet, there is increasing evidence that various aspects of ecological systems, including (but not limited to) species richness, are not at equilibrium. Here, we use simulations to analyse how biodiversity patterns unfold through time. In particular, we focus on the relative time required for various biodiversity patterns (macroecological or phylogenetic) to reach equilibrium. We simulate spatially explicit metacommunities according to the Neutral Theory of Biodiversity (NTB) under three modes of speciation, which differ in how evenly a parent species is split between its two daughter species. We find that species richness stabilizes first, followed by species area relationships (SAR) and finally species abundance distributions (SAD). The difference in timing of equilibrium between these different macroecological patterns is the largest when the split of individuals between sibling species at speciation is the most uneven. Phylogenetic patterns of biodiversity take even longer to stabilize (tens to hundreds of times longer than species richness) so that equilibrium predictions from neutral theory for these patterns are unlikely to be relevant. Our results suggest that it may be unwise to assume that biodiversity patterns are at equilibrium and provide a first step in studying how these patterns unfold through time. © 2016 The Author(s).

Understanding how biodiversity unfolds through time under neutral theory

PubMed Central

2016-01-01

Theoretical predictions for biodiversity patterns are typically derived under the assumption that ecological systems have reached a dynamic equilibrium. Yet, there is increasing evidence that various aspects of ecological systems, including (but not limited to) species richness, are not at equilibrium. Here, we use simulations to analyse how biodiversity patterns unfold through time. In particular, we focus on the relative time required for various biodiversity patterns (macroecological or phylogenetic) to reach equilibrium. We simulate spatially explicit metacommunities according to the Neutral Theory of Biodiversity (NTB) under three modes of speciation, which differ in how evenly a parent species is split between its two daughter species. We find that species richness stabilizes first, followed by species area relationships (SAR) and finally species abundance distributions (SAD). The difference in timing of equilibrium between these different macroecological patterns is the largest when the split of individuals between sibling species at speciation is the most uneven. Phylogenetic patterns of biodiversity take even longer to stabilize (tens to hundreds of times longer than species richness) so that equilibrium predictions from neutral theory for these patterns are unlikely to be relevant. Our results suggest that it may be unwise to assume that biodiversity patterns are at equilibrium and provide a first step in studying how these patterns unfold through time. PMID:26977066

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.

Theoretical modeling of the urinary supersaturation of calcium salts in healthy individuals and kidney stone patients: Precursors, speciation and therapeutic protocols for decreasing its value

NASA Astrophysics Data System (ADS)

Rodgers, Allen L.; Allie-Hamdulay, Shameez; Jackson, Graham E.; Durbach, Ian

2013-11-01

BackgroundSupersaturation (SS) of urinary salts has been extensively invoked for assessing the risk of renal stone formation, but precursors have often been ignored. Our objectives were to establish by computer modeling, which urinary components are essential for calculating reliable SS values, to investigate whether unique equilibrium processes occur in the urine of stone formers (SF) which might account for their higher SS levels relative to healthy controls (N), to determine the relative efficacies of three different, widely-used protocols for lowering urinary SS of calcium salts and to examine the influence of precursors.

Copper speciation in the gill microenvironment of carp (Cyprinus carpio) at various levels of pH.

PubMed

Tao, Shu; Long, Aimin; Xu, Fuliu; Dawson, R W

2002-07-01

The fish gill microenvironment of Cyprinus carpio under stress of copper exposure was investigated. pH and other parameters including free copper activity, alkalinity, and inorganic and organic carbons in the surrounding water (inspired water) and in the gill microenvironment (expired water) were measured or calculated at various levels of pH and varying total copper concentrations. The chemical equilibrium calculation (from MINEQA2) and complexation modeling (mucus-copper) were coupled to calculate both species distribution. The results indicate that the pH in the fish gill microenvironment was different from that in the surrounding water with a balance point around 6.9. The secretion of both CO(2) and mucus was affected in both linear and nonlinear ways when the fish were exposed to elevated concentrations of copper. The complexation capacity of the gill mucus was characterized by a conditional stability constant (logk(Cu-mucus)) of 5.37 along with a complexation equivalent concentration (L(Cu-mucus)) of 0.96 mmol Cu/mg C. For both the fish microenvironment and the surrounding water, the dominant copper species shifted from Cu(2+) to CuCO(3)(0) and to Cu(OH)(2)(0) when the pH of the surrounding water changed from 6.12 to 8.11. The change in copper speciation in the gill microenvironment is smaller than that in the surrounding water due to the pH buffering capacity of the fish gills.

Toward a theory of topopatric speciation: The role of genetic assortative mating

NASA Astrophysics Data System (ADS)

Schneider, David M.; do Carmo, Eduardo; Martins, Ayana B.; de Aguiar, Marcus A. M.

2014-09-01

We discuss a minimalist model of assortative mating for sexually reproducing haploid individuals with two biallelic loci. Assortativeness is introduced in the model by preventing mating between individuals whose alleles differ at both loci. Using methods of dynamical systems and population genetics we provide a full description of the evolution of the system for the case of very large populations. We derive the equations governing the evolution of haplotype frequencies and study the equilibrium solutions, stability, and speed of convergence to equilibrium. We find a constant of motion which allows us to introduce a geometrical construction that makes it straightforward to predict the fate of initial conditions. Finally, we discuss the consequences of this class of assortative mating models, including their possible extensions and implications for sympatric and topopatric speciation.

Diagnostic modeling of trace metal partitioning in south San Francisco Bay

USGS Publications Warehouse

Wood, T. W.; Baptista, A. M.; Kuwabara, J.S.; Flegal, A.R.

1995-01-01

The numerical results indicate that aqueous speciation will control basin-scale spatial variations in the apparent distribution coefficient, Kda, if the system is close to equilibrium. However, basin-scale spatial variations in Kda are determined by the location of the sources of metal and the suspended solids concentration of the receiving water if the system is far from equilibrium. The overall spatial variability in Kda also increases as the system moves away from equilibrium.

The existence of species rests on a metastable equilibrium between inbreeding and outbreeding. An essay on the close relationship between speciation, inbreeding and recessive mutations

PubMed Central

2011-01-01

Background Speciation corresponds to the progressive establishment of reproductive barriers between groups of individuals derived from an ancestral stock. Since Darwin did not believe that reproductive barriers could be selected for, he proposed that most events of speciation would occur through a process of separation and divergence, and this point of view is still shared by most evolutionary biologists today. Results I do, however, contend that, if so much speciation occurs, the most likely explanation is that there must be conditions where reproductive barriers can be directly selected for. In other words, situations where it is advantageous for individuals to reproduce preferentially within a small group and reduce their breeding with the rest of the ancestral population. This leads me to propose a model whereby new species arise not by populations splitting into separate branches, but by small inbreeding groups "budding" from an ancestral stock. This would be driven by several advantages of inbreeding, and mainly by advantageous recessive phenotypes, which could only be retained in the context of inbreeding. Reproductive barriers would thus not arise as secondary consequences of divergent evolution in populations isolated from one another, but under the direct selective pressure of ancestral stocks. Many documented cases of speciation in natural populations appear to fit the model proposed, with more speciation occurring in populations with high inbreeding coefficients, and many recessive characters identified as central to the phenomenon of speciation, with these recessive mutations expected to be surrounded by patterns of limited genomic diversity. Conclusions Whilst adaptive evolution would correspond to gains of function that would, most of the time, be dominant, this type of speciation by budding would thus be driven by mutations resulting in the advantageous loss of certain functions since recessive mutations very often correspond to the inactivation of a gene. A very important further advantage of inbreeding is that it reduces the accumulation of recessive mutations in genomes. A consequence of the model proposed is that the existence of species would correspond to a metastable equilibrium between inbreeding and outbreeding, with excessive inbreeding promoting speciation, and excessive outbreeding resulting in irreversible accumulation of recessive mutations that could ultimately only lead to extinction. Reviewer names Eugene V. Koonin, Patrick Nosil (nominated by Dr Jerzy Jurka), Pierre Pontarotti PMID:22152499

Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

1999-10-01

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid ligand; relative concentration of inorganic, mono-, and dicarboxylate ligands; and the type of metal cation. As an example, in the same solution, dicarboxylic acids have a greater influence on the speciation of Fe+2 and Mg+2 than on the speciation of Zn+2 and Mn+2.

Assessing bioavailability levels of metals in effluent-affected rivers: effect of Fe(III) and chelating agents on the distribution of metal speciation.

PubMed

Han, Shuping; Naito, Wataru; Masunaga, Shigeki

To assess the effects of Fe(III) and anthropogenic ligands on the bioavailability of Ni, Cu, Zn, and Pb, concentrations of bioavailable metals were measured by the DGT (diffusive gradients in thin films) method in some urban rivers, and were compared with concentrations calculated by a chemical equilibrium model (WHAM 7.0). Assuming that dissolved Fe(III) (<0.45 μm membrane filtered) was in equilibrium with colloidal iron oxide, the WHAM 7.0 model estimated that bioavailable concentrations of Ni, Cu, and Zn were slightly higher than the corresponding values estimated assuming that dissolved Fe(III) was absent. In contrast, lower levels of free Pb were predicted by the WHAM 7.0 model when dissolved Fe(III) was included. Estimates showed that most of the dissolved Pb was present as colloidal iron-Pb complex. Ethylene-diamine-tetra-acetic acid (EDTA) concentrations at sampling sites were predicted from the relationship between EDTA and the calculated bioavailable concentration of Zn. When both colloidal iron and predicted EDTA concentrations were included in the WHAM 7.0 calculations, dissolved metals showed a strong tendency to form EDTA complexes, in the order Ni > Cu > Zn > Pb. With the inclusion of EDTA, bioavailable concentrations of Ni, Cu, and Zn predicted by WHAM 7.0 were different from those predicted considering only humic substances and colloidal iron.

Rates of speciation and morphological evolution are correlated across the largest vertebrate radiation.

PubMed

Rabosky, Daniel L; Santini, Francesco; Eastman, Jonathan; Smith, Stephen A; Sidlauskas, Brian; Chang, Jonathan; Alfaro, Michael E

2013-01-01

Several evolutionary theories predict that rates of morphological change should be positively associated with the rate at which new species arise. For example, the theory of punctuated equilibrium proposes that phenotypic change typically occurs in rapid bursts associated with speciation events. However, recent phylogenetic studies have found little evidence linking these processes in nature. Here we demonstrate that rates of species diversification are highly correlated with the rate of body size evolution across the 30,000+ living species of ray-finned fishes that comprise the majority of vertebrate biological diversity. This coupling is a general feature of fish evolution and transcends vast differences in ecology and body-plan organization. Our results may reflect a widespread speciational mode of character change in living fishes. Alternatively, these findings are consistent with the hypothesis that phenotypic 'evolvability'-the capacity of organisms to evolve-shapes the dynamics of speciation through time at the largest phylogenetic scales.

Equilibrium Bird Species Diversity in Atlantic Islands.

PubMed

Valente, Luis; Illera, Juan Carlos; Havenstein, Katja; Pallien, Tamara; Etienne, Rampal S; Tiedemann, Ralph

2017-06-05

Half a century ago, MacArthur and Wilson proposed that the number of species on islands tends toward a dynamic equilibrium diversity around which species richness fluctuates [1]. The current prevailing view in island biogeography accepts the fundamentals of MacArthur and Wilson's theory [2] but questions whether their prediction of equilibrium can be fulfilled over evolutionary timescales, given the unpredictable and ever-changing nature of island geological and biotic features [3-7]. Here we conduct a complete molecular phylogenetic survey of the terrestrial bird species from four oceanic archipelagos that make up the diverse Macaronesian bioregion-the Azores, the Canary Islands, Cape Verde, and Madeira [8, 9]. We estimate the times at which birds colonized and speciated in the four archipelagos, including many previously unsampled endemic and non-endemic taxa and their closest continental relatives. We develop and fit a new multi-archipelago dynamic stochastic model to these data, explicitly incorporating information from 91 taxa, both extant and extinct. Remarkably, we find that all four archipelagos have independently achieved and maintained a dynamic equilibrium over millions of years. Biogeographical rates are homogeneous across archipelagos, except for the Canary Islands, which exhibit higher speciation and colonization. Our finding that the avian communities of the four Macaronesian archipelagos display an equilibrium diversity pattern indicates that a diversity plateau may be rapidly achieved on islands where rates of in situ radiation are low and extinction is high. This study reveals that equilibrium processes may be more prevalent than recently proposed, supporting MacArthur and Wilson's 50-year-old theory. Copyright © 2017 Elsevier Ltd. All rights reserved.

The importance of ligand speciation in environmental research: a case study.

PubMed

Sillanpää, M; Orama, M; Rämö, J; Oikari, A

2001-02-21

The speciations of EDTA and DTPA in process, waste and river waters are modelled and simulated, specifically to the mode of occurrence in the pulp and paper mill effluents and subsequently in receiving waters. Due to relatively short residence times in bleaching process and waste water treatment and slow exchange kinetics, it is expected that the thermodynamic equilibrium is not necessarily reached. Therefore, the initial speciation plays a key role. As such, the simulations have been extended to the process waters of the pulp and paper industry taking into account estimated average conditions. The results reveal that the main species are; Mn and Ca complexes of EDTA and DTPA in pulp mill process waters; Fe(III) and Mn complexes of EDTA and DTPA in waste waters; Fe(III) and Zn complexes of EDTA and DTPA in receiving waters. It is also shown how the increasing concentration of complexing agents effects the speciation. Alkaline earth metal chelation plays a significant role in the speciation of EDTA and DTPA when there is a noticeable molar excess of complexing agents compared with transition metals.

Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153

USGS Publications Warehouse

Bullen, Thomas D.; White, Arthur F.; Childs, Cyril W.

2003-01-01

In a recent contribution [1], Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ;  [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH)x(aq)and Fe(II)(aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4], but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

NASA Astrophysics Data System (ADS)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-10-01

;Clumped-isotope; thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope ;clumps;). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral-solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3-) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

USGS Publications Warehouse

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-01-01

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium.Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3−) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Mechanisms for trace metal enrichment at the surface microlayer in an estuarine salt marsh

USGS Publications Warehouse

Lion, Leonard W.

1982-01-01

The relative contributions of adsorption to particulate surfaces, complexation with surface-active organic ligands and uptake by micro-organisms were evaluated with respect to their importance in the surface microlayer enrichment (‘partitioning’) of Cd, Pb and Cu. The contributions of each process were inferred from field data in which partitioning of the dissolved and particulate forms of Cd, Pb and Cu, total and dissolved organic carbon, particles and total bacteria were observed. In the South San Francisco Bay estuary, particle enrichment appears to control trace metal partitioning. Trace metal association with the particulate phase and the levels of partitioning observed were in the order Pb > Cu > Cd and reflect the calculated equilibrium chemical speciation of these metals in computer-simulated seawater matrices.

Miscibility and Speciation in the Water/carbon Dioxide System

NASA Astrophysics Data System (ADS)

Abramson, E.; Bollengier, O.; Brown, J. M.

2017-12-01

We have been exploring fluid-fluid solubilities and speciation in mixed systems of CO2-H2O. Fluid-fluid immiscibility extends to the highest pressures and temperatures yet explored (7 GPa, 700K). In this region, commonly used COH fluid models agree neither with the data nor among themselves. The range of immiscibility is extended by addition of NaCl, but miscibility limits determined in preliminary experiments are not as expected from extrapolation of lower pressure (<0.2 GPa) results. For majority-water systems (XCO2<0.5) an abrupt increase of solubility with pressure is linked to an observed change in speciation as CO2(aq) reacts with water. The identity of the newly formed species is, as of the writing of this abstract, unknown, but presumed to be either H2CO3 or HCO3-. A reasonable match between the observed equilibria and an application of HKF theory suggests that the new species is, indeed, HCO3-, but with a Raman frequency shifted from that found in the dilute aqueous solution. Application of HKF theory to the CO2(f)-CO2(aq) equilibrium suffers from an incompatibility of the usual formulation of the theory with known molar volumes of CO2(f) at higher pressures. On the basis of these studies we conclude that models of CO2-H2O fluids must take into account major changes in speciation, and that simple equations-of-state, of a few fitted parameters, will not afford an adequate description of such fluids. "First principles" models, tested against real data, seem more likely to yield the desired results. This statement extends as well to the calculation of the dielectric constants of these mixed fluids, the basis of ionic solution chemistry. Further, semi-empirical formulations of solution thermodynamics, which function well at pressures of kbars, ought to be re-worked for use over larger pressure ranges.

Alumino-silicate speciation in aqueous fluids at deep crustal conditions

NASA Astrophysics Data System (ADS)

Mookherjee, M.; Keppler, H.; Manning, C. E.

2014-12-01

Alumina and silica are major oxides in most crustal rocks. While SiO2 is quite soluble in aqueous fluids at metamorphic conditions, behavior of Al2O3 in crustal metamorphic fluids has been poorly understood. It is known that alumina is dramatically less soluble in aqueous fluids and hence it is difficult to explain the common occurrence of quartz with aluminous minerals in metamorphic veins. In order to understand this complex behavior of alumina, we investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 oC. In order to better understand the spectral features of the aqueous fluids, we used first principles simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with KOH solution in equilibrium with Al2O3 show a sharp band at ~620 cm-1 which could be attributed to the [Al(OH)4]1- species. The band grows in intensity with temperature along an isochore. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [Al(OH)4]1- species to dimers [(OH)2-Al-O2-Al(OH)2]2- or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. We are also investigating the effect of SiO2 on the solubility of Al2O3 and the relative energetics of formation of pure alumina dimer [(OH)3-Al-O-Al(OH)3]2- vs. the aluminosilicate dimers, [(OH)3-Al-O-Si(OH)3]2- at deep crustal conditions. Acknowledgement- MM is supported by the US National Science Foundation grant (EAR-1250477).

Aluminum speciation in aqueous fluids at deep crustal pressure and temperature

NASA Astrophysics Data System (ADS)

Mookherjee, Mainak; Keppler, Hans; Manning, Craig E.

2014-05-01

We investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 °C. We have studied aluminum species in (a) pure H2O, (b) 5.3 m KOH solution, and (c) 1 m KOH solution. In order to better understand the spectral features of the aqueous fluids, we used ab initio simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with 5.3 m and 1 m KOH solution in equilibrium with Al2O3 show a sharp band at ˜620 cm-1 which could be attributed to the [ species. The band grows in intensity with temperature along an isochore. A shoulder on the high-frequency side of this band may be due to a hydrated, charge neutral Al(OH)3·H2O species. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [ species to dimers [(OH)2-Al-(OH)2-Al(OH)2] or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. Upon cooling of Al-bearing solutions to room temperatures, Raman bands indicating the precipitation of diaspore (AlOOH) were observed in some experiments. The Raman spectra of the KOH solutions (with or without dissolved alumina) showed a sharp OH stretching band at ˜3614 cm-1 and an in-plane OH bending vibration at ˜1068 cm-1, likely related to an OH- ion with the oxygen atom attached to a water molecule by hydrogen bonding. A weak feature at ˜935 cm-1 may be related to the out-of-plane bending vibration of the same species or to an OH species with a different environment.

Speciation and Toxic Emissions from On road Vehicles, and Particulate Matter Emissions from Light-Duty Gasoline Vehicles in MOVES201X

EPA Science Inventory

Updated methane, non-methane organic gas, and volatile organic compound calculations based on speciation data. Updated speciation and toxic emission rates for new model year 2010 and later heavy-duty diesel engines. Updated particulate matter emission rates for 2004 and later mod...

Composition of COH fluids at 1 GPa: an experimental study on speciation and solubility

NASA Astrophysics Data System (ADS)

Tiraboschi, Carla; Tumiati, Simone; Recchia, Sandro; Ulmer, Peter; Pettke, Thomas; Fumagalli, Patrizia; Poli, Stefano

2014-05-01

COH fluids play a fundamental role in many geological processes, controlling the location of melting in subduction zones and promoting mass transfer from the subducting litosphere to the overlying mantle wedge. The properties of COH fluids are strictly dependent on the composition of the fluid in subduction systems, i.e., the speciation of the volatile components of the fluid itself and the presence of solutes deriving from the dissolution of rock-forming minerals. In the scientific literature, the speciation of COH fluids has been generally determined through thermodynamic calculations using equations of state of simple H2O-non-polar gas systems (e.g., H2O-CO2-CH4), equations that do not consider the complexity related to dissolution processes, which are substantially unexplored in COH fluids and limited so far to aqueous fluids (Newton & Manning, 2002). The aim of this work is to investigate experimentally the speciation and the dissolution of mantle minerals in carbon-saturated COH fluids at buffered fO2 conditions. Our experimental approach relies on two different techniques: 1) analysis by means of quadrupole mass spectrometer (QMS) of the fluids from pierced run capsules to retrieve speciation of volatile components and 2) analysis of frozen COH fluid with laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) to measure the amount of solutes. Experiments were conducted at pressure of 1 GPa and temperatures from 800 to 900° C using a rocking piston cylinder apparatus. Mantle minerals in equilibrium with COH fluid are represented by synthetic forsterite. fO2 conditions were controlled using the double capsule technique and NNO buffer (ΔFMQ=-0.61 at 800° C; ΔFMQ =-0.98 at 900° C). For the speciation experiments, oxalic acid dihydrate and graphite have been used to generate carbon-saturated COH fluid. The speciation was determined by analyzing the quenched COH fluid, retrieved by piercing the capsule in a gas-tight vessel at T =80° C and convoying evolved gases to a QMS through a heated line to avoid the condensation of water. This type of analyzer ensures superior performances in terms of selectivity of molecules to be detected, high acquisition rates and extended linear response range. The influence of dissolved solutes on fluid speciation has been evaluated by comparing experiments in the pure COH system and in the COH+forsterite system. To determine the solubility of forsterite in COH fluids we performed a second set of experiments at the same P , T and fO2 conditions above. Fluids trapped in a diamond layer were analysed by the cryogenic LA-ICP-MS technique described by Aerts et al. (2010). With this method the aqueous part of the COH fluid is frozen prior the opening and maintained frozen during the analysis to avoid any precipitation of solutes. The results will highlight the importance of fluids for the mass transport in subduction zones. Comparison between experimental data and thermodynamic calculation will also be shown. References: Aerts, M., Hack, A.C., Reusser, E., Ulmer, P. (2010) Am. Mineral. 95, 1523-1526. Newton, R.C., Manning, C.E. (2002) Geochim. Cosmochim. Ac. 66, 4165-4176.

Source-dependent and source-independent controls on plutonium oxidation state and colloid associations in groundwater.

PubMed

Buesseler, Ken O; Kaplan, Daniel I; Dai, Minhan; Pike, Steven

2009-03-01

Plutonium (Pu) was characterized for its isotopic composition, oxidation states, and association with colloids in groundwater samples near disposal basins in F-Area of the Savannah River Site and compared to similar samples collected six years earlier. Two sources of Pu were identified, the disposal basins, which contained a 24Pu/l39Pu isotopic signature consistent with weapons grade Pu, and 244Cm, a cocontaminant that is a progenitor radionuclide of 24Pu. 24Pu that originated primarily from 244Cm tended to be appreciably more oxidized (Pu(V/VI)), less associated with colloids (approximately 1 kDa - 0.2 microm), and more mobile than 239Pu, as suggested by our prior studies at this site. This is not evidence of isotope fractionation but rather "source-dependent" controls on 240Pu speciation which are processes that are not at equilibrium, i.e., processes that appear kinetically hindered. There were also "source-independent" controls on 239Pu speciation, which are those processes that follow thermodynamic equilibrium with their surroundings. For example, a groundwater pH increase in one well from 4.1 in 1998 to 6.1 in 2004 resulted in an order of magnitude decrease in groundwater 239Pu concentrations. Similarly, the fraction of 239Pu in the reduced Pu(III/IV) and colloidal forms increased systematically with decreases in redox condition in 2004 vs 1998. This research demonstrates the importance of source-dependent and source-independent controls on Pu speciation which would impact Pu mobility during changes in hydrological, chemical, or biological conditions on both seasonal and decadal time scales, and over short spatial scales. This implies more dynamic shifts in Pu speciation, colloids association, and transport in groundwater than commonly believed.

Fulvic acid-sulfide ion competition for mercury ion binding in the Florida everglades

USGS Publications Warehouse

Reddy, M.M.; Aiken, G.R.

2001-01-01

Negatively charged functional groups of fulvic acid compete with inorganic sulfide ion for mercury ion binding. This competition is evaluated here by using a discrete site-electrostatic model to calculate mercury solution speciation in the presence of fulvic acid. Model calculated species distributions are used to estimate a mercury-fulvic acid apparent binding constant to quantify fulvic acid and sulfide ion competition for dissolved inorganic mercury (Hg(II)) ion binding. Speciation calculations done with PHREEQC, modified to use the estimated mercury-fulvic acid apparent binding constant, suggest that mercury-fulvic acid and mercury-sulfide complex concentrations are equivalent for very low sulfide ion concentrations (about 10-11 M) in Everglades' surface water. Where measurable total sulfide concentration (about 10-7 M or greater) is present in Everglades' surface water, mercury-sulfide complexes should dominate dissolved inorganic mercury solution speciation. In the absence of sulfide ion (for example, in oxygenated Everglades' surface water), fulvic acid binding should dominate Everglades' dissolved inorganic mercury speciation.

Thermodynamic behavior of a phase transition in a model for sympatric speciation

NASA Astrophysics Data System (ADS)

Luz-Burgoa, K.; Moss de Oliveira, S.; Schwämmle, Veit; Sá Martins, J. S.

2006-08-01

We investigate the macroscopic effects of the ingredients that drive the origin of species through sympatric speciation. In our model, sympatric speciation is obtained as we tune up the strength of competition between individuals with different phenotypes. As a function of this control parameter, we can characterize, through the behavior of a macroscopic order parameter, a phase transition from a nonspeciation to a speciation state of the system. The behavior of the first derivative of the order parameter with respect to the control parameter is consistent with a phase transition and exhibits a sharp peak at the transition point. For different resources distribution, the transition point is shifted, an effect similar to pressure in a PVT system. The inverse of the parameter related to a sexual selection strength behaves like an external field in the system and, as thus, is also a control parameter. The macroscopic effects of the biological parameters used in our model are a reminiscent of the behavior of thermodynamic quantities in a phase transition of an equilibrium physical system.

Equilibrium and non-equilibrium dynamics simultaneously operate in the Galápagos islands.

PubMed

Valente, Luis M; Phillimore, Albert B; Etienne, Rampal S

2015-08-01

Island biotas emerge from the interplay between colonisation, speciation and extinction and are often the scene of spectacular adaptive radiations. A common assumption is that insular diversity is at a dynamic equilibrium, but for remote islands, such as Hawaii or Galápagos, this idea remains untested. Here, we reconstruct the temporal accumulation of terrestrial bird species of the Galápagos using a novel phylogenetic method that estimates rates of biota assembly for an entire community. We show that species richness on the archipelago is in an ascending phase and does not tend towards equilibrium. The majority of the avifauna diversifies at a slow rate, without detectable ecological limits. However, Darwin's finches form an exception: they rapidly reach a carrying capacity and subsequently follow a coalescent-like diversification process. Together, these results suggest that avian diversity of remote islands is rising, and challenge the mutual exclusivity of the non-equilibrium and equilibrium ecological paradigms. © 2015 The Authors Ecology Letters published by John Wiley & Sons Ltd and CNRS.

Effects of the microbial siderophore DFO-B on Pb and Cd speciation in aqueous solution.

PubMed

Mishra, Bhoopesh; Haack, Elizabeth A; Maurice, Patricia A; Bunker, Bruce A

2009-01-01

This study investigates the complexation environments of aqueous Pb and Cd in the presence of the trihydroxamate microbial siderophore, desferrioxamine-B (DFO-B) as a function of pH. Complexation of aqueous Pb and Cd with DFO-B was predicted using equilibrium speciation calculation. Synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy at Pb L(III) edge and Cd K edge was used to characterize Pb and Cd-DFO-B complexes at pH values predicted to best represent each of the metal-siderophore complexes. Pb was not found to be complexed measurably by DFO-B at pH 3.0, but was complexed by all three hydroxamate groups to form a totally "caged" hexadentate structure at pH 7.5-9.0. At the intermediate pH value (pH 4.8), a mixture of Pb-DFOB complexes involving binding of the metal through one and two hydroxamate groups was observed. Cd, on the other hand, remained as hydrated Cd2+ at pH 5.0, occurred as a mixture of Cd-DFOB and inorganic species at pH 8.0, and was bound by three hydroxamate groups from DFO-B at pH 9.0. Overall, the solution species observed with EXAFS were consistent with those predicted thermodynamically. However, Pb speciation at higher pH values differed from that predicted and suggests that published constants underestimate the binding constant for complexation of Pb with all three hydroxamate groups of the DFO-B ligand. This molecular-level understanding of metal-siderophore solution coordination provides physical evidence for complexes of Pb and Cd with DFO-B, and is an important first step toward understanding processes at the microbial- and/or mineral-water interface in the presence of siderophores.

Trace Metal-Humic Complexes in Natural Waters: Insights From Speciation Experiments

NASA Astrophysics Data System (ADS)

Stern, J. C.; Salters, V.; Sonke, J.

2006-12-01

The DOM cycle is intimately linked to the cycling and bioavailability of trace metals in aqueous environments. The presence or absence of DOM in the water column can determined whether trace elements will be present in limited quantities as a nutrient, or in surplus quantities as a toxicant. Humic substances (HS), which represent the refractory products of DOM degradation, strongly affect the speciation of trace metals in natural waters. To simulate metal-HS interactions in nature, experiments must be carried out using trace metal concentrations. Sensitive detection systems such as ICP-MS make working with small (nanomolar) concentrations possible. Capillary electrophoresis coupled with ICP-MS (CE-ICP-MS) has recently been identified as a rapid and accurate method to separate metal species and calculate conditional binding constants (log K_c) of metal-humic complexes. CE-ICP-MS was used to measure partitioning of metals between humic substances and a competing ligand (EDTA) and calculate binding constants of rare earth element (REE) and Th, Hf, and Zr-humic complexes at pH 3.5-8 and ionic strength of 0.1. Equilibrium dialysis ligand exchange (EDLE) experiments to validate the CE-ICP-MS method were performed to separate the metal-HS and metal-EDTA species by partitioning due to size exclusion via diffusion through a 1000 Da membrane. CE-ICP-MS experiments were also conducted to compare binding constants of REE with humic substances of various origin, including soil, peat, and aquatic DOM. Results of our experiments show an increase in log K_c with decrease in ionic radius for REE-humic complexes (the lanthanide contraction effect). Conditional binding constants of tetravalent metal-humic complexes were found to be several orders of magnitude higher than REE-humic complexes, indicating that tetravalent metals have a very strong affinity for humic substances. Because thorium is often used as a proxy for the tetravalent actinides, Th-HS binding constants can allow us to assess the importance of tetravalent actinide-humic complexes in groundwater transport from nuclear repositories. Our results suggest that tetravalent actinide-humic complexes couild be more important to account for in predictive speciation models than previously thought.

Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

DOE PAGES

Riddle, Catherine; Czerwinski, Kenneth; Kim, Eunja; ...

2016-01-18

We studied the speciation of pentavalent and hexavalent americium (Am) complexes in nitric acidicby X-ray absorption fine structure spectroscopy (XAFS), UV-visible spectroscopy, and density functional theory (DFT). Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results were consistent with the presence of a mixture of AmO 2 + and AmO 2 2+ with only a small amount AmO 2 present. The resulting average bond distances we found were 1.71 Å for Am=O and 2.44 Å for Am-O. All-electron scalar relativistic calculations were also carried out using DFT to predict the equilibrium geometries and properties ofmore » the AmO 2 + and AmO 2 2+ aquo complexes. Calculated bond distances for the Am(VI) complex are in reasonable agreement with EXAFS data and the computed energy gaps between frontier molecular orbitals suggest a slightly higher kinetic stability and chemical hardness of Am(VI) compared to Am(V).« less

Polysulfide Speciation in the Bulk Electrolyte of a Lithium Sulfur Battery

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

McBrayer, Josefine D.; Beechem, Thomas E.; Perdue, Brian R.

In situ Raman microscopy was used to study polysulfide speciation in the bulk ether electrolyte during the discharge and charge of a Li-S electrochemical cell to assess the complex interplay between chemical and electrochemical reactions in solution. During discharge, long chain polysulfides and the S 3 - radical appear in the electrolyte at 2.4 V indicating a rapid equilibrium of the dissociation reaction to form S 3 -. When charging, however, an increase in the concentration of all polysulfide species was observed. This highlights the importance of the electrolyte to sulfur ratio and suggests a loss in the useful sulfurmore » inventory from the cathode to the electrolyte.« less

Polysulfide Speciation in the Bulk Electrolyte of a Lithium Sulfur Battery

DOE PAGES

McBrayer, Josefine D.; Beechem, Thomas E.; Perdue, Brian R.; ...

2018-03-23

In situ Raman microscopy was used to study polysulfide speciation in the bulk ether electrolyte during the discharge and charge of a Li-S electrochemical cell to assess the complex interplay between chemical and electrochemical reactions in solution. During discharge, long chain polysulfides and the S 3 - radical appear in the electrolyte at 2.4 V indicating a rapid equilibrium of the dissociation reaction to form S 3 -. When charging, however, an increase in the concentration of all polysulfide species was observed. This highlights the importance of the electrolyte to sulfur ratio and suggests a loss in the useful sulfurmore » inventory from the cathode to the electrolyte.« less

Reactivity of BrCl, Br₂, BrOCl, Br₂O, and HOBr toward dimethenamid in solutions of bromide + aqueous free chlorine.

PubMed

Sivey, John D; Arey, J Samuel; Tentscher, Peter R; Roberts, A Lynn

2013-02-05

HOBr, formed via oxidation of bromide by free available chlorine (FAC), is frequently assumed to be the sole species responsible for generating brominated disinfection byproducts (DBPs). Our studies reveal that BrCl, Br(2), BrOCl, and Br(2)O can also serve as brominating agents of the herbicide dimethenamid in solutions of bromide to which FAC was added. Conditions affecting bromine speciation (pH, total free bromine concentration ([HOBr](T)), [Cl(-)], and [FAC](o)) were systematically varied, and rates of dimethenamid bromination were measured. Reaction orders in [HOBr](T) ranged from 1.09 (±0.17) to 1.67 (±0.16), reaching a maximum near the pK(a) of HOBr. This complex dependence on [HOBr](T) implicates Br(2)O as an active brominating agent. That bromination rates increased with increasing [Cl(-)], [FAC](o) (at constant [HOBr](T)), and excess bromide (where [Br(-)](o)>[FAC](o)) implicate BrCl, BrOCl, and Br(2), respectively, as brominating agents. As equilibrium constants for the formation of Br(2)O and BrOCl (aq) have not been previously reported, we have calculated these values (and their gas-phase analogues) using benchmark-quality quantum chemical methods [CCSD(T) up to CCSDTQ calculations plus solvation effects]. The results allow us to compute bromine speciation and hence second-order rate constants. Intrinsic brominating reactivity increased in the order: HOBr ≪ Br(2)O < BrOCl ≈ Br(2) < BrCl. Our results indicate that species other than HOBr can influence bromination rates under conditions typical of drinking water and wastewater chlorination.

Phylogenies support out-of-equilibrium models of biodiversity.

PubMed

Manceau, Marc; Lambert, Amaury; Morlon, Hélène

2015-04-01

There is a long tradition in ecology of studying models of biodiversity at equilibrium. These models, including the influential Neutral Theory of Biodiversity, have been successful at predicting major macroecological patterns, such as species abundance distributions. But they have failed to predict macroevolutionary patterns, such as those captured in phylogenetic trees. Here, we develop a model of biodiversity in which all individuals have identical demographic rates, metacommunity size is allowed to vary stochastically according to population dynamics, and speciation arises naturally from the accumulation of point mutations. We show that this model generates phylogenies matching those observed in nature if the metacommunity is out of equilibrium. We develop a likelihood inference framework that allows fitting our model to empirical phylogenies, and apply this framework to various mammalian families. Our results corroborate the hypothesis that biodiversity dynamics are out of equilibrium. © 2015 John Wiley & Sons Ltd/CNRS.

Effects of iron on arsenic speciation and redox chemistry in acid mine water

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

2005-01-01

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

Temporal assessment of copper speciation, bioavailability and toxicity in UK freshwaters using chemical equilibrium and biotic ligand models: Implications for compliance with copper environmental quality standards.

PubMed

Lathouri, Maria; Korre, Anna

2015-12-15

Although significant progress has been made in understanding how environmental factors modify the speciation, bioavailability and toxicity of metals such as copper in aquatic environments, the current methods used to establish water quality standards do not necessarily consider the different geological and geochemical characteristics of a given site and the factors that affect copper fate, bioavailability potential and toxicity. In addition, the temporal variation in the concentration and bioavailable metal fraction is also important in freshwater systems. The work presented in this paper illustrates the temporal and seasonal variability of a range of water quality parameters, and Cu speciation, bioavailability and toxicity at four freshwaters sites in the UK. Rivers Coquet, Cree, Lower Clyde and Eden (Kent) were selected to cover a broad range of different geochemical environments and site characteristics. The monitoring data used covered a period of around six years at almost monthly intervals. Chemical equilibrium modelling was used to study temporal variations in Cu speciation and was combined with acute toxicity modelling to assess Cu bioavailability for two aquatic species, Daphnia magna and Daphnia pulex. The estimated copper bioavailability, toxicity levels and the corresponding ecosystem risks were analysed in relation to key water quality parameters (alkalinity, pH and DOC). Although copper concentrations did not vary much during the sampling period or between the seasons at the different sites; copper bioavailability varied markedly. In addition, through the chronic-Cu BLM-based on the voluntary risk assessment approach, the potential environmental risk in terms of the chronic toxicity was assessed. A much higher likelihood of toxicity effects was found during the cold period at all sites. It is suggested that besides the metal (copper) concentration in the surface water environment, the variability and seasonality of other important water quality parameters should be considered in setting appropriately protective environmental quality standards for metals. Copyright © 2015 Elsevier B.V. All rights reserved.

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

USGS Publications Warehouse

Ellis, A.S.; Johnson, T.M.; Bullen, T.D.

2004-01-01

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr-(VI) and Cr(VI) adsorbed onto ??-Al2O3 and goethite is less than 0.04???. (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO42- was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in ??53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

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

PubMed

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

2010-11-15

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

Measuring free metal ion concentrations in situ in natural waters using the Donnan Membrane Technique.

PubMed

Kalis, Erwin J J; Weng, Liping; Dousma, Freerk; Temminghoff, Erwin J M; Van Riemsdijk, Willem H

2006-02-01

Metal toxicity is not related to the total but rather to the free or labile metal ion concentration. One of the techniques that can be used to measure several free metal ion concentrations simultaneously is the Donnan Membrane Technique (DMT) in combination with the inductively coupled plasma-mass spectrometer (ICP-MS). However, free metal ion concentrations in natural waters are commonly below the detection limit of ICP-MS. We decreased the detection limit by making use of a ligand, and we developed a field DMT cell that can be applied in situ in natural waters. A kinetic approach can be used to calculate free metal ion concentrations when the equilibrium time becomes too large. The field DMT measured in situ in natural waters a free metal ion concentration ranging from 0.015% (Cu) to 13% (Zn) of a total metal concentration ranging from 0.06 nM (Cd) to 237 nM (Zn). The free metal ion concentrations were difficult to predict using an equilibrium speciation model, probably due to the uncertainty in the nature of the dissolved organic matter or the presence of other reactive colloids. It is shown that DMT can follow changes in the free metal ion concentration on times scales less than a day under certain conditions.

Clustering and phase transitions on a neutral landscape

NASA Astrophysics Data System (ADS)

Scott, Adam D.; King, Dawn M.; Marić, Nevena; Bahar, Sonya

2013-06-01

Recent computational studies have shown that speciation can occur under neutral conditions, i.e., when the simulated organisms all have identical fitness. These works bear comparison with mathematical studies of clustering on neutral landscapes in the context of branching and coalescing random walks. Here, we show that sympatric clustering/speciation can occur on a neutral landscape whose dimensions specify only the simulated organisms’ phenotypes. We demonstrate that clustering occurs not only in the case of assortative mating, but also in the case of asexual fission; it is not observed in the control case of random mating. We find that the population size and the number of clusters undergo a second-order non-equilibrium phase transition as the maximum mutation size is varied.

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial magma ocean. Whether such endogenous isotopic heterogeneity would survive as an observable signature in the modern silicate Earth is an open question.

Dynamic coupled metal transport-speciation model: application to assess a zinc-contaminated lake.

PubMed

Bhavsar, Satyendra P; Diamond, Miriam L; Gandhi, Nilima; Nilsen, Joel

2004-10-01

A coupled metal transport and speciation/complexation model (TRANSPEC) has been developed to estimate the speciation and fate of multiple interconverting species in surface aquatic systems. Dynamic-TRANSPEC loosely, sequentially couples the speciation/complexation and fate modules that, for the unsteady state formulation, run alternatively at every time step. The speciation module first estimates species abundance using, in this version, MINEQL+ considering time-dependent changes in water and pore-water chemistry. The fate module is based on the quantitative water air sediment interaction (QWASI) model and fugacity/aquivalence formulation, with the option of using a pseudo-steady state solution to account for past discharges. Similarly to the QWASI model for organic contaminants, TRANSPEC assumes the instantaneous equilibrium distribution of metal species among dissolved, colloidal, and particulate phases based on ambient chemistry parameters that can be collected through conventional field methods. The model is illustrated with its application to Ross Lake (Manitoba, Canada) that has elevated Zn concentrations due to discharges over 70 years from a mining operation. Using measurements from field studies, the model reproduces year-round variations in Zn water concentrations. A 10-year projection for current conditions suggests decreasing Zn remobilization and export from the lake. Decreasing Zn loadings increases sediment-to-water transport but decreases water concentrations, and vice versa. Species distribution is affected by pH such that a decrease in pH increases metal export from the lake and vice versa.

[Speciation and Risk Characteristics of Heavy Metals in the Sediments of the Yangtze Estuary].

PubMed

Yin, Su; Feng, Cheng-hong; Li, Yang-yang; Yin, Li-feng; Shen, Zhen-yao

2016-03-15

Based on the investigation on the distribution of total contents and speciation of 8 heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, Zn) in the surface sediments at 14 typical sites of the Yangtze Estuary during three hydrological seasons ( wet, normal, and dry seasons) , this study applied equilibrium partitioning approach to build the sediment quality guidelines (SQGs) of the Yangtze Estuary, and assessed ecological risks of the heavy metals. The relationship between ecological risk and speciation of heavy metals was also revealed. The results showed that, except for Cd, the residual fraction was the main speciation of heavy metals, especially for As, Cr and Hg, their residual fraction proportions were all over 90%. The sediment quality guidelines of the Yangtze Estuary for As, Cd, Cr, Cu, Hg, Ni, Pb, Zn were 43.29, 0.672, 79.65, 19.08, 0.569, 339.09, 30.87, 411.36 µg · g⁻¹, respectively. Cu had the highest ecological risk to aquatic organisms. The upstream of Yangtze Estuary was mainly affected by Yangtze River runoff, where the risks were relatively high in wet season and relatively low in normal and dry seasons. However, the downstream of the estuary was mainly affected by municipal sewage of cities like Shanghai, where the risks were relatively high, especially in normal and dry seasons. There were three different relationships between the ecological risks and speciation of the eight heavy metals.

Invasive species and biodiversity crises: testing the link in the late devonian.

PubMed

Stigall, Alycia L

2010-12-29

During the Late Devonian Biodiversity Crisis, the primary driver of biodiversity decline was the dramatic reduction in speciation rates, not elevated extinction rates; however, the causes of speciation decline have been previously unstudied. Speciation, the formation of new species from ancestral populations, occurs by two primary allopatric mechanisms: vicariance, where the ancestral population is passively divided into two large subpopulations that later diverge and form two daughter species, and dispersal, in which a small subset of the ancestral population actively migrates then diverges to form a new species. Studies of modern and fossil clades typically document speciation by vicariance in much higher frequencies than speciation by dispersal. To assess the mechanism behind Late Devonian speciation reduction, speciation rates were calculated within stratigraphically constrained species-level phylogenetic hypotheses for three representative clades and mode of speciation at cladogenetic events was assessed across four clades in three phyla: Arthropoda, Brachiopoda, and Mollusca. In all cases, Devonian taxa exhibited a congruent reduction in speciation rate between the Middle Devonian pre-crisis interval and the Late Devonian crisis interval. Furthermore, speciation via vicariance is almost entirely absent during the crisis interval; most episodes of speciation during this time were due to dispersal. The shutdown of speciation by vicariance during this interval was related to widespread interbasinal species invasions. The lack of Late Devonian vicariance is diametrically opposed to the pattern observed in other geologic intervals, which suggests the loss of vicariant speciation attributable to species invasions during the Late Devonian was a causal factor in the biodiversity crisis. Similarly, modern ecosystems, in which invasive species are rampant, may be expected to exhibit similar shutdown of speciation by vicariance as an outcome of the modern biodiversity crisis.

Reactive solute transport in streams: 1. Development of an equilibrium- based model

USGS Publications Warehouse

Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.

1996-01-01

An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

The fundamental flaw of the HSAB principle is revealed by a complete speciation analysis of the [PtCl(6-n)Br(n)](2-) (n = 0-6) system.

PubMed

Gerber, W J; van Wyk, P-H; van Niekerk, D M E; Koch, K R

2015-02-28

Bjerrum's model of step-wise ligand exchange is extended to compute a complete speciation diagram for the [PtCl6-nBrn](2-) (n = 0-6) system including all 17 equilibrium constants concerning the Pt(IV) chlorido-bromido exchange reaction network (HERN). In contrast to what the hard soft acid base (HSAB) principle "predicts", the thermodynamic driving force for the replacement of chloride by bromide in an aqueous matrix, for each individual ligand exchange reaction present in the Pt(IV) HERN, is due to the difference in halide hydration energy and not bonding interactions present in the acid-base complex. A generalized thermodynamic test calculation was developed to illustrate that the HSAB classified class (b) metal cations Ag(+), Au(+), Au(3+), Rh(3+), Cd(2+), Pt(2+), Pt(4+), Fe(3+), Cd(2+), Sn(2+) and Zn(2+) all form thermodynamically stable halido complexes in the order F(-) ≫ Cl(-) > Br(-) > I(-) irrespective of the sample matrix. The bonding interactions in the acid-base complex, e.g. ionic-covalent σ-bonding, Π-bonding and electron correlation effects, play no actual role in the classification of these metal cations using the HSAB principle. Instead, it turns out that the hydration/solvation energy of halides is the reason why metal cations are categorized into two classes using the HSAB principle which highlights the fundamental flaw of the HSAB principle.

Simultaneous Speciation, Structure, and Equilibrium Constant Determination in the Ni2+-EDTA-CN- Ternary System via High-Resolution Laboratory X-ray Absorption Fine Structure Spectroscopy and Theoretical Calculations.

PubMed

Bajnóczi, Éva G; Németh, Zoltán; Vankó, György

2017-11-20

Even quite simple chemical systems can involve many components and chemical states, and sometimes it can be very difficult to differentiate them by their hardly separable physical-chemical properties. The Ni II -EDTA-CN - (EDTA = ethylenediaminetetraacetic acid) ternary system is a good example for this problem where, in spite of its fairly simple components and numerous investigations, several molecular combinations can exist, all of them not having been identified unambiguously yet. In order to achieve a detailed understanding of the reaction steps and chemical equilibria, methods are required in which the structural transitions in the different reaction steps can be followed via element-selective complex spectral feature sets. With the help of our recently developed von Hámos type high-resolution laboratory X-ray absorption spectrometer, both the structural variations and stability constants of the forming complexes were determined from the same measurement series, proving that X-ray absorption spectroscopy can be considered as a multifaced, table-top tool in coordination chemistry. Furthermore, with the help of theoretical calculations, independent structural evidence was also given for the formation of the [NiEDTA(CN)] 3- mixed complex.

Complexation of Nickel Ions by Boric Acid or (Poly)borates.

PubMed

Graff, Anais; Barrez, Etienne; Baranek, Philippe; Bachet, Martin; Bénézeth, Pascale

2017-01-01

An experiment based on electrochemical reactions and pH monitoring was performed in which nickel ions were gradually formed by oxidation of a nickel metal electrode in a solution of boric acid. Based on the experimental results and aqueous speciation modeling, the evolution of pH showed the existence of significant nickel-boron complexation. A triborate nickel complex was postulated at high boric acid concentrations when polyborates are present, and the equilibrium constants were determined at 25, 50 and 70 °C. The calculated enthalpy and entropy at 25 °C for the formation of the complex from boric acid and Ni 2+ ions are respectively equal to (65.6 ± 3.1) kJ·mol -1 and (0.5 ± 11.1) J·K -1 ·mol -1 . The results of this study suggest that complexation of nickel ions by borates can significantly enhance the solubility of nickel metal and nickel oxide depending on the concentration of boric acid and pH. First principles calculations were investigated and tend to show that the complex is thermodynamically stable and the nickel cation in solution should interact more strongly with the [Formula: see text] than with boric acid.

New analytic results for speciation times in neutral models.

PubMed

Gernhard, Tanja

2008-05-01

In this paper, we investigate the standard Yule model, and a recently studied model of speciation and extinction, the "critical branching process." We develop an analytic way-as opposed to the common simulation approach-for calculating the speciation times in a reconstructed phylogenetic tree. Simple expressions for the density and the moments of the speciation times are obtained. Methods for dating a speciation event become valuable, if for the reconstructed phylogenetic trees, no time scale is available. A missing time scale could be due to supertree methods, morphological data, or molecular data which violates the molecular clock. Our analytic approach is, in particular, useful for the model with extinction, since simulations of birth-death processes which are conditioned on obtaining n extant species today are quite delicate. Further, simulations are very time consuming for big n under both models.

In situ Raman study of dissolved CaCO3 minerals under subduction zone conditions

NASA Astrophysics Data System (ADS)

Facq, S.; Daniel, I.; Sverjensky, D. A.

2012-12-01

The fate and the characteristics of the Earth's deep carbon reservoirs are still not well understood [1]. The connection between the surficial and the deep-Earth carbon cycles occurs at subduction zones where carbon is transported into the mantle and where hydrous silicates and carbonate minerals break down releasing H2O and C-species in fluids associated with mantle metasomatism and the generation of arc volcanism [2]. In order to obtain mass balance between recycling and burial in the deep mantle, the study of the dissolution of CaCO3 minerals in equilibrium with aqueous fluids under mantle conditions is crucial. We report a novel integrated experimental and theoretical study of the equilibration of CaCO3 minerals with aqueous solutions (pure water or NaCl solutions) at high pressures and temperatures (0.5 to 8 GPa and 250 to 500 °C). The fluid speciation was studied using in situ Raman spectroscopy coupled to an externally heated membrane type DAC equipped with 500 μm pure synthetic diamond anvils. In a typical experiment, the aqueous fluid and a calcite crystal [3] were loaded in a rhenium gasket. The pressure was determined from the calibrated shift of the carbonate υ1 symmetric stretching mode of aragonite and the temperature measured with a K-type thermocouple. Raman spectra were recorded using a Labram HR800 Raman spectrometer (Horiba Jobin-Yvon) coupled to a Spectra Physics Ar+ laser. At equilibrium with an aragonite crystal, the Raman data show that bicarbonate is the most abundant species in low-pressure fluids (below 4 GPa) whereas carbonate becomes progressively dominant at higher pressure. After correction from their Raman cross-sections [4], the relative amounts of dissolved carbonate and bicarbonate were estimated from the areas of the Raman bands of the carbonate and bicarbonate ions (υ1 and υ5 symmetric stretching modes, respectively). The presence of sodium chloride influences the speciation by extending the pressure field where the bicarbonate species is dominant in the fluid. The Raman data were also used to constrain a theoretical thermodynamic model of the fluid speciation in equilibrium with CaCO3. Building on published calcite solubility data from 400 - 700 °C and 2 - 16 kb [3, 5], revised thermodynamic properties of aqueous CO2 and HCO3-, data for the aqueous CaHCO3+ complex from 4 to 90 °C [6], and estimated dielectric constants of water, enabled an equation of state characterization of the standard Gibbs free energy of CaHCO3+ at the conditions of the Raman study. At 300 - 400 °C, the Raman speciation results were used to constrain equilibrium constants involving the carbonate ion. The results indicate that CO2 is a minor species in fluids in equilibrium with aragonite at 300 - 500 °C and P > 1.0 GPa. Instead, the CaHCO3+ species becomes important at high pressures until carbonate ion becomes the dominant C-species. [1] Marty, B. and Tolstikhin, I.N., Chemical Geology 145, 233 (1998) [2] Schmidt, M.W. and Poli, S., Earth and Planetary Science Letters 163, 163 (1998) [3] Caciagli, N.C. and Manning, C.E., Contributions to Mineralogy and Petrology 146, 275 (2003) [4] Frantz, J., Chemical Geology 152, 211 (1998) [5] Fein, J.B. and Walther, J.V., Contributions to Mineralogy and Petrology 103, 317 (1989) [6] Plummer, L.N. and Busenberg, E., Geochimica et Cosmochimica Acta 46, 1011 (1982)

Q-Speciation and Network Structure Evolution in Invert Calcium Silicate Glasses.

PubMed

Kaseman, Derrick C; Retsinas, A; Kalampounias, A G; Papatheodorou, G N; Sen, S

2015-07-02

Binary silicate glasses in the system CaO-SiO2 are synthesized over an extended composition range (42 mol % ≤ CaO ≤ 61 mol %), using container-less aerodynamic levitation techniques and CO2-laser heating. The compositional evolution of Q speciation in these glasses is quantified using (29)Si and (17)O magic angle spinning nuclear magnetic resonance spectroscopy. The results indicate progressive depolymerization of the silicate network upon addition of CaO and significant deviation of the Q speciation from the binary model. The equilibrium constants for the various Q species disproportionation reactions for these glasses are found to be similar to (much smaller than) those characteristic of Li (Mg)-silicate glasses, consistent with the corresponding trends in the field strengths of these modifier cations. Increasing CaO concentration results in an increase in the packing density and structural rigidity of these glasses and consequently in their glass transition temperature Tg. This apparent role reversal of conventional network-modifying cations in invert alkaline-earth silicate glasses are compared and contrasted with that in their alkali silicate counterparts.

Speciation in the Fe(III)-Cl(I)-H2O System at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C)

NASA Astrophysics Data System (ADS)

Jamett, Nathalie E.; Hernández, Pía C.; Casas, Jesús M.; Taboada, María E.

2018-02-01

This article presents the results on speciation of ferric iron generated by the dissolution of chemical reagent hydromolysite (ferric chloride hexahydrate, FeCl3:6H2O) in water at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C). Experiments were performed with a thermoregulated system up to the equilibrium point, as manifested by solution pH. Solution samples were analyzed in terms of concentration, pH, and electrical conductivity. Measurements of density and refractive index were obtained at different temperatures and iron concentrations. A decrease of pH was observed with the increase in the amount of dissolved iron, indicating that ferric chloride is a strong electrolyte that reacts readily with water. Experimental results were modeled using the hydrogeochemical code PHREEQC in order to obtain solution speciation. Cations and neutral and anion complexes were simultaneously present in the system at the studied conditions according to model simulations, where dominant species included Cl-, FeCl2+, FeCl2 +, FeOHCl 2 0 , and H+. A decrease in the concentration of Cl- and Fe3+ ions took place with increasing temperature due to the association of Fe-Cl species. Standard equilibrium constants for the formation of FeOHCl 2 0 obtained in this study were log Kf0 = -0.8 ± 0.01 at 298.15 K (25 °C), -0.94 ± 0.02 at 313.15 K (40 °C), and -1.03 ± 0.01 at 333.15 K (60 °C).

Calculation of individual isotope equilibrium constants for implementation in geochemical models

USGS Publications Warehouse

Thorstenson, Donald C.; Parkhurst, David L.

2002-01-01

Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

Speciation below ground: Tempo and mode of diversification in a radiation of endogean ground beetles.

PubMed

Andújar, Carmelo; Pérez-González, Sergio; Arribas, Paula; Zaballos, Juan P; Vogler, Alfried P; Ribera, Ignacio

2017-11-01

Dispersal is a critical factor determining the spatial scale of speciation, which is constrained by the ecological characteristics and distribution of a species' habitat and the intrinsic traits of species. Endogean taxa are strongly affected by the unique qualities of the below-ground environment and its effect on dispersal, and contrasting reports indicate either high dispersal capabilities favoured by small body size and mediated by passive mechanisms, or low dispersal due to restricted movement and confinement inside the soil. We studied a species-rich endogean ground beetle lineage, Typhlocharina, including three genera and more than 60 species, as a model for the evolutionary biology of dispersal and speciation in the deep soil. A time-calibrated molecular phylogeny generated from >400 individuals was used to delimit candidate species, to study the accumulation of lineages through space and time by species-area-age relationships and to determine the geographical structure of the diversification using the relationship between phylogenetic and geographic distances across the phylogeny. Our results indicated a small spatial scale of speciation in Typhlocharina and low dispersal capacity combined with sporadic long distance, presumably passive dispersal events that fuelled the speciation process. Analysis of lineage growth within Typhlocharina revealed a richness plateau correlated with the range of distribution of lineages, suggesting a long-term species richness equilibrium mediated by density dependence through limits of habitat availability. The interplay of area- and age-dependent processes ruling the lineage diversification in Typhlocharina may serve as a general model for the evolution of high species diversity in endogean mesofauna. © 2017 John Wiley & Sons Ltd.

Effects of Cloud Formation on the Speciation of Glyoxal and Methylglyoxal Hydrates and Polymers in Aerosols

NASA Astrophysics Data System (ADS)

Houghton, K. A.; Goh, P.; Spangler, R.; Schweitzer, W.; Khaled, K. A., Jr.; Berry, J.; Van Wyngarden, A. L.

2017-12-01

During cloud formation, atmospheric aerosols take up large quantities of water; the ensuing, rapid changes in water content and acidity may cause organic species within these aerosols to undergo various reactions such as hydration, hydrolysis, and/or polymerization. Glyoxal and methylglyoxal are among the most common organic molecules found within atmospheric aerosols, and prior experimental work has demonstrated that their speciation is altered during cloud processing. Due to the low water content of atmospheric aerosols, organics such as glyoxal and methylglyoxal are suspected to be significantly polymerized before cloud formation, as supported by the observation of polymers in ambient aerosols. Some of these polymerization reactions may be reversible; thus, these polymers may be subject to decomposition during cloud formation. The subsequent changes in the speciation of glyoxal and methylglyoxal polymers following cloud processing may alter the climate forcing properties of that aerosol population. The details of which polymers decompose and whether these decomposition reactions occur with sufficient speed to achieve equilibrium during the average lifetime of a cloud droplet remain unclear. Here, we use high resolution quadrupole mass spectrometry to investigate the kinetics of glyoxal and methylglyoxal speciation reactions after dilution, simulating the effects of cloud droplet formation on aerosol particles. Our data reveal that after dilution, polymers (up to the pentamer and octamer for glyoxal and methylglyoxal, respectively) persist in solution for more than 90 minutes. Furthermore, polymer speciation continues to change for hours after dilution, indicating that kinetics of at least some polymer interconversion reactions are slow with respect to a typical cloud droplet lifetime.

Thallium and Silver binding to dissolved organic matter

NASA Astrophysics Data System (ADS)

Benedetti, M. F.; Martin, L.; Simonucci, C.; Viollier, E.

2017-12-01

Silver (Ag) and thallium (Tl) are potential contaminants at the vicinity of mining sites and are harmful pollutants. Silver can be found in mine but also as released by the dissolution of Silver nanoparticles, a major new emerging contaminant. Tl is both lithophilic and calcophilic elements and found in sulphur ores (associated with lead, zinc, antimony…) or in rocks containing K-feldspar. Speciation of Ag and Tl is poorly known mainly due to their low concentrations in aquatic environments. Review of Ag and Tl geochemistry clearly shows a lack of quantitative information about interactions with natural organic matter. Organic ligands could play an important role in Ag or Tl bioavailability, chemical reactivity (adsorption or photo oxidation inhibition or catalysis) and hence geochemical transfers. Based on equilibrium between two solutions that are separated by a selectively permeable membrane, the so-called "Donnan membrane technique" (DMT) provides a measure of free ion concentrations. Analytes measurements are performed by HR-ICP-MS Element 2 (Thermo Scientific). Experimental setup allows the Donnan equilibrium to be reached after 100 and 120 hours for Tl. Experiments performed with purified natural organic matter allow calculating complexation constants in multiple pH conditions. With this work, we contribute new data and interpretations to an active debate on Ag and Tl geochemical modeling. In conclusion, this work brings a new view on risk assessment for mining activities.

The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations.

PubMed

Niksa, Stephen; Fujiwara, Naoki

2005-07-01

This article introduces a predictive capability for Hg retention in any Ca-based wet flue gas desulfurization (FGD) scrubber, given mercury (Hg) speciation at the FGD inlet, the flue gas composition, and the sulphur dioxide (SO2) capture efficiency. A preliminary statistical analysis of data from 17 full-scale wet FGDs connects flue gas compositions, the extents of Hg oxidation at FGD inlets, and Hg retention efficiencies. These connections clearly signal that solution chemistry within the FGD determines Hg retention. A more thorough analysis based on thermochemical equilibrium yields highly accurate predictions for total Hg retention with no parameter adjustments. For the most reliable data, the predictions were within measurement uncertainties for both limestone and Mg/lime systems operating in both forced and natural oxidation mode. With the U.S. Environmental Protection Agency's (EPA) Information Collection Request (ICR) database, the quantitative performance was almost as good for the most modern FGDs, which probably conform to the very high SO2 absorption efficiencies assumed in the calculations. The large discrepancies for older FGDs are tentatively attributed to the unspecified SO2 capture efficiencies and operating temperatures and to the possible elimination of HCl in prescrubbers. The equilibrium calculations suggest that Hg retention is most sensitive to inlet HCl and O2 levels and the FGD temperature; weakly dependent on SO2 capture efficiency; and insensitive to HgCl2, NO, CA:S ratio, slurry dilution level in limestone FGDs, and MgSO3 levels in Mg/lime systems. Consequently, systems with prescrubbers to eliminate HCl probably retain less Hg than fully integrated FGDs. The analysis also predicts re-emission of Hg(O) but only for inlet O2 levels that are much lower than those in full-scale FGDs.

Uranium(VI) Binding Forms in Selected Human Body Fluids: Thermodynamic Calculations versus Spectroscopic Measurements.

PubMed

Osman, Alfatih A A; Geipel, Gerhard; Barkleit, Astrid; Bernhard, Gert

2015-02-16

Human exposure to uranium increasingly becomes a subject of interest in many scientific disciplines such as environmental medicine, toxicology, and radiation protection. Knowledge about uranium chemical binding forms(speciation) in human body fluids can be of great importance to understand not only its biokinetics but also its relevance in risk assessment and in designing decorporation therapy in the case of accidental overexposure. In this study, thermodynamic calculations of uranium speciation in relevant simulated and original body fluids were compared with spectroscopic data after ex-situ uranium addition. For the first time, experimental data on U(VI) speciation in body fluids (saliva, sweat, urine) was obtained by means of cryogenic time-resolved laser-induced fluorescence spectroscopy (cryo-TRLFS) at 153 K. By using the time dependency of fluorescence decay and the band positions of the emission spectra, various uranyl complexes were demonstrated in the studied samples. The variations of the body fluids in terms of chemical composition, pH, and ionic strength resulted in different binding forms of U(VI). The speciation of U(VI) in saliva and in urine was affected by the presence of bioorganic ligands, whereas in sweat, the distribution depends mainly on inorganic ligands. We also elucidated the role of biological buffers, i.e., phosphate (H(2)PO(4−)/HPO(4)(2−)) on U(VI) distribution, and the system Ca(2+)/UO(2)(2+)/PO(4)(3−) was discussed in detail in both saliva and urine. The theoretical speciation calculations of the main U(VI) species in the investigated body fluids were significantly consistent with the spectroscopic data. Laser fluorescence spectroscopy showed success and reliability for direct determination of U(VI) in such biological matrices with the possibility for further improvement.

Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage.

PubMed

Shakeri Yekta, Sepehr; Lindmark, Amanda; Skyllberg, Ulf; Danielsson, Asa; Svensson, Bo H

2014-03-30

The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼ 20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

Calculation of individual isotope equilibrium constants for geochemical reactions

USGS Publications Warehouse

Thorstenson, D.C.; Parkhurst, D.L.

2004-01-01

Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO2 in an acidic aqueous solution. ?? 2004 Elsevier Ltd.

Cocrystal solubility product analysis - Dual concentration-pH mass action model not dependent on explicit solubility equations.

PubMed

Avdeef, Alex

2017-12-15

A novel general computational approach is described to address many aspects of cocrystal (CC) solubility product (K sp ) determination of drug substances. The CC analysis program, pDISOL-X, was developed and validated with published model systems of various acid-base combinations of active pharmaceutical ingredients (APIs) and coformers: (i) carbamazepine cocrystal systems with 4-aminobenzoic acid, cinnamic acid, saccharin, and salicylic acid, (ii) for indomethacin with saccharin, (iii) for nevirapine with maleic acid, saccharin, and salicylic acid, and (iv) for gabapentin with 3-hydroxybenzoic acid. In all systems but gabapentin, the coformer is much more soluble than the API. The model systems selected are those with available published dual concentration-pH data, one set for the API and one set for the coformer, generally measured at eutectic points (thermodynamically-stable three phases: solution, cocrystal, and crystalline API or coformer). The carbamazepine-cinnamic acid CC showed a substantial elevation in the API equilibrium concentration above pH5, consistent with the formation of a complex between carbamazepine and cinnamate anion. The analysis of the gabapentin:3-hydroxybenzoic acid 1:1 CC system indicated four zones of solid suspensions: coformer (pH<3.25), coformer and cocrystal eutectic (pH3.25-4.44), cocrystal (pH4.44-5.62), and API (pH>5.62). The general approach allows for testing of many possible equilibrium models, including those comprising drug-coformer complexation. The program calculates the ionic strength at each pH. From this, the equilibrium constants are adjusted for activity effects, based on the Stokes-Robinson hydration theory. The complete speciation analysis of the CC systems may provide useful insights into pH-sensitive dissolution effects that could potentially influence bioavailability. Copyright © 2017 Elsevier B.V. All rights reserved.

Phytoextraction of cadmium by Ipomoea aquatica (water spinach) in hydroponic solution: effects of cadmium speciation.

PubMed

Wang, Kai-Sung; Huang, Lung-Chiu; Lee, Hong-Shen; Chen, Pai-Ye; Chang, Shih-Hsien

2008-06-01

Phytoextraction is a promising technique to remediate heavy metals from contaminated wastewater. However, the interactions of multi-contaminants are not fully clear. This study employed cadmium, Triton X-100 (TX-100), and EDTA to investigate their interactions on phytotoxicity and Cd phytoextraction of Ipomoea aquatica (water spinach) in simulated wastewater. The Cd speciation was estimated by a chemical equilibrium model and MINEQL+. Statistic regression was applied to evaluate Cd speciation on Cd uptake in shoots and stems of I. aquatica. Results indicated that the root length was a more sensitive parameter than root weight and shoot weight. Root elongation was affected by Cd in the Cd-EDTA solution and TX-100 in the Cd-TX-100 solution. Both the root length and the root biomass were negatively correlated with the total soluble Cd ions. In contrast, Cd phytoextraction of I. aquatic was correlated with the aqueous Cd ions in the free and complex forms rather than in the chelating form. Additionally, the high Cd bioconcentration factors of I. aquatica (375-2227 l kg(-1) for roots, 45-144 l kg(-1) for shoots) imply that I. aquatica is a potential aquatic plant to remediate Cd-contaminated wastewater.

Kinetics of heavy metal adsorption and desorption in soil: Developing a unified model based on chemical speciation

NASA Astrophysics Data System (ADS)

Peng, Lanfang; Liu, Paiyu; Feng, Xionghan; Wang, Zimeng; Cheng, Tao; Liang, Yuzhen; Lin, Zhang; Shi, Zhenqing

2018-03-01

Predicting the kinetics of heavy metal adsorption and desorption in soil requires consideration of multiple heterogeneous soil binding sites and variations of reaction chemistry conditions. Although chemical speciation models have been developed for predicting the equilibrium of metal adsorption on soil organic matter (SOM) and important mineral phases (e.g. Fe and Al (hydr)oxides), there is still a lack of modeling tools for predicting the kinetics of metal adsorption and desorption reactions in soil. In this study, we developed a unified model for the kinetics of heavy metal adsorption and desorption in soil based on the equilibrium models WHAM 7 and CD-MUSIC, which specifically consider metal kinetic reactions with multiple binding sites of SOM and soil minerals simultaneously. For each specific binding site, metal adsorption and desorption rate coefficients were constrained by the local equilibrium partition coefficients predicted by WHAM 7 or CD-MUSIC, and, for each metal, the desorption rate coefficients of various binding sites were constrained by their metal binding constants with those sites. The model had only one fitting parameter for each soil binding phase, and all other parameters were derived from WHAM 7 and CD-MUSIC. A stirred-flow method was used to study the kinetics of Cd, Cu, Ni, Pb, and Zn adsorption and desorption in multiple soils under various pH and metal concentrations, and the model successfully reproduced most of the kinetic data. We quantitatively elucidated the significance of different soil components and important soil binding sites during the adsorption and desorption kinetic processes. Our model has provided a theoretical framework to predict metal adsorption and desorption kinetics, which can be further used to predict the dynamic behavior of heavy metals in soil under various natural conditions by coupling other important soil processes.

Parapatric speciation in three islands: dynamics of geographical configuration of allele sharing

PubMed Central

Iwasa, Yoh

2017-01-01

We studied the time to speciation by geographical isolation for a species living on three islands connected by rare migration. We assumed that incompatibility was controlled by a number of quantitative loci and that individuals differing in loci by more than a threshold did not mix genetically with each other. For each locus, we defined the geographical configuration (GC), which specifies islands with common alleles, and traced the stochastic transitions between different GCs. From these results, we calculated the changes in genetic distances. As a single migration event provides an opportunity for transitions in multiple loci, the GCs of different loci are correlated, which can be evaluated by constructing the stochastic differential equations of the number of loci with different GCs. Our model showed that the low number of incompatibility loci facilitates parapatric speciation and that migrants arriving as a group shorten the waiting time to speciation compared with the same number of migrants arriving individually. We also discuss how speciation rate changes with geographical structure. PMID:28386439

Biogeochemical controls on mercury methylation in the Allequash Creek wetland.

PubMed

Creswell, Joel E; Shafer, Martin M; Babiarz, Christopher L; Tan, Sue-Zanne; Musinsky, Abbey L; Schott, Trevor H; Roden, Eric E; Armstrong, David E

2017-06-01

We measured mercury methylation potentials and a suite of related biogeochemical parameters in sediment cores and porewater from two geochemically distinct sites in the Allequash Creek wetland, northern Wisconsin, USA. We found a high degree of spatial variability in the methylation rate potentials but no significant differences between the two sites. We identified the primary geochemical factors controlling net methylmercury production at this site to be acid-volatile sulfide, dissolved organic carbon, total dissolved iron, and porewater iron(II). Season and demethylation rates also appear to regulate net methylmercury production. Our equilibrium speciation modeling demonstrated that sulfide likely regulated methylation rates by controlling the speciation of inorganic mercury and therefore its bioavailability to methylating bacteria. We found that no individual geochemical parameter could explain a significant amount of the observed variability in mercury methylation rates, but we found significant multivariate relationships, supporting the widely held understanding that net methylmercury production is balance of several simultaneously occurring processes.

Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

NASA Technical Reports Server (NTRS)

Levine, J. S.; Summers, M. E.; Ewell, M.

2010-01-01

The detection of methane (CH4) in the atmosphere of Mars by Mars Express and Earth-based spectroscopy is very surprising, very puzzling, and very intriguing. On Earth, about 90% of atmospheric ozone is produced by living systems. A major question concerning methane on Mars is its origin - biological or geological. Thermodynamic equilibrium calculations indicated that methane cannot be produced by atmospheric chemical/photochemical reactions. Thermodynamic equilibrium calculations for three gases, methane, ammonia (NH3) and nitrous oxide (N2O) in the Earth s atmosphere are summarized in Table 1. The calculations indicate that these three gases should not exist in the Earth s atmosphere. Yet they do, with methane, ammonia and nitrous oxide enhanced 139, 50 and 12 orders of magnitude above their calculated thermodynamic equilibrium concentration due to the impact of life! Thermodynamic equilibrium calculations have been performed for the same three gases in the atmosphere of Mars based on the assumed composition of the Mars atmosphere shown in Table 2. The calculated thermodynamic equilibrium concentrations of the same three gases in the atmosphere of Mars is shown in Table 3. Clearly, based on thermodynamic equilibrium calculations, methane should not be present in the atmosphere of Mars, but it is in concentrations approaching 30 ppbv from three distinct regions on Mars.

Application of surface complexation models to anion adsorption by natural materials.

PubMed

Goldberg, Sabine

2014-10-01

Various chemical models of ion adsorption are presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model, are described in the present study. Characteristics common to all the surface complexation models are equilibrium constant expressions, mass and charge balances, and surface activity coefficient electrostatic potential terms. Methods for determining parameter values for surface site density, capacitances, and surface complexation constants also are discussed. Spectroscopic experimental methods of establishing ion adsorption mechanisms include vibrational spectroscopy, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity. Experimental determinations of point of zero charge shifts and ionic strength dependence of adsorption results and molecular modeling calculations also can be used to deduce adsorption mechanisms. Applications of the surface complexation models to heterogeneous natural materials, such as soils, using the component additivity and the generalized composite approaches are described. Emphasis is on the generalized composite approach for predicting anion adsorption by soils. Continuing research is needed to develop consistent and realistic protocols for describing ion adsorption reactions on soil minerals and soils. The availability of standardized model parameter databases for use in chemical speciation-transport models is critical. Published 2014 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and as such, is in the public domain in the in the United States of America.

Global isolation by distance despite strong regional phylogeography in a small metazoan

PubMed Central

Mills, Scott; Lunt, David H; Gómez, Africa

2007-01-01

Background Small vagile eukaryotic organisms, which comprise a large proportion of the Earth's biodiversity, have traditionally been thought to lack the extent of population structuring and geographic speciation observed in larger taxa. Here we investigate the patterns of genetic diversity, amongst populations of the salt lake microscopic metazoan Brachionus plicatilis s. s. (sensu stricto) (Rotifera: Monogononta) on a global scale. We examine the phylogenetic relationships of geographic isolates from four continents using a 603 bp fragment of the mitochondrial COI gene to investigate patterns of phylogeographic subdivision in this species. In addition we investigate the relationship between genetic and geographic distances on a global scale to try and reconcile the paradox between the high vagility of this species and the previously reported patterns of restricted gene flow, even over local spatial scales. Results Analysis of global sequence diversity of B. plicatilis s. s. reveals the presence of four allopatric genetic lineages: North American-Far East Asian, Western Mediterranean, Australian, and an Eastern Mediterranean lineage represented by a single isolate. Geographically orientated substructure is also apparent within the three best sampled lineages. Surprisingly, given this strong phylogeographic structure, B. plicatilis s. s. shows a significant correlation between geographic and genetic distance on a global scale ('isolation by distance' – IBD). Conclusion Despite its cosmopolitan distribution and potential for high gene flow, B. plicatilis s. s. is strongly structured at a global scale. IBD patterns have traditionally been interpreted to indicate migration-drift equilibrium, although in this system equilibrium conditions are incompatible with the observed genetic structure. Instead, we suggest the pattern may have arisen through persistent founder effects, acting in a similar fashion to geographic barriers for larger organisms. Our data indicates that geographic speciation, contrary to historical views, is likely to be very important in microorganisms. By presenting compelling evidence for geographic speciation in a small eukaryote we add to the growing body of evidence that is forcing us to rethink our views of global biodiversity. PMID:17999774

An in vitro study of interactions between insulin-mimetic zinc(II) complexes and selected plasma components.

PubMed

Enyedy, Eva Anna; Horváth, László; Gajda-Schrantz, Krisztina; Galbács, Gábor; Kiss, Tamás

2006-12-01

The speciations of some potent insulin-mimetic zinc(II) complexes of bidentate ligands: maltol and 1,2-dimethyl-3-hydroxypyridinone with (O,O) and picolinic acid with (N,O) coordination modes, were studied via solution equilibrium investigations of the ternary complex formation in the presence of small relevant bioligands of the blood serum such as cysteine, histidine and citric acid. Results show that formation of the ternary complexes, especially with cysteine, is favoured at physiological pH range in almost all systems studied. Besides these low molecular mass binders, serum proteins among others albumin and transferrin can bind zinc(II) or its complexes. Accordingly, the distribution of zinc(II) between the small and high molecular mass fractions of the serum was also studied by ultrafiltration. Modelling calculations relating to the distribution of zinc(II), using the stability constants of the ternary complexes studied and those of the serum proteins reported in the literature, confirmed the ultrafiltration results, namely, the primary role of albumin in zinc(II) binding among the low and high molecular mass components of the serum.

Experimental determination of iron isotope fractionations among Fe aq 2 + -FeSaq-Mackinawite at low temperatures: Implications for the rock record

NASA Astrophysics Data System (ADS)

Wu, Lingling; Druschel, Greg; Findlay, Alyssa; Beard, Brian L.; Johnson, Clark M.

2012-07-01

The Fe isotope fractionation factors among aqueous ferrous iron (Fe aq 2 +), aqueous FeS clusters (FeSaq), and nanoparticulate mackinawite under neutral and mildly acidic and alkaline pH conditions have been determined using the three-isotope method. Combined voltammetric analysis and geochemical modeling were used to determine the Fe speciation in the experimental systems. The equilibrium 56Fe/54Fe fractionation factor at 20 °C and pH 7 has been determined to be -0.32 ± 0.29 (2σ)‰ between Fe aq 2 + (minor FeSaq also present in the experiment) and mackinawite. This fractionation factor was essentially constant when pH was changed to 6 or 8. When equal molarity of HS- and Fe aq 2 + were added to the system, however, the isotopic fractionation at pH 7 changed to -0.64 ± 0.36 (2σ)‰, correlating with a significant increase in the proportion of FeHS+ and FeSaq. These results highlight a more important role of aqueous Fe-S speciation in the equilibrium Fe isotope fractionation factor than recognized in previous studies. The isotopic fractionation remained constant when temperature was increased from 20 °C to 35 °C for fractionation factors between Fe aq 2 + , and mackinawite and between dominantly FeHS+ and mackinawite. Synthesis experiments similar to those of Butler et al. (2005) and Guilbaud et al. (2010) at pH 4 show consistent results: over time, the aqueous Fe-mackinawite fractionation decreases but even after 38 days of aging the fractionation factor is far from the equilibrium value inferred using the three-isotope method. In contrast, at near-neutral pH the fractionation factor for the synthesis experiment reached the equilibrium value in 38 days. These differences are best explained by noting that at low pH the FeS mackinawite particles coarsen more rapidly via particle aggregation, which limits isotopic exchange, whereas at higher pH mackinawite aggregation is limited, and Fe isotope exchange occurs more rapidly, converging on the equilibrium value. These results suggest that mackinawite formed in natural environments at near-neutral or alkaline pH are unlikely to retain kinetic isotope fractionations, but are more likely to reflect equilibrium isotope compositions. This in turn has important implications for interpreting iron isotope compositions of Fe sulfides in natural systems.

Combined EXAFS Spectroscopic and Quantum Chemical Study on the Complex Formation of Am(III) with Formate.

PubMed

Fröhlich, Daniel R; Kremleva, Alena; Rossberg, André; Skerencak-Frech, Andrej; Koke, Carsten; Krüger, Sven; Rösch, Notker; Panak, Petra J

2017-06-19

The complexation of Am(III) with formate in aqueous solution is studied as a function of the pH value using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy, iterative transformation factor analysis (ITFA), and quantum chemical calculations. The Am L III -edge EXAFS spectra are analyzed to determine the molecular structure (coordination numbers; Am-O and Am-C distances) of the formed Am(III)-formate species and to track the shift of the Am(III) speciation with increasing pH. The experimental data are compared to predictions from density functional calculations. The results indicate that formate binds to Am(III) in a monodentate fashion, in agreement with crystal structures of lanthanide formates. Furthermore, the investigations are complemented by thermodynamic speciation calculations to verify further the results obtained.

A forecast for extinction debt in the presence of speciation.

PubMed

Sgardeli, Vasiliki; Iwasa, Yoh; Varvoglis, Harry; Halley, John M

2017-02-21

Predicting biodiversity relaxation following a disturbance is of great importance to conservation biology. Recently-developed models of stochastic community assembly allow us to predict the evolution of communities on the basis of mechanistic processes at the level of individuals. The neutral model of biodiversity, in particular, has provided closed-form solutions for the relaxation of biodiversity in isolated communities (no immigration or speciation). Here, we extend these results by deriving a relaxation curve for a neutral community in which new species are introduced through the mechanism of random fission speciation (RFS). The solution provides simple closed-form expressions for the equilibrium species richness, the relaxation time and the species-individual curve, which are good approximation to the more complicated formulas existing for the same model. The derivation of the relaxation curve is based on the assumption of a broken-stick species-abundance distribution (SAD) as an initial community configuration; yet for commonly observed SADs, the maximum deviation from the curve does not exceed 10%. Importantly, the solution confirms theoretical results and observations showing that the relaxation time increases with community size and thus habitat area. Such simple and analytically tractable models can help crystallize our ideas on the leading factors affecting biodiversity loss. Copyright © 2016 Elsevier Ltd. All rights reserved.

REE speciation in low-temperature acidic waters and the competitive effects of aluminum

USGS Publications Warehouse

Gimeno, Serrano M.J.; Auque, Sanz L.F.; Nordstrom, D. Kirk

2000-01-01

The effect of simultaneous competitive speciation of dissolved rare earth elements (REEs) in acidic waters (pH 3.3 to 5.2) has been evaluated by applying the PHREEQE code to the speciation of water analyses from Spain, Brazil, USA, and Canada. The main ions that might affect REE are Al3+, F-, SO42-, and PO43-. Fluoride, normally a significant complexer of REEs, is strongly associated with Al3+ in acid waters and consequently has little influence on REEs. The inclusion of aluminum concentrations in speciation calculations for acidic waters is essential for reliable speciation of REEs. Phosphate concentrations are too low (10-4 to 10-7 m) to affect REE speciation. Consequently, SO42- is the only important complexing ligand for REEs under these conditions. According to Millero [Millero, F.J., 1992. Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength. Geochim. Cosmochim. Acta, 56, 3123-3132], the lanthanide sulfate stability constants are nearly constant with increasing atomic number so that no REE fractionation would be anticipated from aqueous complexation in acidic waters. Hence, REE enrichments or depletions must arise from mass transfer reactions. (C) 2000 Elsevier Science B.V. All rights reserved.

Geochemical modeling of mercury speciation in surface water and implications on mercury cycling in the everglades wetland.

PubMed

Jiang, Ping; Liu, Guangliang; Cui, Wenbin; Cai, Yong

2018-06-01

The geochemical model PHREEQC, abbreviated from PH (pH), RE (redox), EQ (equilibrium), and C (program written in C), was employed on the datasets generated by the USEPA Everglades Regional Environmental Monitoring and Assessment Program (R-EMAP) to determine the speciation distribution of inorganic mercury (iHg) in Everglades water and to explore the implications of iHg speciation on mercury cycling. The results suggest that sulfide and DOM were the key factors that regulate inorganic Hg speciation in the Everglades. When sulfide was present at measurable concentrations (>0.02 mg/L), Hg-S complexes dominated iHg species, occurring in the forms of HgS 2 2- , HgHS 2 - , and Hg(HS) 2 that were affected by a variety of environmental factors. When sulfide was assumed nonexistent, Hg-DOM complexes occurred as the predominant Hg species, accounting for almost 100% of iHg species. However, when sulfide was presumably present at a very low, environmentally relevant concentration (3.2 × 10 -7  mg/L), both Hg-DOM and Hg-S complexes were present as the major iHg species. These Hg-S species and Hg-DOM complex could be related to methylmercury (MeHg) in environmental matrices such floc, periphyton, and soil, and the correlations are dependent upon different circumstances (e.g., sulfide concentrations). The implications of the distribution of iHg species on MeHg production and fate in the Everglades were discussed. Copyright © 2018 Elsevier B.V. All rights reserved.

Conjugate Acid-Base Pairs, Free Energy, and the Equilibrium Constant

ERIC Educational Resources Information Center

Beach, Darrell H.

1969-01-01

Describes a method of calculating the equilibrium constant from free energy data. Values of the equilibrium constants of six Bronsted-Lowry reactions calculated by the author's method and by a conventional textbook method are compared. (LC)

Non-equilibrium calculations of atmospheric processes initiated by electron impact.

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.

2007-05-01

Electron impact in the atmosphere produces ionisation, dissociation, electronic excitation and vibrational excitation of atoms and molecules. The products can then take part in chemical reactions, recombination with electrons, or radiative or collisional deactivation. While most such processes are fast, some longer--lived species do not reach equilibrium. The electron source (photoelectrons or auroral electrons) also varies over time and longer-lived species can move substantially in altitude by molecular, ambipolar or eddy diffusion. Hence non-equilibrium calculations are required in some circumstances. Such time-step calculations need to have sufficiently short steps so that the fastest processes are still calculated correctly, but this can lead to computation times that are too large. Hence techniques to allow for longer time steps by incorporating equilibrium calculations are described. Examples are given for results of atmospheric non-equilibrium calculations, including the populations of the vibrational levels of ground state N2, the electron density and its dependence on vibrationally excited N2, predictions of nitric oxide density, and detailed processes during short duration auroral events.

PEaCH4 v.2.0: A modelling platform to predict early diagenetic processes in marine sediments with a focus on biogenic methane - Case study: Offshore Namibia

NASA Astrophysics Data System (ADS)

Arning, Esther T.; Häußler, Steffen; van Berk, Wolfgang; Schulz, Hans-Martin

2016-07-01

The modelling of early diagenetic processes in marine sediments is of interest in marine science, and in the oil and gas industry, here, especially with respect to methane occurrence and gas hydrate formation as resources. Early diagenesis in marine sediments evolves from a complex web of intertwining (bio)geochemical reactions. It comprises microbially catalysed reactions and inorganic mineral-water-gas interactions. A model that will describe and consider all of these reactions has to be complex. However, it should be user-friendly, as well as to be applicable for a broad community and not only for experts in the field of marine chemistry. The presented modelling platform PeaCH4 v.2.0 combines both aspects, and is Microsoft Excel©-based. The modelling tool is PHREEQC (version 2), a computer programme for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. The conceptual PEaCH4 model is based on the conversion of sediment-bound degradable organic matter. PEaCH4 v.2.0 was developed to quantify and predict early diagenetic processes in marine sediments with the focus on biogenic methane formation and its phase behaviour, and allows carbon mass balancing. In regard to the irreversible degradation of organic matter, it comprises a "reaction model" and a "kinetic model" to predict methane formation. Both approaches differ in their calculations and outputs as the "kinetic model" considers the modelling time to integrate temperature dependent biogenic methane formation in its calculations, whereas the "reaction model" simply relies on default organic matter degradation. With regard to the inorganic mineral-water-gas interactions, which are triggered by irreversible degradation of organic matter, PEaCH4 v.2.0 is based on chemical equilibrium thermodynamics, appropriate mass-action laws, and their temperature dependent equilibrium constants. The programme is exemplarily presented with the example of upwelling sediments off Namibia, ODP Leg 175, Site 1082. The application demonstrates that the modelling platform PEaCH4 v.2.0 provides a user-friendly, but complex scientific tool that delivers retraceable information about early diagenetic processes and products in marine sediments.

Surface reactions kinetics between nanocrystalline magnetite and uranyl.

PubMed

Missana, Tiziana; Maffiotte, César; García-Gutiérrez, Miguel

2003-05-01

Magnetite is the most important end member of iron corrosion products under reducing environment, which is the condition expected in a deep geological high level radioactive waste disposal. Nanocrystalline magnetite was synthesized in the laboratory and its physicochemical properties were analyzed in detail. The kinetics of the adsorption of U(VI) and the kinetics of the actinide reduction to a lower oxidation state, in presence of the oxide, were studied by means of batch sorption techniques and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that the uranium sorption and reduction processes on the magnetite surface have very fast kinetics (hours), the reduction process being triggered by sorption. XPS measurements showed that the speciation of uranium at the surface does not show significant changes with time (from 1 day to 3 months), as well as the quantity of uranium detected at the surface. The surface speciation depended on the initial pH of the contact solution. Considering that the Eh of equilibrium between magnetite and the solution, under our experimental conditions, is slightly positive (50-100 mV), the uranium reduction would also be thermodynamically possible within the liquid phase. However, the kinetics of reduction in the liquid occur at a much slower rate which, in turn, has to depend on the attainment of the magnetite/solution equilibrium. The decrease of uranium in solution, observed after the uranyl adsorption stage, and particularly at acidic pH, is most probably due to the precipitation of U(IV) formed in the solution.

Complexation of Cd, Ni, and Zn by DOC in polluted groundwater: A comparison of approaches using resin exchange, aquifer material sorption, and computer speciation models (WHAM and MINTEQA2)

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

Christensen, J.B.; Christensen, T.H.

1999-11-01

Complexation of cadmium (Cd), nickel (Ni), and zinc (Zn) by dissolved organic carbon (DOC) in leachate-polluted groundwater was measured using a resin equilibrium method and an aquifer material sorption technique. The first method is commonly used in complexation studies, while the second method better represents aquifer conditions. The two approaches gave similar results. Metal-DOC complexation was measured over a range of DOC concentrations using the resin equilibrium method, and the results were compared to simulations made by two speciation models containing default databases on metal-DOC complexes (WHAM and MINTEQA2). The WHAM model gave reasonable estimates of Cd and Ni complexationmore » by DOC for both leachate-polluted groundwater samples. The estimated effect of complexation differed less than 50% from the experimental values corresponding to a deviation on the activity of the free metal ion of a factor of 2.5. The effect of DOC complexation for Zn was largely overestimated by the WHAM model, and it was found that using a binding constant of 1.7 instead of the default value of 1.3 would improve the fit between the simulations and experimental data. The MINTEQA2 model gave reasonable predictions of the complexation of Cd and Zn by DOC, whereas deviations in the estimated activity of the free Ni{sup 2+} ion as compared to experimental results are up to a factor of 5.« less

Speciation of Mg in biogenic calcium carbonates

NASA Astrophysics Data System (ADS)

Farges, F.; Meibom, A.; Flank, A.-M.; Lagarde, P.; Janousch, M.; Stolarski, J.

2009-11-01

A selection of marine biominerals, mostly aragonitic coral skeletons were probed at the Mg K-edge by XANES spectroscopy coupled to μXRF methods and compared to an extensive set of relevant model compounds (silicates, carbonates, oxides and organic). Extensive methodologies are required to better describe the speciation of Mg in those minerals. A combination of ab-initio XANES calculations for defective clusters around Mg in aragonite together with wavelets analyzes of the XANES region are required to robustly interpret the spectra. When using those methodologies, the speciation of Mg ranges from a magnesite-type environment in some scleractinian corals to an organic-type environment. In all environments, the Mg-domains probed appear to be less than 1 nm in size.

A Brief User's Guide to the Excel ® -Based DF Calculator

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

Jubin, Robert T.

2016-06-01

To understand the importance of capturing penetrating forms of iodine as well as the other volatile radionuclides, a calculation tool was developed in the form of an Excel ® spreadsheet to estimate the overall plant decontamination factor (DF). The tool requires the user to estimate splits of the volatile radionuclides within the major portions of the reprocessing plant, speciation of iodine and individual DFs for each off-gas stream within the Used Nuclear Fuel reprocessing plant. The Impact to the overall plant DF for each volatile radionuclide is then calculated by the tool based on the specific user choices. The Excelmore » ® spreadsheet tracks both elemental and penetrating forms of iodine separately and allows changes in the speciation of iodine at each processing step. It also tracks 3H, 14C and 85Kr. This document provides a basic user's guide to the manipulation of this tool.« less

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

Karin Lundholm; Dan Bostroem; Anders Nordin

The EU Directive on incineration of waste regulates the harmful emissions of particles and twelve toxic elements, including copper, chromium, and arsenic. Using a 15 kW pellets-fueled grate burner, experiments were performed to determine the fate of copper, chromium, and arsenic during combustion of chromate copper arsenate (CCA) preservative wood. The fate and speciation of copper, chromium, and arsenic were determined from analysis of the flue gas particles and the bottom ash using SEM-EDS, XRD, XPS, and ICP-AES. Chemical equilibrium model calculations were performed to interpret the experimental findings. The results revealed that about 5% copper, 15% chromium, and 60%more » arsenic were volatilized during combustion of pure CCA-wood, which is lower than predicted volatilization from the individual arsenic, chromium, and copper oxides. This is explained by the formation of more stable refractory complex oxide phases for which the stability trends and patterns are presented. When co-combusted with peat, an additional stabilization of these phases was obtained and thus a small but noteworthy decrease in volatilization of all three elements was observed. The major identified phases for all fuels were CuCrO{sub 2}(s), (Fe,Mg,Cu)(Cr,Fe,Al)O{sub 4}(s), Cr{sub 2}O{sub 3}(s), and Ca{sub 3}(AsO{sub 4}){sub 2}(s). Arsenic was also identified in the fine particles as KH{sub 2}AsO{sub 4}(s) and As{sub 2}O{sub 3}). A strong indication of hexavalent chromium in the form of K{sub 2}CrO{sub 4} or as a solid solution between K{sub 3}Na(CrO{sub 4}){sub 2} and K{sub 3}Na(SO{sub 4}){sub 2} was found in the fine particles. Good qualitative agreement was observed between experimental data and chemical equilibrium model calculations. 38 refs., 6 figs., 2 tabs.« less

Variation of the NMVOC speciation in the solvent sector and the sensitivity of modelled tropospheric ozone

NASA Astrophysics Data System (ADS)

von Schneidemesser, E.; Coates, J.; Denier van der Gon, H. A. C.; Visschedijk, A. J. H.; Butler, T. M.

2016-06-01

Non-methane volatile organic compounds (NMVOCs) are detrimental to human health owing to the toxicity of many of the NMVOC species, as well as their role in the formation of secondary air pollutants such as tropospheric ozone (O3) and secondary organic aerosol. The speciation and amount of NMVOCs emitted into the troposphere are represented in emission inventories (EIs) for input to chemical transport models that predict air pollutant levels. Much of the information in EIs pertaining to speciation of NMVOCs is likely outdated, but before taking on the task of providing an up-to-date and highly speciated EI, a better understanding of the sensitivity of models to the change in NMVOC input would be highly beneficial. According to the EIs, the solvent sector is the most important sector for NMVOC emissions. Here, the sensitivity of modelled tropospheric O3 to NMVOC emission inventory speciation was investigated by comparing the maximum potential difference in O3 produced using a variety of reported solvent sector EI speciations in an idealized study using a box model. The sensitivity was tested using three chemical mechanisms that describe O3 production chemistry, typically employed for different types of modelling scales - point (MCM v3.2), regional (RADM2), and global (MOZART-4). In the box model simulations, a maximum difference of 15 ppbv (ca. 22% of the mean O3 mixing ratio of 69 ppbv) between the different EI speciations of the solvent sector was calculated. In comparison, for the same EI speciation, but comparing the three different mechanisms, a maximum difference of 6.7 ppbv was observed. Relationships were found between the relative contribution of NMVOC compound classes (alkanes and oxygenated species) in the speciations to the amount of Ox produced in the box model. These results indicate that modelled tropospheric O3 is sensitive to the speciation of NMVOCs as specified by emission inventories, suggesting that detailed updates to the EI speciation information would be warranted. Furthermore, modelled tropospheric O3 was also sensitive to the choice of chemical mechanism and further evaluation of both of these sensitivities in more realistic chemical-transport models is needed.

Concentrations and speciation of arsenic along a groundwater flow-path in the Upper Floridan aquifer, Florida, USA

NASA Astrophysics Data System (ADS)

Haque, S. E.; Johannesson, K. H.

2006-05-01

Arsenic (As) concentrations and speciation were determined in groundwaters along a flow-path in the Upper Floridan aquifer (UFA) to investigate the biogeochemical “evolution“ of As in this relatively pristine aquifer. Dissolved inorganic As species were separated in the field using anion-exchange chromatography and subsequently analyzed by inductively coupled plasma mass spectrometry. Total As concentrations are higher in the recharge area groundwaters compared to down-gradient portions of UFA. Redox conditions vary from relatively oxic to anoxic along the flow-path. Mobilization of As species in UFA groundwaters is influenced by ferric iron reduction and subsequent dissolution, sulfate reduction, and probable pyrite precipitation that are inferred from the data to occur along distinct regions of the flow-path. In general, the distribution of As species are consistent with equilibrium thermodynamics, such that arsenate dominates in more oxidizing waters near the recharge area, and arsenite predominates in the progressively reducing groundwaters beyond the recharge area.

Limited by the roof of the world: mountain radiations of Apollo swallowtails controlled by diversity-dependence processes.

PubMed

Condamine, Fabien L

2018-03-01

Mountainous areas contain a substantial part of the world species richness, but the evolutionary origins and diversification of this biodiversity remain elusive. Diversification may result from differences in clade age (longer time to diversify), net diversification rates (faster speciation rate) or carrying capacities (number of niches). The likelihood of these macroevolutionary scenarios was assessed for six clades of Apollo swallowtails ( Parnassius ) that diversified mainly in the Himalayan-Tibetan region. The analyses suggest that neither the clade age nor the speciation rate could explain the mountain butterfly diversification. Instead diversity-dependence models were strongly supported for each group. Models further estimated clades' carrying capacities, which approximate to the current number of species, indicating that diversity equilibrium has been reached (or close to being reached). The results suggest that diversification of mountain butterflies was controlled by ecological limits, which governed the number of niches, and provide macroevolutionary justification for regarding mountains as islands. © 2018 The Author(s).

Dissolved sulfides in the oxic water column of San Francisco Bay, California

USGS Publications Warehouse

Kuwabara, J.S.; Luther, G.W.

1993-01-01

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.

Simulating the reactions of CO2 in aqueous monoethanolamine solution by reaction ensemble Monte Carlo using the continuous fractional component method.

PubMed

Balaji, Sayee Prasaad; Gangarapu, Satesh; Ramdin, Mahinder; Torres-Knoop, Ariana; Zuilhof, Han; Goetheer, Earl L V; Dubbeldam, David; Vlugt, Thijs J H

2015-06-09

Molecular simulations were used to compute the equilibrium concentrations of the different species in CO2/monoethanolamine solutions for different CO2 loadings. Simulations were performed in the Reaction Ensemble using the continuous fractional component Monte Carlo method at temperatures of 293, 333, and 353 K. The resulting computed equilibrium concentrations are in excellent agreement with experimental data. The effect of different reaction pathways was investigated. For a complete understanding of the equilibrium speciation, it is essential to take all elementary reactions into account because considering only the overall reaction of CO2 with MEA is insufficient. The effects of electrostatics and intermolecular van der Waals interactions were also studied, clearly showing that solvation of reactants and products is essential for the reaction. The Reaction Ensemble Monte Carlo using the continuous fractional component method opens the possibility of investigating the effects of the solvent on CO2 chemisorption by eliminating the need to study different reaction pathways and concentrate only on the thermodynamics of the system.

Determining Equilibrium Position For Acoustical Levitation

NASA Technical Reports Server (NTRS)

Barmatz, M. B.; Aveni, G.; Putterman, S.; Rudnick, J.

1989-01-01

Equilibrium position and orientation of acoustically-levitated weightless object determined by calibration technique on Earth. From calibration data, possible to calculate equilibrium position and orientation in presence of Earth gravitation. Sample not levitated acoustically during calibration. Technique relies on Boltzmann-Ehrenfest adiabatic-invariance principle. One converts resonant-frequency-shift data into data on normalized acoustical potential energy. Minimum of energy occurs at equilibrium point. From gradients of acoustical potential energy, one calculates acoustical restoring force or torque on objects as function of deviation from equilibrium position or orientation.

NetpathXL - An Excel Interface to the Program NETPATH

USGS Publications Warehouse

Parkhurst, David L.; Charlton, Scott R.

2008-01-01

NetpathXL is a revised version of NETPATH that runs under Windows? operating systems. NETPATH is a computer program that uses inverse geochemical modeling techniques to calculate net geochemical reactions that can account for changes in water composition between initial and final evolutionary waters in hydrologic systems. The inverse models also can account for the isotopic composition of waters and can be used to estimate radiocarbon ages of dissolved carbon in ground water. NETPATH relies on an auxiliary, database program, DB, to enter the chemical analyses and to perform speciation calculations that define total concentrations of elements, charge balance, and redox state of aqueous solutions that are then used in inverse modeling. Instead of DB, NetpathXL relies on Microsoft Excel? to enter the chemical analyses. The speciation calculation formerly included in DB is implemented within the program NetpathXL. A program DBXL can be used to translate files from the old DB format (.lon files) to NetpathXL spreadsheets, or to create new NetpathXL spreadsheets. Once users have a NetpathXL spreadsheet with the proper format, new spreadsheets can be generated by copying or saving NetpathXL spreadsheets. In addition, DBXL can convert NetpathXL spreadsheets to PHREEQC input files. New capabilities in PHREEQC (version 2.15) allow solution compositions to be written to a .lon file, and inverse models developed in PHREEQC to be written as NetpathXL .pat and model files. NetpathXL can open NetpathXL spreadsheets, NETPATH-format path files (.pat files), and NetpathXL-format path files (.pat files). Once the speciation calculations have been performed on a spreadsheet file or a .pat file has been opened, the NetpathXL calculation engine is identical to the original NETPATH. Development of models and viewing results in NetpathXL rely on keyboard entry as in NETPATH.

Use of JANAF Tables in Equilibrium Calculations and Partition Function Calculations for an Undergraduate Physical Chemistry Course

ERIC Educational Resources Information Center

Cleary, David A.

2014-01-01

The usefulness of the JANAF tables is demonstrated with specific equilibrium calculations. An emphasis is placed on the nature of standard chemical potential calculations. Also, the use of the JANAF tables for calculating partition functions is examined. In the partition function calculations, the importance of the zero of energy is highlighted.

A synthesis of the theories and concepts of early human evolution.

PubMed

Maslin, Mark A; Shultz, Susanne; Trauth, Martin H

2015-03-05

Current evidence suggests that many of the major events in hominin evolution occurred in East Africa. Hence, over the past two decades, there has been intensive work undertaken to understand African palaeoclimate and tectonics in order to put together a coherent picture of how the environment of Africa has varied over the past 10 Myr. A new consensus is emerging that suggests the unusual geology and climate of East Africa created a complex, environmentally very variable setting. This new understanding of East African climate has led to the pulsed climate variability hypothesis that suggests the long-term drying trend in East Africa was punctuated by episodes of short alternating periods of extreme humidity and aridity which may have driven hominin speciation, encephalization and dispersals out of Africa. This hypothesis is unique as it provides a conceptual framework within which other evolutionary theories can be examined: first, at macro-scale comparing phylogenetic gradualism and punctuated equilibrium; second, at a more focused level of human evolution comparing allopatric speciation, aridity hypothesis, turnover pulse hypothesis, variability selection hypothesis, Red Queen hypothesis and sympatric speciation based on sexual selection. It is proposed that each one of these mechanisms may have been acting on hominins during these short periods of climate variability, which then produce a range of different traits that led to the emergence of new species. In the case of Homo erectus (sensu lato), it is not just brain size that changes but life history (shortened inter-birth intervals, delayed development), body size and dimorphism, shoulder morphology to allow thrown projectiles, adaptation to long-distance running, ecological flexibility and social behaviour. The future of evolutionary research should be to create evidence-based meta-narratives, which encompass multiple mechanisms that select for different traits leading ultimately to speciation.

A synthesis of the theories and concepts of early human evolution

PubMed Central

Maslin, Mark A.; Shultz, Susanne; Trauth, Martin H.

2015-01-01

Current evidence suggests that many of the major events in hominin evolution occurred in East Africa. Hence, over the past two decades, there has been intensive work undertaken to understand African palaeoclimate and tectonics in order to put together a coherent picture of how the environment of Africa has varied over the past 10 Myr. A new consensus is emerging that suggests the unusual geology and climate of East Africa created a complex, environmentally very variable setting. This new understanding of East African climate has led to the pulsed climate variability hypothesis that suggests the long-term drying trend in East Africa was punctuated by episodes of short alternating periods of extreme humidity and aridity which may have driven hominin speciation, encephalization and dispersals out of Africa. This hypothesis is unique as it provides a conceptual framework within which other evolutionary theories can be examined: first, at macro-scale comparing phylogenetic gradualism and punctuated equilibrium; second, at a more focused level of human evolution comparing allopatric speciation, aridity hypothesis, turnover pulse hypothesis, variability selection hypothesis, Red Queen hypothesis and sympatric speciation based on sexual selection. It is proposed that each one of these mechanisms may have been acting on hominins during these short periods of climate variability, which then produce a range of different traits that led to the emergence of new species. In the case of Homo erectus (sensu lato), it is not just brain size that changes but life history (shortened inter-birth intervals, delayed development), body size and dimorphism, shoulder morphology to allow thrown projectiles, adaptation to long-distance running, ecological flexibility and social behaviour. The future of evolutionary research should be to create evidence-based meta-narratives, which encompass multiple mechanisms that select for different traits leading ultimately to speciation. PMID:25602068

Prediction of the bioavailability of potentially toxic elements in freshwaters. Comparison between speciation models and passive samplers.

PubMed

Sierra, Jordi; Roig, Neus; Giménez Papiol, Gemma; Pérez-Gallego, Elena; Schuhmacher, Marta

2017-12-15

The aim of this work is to predict the bioavailability of the Potentially Toxic Elements (PTEs) Cd, Pb, Hg, Ni, Cu, Zn, As, Cr and Se in 6 sites within the Ebro River basin. In situ Diffusive gradient in thin-films (DGTs) and classical sampling have been used and compared. The potentially bioavailable fractions of each PTE was estimated by modelling their chemical speciation using three programs (WHAM 7.0, Visual MINTEQ 3.1 and Bio-met), following the suggestions published in recent European regulations. Results of the equilibrium-based models WHAM 7.0 and Visual MINTEQ 3.1 indicate that As, Cd, Ni, Se and Zn, predominate as free metals ions or forming inorganic soluble complexes. Copper, Pb and Hg bioavailability is conditioned by their affinity to dissolved humic substances. According to Visual MINTEQ 3.1, Cr is subjected to redox reactions, being Cr (VI) present (at low concentrations) in the studied rivers. According to Bio-met model, the bioavailability of Cu and Zn is highly influenced by soluble organic matter and water hardness, respectively. For most PTEs, the bioavailability estimated by deploying DGTs in river waters tends to be slightly lower than the estimation obtained with speciation models, since in real conditions more environmental factors take place comparing to the finite number of parameters considered in models. Copyright © 2017 Elsevier B.V. All rights reserved.

Reactive transport modeling of the enhancement of density-driven CO 2 convective mixing in carbonate aquifers and its potential implication on geological carbon sequestration

DOE PAGES

Islam, Akand; Sun, Alexander Y.; Yang, Changbing

2016-04-20

We study the convection and mixing of CO 2 in a brine aquifer, where the spread of dissolved CO 2 is enhanced because of geochemical reactions with the host formations (calcite and dolomite), in addition to the extensively studied, buoyancy-driven mixing. The nonlinear convection is investigated under the assumptions of instantaneous chemical equilibrium, and that the dissipation of carbonate rocks solely depends on flow and transport and chemical speciation depends only on the equilibrium thermodynamics of the chemical system. The extent of convection is quantified in term of the CO 2 saturation volume of the storage formation. Our results suggestmore » that the density increase of resident species causes significant enhancement in CO 2 dissolution, although no significant porosity and permeability alterations are observed. Furthermore, early saturation of the reservoir can have negative impact on CO 2 sequestration.« less

Reactive Transport Modeling of the Enhancement of Density-Driven CO2 Convective Mixing in Carbonate Aquifers and its Potential Implication on Geological Carbon Sequestration.

PubMed

Islam, Akand; Sun, Alexander Y; Yang, Changbing

2016-04-20

We study the convection and mixing of CO2 in a brine aquifer, where the spread of dissolved CO2 is enhanced because of geochemical reactions with the host formations (calcite and dolomite), in addition to the extensively studied, buoyancy-driven mixing. The nonlinear convection is investigated under the assumptions of instantaneous chemical equilibrium, and that the dissipation of carbonate rocks solely depends on flow and transport and chemical speciation depends only on the equilibrium thermodynamics of the chemical system. The extent of convection is quantified in term of the CO2 saturation volume of the storage formation. Our results suggest that the density increase of resident species causes significant enhancement in CO2 dissolution, although no significant porosity and permeability alterations are observed. Early saturation of the reservoir can have negative impact on CO2 sequestration.

Volcanic gas composition, metal dispersion and deposition during explosive volcanic eruptions on the Moon

NASA Astrophysics Data System (ADS)

Renggli, C. J.; King, P. L.; Henley, R. W.; Norman, M. D.

2017-06-01

The transport of metals in volcanic gases on the Moon differs greatly from their transport on the Earth because metal speciation depends largely on gas composition, temperature, pressure and oxidation state. We present a new thermochemical model for the major and trace element composition of lunar volcanic gas during pyroclastic eruptions of picritic magmas calculated at 200-1500 °C and over 10-9-103 bar. Using published volatile component concentrations in picritic lunar glasses, we have calculated the speciation of major elements (H, O, C, Cl, S and F) in the coexisting volcanic gas as the eruption proceeds. The most abundant gases are CO, H2, H2S, COS and S2, with a transition from predominantly triatomic gases to diatomic gases with increasing temperatures and decreasing pressures. Hydrogen occurs as H2, H2S, H2S2, HCl, and HF, with H2 making up 0.5-0.8 mol fractions of the total H. Water (H2O) concentrations are at trace levels, which implies that H-species other than H2O need to be considered in lunar melts and estimates of the bulk lunar composition. The Cl and S contents of the gas control metal chloride gas species, and sulfide gas and precipitated solid species. We calculate the speciation of trace metals (Zn, Ga, Cu, Pb, Ni, Fe) in the gas phase, and also the pressure and temperature conditions at which solids form from the gas. During initial stages of the eruption, elemental gases are the dominant metal species. As the gas loses heat, chloride and sulfide species become more abundant. Our chemical speciation model is applied to a lunar pyroclastic eruption model with isentropic gas decompression. The relative abundances of the deposited metal-bearing solids with distance from the vent are predicted for slow cooling rates (<5 °C/s). Close to a volcanic vent we predict native metals are deposited, whereas metal sulfides dominate with increasing distance from the vent. Finally, the lunar gas speciation model is compared with the speciation of a H2O-, CO2- and Cl-rich volcanic gas from Erta Ale volcano (Ethiopia) as an analogy for more oxidized planetary eruptions. In the terrestrial Cl-rich gas the metals are predominantly transported as chlorides, as opposed to metallic vapors and sulfides in the lunar gas. Due to the presence of Cl-species, metal transport is more efficient in the volcanic gas from Erta Ale compared to the Moon.

The non-equilibrium allele frequency spectrum in a Poisson random field framework.

PubMed

Kaj, Ingemar; Mugal, Carina F

2016-10-01

In population genetic studies, the allele frequency spectrum (AFS) efficiently summarizes genome-wide polymorphism data and shapes a variety of allele frequency-based summary statistics. While existing theory typically features equilibrium conditions, emerging methodology requires an analytical understanding of the build-up of the allele frequencies over time. In this work, we use the framework of Poisson random fields to derive new representations of the non-equilibrium AFS for the case of a Wright-Fisher population model with selection. In our approach, the AFS is a scaling-limit of the expectation of a Poisson stochastic integral and the representation of the non-equilibrium AFS arises in terms of a fixation time probability distribution. The known duality between the Wright-Fisher diffusion process and a birth and death process generalizing Kingman's coalescent yields an additional representation. The results carry over to the setting of a random sample drawn from the population and provide the non-equilibrium behavior of sample statistics. Our findings are consistent with and extend a previous approach where the non-equilibrium AFS solves a partial differential forward equation with a non-traditional boundary condition. Moreover, we provide a bridge to previous coalescent-based work, and hence tie several frameworks together. Since frequency-based summary statistics are widely used in population genetics, for example, to identify candidate loci of adaptive evolution, to infer the demographic history of a population, or to improve our understanding of the underlying mechanics of speciation events, the presented results are potentially useful for a broad range of topics. Copyright © 2016 Elsevier Inc. All rights reserved.

Cycling of mercury across the sediment-water interface in seepage lakes: Chapter 13, Advances in Chemistry

USGS Publications Warehouse

Hurley, James P.; Krabbenhoft, David P.; Babiarz, Christopher L.; Andren, Anders

1994-01-01

The magnitude and direction of Hg fluxes across the sediment—water interface were estimated by groundwater, dry bulk sediment, sediment pore water, sediment trap, and water-column analyses in two northern Wisconsin seepage lakes. Little Rock Lake (Treatment Basin) received no groundwater discharge during the study period (1988—1990), and Follette Lake received continuous groundwater discharge. In Little Rock Lake, settling of particulate matter accounted for the major Hg delivery mechanism to the sediment—water interface. Upward diffusion of Hg from sediment pore waters below 2—4-cm sediment depth was apparently a minor source during summer stratification. Time-series comparisons suggested that the observed buildup of Hg in the hypolimnion of Little Rock Lake was attributable to dissolution and diffusion of Hg from recently fallen particulate matter close to the sediment—water interface. Groundwater inflow represented an important source of new Hg, and groundwater outflow accounted for significant removal of Hg from Pallette Lake. Equilibrium speciation calculations revealed that association of Hg with organic matter may control solubility in well-oxygenated waters, whereas in anoxic environments sulfur (polysulfide and bisulfide) complexation governs dissolved total Hg levels.

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano.

PubMed

Floor, Geerke H; Iglesías, Mònica; Román-Ross, Gabriela; Corvini, Philippe F X; Lenz, Markus

2011-09-01

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH<4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L(-1) using (78)Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H(2)SO(4) and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments. Copyright © 2011 Elsevier Ltd. All rights reserved.

Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations.

PubMed

Yuhara, Daisuke; Brumby, Paul E; Wu, David T; Sum, Amadeu K; Yasuoka, Kenji

2018-05-14

To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Yuhara, Daisuke; Brumby, Paul E.; Wu, David T.; Sum, Amadeu K.; Yasuoka, Kenji

2018-05-01

To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

Classical calculation of the equilibrium constants for true bound dimers using complete potential energy surface.

PubMed

Buryak, Ilya; Vigasin, Andrey A

2015-12-21

The present paper aims at deriving classical expressions which permit calculation of the equilibrium constant for weakly interacting molecular pairs using a complete multidimensional potential energy surface. The latter is often available nowadays as a result of the more and more sophisticated and accurate ab initio calculations. The water dimer formation is considered as an example. It is shown that even in case of a rather strongly bound dimer the suggested expression permits obtaining quite reliable estimate for the equilibrium constant. The reliability of our obtained water dimer equilibrium constant is briefly discussed by comparison with the available data based on experimental observations, quantum calculations, and the use of RRHO approximation, provided the latter is restricted to formation of true bound states only.

Classical calculation of the equilibrium constants for true bound dimers using complete potential energy surface

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

Buryak, Ilya; Vigasin, Andrey A., E-mail: vigasin@ifaran.ru

The present paper aims at deriving classical expressions which permit calculation of the equilibrium constant for weakly interacting molecular pairs using a complete multidimensional potential energy surface. The latter is often available nowadays as a result of the more and more sophisticated and accurate ab initio calculations. The water dimer formation is considered as an example. It is shown that even in case of a rather strongly bound dimer the suggested expression permits obtaining quite reliable estimate for the equilibrium constant. The reliability of our obtained water dimer equilibrium constant is briefly discussed by comparison with the available data basedmore » on experimental observations, quantum calculations, and the use of RRHO approximation, provided the latter is restricted to formation of true bound states only.« less

Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

USGS Publications Warehouse

Deng, Y.; Nordstrom, D. Kirk; McCleskey, R. Blaine

2011-01-01

Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1–10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006–2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H+ and Al3+ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3–30% for more than 90% of samples at or above 10−6 molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F−, and major complexes (HF(aq)0">HF(aq)0, AlF2+, AlF2+">AlF2+and AlF30">AlF30) account for more than 95% of total fluoride. Occasionally, some complex species like AlF4-">AlF4-, FeF2+, FeF2+">FeF2+, MgF+ and BF2(OH)2-">BF2(OH)2- may comprise 1–10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.

[Primary speciation analysis of iron in edible flowers].

PubMed

Peng, Shan-shan; Huang, Guo-qing

2003-02-01

In this paper seven primary speciations of iron in three edible flowers, i.e. chrysanthemum, cottonrose hibiscus and honeysucker have been studied by atomic absorption spectrometry. Speciation parameters of iron such as extractive rate, residue rate, immerse-residue ratio in the samples were calculated. It was found that the first extractive rates of Fe were higher than the second ones in all three edible flowers, and the immerse-residue ratios of Fe were similar to the extractive rates. But the extraction of iron in all three edible flowers were no more than fifty percent. It is showed that the iron isn't easy to extract by water in the three edible flowers. The recovery was in the range of 96.5%-103.2% and RSD was in the range of 1.2%-3.1%. The results were satisfactory.

Metal Ion Speciation and Dissolved Organic Matter Composition in Soil Solutions

NASA Astrophysics Data System (ADS)

Benedetti, M. F.; Ren, Z. L.; Bravin, M.; Tella, M.; Dai, J.

2014-12-01

Knowledge of the speciation of heavy metals and the role of dissolved organic matter (DOM) in soil solution is a key to understand metal mobility and ecotoxicity. In this study, soil column-Donnan membrane technique (SC-DMT) was used to measure metal speciation of Cd, Cu, Ni, Pb, and Zn in eighteen soil solutions, covering a wide range of metal sources and concentrations. DOM composition in these soil solutions was also determined. Our results show that in soil solution Pb and Cu are dominant in complex form, whereas Cd, Ni and Zn mainly exist as free ions; for the whole range of soil solutions, only 26.2% of DOM is reactive and consists mainly of fulvic acid (FA). The metal speciation measured by SC-DMT was compared to the predicted ones obtained via the NICA-Donnan model using the measured FA concentrations. The free ion concentrations predicted by speciation modelling were in good agreement with the measurements. Diffusive gradients in thin-films gels (DGT) were also performed to quantify the labile metal species in the fluxes from solid phase to solution in fourteen soils. The concentrations of metal species detected by DGT were compared with the free ion concentrations measured by DMT and the maximum concentrations calculated based on the predicted metal speciation in SC-DMT soil solutions. It is concluded that both inorganic species and a fraction of FA bound species account for the amount of labile metals measured by DGT, consistent with the dynamic features of this technique. The comparisons between measurements using analytical techniques and mechanistic model predictions provided mutual validation in their performance. Moreover, we show that to make accurate modelling of metal speciation in soil solutions, the knowledge of DOM composition is the crucial information, especially for Cu; like in previous studies the modelling of Pb speciation is not optimal and an updated of Pb generic binding parameters is required to reduce model prediction uncertainties.

Teaching the Concept of Gibbs Energy Minimization through Its Application to Phase-Equilibrium Calculation

ERIC Educational Resources Information Center

Privat, Romain; Jaubert, Jean-Noe¨l; Berger, Etienne; Coniglio, Lucie; Lemaitre, Ce´cile; Meimaroglou, Dimitrios; Warth, Vale´rie

2016-01-01

Robust and fast methods for chemical or multiphase equilibrium calculation are routinely needed by chemical-process engineers working on sizing or simulation aspects. Yet, while industrial applications essentially require calculation tools capable of discriminating between stable and nonstable states and converging to nontrivial solutions,…

Thermodynamic equilibrium calculations of dimethyl ether steam reforming and dimethyl ether hydrolysis

NASA Astrophysics Data System (ADS)

Semelsberger, Troy A.; Borup, Rodney L.

The production of a hydrogen-rich fuel-cell feed by dimethyl ether (DME) steam reforming was investigated using calculations of thermodynamic equilibrium as a function of steam-to-carbon ratio (0.00-4.00), temperature (100-600 °C), pressure (1-5 atm), and product species. Species considered were acetone, acetylene, carbon dioxide, carbon monoxide, dimethyl ether, ethane, ethanol, ethylene, formaldehyde, formic acid, hydrogen, isopropanol, methane, methanol, methyl-ethyl ether, n-propanol and water. Thermodynamic equilibrium calculations of DME steam reforming indicate complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide at temperatures greater than 200 °C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure ( P = 1 atm). Increasing the operating pressure shifts the equilibrium toward the reactants; increasing the pressure from 1 to 5 atm decreases the conversion of dimethyl ether from 99.5 to 76.2%. The trend of thermodynamically stable products in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol-formaldehyde, formic acid, and acetylene were not observed. Based on the equilibrium calculations, the optimal processing conditions for dimethyl ether steam reforming occur at a steam-to-carbon ratio of 1.50, a pressure of 1 atm, and a temperature of 200 °C. These thermodynamic equilibrium calculations show dimethyl ether processed with steam will produce hydrogen-rich fuel-cell feeds—with hydrogen concentrations exceeding 70%. The conversion of dimethyl ether via hydrolysis (considering methanol as the only product) is limited by thermodynamic equilibrium. Equilibrium conversion increases with temperature and steam-to-carbon ratio. A maximum dimethyl ether conversion of 62% is achieved at a steam-to-carbon ratio of 5.00 and a processing temperature of 600 °C.

Evolutionary dynamics of ecological niche in three Rhinogobio fishes from the upper Yangtze River inferred from morphological traits

PubMed Central

Wang, Meirong; Liu, Fei; Lin, Pengcheng; Yang, Shaorong; Liu, Huanzhang

2015-01-01

In the past decades, it has been debated whether ecological niche should be conserved among closely related species (phylogenetic niche conservatism, PNC) or largely divergent (traditional ecological niche theory and ecological speciation) and whether niche specialist and generalist might remain in equilibrium or niche generalist could not appear. In this study, we employed morphological traits to describe ecological niche and test whether different niche dimensions exhibit disparate evolutionary patterns. We conducted our analysis on three Rhinogobio fish species (R. typus,R. cylindricus, and R. ventralis) from the upper Yangtze River, China. Among the 32 measured morphological traits except body length, PCA extracted the first four principal components with their loading scores >1.000. To find the PNC among species, Mantel tests were conducted with the Euclidean distances calculated from the four principal components (representing different niche dimensions) against the pairwise distances calculated from mitochondrial cytochrome b sequence variations. The results showed that the second and the third niche dimension, both related to swimming ability and behavior, exhibited phylogenetic conservatism. Further comparison on niche breadth among these three species revealed that the fourth dimension of R. typus showed the greatest width, indicating that this dimension exhibited niche generalism. In conclusion, our results suggested that different niche dimensions could show different evolutionary dynamic patterns: they may exhibit PNC or not, and some dimensions may evolve generalism. PMID:25691981

Geochemistry of some rare earth elements in groundwater, Vierlingsbeek, The Netherlands.

PubMed

Janssen, René P T; Verweij, Wilko

2003-03-01

Groundwater samples were taken from seven bore holes at depths ranging from 2 to 41m nearby drinking water pumping station Vierlingsbeek, The Netherlands and analysed for Y, La, Ce, Pr, Nd, Sm and Eu. Shale-normalized patterns were generally flat and showed that the observed rare earth elements (REE) were probably of natural origin. In the shallow groundwaters the REEs were light REE (LREE) enriched, probably caused by binding of LREEs to colloids. To improve understanding of the behaviour of the REE, two approaches were used: calculations of the speciation and a statistical approach. For the speciation calculations, complexation and precipitation reactions including inorganic and dissolved organic carbon (DOC) compounds, were taken into account. The REE speciation showed REE(3+), REE(SO(4))(+), REE(CO(3))(+) and REE(DOC) being the major species. Dissolution of pure REE precipitates and REE-enriched solid phases did not account for the observed REEs in groundwater. Regulation of REE concentrations by adsorption-desorption processes to Fe(III)(OH)(3) and Al(OH)(3) minerals, which were calculated to be present in nearly all groundwaters, is a probable explanation. The statistical approach (multiple linear regression) showed that pH is by far the most significant groundwater characteristic which contributes to the variation in REE concentrations. Also DOC, SO(4), Fe and Al contributed significantly, although to a much lesser extent, to the variation in REE concentrations. This is in line with the calculated REE-species in solution and REE-adsorption to iron and aluminium (hydr)oxides. Regression equations including only pH, were derived to predict REE concentrations in groundwater. External validation showed that these regression equations were reasonably successful to predict REE concentrations of groundwater of another drinking water pumping station in quite different region of The Netherlands.

An experimental study of the solubility and speciation of tantalum in fluoride-bearing aqueous solutions at elevated temperature

DOE PAGES

Timofeev, Alexander; Migdisov, Art. A.; Williams-Jones, A. E.

2016-10-27

Here, the solubility of Ta 2O 5 (solid) and the speciation of tantalum in HF-bearing aqueous solutions have been determined at temperatures of 100-250 °C and vapour-saturated water pressure. Tantalum is transported as the species Ta(OH) 5 0 at low HF concentration and pH ~1-3. At higher HF concentration, tantalum mobility is controlled by the species TaF 3(OH) 3- and TaF 5; the presence of TaF 5 0 is only evident at ≤150 °C. Equilibrium constants range from -17.4 ± 0.45 to -16.4 ± 0.12 for the formation of Ta(OH) 5 from crystalline Ta 2O 5 and from -8.24 ±more » 0.64 to -8.55 ± 0.68 for the formation of TaF 3(OH) 3- at 100 and 250 °C, respectively. For TaF 5 0, they were determined to be 0.13 at 100 °C and -0.35 at 150 °C.« less

Non-Equilibrium Properties from Equilibrium Free Energy Calculations

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Wilson, Michael A.

2012-01-01

Calculating free energy in computer simulations is of central importance in statistical mechanics of condensed media and its applications to chemistry and biology not only because it is the most comprehensive and informative quantity that characterizes the eqUilibrium state, but also because it often provides an efficient route to access dynamic and kinetic properties of a system. Most of applications of equilibrium free energy calculations to non-equilibrium processes rely on a description in which a molecule or an ion diffuses in the potential of mean force. In general case this description is a simplification, but it might be satisfactorily accurate in many instances of practical interest. This hypothesis has been tested in the example of the electrodiffusion equation . Conductance of model ion channels has been calculated directly through counting the number of ion crossing events observed during long molecular dynamics simulations and has been compared with the conductance obtained from solving the generalized Nernst-Plank equation. It has been shown that under relatively modest conditions the agreement between these two approaches is excellent, thus demonstrating the assumptions underlying the diffusion equation are fulfilled. Under these conditions the electrodiffusion equation provides an efficient approach to calculating the full voltage-current dependence routinely measured in electrophysiological experiments.

A method of solid-solid phase equilibrium calculation by molecular dynamics

NASA Astrophysics Data System (ADS)

Karavaev, A. V.; Dremov, V. V.

2016-12-01

A method for evaluation of solid-solid phase equilibrium curves in molecular dynamics simulation for a given model of interatomic interaction is proposed. The method allows to calculate entropies of crystal phases and provides an accuracy comparable with that of the thermodynamic integration method by Frenkel and Ladd while it is much simpler in realization and less intense computationally. The accuracy of the proposed method was demonstrated in MD calculations of entropies for EAM potential for iron and for MEAM potential for beryllium. The bcc-hcp equilibrium curves for iron calculated for the EAM potential by the thermodynamic integration method and by the proposed one agree quite well.

The effects of intraspecific competition and stabilizing selection on a polygenic trait.

PubMed Central

Bürger, Reinhard; Gimelfarb, Alexander

2004-01-01

The equilibrium properties of an additive multilocus model of a quantitative trait under frequency- and density-dependent selection are investigated. Two opposing evolutionary forces are assumed to act: (i) stabilizing selection on the trait, which favors genotypes with an intermediate phenotype, and (ii) intraspecific competition mediated by that trait, which favors genotypes whose effect on the trait deviates most from that of the prevailing genotypes. Accordingly, fitnesses of genotypes have a frequency-independent component describing stabilizing selection and a frequency- and density-dependent component modeling competition. We study how the equilibrium structure, in particular, number, degree of polymorphism, and genetic variance of stable equilibria, is affected by the strength of frequency dependence, and what role the number of loci, the amount of recombination, and the demographic parameters play. To this end, we employ a statistical and numerical approach, complemented by analytical results, and explore how the equilibrium properties averaged over a large number of genetic systems with a given number of loci and average amount of recombination depend on the ecological and demographic parameters. We identify two parameter regions with a transitory region in between, in which the equilibrium properties of genetic systems are distinctively different. These regions depend on the strength of frequency dependence relative to pure stabilizing selection and on the demographic parameters, but not on the number of loci or the amount of recombination. We further study the shape of the fitness function observed at equilibrium and the extent to which the dynamics in this model are adaptive, and we present examples of equilibrium distributions of genotypic values under strong frequency dependence. Consequences for the maintenance of genetic variation, the detection of disruptive selection, and models of sympatric speciation are discussed. PMID:15280253

One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Mccollom, Tom; Schrenk, Matt; Cardace, Dawn

2011-01-01

Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

BIOCHEM-ORCHESTRA: a tool for evaluating chemical speciation and ecotoxicological impacts of heavy metals on river flood plain systems.

PubMed

Vink, J P M; Meeussen, J C L

2007-08-01

The chemical speciation model BIOCHEM was extended with ecotoxicological transfer functions for uptake of metals (As, Cd, Cu, Ni, Pb, and Zn) by plants and soil invertebrates. It was coupled to the object-oriented framework ORCHESTRA to achieve a flexible and dynamic decision support system (DSS) to analyse natural or anthropogenic changes that occur in river systems. The DSS uses the chemical characteristics of soils and sediments as input, and calculates speciation and subsequent uptake by biota at various scenarios. Biotic transfer functions were field-validated, and actual hydrological conditions were derived from long-term monitoring data. The DSS was tested for several scenarios that occur in the Meuse catchment areas, such as flooding and sedimentation of riverine sediments on flood plains. Risks are expressed in terms of changes in chemical mobility, and uptake by flood plain key species (flora and fauna).

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Technical Reports Server (NTRS)

Glass, Christopher E.

1990-01-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Astrophysics Data System (ADS)

Glass, Christopher E.

1990-08-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Deposition and reentrainment of Brownian particles in porous media under unfavorable chemical conditions: some concepts and applications.

PubMed

Hahn, Melinda W; O'Meliae, Charles R

2004-01-01

The deposition and reentrainment of particles in porous media have been examined theoretically and experimentally. A Brownian Dynamics/Monte Carlo (MC/BD) model has been developed that simulates the movement of Brownian particles near a collector under "unfavorable" chemical conditions and allows deposition in primary and secondary minima. A simple Maxwell approach has been used to estimate particle attachment efficiency by assuming deposition in the secondary minimum and calculating the probability of reentrainment. The MC/BD simulations and the Maxwell calculations support an alternative view of the deposition and reentrainment of Brownian particles under unfavorable chemical conditions. These calculations indicate that deposition into and subsequent release from secondary minima can explain reported discrepancies between classic model predictions that assume irreversible deposition in a primary well and experimentally determined deposition efficiencies that are orders of magnitude larger than Interaction Force Boundary Layer (IFBL) predictions. The commonly used IFBL model, for example, is based on the notion of transport over an energy barrier into the primary well and does not address contributions of secondary minimum deposition. A simple Maxwell model based on deposition into and reentrainment from secondary minima is much more accurate in predicting deposition rates for column experiments at low ionic strengths. It also greatly reduces the substantial particle size effects inherent in IFBL models, wherein particle attachment rates are predicted to decrease significantly with increasing particle size. This view is consistent with recent work by others addressing the composition and structure of the first few nanometers at solid-water interfaces including research on modeling water at solid-liquid interfaces, surface speciation, interfacial force measurements, and the rheological properties of concentrated suspensions. It follows that deposition under these conditions will depend on the depth of the secondary minimum and that some transition between secondary and primary depositions should occur when the height of the energy barrier is on the order of several kT. When deposition in secondary minima predominates, observed deposition should increase with increasing ionic strength, particle size, and Hamaker constant. Since an equilibrium can develop between bound and bulk particles, the collision efficiency [alpha] can no longer be considered a constant for a given physical and chemical system. Rather, in many cases it can decrease over time until it eventually reaches zero as equilibrium is established.

Computational methods for reactive transport modeling: A Gibbs energy minimization approach for multiphase equilibrium calculations

NASA Astrophysics Data System (ADS)

Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg

2016-02-01

We present a numerical method for multiphase chemical equilibrium calculations based on a Gibbs energy minimization approach. The method can accurately and efficiently determine the stable phase assemblage at equilibrium independently of the type of phases and species that constitute the chemical system. We have successfully applied our chemical equilibrium algorithm in reactive transport simulations to demonstrate its effective use in computationally intensive applications. We used FEniCS to solve the governing partial differential equations of mass transport in porous media using finite element methods in unstructured meshes. Our equilibrium calculations were benchmarked with GEMS3K, the numerical kernel of the geochemical package GEMS. This allowed us to compare our results with a well-established Gibbs energy minimization algorithm, as well as their performance on every mesh node, at every time step of the transport simulation. The benchmark shows that our novel chemical equilibrium algorithm is accurate, robust, and efficient for reactive transport applications, and it is an improvement over the Gibbs energy minimization algorithm used in GEMS3K. The proposed chemical equilibrium method has been implemented in Reaktoro, a unified framework for modeling chemically reactive systems, which is now used as an alternative numerical kernel of GEMS.

Formation of nitric acid hydrates - A chemical equilibrium approach

NASA Technical Reports Server (NTRS)

Smith, Roland H.

1990-01-01

Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

The stability of amino acids at submarine hydrothermal vent temperatures

NASA Technical Reports Server (NTRS)

Bada, Jeffrey L.; Miller, Stanley L.; Zhao, Meixun

1995-01-01

It has been postulated that amino acid stability at hydrothermal vent temperatures is controlled by a metastable thermodynamic equilibrium rather than by kinetics. Experiments reported here demonstrate that the amino acids are irreversibly destroyed by heating at 240 C and that quasi-equilibrium calculations give misleading descriptions of the experimental observations. Equilibrium thermodynamic calculations are not applicable to organic compounds under high-temperature submarine vent conditions.

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

NASA Technical Reports Server (NTRS)

Stern, Jennifer C.; Foustoukos, Dionysis I.; Sonke, Jeroen E.; Salters, Vincent J. M.

2014-01-01

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

Molten silicate mantle during a giant impact. Speciation from vapor to supercritical state

NASA Astrophysics Data System (ADS)

Caracas, R.; Stewart, S. T.

2017-12-01

We employ large-scale first-principles molecular dynamics simulations to understand the physical and chemical behavior of the molten protolunar disk, at the atomic level. We consider the average composition of the Earth's mantle as proposed by Sun and McDonough (1995). We cover the 0.75 - 7.5 g/cm3 density range and 2000 - 10000 K temperature range. This allows us to investigate the entire disk, from the interior of the molten core to the outer regions of the vaporized disk. At high density, the liquid is highly polymerized and viscous, consistent with previous studies. At low density and low temperatures, in the 2000 to 4000 K range, we capture the nucleation of bubbles. The bubbles contain a low-density gas phase rich in individual alkaline and calc-alkaline cations and SiOx groups. When volatiles are present in the system, such molecular species are the first ones to evaporate and be present in these bubbles. We propose numerical tools to detect the liquid-vapor equilibrium. The critical curves are reached consistently regardless of the thermodynamic path we chose to obtain the low densities. We analyze the equilibrium between the gas of the bubbles and the liquid. At high temperature, we identify the supercritical region characterized by one homogeneous fluid, rich in ionic species. We show that the chemical speciation is very different from the one obtained at ambient pressure conditions. Critical curves are necessary to understand the separation and degassing of volatiles during the recovery from a giant impact. Acknowledgements: This research was supported by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement n°681818 - IMPACT). The ab initio simulations were performed on the GENCI supercomputers, under eDARI/CINES grants x106368.

Computer program for calculation of complex chemical equilibrium compositions and applications. Part 1: Analysis

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Mcbride, Bonnie J.

1994-01-01

This report presents the latest in a number of versions of chemical equilibrium and applications programs developed at the NASA Lewis Research Center over more than 40 years. These programs have changed over the years to include additional features and improved calculation techniques and to take advantage of constantly improving computer capabilities. The minimization-of-free-energy approach to chemical equilibrium calculations has been used in all versions of the program since 1967. The two principal purposes of this report are presented in two parts. The first purpose, which is accomplished here in part 1, is to present in detail a number of topics of general interest in complex equilibrium calculations. These topics include mathematical analyses and techniques for obtaining chemical equilibrium; formulas for obtaining thermodynamic and transport mixture properties and thermodynamic derivatives; criteria for inclusion of condensed phases; calculations at a triple point; inclusion of ionized species; and various applications, such as constant-pressure or constant-volume combustion, rocket performance based on either a finite- or infinite-chamber-area model, shock wave calculations, and Chapman-Jouguet detonations. The second purpose of this report, to facilitate the use of the computer code, is accomplished in part 2, entitled 'Users Manual and Program Description'. Various aspects of the computer code are discussed, and a number of examples are given to illustrate its versatility.

Testing the Underlying Chemical Principles of the Biotic Ligand Model (BLM) to Marine Copper Systems: Measuring Copper Speciation Using Fluorescence Quenching.

PubMed

Tait, Tara N; McGeer, James C; Smith, D Scott

2018-01-01

Speciation of copper in marine systems strongly influences the ability of copper to cause toxicity. Natural organic matter (NOM) contains many binding sites which provides a protective effect on copper toxicity. The purpose of this study was to characterize copper binding with NOM using fluorescence quenching techniques. Fluorescence quenching of NOM with copper was performed on nine sea water samples. The resulting stability constants and binding capacities were consistent with literature values of marine NOM, showing strong binding with [Formula: see text] values from 7.64 to 10.2 and binding capacities ranging from 15 to 3110 nmol mg [Formula: see text] Free copper concentrations estimated at total dissolved copper concentrations corresponding to previously published rotifer effect concentrations, in the same nine samples, were statistically the same as the range of free copper calculated for the effect concentration in NOM-free artificial seawater. These data confirms the applicability of fluorescence spectroscopy techniques for NOM and copper speciation characterization in sea water and demonstrates that such measured speciation is consistent with the chemical principles underlying the biotic ligand model approach for bioavailability-based metals risk assessment.

Teaching an Old Dog an Old Trick: FREE-FIX and Free-Boundary Axisymmetric MHD Equilibrium

NASA Astrophysics Data System (ADS)

Guazzotto, Luca

2015-11-01

A common task in plasma physics research is the calculation of an axisymmetric equilibrium for tokamak modeling. The main unknown of the problem is the magnetic poloidal flux ψ. The easiest approach is to assign the shape of the plasma and only solve the equilibrium problem in the plasma / closed-field-lines region (the ``fixed-boundary approach''). Often, one may also need the vacuum fields, i.e. the equilibrium in the open-field-lines region, requiring either coil currents or ψ on some closed curve outside the plasma to be assigned (the ``free-boundary approach''). Going from one approach to the other is a textbook problem, involving the calculation of Green's functions and surface integrals in the plasma. However, no tools are readily available to perform this task. Here we present a code (FREE-FIX) to compute a boundary condition for a free-boundary equilibrium given only the corresponding fixed-boundary equilibrium. An improvement to the standard solution method, allowing for much faster calculations, is presented. Applications are discussed. PPPL fund 245139 and DOE grant G00009102.

FastChem: An ultra-fast equilibrium chemistry

NASA Astrophysics Data System (ADS)

Kitzmann, Daniel; Stock, Joachim

2018-04-01

FastChem is an equilibrium chemistry code that calculates the chemical composition of the gas phase for given temperatures and pressures. Written in C++, it is based on a semi-analytic approach, and is optimized for extremely fast and accurate calculations.

Approach of the Molten Salt Chemistry for Aluminium Production: High Temperature NMR Measurements, Molecular Dynamics and DFT Calculations

NASA Astrophysics Data System (ADS)

Machado, Kelly; Zanghi, Didier; Sarou-Kanian, Vincent; Cadars, Sylvian; Burbano, Mario; Salanne, Mathieu; Bessada, Catherine

In aluminum production, the electrolyte is a molten fluorides mixture typically around 1000°C. In order to have a better understanding of the industrial process, it is necessary to have a model which will describe the molten salts on a wide range of compositions and temperatures, to accurately cover all the combinations that may be encountered in an operating electrolysis vessel. The aim of this study is to describe the speciation in the electrolyte in terms of anionic species in the bulk materials far from electrodes. To determine the speciation in situ at high temperature in the absence of an electrical field, we develop an original approach combining experimental methods such as Nuclear Magnetic Resonance spectroscopy (NMR) at high temperature with Molecular Dynamics (MD) simulation coupled with first principle calculations based on Density Functional Theory (DFT). This approach allows the calculation of NMR parameters and the comparison with the experimental ones. It will be provide an additional validation and constraint of the model used for MD. We test this approach on the model NaF-AlF3 system.

Vapor-liquid equilibrium thermodynamics of N2 + CH4 - Model and Titan applications

NASA Technical Reports Server (NTRS)

Thompson, W. R.; Zollweg, John A.; Gabis, David H.

1992-01-01

A thermodynamic model is presented for vapor-liquid equilibrium in the N2 + CH4 system, which is implicated in calculations of the Titan tropospheric clouds' vapor-liquid equilibrium thermodynamics. This model imposes constraints on the consistency of experimental equilibrium data, and embodies temperature effects by encompassing enthalpy data; it readily calculates the saturation criteria, condensate composition, and latent heat for a given pressure-temperature profile of the Titan atmosphere. The N2 content of condensate is about half of that computed from Raoult's law, and about 30 percent greater than that computed from Henry's law.

Tokamak plasma high field side response to an n = 3 magnetic perturbation: a comparison of 3D equilibrium solutions from seven different codes

NASA Astrophysics Data System (ADS)

Reiman, A.; Ferraro, N. M.; Turnbull, A.; Park, J. K.; Cerfon, A.; Evans, T. E.; Lanctot, M. J.; Lazarus, E. A.; Liu, Y.; McFadden, G.; Monticello, D.; Suzuki, Y.

2015-06-01

In comparing equilibrium solutions for a DIII-D shot that is amenable to analysis by both stellarator and tokamak three-dimensional (3D) equilibrium codes, a significant disagreement has been seen between solutions of the VMEC stellarator equilibrium code and solutions of tokamak perturbative 3D equilibrium codes. The source of that disagreement has been investigated, and that investigation has led to new insights into the domain of validity of the different equilibrium calculations, and to a finding that the manner in which localized screening currents at low order rational surfaces are handled can affect global properties of the equilibrium solution. The perturbative treatment has been found to break down at surprisingly small perturbation amplitudes due to overlap of the calculated perturbed flux surfaces, and that treatment is not valid in the pedestal region of the DIII-D shot studied. The perturbative treatment is valid, however, further into the interior of the plasma, and flux surface overlap does not account for the disagreement investigated here. Calculated equilibrium solutions for simple model cases and comparison of the 3D equilibrium solutions with those of other codes indicate that the disagreement arises from a difference in handling of localized currents at low order rational surfaces, with such currents being absent in VMEC and present in the perturbative codes. The significant differences in the global equilibrium solutions associated with the presence or absence of very localized screening currents at rational surfaces suggests that it may be possible to extract information about localized currents from appropriate measurements of global equilibrium plasma properties. That would require improved diagnostic capability on the high field side of the tokamak plasma, a region difficult to access with diagnostics.

Minimizing the Free Energy: A Computer Method for Teaching Chemical Equilibrium Concepts.

ERIC Educational Resources Information Center

Heald, Emerson F.

1978-01-01

Presents a computer method for teaching chemical equilibrium concepts using material balance conditions and the minimization of the free energy. Method for the calculation of chemical equilibrium, the computer program used to solve equilibrium problems and applications of the method are also included. (HM)

Complications in Determining Oxygen Fugacities From Olivine-Melt Equilibrium Illustrated by the Pu'u'O'o Lavas, Hawaii

NASA Astrophysics Data System (ADS)

McCann, V. E.; Barton, M.; Thornber, C. R.

2005-12-01

We have shown previously that oxygen fugacities calculated from olivine-melt equilibrium using rim compositions agree well with those calculated from analyzed Fe3+/σFe for MORB and for Icelandic OIB (MORB - average ΔFMQ -0.72 versus -0.70, Iceland average ΔFMQ -0.49 versus -0.58). The agreement between oxygen fugacities calculated from Ol-melt equilibrium and those calculated from analyzed Fe3+/σFe is excellent for individual samples of MORB from the FAMOUS region and Blanco Trough ( difference in calculated ΔFMQ < 0.30). Published analyses of Fe3+/σFe yield oxygen fugacilties of ΔFMQ= -0.72±0.43 for lavas from Kilauea and Mauna Loa, and ΔFMQ=0.91±0.72 for Loihi, very close to those for MORB. Oxygen fugacities determined using carefully selected Ol-melt analyses (ΔFMQ= -0.43±0.32) are in reasonable agreement with those determined from Fe3+/σFe for Kilauea and Mauna Loa, and agreement between fO2 calculated from Ol-melt equilibrium (ΔFMQ= -0.26) and that calculated from Fe3+/σFe (ΔFMQ= -0.64) is excellent for one sample from Kilauea. However, olivine-melt pairs from some samples, including those from the Pu'u'O'o lavas, yield anomalously high or low estimates of fO2 (average ΔFMQ =-0.6907, range -4.07 to +0.34). We suggest that these anomalous values reflect the complex history of olivines in these lavas, in particular the effects of magma mixing. Some olivines in the Pu'u'O'o lavas clearly have rims that are anomalously rich in Fa, whereas others have rims that are anomalously rich in Fo and do not appear to have equilibrium compositions. Given the dependence of olivine composition on melt Fe3+/σFe, there is no simple method to determine the equilibrium composition of olivine for a particular melt. However, detailed zoning profiles and analyses of microphenocrysts allow probable equilibrium compositions to be identified. We suggest that the average fO2 of Hawaiian lavas lies close to (ΔFMQ= -1) based on published results using spinel-melt equilibrium and Fe-Ni exchange between olivine and sulfide liquid. Olivine-glass inclusion data for Koolau samples also suggest (ΔFMQ= ~-1).

TEA: A Code Calculating Thermochemical Equilibrium Abundances

NASA Astrophysics Data System (ADS)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver

2016-07-01

We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. We tested the code against the method of Burrows & Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows & Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but with higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.

TEA: A CODE CALCULATING THERMOCHEMICAL EQUILIBRIUM ABUNDANCES

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

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver, E-mail: jasmina@physics.ucf.edu

2016-07-01

We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature–pressure pairs. We tested the code against the method of Burrows and Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows and Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but withmore » higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.« less

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

Ivanov, A. A., E-mail: aai@a5.kiam.ru; Martynov, A. A., E-mail: martynov@a5.kiam.ru; Medvedev, S. Yu., E-mail: medvedev@a5.kiam.ru

In the MHD tokamak plasma theory, the plasma pressure is usually assumed to be isotropic. However, plasma heating by neutral beam injection and RF heating can lead to a strong anisotropy of plasma parameters and rotation of the plasma. The development of MHD equilibrium theory taking into account the plasma inertia and anisotropic pressure began a long time ago, but until now it has not been consistently applied in computational codes for engineering calculations of the plasma equilibrium and evolution in tokamak. This paper contains a detailed derivation of the axisymmetric plasma equilibrium equation in the most general form (withmore » arbitrary rotation and anisotropic pressure) and description of the specialized version of the SPIDER code. The original method of calculation of the equilibrium with an anisotropic pressure and a prescribed rotational transform profile is proposed. Examples of calculations and discussion of the results are also presented.« less

Modelling of chemical degradation of blended cement-based materials by leaching cycles with Callovo-Oxfordian porewater

NASA Astrophysics Data System (ADS)

Olmeda, Javier; Henocq, Pierre; Giffaut, Eric; Grivé, Mireia

2017-06-01

The present work describes a thermodynamic model based on pore water replacement cycles to simulate the chemical evolution of blended cement (BFS + FA) by interaction with external Callovo-Oxfordian (COx) pore water. In the framework of the radioactive waste management, the characterization of the radionuclide behaviour (solubility/speciation, adsorption) in cementitious materials needs to be done for several chemical degradation states (I to IV). In particular, in the context of the deep geological radioactive waste disposal project (Cigéo), cement-based materials will be chemically evolved with time in contact with the host-rock (COx formation). The objective of this study is to provide an equilibrium solution composition for each degradation state for a CEM-V cement-based material to support the adsorption and diffusion experiments reproducing any state of degradation. Calculations have been performed at 25 °C using the geochemical code PhreeqC and an up-to-date thermodynamic database (ThermoChimie v.9.0.b) coupled to SIT approach for ionic strength correction. The model replicates experimental data with accuracy. The approach followed in this study eases the analysis of the chemical evolution in both aqueous and solid phase to obtain a fast assessment of the geochemical effects associated to an external water intrusion of variable composition on concrete structures.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

PubMed

Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

2016-08-16

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

A quantitative speciation model for the adsorption of organic pollutants on activated carbon.

PubMed

Grivé, M; García, D; Domènech, C; Richard, L; Rojo, I; Martínez, X; Rovira, M

2013-01-01

Granular activated carbon (GAC) is commonly used as adsorbent in water treatment plants given its high capacity for retaining organic pollutants in aqueous phase. The current knowledge on GAC behaviour is essentially empirical, and no quantitative description of the chemical relationships between GAC surface groups and pollutants has been proposed. In this paper, we describe a quantitative model for the adsorption of atrazine onto GAC surface. The model is based on results of potentiometric titrations and three types of adsorption experiments which have been carried out in order to determine the nature and distribution of the functional groups on the GAC surface, and evaluate the adsorption characteristics of GAC towards atrazine. Potentiometric titrations have indicated the existence of at least two different families of chemical groups on the GAC surface, including phenolic- and benzoic-type surface groups. Adsorption experiments with atrazine have been satisfactorily modelled with the geochemical code PhreeqC, assuming that atrazine is sorbed onto the GAC surface in equilibrium (log Ks = 5.1 ± 0.5). Independent thermodynamic calculations suggest a possible adsorption of atrazine on a benzoic derivative. The present work opens a new approach for improving the adsorption capabilities of GAC towards organic pollutants by modifying its chemical properties.

Charging Properties of Cassiterite (alpha-SnO2) surfaces in NaCl and RbCl Ionic Media.

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite (alpha-SnO2) surfaces at 10-50 degrees C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 degrees C, respectively. This is contrary to the situation on the isostructural alpha-TiO2 (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb+ is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH(-0.40)) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with increasing negative surface charge, and at pH 10, roughly 40% of the terminal sites are predicted to form cation complexes, whereas anion complexation is minor throughout the studied pH range.« less

Charging properties of cassiterite (alfa-SnO2) surfaces

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, L.

The acid-base properties of cassiterite (alfa-SnO2) surfaces at 10 50 C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH-range 4.0 to 4.5 at all conditions and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical Molecular Dynamics (MD) simulations, was analyzed in detail and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural alfa-TiO2 (rutile), apparently due to the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, while adsorbed rubidium ions form comparable amounts of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on surface charge density (pH), while the distribution of adsorbed Rb+ is almost independent of pH. A Surface Complexation Model (SCM) capable of accurately describing both the measured surface charge and the MD predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH-0.40) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH-range (2.7 10), illustrating the ability of positively and negatively charged surface groups to coexist. Complexation of the medium cations increases significantly with increasing negative surface charge and at pH 10 roughly 40 percent of the terminal sites are predicted to form cation complexes, while anion complexation is minor throughout the studied pH-range.« less

Rheological Predictions of Network Systems Swollen with Entangled Solvent

DTIC Science & Technology

2014-04-01

represent binary entanglements and the crosses represent cross-links. Both of which are fixed in space for Green– Kubo calculations or moved affinely for...Two types of calculations can be performed, equilibrium (or Green– Kubo ) calculations in which the rate of deformation tensor21,22 is set to zero and the...autocorrelation function of stress at equilibrium is followed; or flow calculations in which a specific flow field is applied and the stress as a

Particle orbits in two-dimensional equilibrium models for the magnetotail

NASA Technical Reports Server (NTRS)

Karimabadi, H.; Pritchett, P. L.; Coroniti, F. V.

1990-01-01

Assuming that there exist an equilibrium state for the magnetotail, particle orbits are investigated in two-dimensional kinetic equilibrium models for the magnetotail. Particle orbits in the equilibrium field are compared with those calculated earlier with one-dimensional models, where the main component of the magnetic field (Bx) was approximated as either a hyperbolic tangent or a linear function of z with the normal field (Bz) assumed to be a constant. It was found that the particle orbits calculated with the two types of models are significantly different, mainly due to the neglect of the variation of Bx with x in the one-dimensional fields.

FORTRAN 4 computer program for calculation of thermodynamic and transport properties of complex chemical systems

NASA Technical Reports Server (NTRS)

Svehla, R. A.; Mcbride, B. J.

1973-01-01

A FORTRAN IV computer program for the calculation of the thermodynamic and transport properties of complex mixtures is described. The program has the capability of performing calculations such as:(1) chemical equilibrium for assigned thermodynamic states, (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. Condensed species, as well as gaseous species, are considered in the thermodynamic calculation; but only the gaseous species are considered in the transport calculations.

Proton bombarded reactions of Calcium target nuclei

NASA Astrophysics Data System (ADS)

Tel, Eyyup; Sahan, Muhittin; Sarpün, Ismail Hakki; Kavun, Yusuf; Gök, Ali Armagan; Depedelen, Mesut

2017-09-01

In this study, proton bombarded nuclear reactions calculations of Calcium target nuclei have been investigated in the incident proton energy range of 1-50 MeV. The excitation functions for 40Ca target nuclei reactions have been calculated by using PCROSS nuclear reaction calculation code. Weisskopf-Ewing and the full exciton models were used for equilibrium and for pre-equilibrium calculations, respectively. The excitation functions for 40Ca target nuclei reactions (p,α), (p,n), (p,p) have been calculated using the semi-empirical formula Tel et al. [5].

Computing Properties Of Chemical Mixtures At Equilibrium

NASA Technical Reports Server (NTRS)

Mcbride, B. J.; Gordon, S.

1995-01-01

Scientists and engineers need data on chemical equilibrium compositions to calculate theoretical thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93 is general program that calculates chemical equilibrium compositions and properties of mixtures for any chemical system for which thermodynamic data are available. Includes thermodynamic data for more than 1,300 gaseous and condensed species and thermal-transport data for 151 gases. Written in FORTRAN 77.

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

USGS Publications Warehouse

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

2007-01-01

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

Computer program determines chemical composition of physical system at equilibrium

NASA Technical Reports Server (NTRS)

Kwong, S. S.

1966-01-01

FORTRAN 4 digital computer program calculates equilibrium composition of complex, multiphase chemical systems. This is a free energy minimization method with solution of the problem reduced to mathematical operations, without concern for the chemistry involved. Also certain thermodynamic properties are determined as byproducts of the main calculations.

Calculating Shocks In Flows At Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Eberhardt, Scott; Palmer, Grant

1988-01-01

Boundary conditions prove critical. Conference paper describes algorithm for calculation of shocks in hypersonic flows of gases at chemical equilibrium. Although algorithm represents intermediate stage in development of reliable, accurate computer code for two-dimensional flow, research leading up to it contributes to understanding of what is needed to complete task.

Group selection and the development of the biological species concept

PubMed Central

Mallet, James

2010-01-01

The development of what became known as the biological species concept began with a paper by Theodosius Dobzhansky in 1935, and was amplified by a mutualistic interaction between Dobzhansky, Alfred Emerson and Ernst Mayr after the second world war. By the 1950s and early 1960s, these authors had developed an influential concept of species as coadapted genetic complexes at equilibrium. At this time many features of species were seen as group advantages maintained by selection to avoid breakdown of beneficial coadaptation and the ‘gene pool’. Speciation thus seemed difficult. It seemed to require, more so than today, an external deus ex machina, such as allopatry or the founder effect, rather than ordinary within-species processes of natural selection, sexual selection, drift and gene flow. In the mid-1960s, the distinctions between group and individual selection were clarified. Dobzhansky and Mayr both understood the implications, but their views on species changed little. These group selectionist ideas now seem peculiar, and are becoming distinctly less popular today. Few vestiges of group selectionism and species-level adaptationism remain in recent reviews of speciation. One wonders how many of our own cherished views on evolution will seem as odd to future biologists. PMID:20439286

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

PubMed Central

Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurtén, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D'Ambro, Emma L.; Thornton, Joel A.

2016-01-01

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas–particle equilibrium and (ii) have a short particle-phase lifetime (∼2–4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. PMID:26811465

Tungsten Speciation and Solubility in Munitions-Impacted Soils.

PubMed

Bostick, Benjamín C; Sun, Jing; Landis, Joshua D; Clausen, Jay L

2018-02-06

Considerable questions persist regarding tungsten geochemistry in natural systems, including which forms of tungsten are found in soils and how adsorption regulates dissolved tungsten concentrations. In this study, we examine tungsten speciation and solubility in a series of soils at firing ranges in which tungsten rounds were used. The metallic, mineral, and adsorbed forms of tungsten were characterized using X-ray absorption spectroscopy and X-ray microprobe, and desorption isotherms for tungsten in these soils were used to characterize its solid-solution partitioning behavior. Data revealed the complete and rapid oxidation of tungsten metal to hexavalent tungsten(VI) and the prevalence of adsorbed polymeric tungstates in the soils rather than discrete mineral phases. These polymeric complexes were only weakly retained in the soils, and porewaters in equilibrium with contaminated soils had 850 mg L -1 tungsten, considerably in excess of predicted solubility. We attribute the high solubility and limited adsorption of tungsten to the formation of polyoxometalates such as W 12 SiO 40 4- , an α-Keggin cluster, in soil solutions. Although more research is needed to confirm which of such polyoxometalates are present in soils, their formation may not only increase the solubility of tungsten but also facilitate its transport and influence its toxicity.

A "User-Friendly" Program for Vapor-Liquid Equilibrium.

ERIC Educational Resources Information Center

Da Silva, Francisco A.; And Others

1991-01-01

Described is a computer software package suitable for teaching and research in the area of multicomponent vapor-liquid equilibrium. This program, which has a complete database, can accomplish phase-equilibrium calculations using various models and graph the results. (KR)

High-temperature partition functions, specific heats and spectral radiative properties of diatomic molecules with an improved calculation of energy levels

NASA Astrophysics Data System (ADS)

Qin, Z.; Zhao, J. M.; Liu, L. H.

2018-05-01

The level energies of diatomic molecules calculated by the frequently used Dunham expansion will become less accurate for high-lying vibrational and rotational levels. In this paper, the potential curves for the lower-lying electronic states with accurate spectroscopic constants are reconstructed using the Rydberg-Klein-Rees (RKR) method, which are extrapolated to the dissociation limits by fitting of the theoretical potentials, and the rest of the potential curves are obtained from the ab-initio results in the literature. Solving the rotational dependence of the radial Schrödinger equation over the obtained potential curves, we determine the rovibrational level energies, which are then used to calculate the equilibrium and non-equilibrium thermodynamic properties of N2, N2+, NO, O2, CN, C2, CO and CO+. The partition functions and the specific heats are systematically validated by available data in the literature. Finally, we calculate the radiative source strengths of diatomic molecules in thermodynamic equilibrium, which agree well with the available values in the literature. The spectral radiative intensities for some diatomic molecules in thermodynamic non-equilibrium are calculated and validated by available experimental data.

Particulate matter speciation profiles for light-duty gasoline vehicles in the United States.

PubMed

Sonntag, Darrell B; Baldauf, Richard W; Yanca, Catherine A; Fulper, Carl R

2014-05-01

Representative profiles for particulate matter particles less than or equal to 2.5 microm (PM2.5) are developed from the Kansas City Light-Duty Vehicle Emissions Study for use in the US. Environmental Protection Agency (EPA) vehicle emission model, the Motor Vehicle Emission Simulator (MOVES), and for inclusion in the EPA SPECIATE database for speciation profiles. The profiles are compatible with the inputs of current photochemical air quality models, including the Community Multiscale Air Quality Aerosol Module Version 6 (AE6). The composition of light-duty gasoline PM2.5 emissions differs significantly between cold start and hot stabilized running emissions, and between older and newer vehicles, reflecting both impacts of aging/deterioration and changes in vehicle technology. Fleet-average PM2.5 profiles are estimated for cold start and hot stabilized running emission processes. Fleet-average profiles are calculated to include emissions from deteriorated high-emitting vehicles that are expected to continue to contribute disproportionately to the fleet-wide PM2.5 emissions into the future. The profiles are calculated using a weighted average of the PM2.5 composition according to the contribution of PM2.5 emissions from each class of vehicles in the on-road gasoline fleet in the Kansas City Metropolitan Statistical Area. The paper introduces methods to exclude insignificant measurements, correct for organic carbon positive artifact, and control for contamination from the testing infrastructure in developing speciation profiles. The uncertainty of the PM2.5 species fraction in each profile is quantified using sampling survey analysis methods. The primary use of the profiles is to develop PM2.5 emissions inventories for the United States, but the profiles may also be used in source apportionment, atmospheric modeling, and exposure assessment, and as a basis for light-duty gasoline emission profiles for countries with limited data. PM2.5 speciation profiles were developed from a large sample of light-duty gasoline vehicles tested in the Kansas City area. Separate PM2.5 profiles represent cold start and hot stabilized running emission processes to distinguish important differences in chemical composition. Statistical analysis was used to construct profiles that represent PM2.5 emissions from the U.S. vehicle fleet based on vehicles tested from the 2005 calendar year Kansas City metropolitan area. The profiles have been incorporated into the EPA MOVES emissions model, as well as the EPA SPECIATE database, to improve emission inventories and provide the PM2.5 chemical characterization needed by CMAQv5.0 for atmospheric chemistry modeling.

Does environmental stability stimulate species renovation?

NASA Astrophysics Data System (ADS)

Casellato, C.; Erba, E.

2009-04-01

The Tithonian-Berriasian time interval is characterized by a major calcareous nannoplankton speciation episode: several coccolith and nannolith genera and species first appear and rapidly evolve, reaching a high diversity, abundance, and calcification degree. The history of calcareous nannoplankton indicates that times of accelerated rates of radiations (or extinctions) generally correlate with global changes in the geosphere, hydrosphere and atmosphere suggesting that evolutionary patterns are intimately linked to environmental modifications (Roth, 1989; Bown et al., 2004; Erba, 2006). Nevertheless, the Tithonian-Berriasian interval provides examples of intra- and intergeneric accelerated evolutionary rates (an origination event) during a time period of general environmental stability, in absence of coeval environmental change evidence. The Tithonian - Early Berriasian can be regarded as a "quiet" interval as far as the C cycle is concerned; the _13C curve shows a gradual minor decline after the Oxfordian anomalies and prior to the Valanginian event. The Tithonian-Berriasian speciation episode provides an excellent opportunity to study modo and tempo of calcareous nannoplankton evolution relative to absent environmental change, which is believed to be instrumental for driving biological evolution. Nannofossils have been investigated in sections from the Tethys and Atlantic oceans in order to discriminate among local, regional or global causes, and to verify possible diachroneity in calcareous phytoplankton evolution and/or in response to global changes. Calcareous nannofossil species richness, first and last occurrences and relative abundance were achieved. Different evolution modes have been proposed since Darwin's Evolutionary Theory: Phyletic Gradualism (Darwin, 1859), Punctuated Equilibrium (Gould & Eldredge, 1977) and Punctuated Gradualism (Malmgren et al., 1984). Phyletic gradualism holds that new species arise from slow, steady transformation of populations providing gradational fossil series linking separate phylogenetic species. Punctuated gradualism implies long-lasting evolutionary stasis interrupted by rapid, but gradual phyletic transformation without lineage splitting. Punctuated equilibrium explains the appearance of new species by rapid speciation occurring in small peripheral isolated populations, followed by migration to other areas where fossil sequence usually shows a series of sharp morphological breaks. The Tithonian-Berriasian nannoplankton speciation episode is characterized by the first occurrence of several new nannolith genera (Conusphaera, Polycostella, Pseudolithraphidites and Lithraphidites, Nannoconus, Assipetra, Braarudoaphaera and Micrantolithus), few new coccoliths genera (Umbria, Rhagodiscus, Cruciellipsis) and several coccoliths and nannolith new species. Most new species rapidly evolved generating related new species or subspecies, often in a time interval shorter than two millions of years, providing examples of all speciation modes. The appearance of highly calcified nannoplankton and its evolution in the Tithonian-Berriasian interval were possibly controlled by abiotic factors, such as seawater chemistry (Mg/Ca ratio and pCO2) and temperature (cool climatic episode). On the other hand this speciation episode corresponds to an interval of environmental stability, probably favoring diversification and expansion of calcareous nannoplankton, adapted to oligotrophic oceans. Nannoliths seem to have experienced all three evolutionary modes, while coccoliths provide examples for only two of them. Evolutionary patterns in the studied interval permit the following considerations: at specific level both nannoliths and coccoliths gradually evolve in time intervals of more that 1 Ma, while at generic level a rapid speciation is most common. Bown, P.R., Lees, J.A., Young, J.R. (2004). Calcareous nannoplankton evolution and diversity through time. In: Thierstein, H.R., Young, J.R. (Eds.), Coccolithophores. From Molecular Processes to Global Impact. Springer-Verlag, Berlin, pp. 481 - 508. Darwin, C. (1859). L'Origine delle specie. In: L'Evoluzione. Newton, 1994 Erba, E. (2006). The first 150 million years history of calcareous nannoplankton: Biosphere - Geosphere interaction. Paleogeogr. Paleoclimatol.Paleoecol. 232, 237-250. Gould, S.J. & Eldredge, N. (1977). Punctuated equilibria: the tempo and mode of evolution reconsidered. Paleobiology 3:115-151. Malmgren, B.A., Berggren, W.A. & Lohmann, G.P. (1984). Species formation through Punctuated Gradualism in Planktonic Foraminifera. Science 225, 317-319. Roth, P.H. (1989). Ocean circulation and calcareous nannoplankton evolution during the Jurassic and Cretaceous. Palaeogeogr. Palaeoclimatol. Palaeoecol. 74, 111 - 126. Stenseth, N.C. & Maynard Smith, J. (1984). Coevolution in ecosystems: rred queen evolution or stasis? Evolution 38, 870-880. Van Valen, L. (1973). A new evolutionary law. Evolutionary Theory 1:1-30.

A General Method for Automatic Computation of Equilibrium Compositions and Theoretical Rocket Performance of Propellants

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Zeleznik, Frank J.; Huff, Vearl N.

1959-01-01

A general computer program for chemical equilibrium and rocket performance calculations was written for the IBM 650 computer with 2000 words of drum storage, 60 words of high-speed core storage, indexing registers, and floating point attachments. The program is capable of carrying out combustion and isentropic expansion calculations on a chemical system that may include as many as 10 different chemical elements, 30 reaction products, and 25 pressure ratios. In addition to the equilibrium composition, temperature, and pressure, the program calculates specific impulse, specific impulse in vacuum, characteristic velocity, thrust coefficient, area ratio, molecular weight, Mach number, specific heat, isentropic exponent, enthalpy, entropy, and several thermodynamic first derivatives.

Calculating and Visualizing Thermodynamic Equilibrium: A Tutorial on the Isolated System with an Internal Adiabatic Piston

ERIC Educational Resources Information Center

Ferreira, Joao Paulo M.

2007-01-01

The problem of the equilibrium state of an isolated composite system with a movable internal adiabatic wall is a recurrent one in the literature. Classical equilibrium thermodynamics is unable to predict the equilibrium state, unless supplemented with information about the process taking place. This conclusion is clearly demonstrated in this…

Systematic Approach to Calculate the Concentration of Chemical Species in Multi-Equilibrium Problems

ERIC Educational Resources Information Center

Baeza-Baeza, Juan Jose; Garcia-Alvarez-Coque, Maria Celia

2011-01-01

A general systematic approach is proposed for the numerical calculation of multi-equilibrium problems. The approach involves several steps: (i) the establishment of balances involving the chemical species in solution (e.g., mass balances, charge balance, and stoichiometric balance for the reaction products), (ii) the selection of the unknowns (the…

Quantum-chemical calculations and electron diffraction study of the equilibrium molecular structure of vitamin K3

NASA Astrophysics Data System (ADS)

Khaikin, L. S.; Tikhonov, D. S.; Grikina, O. E.; Rykov, A. N.; Stepanov, N. F.

2014-05-01

The equilibrium molecular structure of 2-methyl-1,4-naphthoquinone (vitamin K3) having C s symmetry is experimentally characterized for the first time by means of gas-phase electron diffraction using quantum-chemical calculations and data on the vibrational spectra of related compounds.

A superlinear iteration method for calculation of finite length journal bearing's static equilibrium position.

PubMed

Zhou, Wenjie; Wei, Xuesong; Wang, Leqin; Wu, Guangkuan

2017-05-01

Solving the static equilibrium position is one of the most important parts of dynamic coefficients calculation and further coupled calculation of rotor system. The main contribution of this study is testing the superlinear iteration convergence method-twofold secant method, for the determination of the static equilibrium position of journal bearing with finite length. Essentially, the Reynolds equation for stable motion is solved by the finite difference method and the inner pressure is obtained by the successive over-relaxation iterative method reinforced by the compound Simpson quadrature formula. The accuracy and efficiency of the twofold secant method are higher in comparison with the secant method and dichotomy. The total number of iterative steps required for the twofold secant method are about one-third of the secant method and less than one-eighth of dichotomy for the same equilibrium position. The calculations for equilibrium position and pressure distribution for different bearing length, clearance and rotating speed were done. In the results, the eccentricity presents linear inverse proportional relationship to the attitude angle. The influence of the bearing length, clearance and bearing radius on the load-carrying capacity was also investigated. The results illustrate that larger bearing length, larger radius and smaller clearance are good for the load-carrying capacity of journal bearing. The application of the twofold secant method can greatly reduce the computational time for calculation of the dynamic coefficients and dynamic characteristics of rotor-bearing system with a journal bearing of finite length.

A superlinear iteration method for calculation of finite length journal bearing's static equilibrium position

PubMed Central

Zhou, Wenjie; Wei, Xuesong; Wang, Leqin

2017-01-01

Solving the static equilibrium position is one of the most important parts of dynamic coefficients calculation and further coupled calculation of rotor system. The main contribution of this study is testing the superlinear iteration convergence method—twofold secant method, for the determination of the static equilibrium position of journal bearing with finite length. Essentially, the Reynolds equation for stable motion is solved by the finite difference method and the inner pressure is obtained by the successive over-relaxation iterative method reinforced by the compound Simpson quadrature formula. The accuracy and efficiency of the twofold secant method are higher in comparison with the secant method and dichotomy. The total number of iterative steps required for the twofold secant method are about one-third of the secant method and less than one-eighth of dichotomy for the same equilibrium position. The calculations for equilibrium position and pressure distribution for different bearing length, clearance and rotating speed were done. In the results, the eccentricity presents linear inverse proportional relationship to the attitude angle. The influence of the bearing length, clearance and bearing radius on the load-carrying capacity was also investigated. The results illustrate that larger bearing length, larger radius and smaller clearance are good for the load-carrying capacity of journal bearing. The application of the twofold secant method can greatly reduce the computational time for calculation of the dynamic coefficients and dynamic characteristics of rotor-bearing system with a journal bearing of finite length. PMID:28572997

CET89 - CHEMICAL EQUILIBRIUM WITH TRANSPORT PROPERTIES, 1989

NASA Technical Reports Server (NTRS)

Mcbride, B.

1994-01-01

Scientists and engineers need chemical equilibrium composition data to calculate the theoretical thermodynamic properties of a chemical system. This information is essential in the design and analysis of equipment such as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical processing equipment. The substantial amount of numerical computation required to obtain equilibrium compositions and transport properties for complex chemical systems led scientists at NASA's Lewis Research Center to develop CET89, a program designed to calculate the thermodynamic and transport properties of these systems. CET89 is a general program which will calculate chemical equilibrium compositions and mixture properties for any chemical system with available thermodynamic data. Generally, mixtures may include condensed and gaseous products. CET89 performs the following operations: it 1) obtains chemical equilibrium compositions for assigned thermodynamic states, 2) calculates dilute-gas transport properties of complex chemical mixtures, 3) obtains Chapman-Jouguet detonation properties for gaseous species, 4) calculates incident and reflected shock properties in terms of assigned velocities, and 5) calculates theoretical rocket performance for both equilibrium and frozen compositions during expansion. The rocket performance function allows the option of assuming either a finite area or an infinite area combustor. CET89 accommodates problems involving up to 24 reactants, 20 elements, and 600 products (400 of which may be condensed). The program includes a library of thermodynamic and transport properties in the form of least squares coefficients for possible reaction products. It includes thermodynamic data for over 1300 gaseous and condensed species and transport data for 151 gases. The subroutines UTHERM and UTRAN convert thermodynamic and transport data to unformatted form for faster processing. The program conforms to the FORTRAN 77 standard, except for some input in NAMELIST format. It requires about 423 KB memory, and is designed to be used on mainframe, workstation, and mini computers. Due to its memory requirements, this program does not readily lend itself to implementation on MS-DOS based machines.

Equation of state of detonation products based on statistical mechanical theory

NASA Astrophysics Data System (ADS)

Zhao, Yanhong; Liu, Haifeng; Zhang, Gongmu; Song, Haifeng

2015-06-01

The equation of state (EOS) of gaseous detonation products is calculated using Ross's modification of hard-sphere variation theory and the improved one-fluid van der Waals mixture model. The condensed phase of carbon is a mixture of graphite, diamond, graphite-like liquid and diamond-like liquid. For a mixed system of detonation products, the free energy minimization principle is used to calculate the equilibrium compositions of detonation products by solving chemical equilibrium equations. Meanwhile, a chemical equilibrium code is developed base on the theory proposed in this article, and then it is used in the three typical calculations as follow: (i) Calculation for detonation parameters of explosive, the calculated values of detonation velocity, the detonation pressure and the detonation temperature are in good agreement with experimental ones. (ii) Calculation for isentropic unloading line of RDX explosive, whose starting points is the CJ point. Comparison with the results of JWL EOS it is found that the calculated value of gamma is monotonically decreasing using the presented theory in this paper, while double peaks phenomenon appears using JWL EOS.

Equation of state of detonation products based on statistical mechanical theory

NASA Astrophysics Data System (ADS)

Zhao, Yanhong; Liu, Haifeng; Zhang, Gongmu; Song, Haifeng; Iapcm Team

2013-06-01

The equation of state (EOS) of gaseous detonation products is calculated using Ross's modification of hard-sphere variation theory and the improved one-fluid van der Waals mixture model. The condensed phase of carbon is a mixture of graphite, diamond, graphite-like liquid and diamond-like liquid. For a mixed system of detonation products, the free energy minimization principle is used to calculate the equilibrium compositions of detonation products by solving chemical equilibrium equations. Meanwhile, a chemical equilibrium code is developed base on the theory proposed in this article, and then it is used in the three typical calculations as follow: (i) Calculation for detonation parameters of explosive, the calculated values of detonation velocity, the detonation pressure and the detonation temperature are in good agreement with experimental ones. (ii) Calculation for isentropic unloading line of RDX explosive, whose starting points is the CJ point. Comparison with the results of JWL EOS it is found that the calculated value of gamma is monotonically decreasing using the presented theory in this paper, while double peaks phenomenon appears using JWL EOS.

An implicit flux-split algorithm to calculate hypersonic flowfields in chemical equilibrium

NASA Technical Reports Server (NTRS)

Palmer, Grant

1987-01-01

An implicit, finite-difference, shock-capturing algorithm that calculates inviscid, hypersonic flows in chemical equilibrium is presented. The flux vectors and flux Jacobians are differenced using a first-order, flux-split technique. The equilibrium composition of the gas is determined by minimizing the Gibbs free energy at every node point. The code is validated by comparing results over an axisymmetric hemisphere against previously published results. The algorithm is also applied to more practical configurations. The accuracy, stability, and versatility of the algorithm have been promising.

Aggregation of 2-aminobenzimidazole--a combined experimental and theoretical investigation.

PubMed

Angelova, Silvia E; Spassova, Milena I; Deneva, Vera V; Rogojerov, Marin I; Antonov, Liudmil M

2011-06-20

An investigation of 2-aminobenzimidazole was carried out by calculations at HF, MP2, and DFT levels of theory and also by UV and IR spectroscopy. The quantum chemical calculations predict a full shift of the equilibrium towards the amino form, but the absorption spectra in different solvents distinctly show a two-component equilibrium system. Examination of possible equilibria in solution shows that an equilibrium between two dimeric forms of the amino tautomer of 2-aminobenzimidazole explains the spectral observations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper speciation in sulfidic solutions at low sulfur activity: Further evidence for cluster complexes?

NASA Astrophysics Data System (ADS)

Thompson, Richard A.; Helz, George R.

1994-07-01

The solubility of two as0-buffering assemblages in the Cu-S system have been studied: chalcocite-djurleite (Cc-Dj) and anilite-covellite (An-Cv). Ion activity products, [Cu +]HS -] 1/2[H +] - 1/2 (25°C, I = 0) at equilibrium, derived from solubility measurements in penicillamine solutions, are 10 -17.01 ± 0.05 (Cc-Dj) and 10 -17.14 ± 0.10 (An-Cv), from which ΔG° f = -82.11 kJ/mol for Cc and -74.77 kJ/mol for An. In the An-Cv assemblage, aCu2S = 0.55 (2 σ = 0.2) vs. 1.00 in the Cc-containing assemblage. The difference in aCu2S between the two assemblages is used in a novel way to estimate stoichiometry of Cu-HS complexes. The solubility of both assemblages (0.7-0.01 M NaHS, pH 7-12.5, 25°C) can be fit with a model incorporating the same two chemical species, one containing an odd number of Cu atoms (Cu(HS) 2-3, CU 3S 4H 2-3, or a higher multimer) and the other containing an even number of Cu atoms (Cu 2S(HS) 22-, Cu 4S 4H 22-, etc.). The trimer-tetramer model fits the combined data for the two assemblages distinctly better than the monomer-dimer model, but this result is very sensitive to uncertainty in aCu2S. Along with EXAFS results, the weight of the evidence favors small cluster complexes (2-5 Cu atoms), but is inconclusive at the present level of resolution. Multimers can be rationalized because condensation of metal-centered monomers to clusters provides a means for soft acid/base elements to maintain favored coordination geometries at low ligand to metal ratios. Based on the fitting methods developed here, previous covellite solubility data from this laboratory are reinterpreted in terms of Cu 2S 2(HS) 33-, Cu 2S 3)(S 4) 2-, and Cu(S 9)S 10) 3-; the last of these could also be represented by the trimer, Cu 3(S 7) 33-, which is homologous with a known complex. With the measured equilibrium constants, the speciation of Cu in the sulfidic zone of the Black Sea is calculated. Covellite is the stable Cu-S mineral, but the sulfidic water column is vastly supersaturated with respect to it. Most of the sulfidic water column is modestly (2.5-5.5 times) supersaturated with respect to Cc, hinting that this mineral metastably controls ΣCu. The slight supersaturation suggests that Cc occurs as 10-100 nm particles.

A Simple Method to Calculate the Temperature Dependence of the Gibbs Energy and Chemical Equilibrium Constants

ERIC Educational Resources Information Center

Vargas, Francisco M.

2014-01-01

The temperature dependence of the Gibbs energy and important quantities such as Henry's law constants, activity coefficients, and chemical equilibrium constants is usually calculated by using the Gibbs-Helmholtz equation. Although, this is a well-known approach and traditionally covered as part of any physical chemistry course, the required…

Speciations and Extinctions in a Self-Organizing Critical Model of Tree-Like Evolution

NASA Astrophysics Data System (ADS)

Kramer, M.; Vandewalle, N.; Ausloos, M.

1996-04-01

We study analytically a simple model of a self-organized critical evolution. The model considers both extinction and speciation events leading to the growth of phylogenetic-like trees. Through a mean-field like theory, we study the evolution of the local configurations for the tree leaves. The fitness threshold, below which life activity takes place through avalanches of all sizes is calculated. The transition between speciating (evolving) and dead trees is obtained and is in agreement with numerical simulations. Moreover, this theoretical work suggests that the structure of the tree is strongly dependent on the extinction strength. Nous étudions analytiquement un modèle simple d'évolution auto-organisée critique. Le modèle considère des extinctions et des spéciations conduisant à une croissance d'arbre phylogénétiques. Nous étudions ici par une théorie de champ moyen l'évolution des configurations des extrémités de l'arbre. Le seuil critique de “fitness” en-dessous duquel des explosions d'activité biologique de toutes tailles se produisent est calculé. La transition entre arbres croissants et arbres éteints est également obtenue en accord avec les simulations. En outre, ce travail théorique suggère que la structure des arbres générés dépend fortement du paramètre d'extinctions.

BeerOz, a set of Matlab routines for the quantitative interpretation of spectrophotometric measurements of metal speciation in solution

NASA Astrophysics Data System (ADS)

Brugger, Joël

2007-02-01

The modelling of the speciation and mobility of metals under surface and hydrothermal conditions relies on the availability of accurate thermodynamic properties for all relevant minerals, aqueous species, gases and surface species. Spectroscopic techniques obeying the Beer-Lambert law can be used to obtain thermodynamic properties for reactions among aqueous species (e.g., ligand substitution; protonation). BeerOz is a set of Matlab routines designed to perform both qualitative and quantitative analysis of spectroscopic data following the Beer-Lambert law. BeerOz is modular and can be customised for particular experimental strategies or for simultaneous refinement of several datasets obtained using different techniques. Distribution of species calculations are performed using an implementation of the EQBRM code, which allows for customised activity coefficient calculations. BeerOz also contains routines to study the n-dimensional solution space, in order to provide realistic estimates of errors and test for the existence of multiple local minima and correlation between the different refined variables. The paper reviews the physical principles underlying the qualitative and quantitative analysis of spectroscopic data collected on aqueous speciation, in particular for studying successive ligand replacement reactions, and presents the non-linear least-squares algorithm implemented in BeerOz. The discussion is illustrated using UV-Vis spectra collected on acidic Fe(III) solutions containing varying LiCl concentrations, and showing the change from the hexaaquo Fe(H 2O) 63+ complex to the tetrahedral FeCl 4- complex.

Uranium aqueous speciation in the vicinity of the former uranium mining sites using the diffusive gradients in thin films and ultrafiltration techniques.

PubMed

Drozdzak, Jagoda; Leermakers, Martine; Gao, Yue; Elskens, Marc; Phrommavanh, Vannapha; Descostes, Michael

2016-03-24

The performance of the Diffusive Gradients in Thin films (DGT) technique with Chelex(®)-100, Metsorb™ and Diphonix(®) as binding phases was evaluated in the vicinity of the former uranium mining sites of Chardon and L'Ecarpière (Loire-Atlantique department in western France). This is the first time that the DGT technique with three different binding agents was employed for the aqueous U determination in the context of uranium mining environments. The fractionation and speciation of uranium were investigated using a multi-methodological approach using filtration (0.45 μm, 0.2 μm), ultrafiltration (500 kDa, 100 kDa and 10 kDa) coupled to geochemical speciation modelling (PhreeQC) and the DGT technique. The ultrafiltration data showed that at each sampling point uranium was present mostly in the 10 kDa truly dissolved fraction and the geochemical modelling speciation calculations indicated that U speciation was markedly predominated by CaUO2(CO3)3(2-). In natural waters, no significant difference was observed in terms of U uptake between Chelex(®)-100 and Metsorb™, while similar or inferior U uptake was observed on Diphonix(®) resin. In turn, at mining influenced sampling spots, the U accumulation on DGT-Diphonix(®) was higher than on DGT-Chelex(®)-100 and DGT-Metsorb™, probably because their performance was disturbed by the extreme composition of the mining waters. The use of Diphonix(®) resin leads to a significant advance in the application and development of the DGT technique for determination of U in mining influenced environments. This investigation demonstrated that such multi-technique approach provides a better picture of U speciation and enables to assess more accurately the potentially bioavailable U pool. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparing WHAM 6 and MINEQL+ 4.5 for the chemical speciation of Cu2+ in the rhizosphere of forest soils.

PubMed

Cloutier-Hurteau, Benoît; Sauvé, Sébastien; Courchesne, François

2007-12-01

Metal speciation data calculated by modeling could give useful information regarding the fate of metals in the rhizospheric environment. However, no comparative study has evaluated the relative accuracy of speciation models in this microenvironment. Consequently, the present study evaluates the reliability of free Cu ion (Cu2+) activity modeled by WHAM 6 and MINEQL+ 4.5 for 18 bulk and 18 rhizospheric soil samples collected in two Canadian forested areas located near industrial facilities. The modeling of Cu speciation was performed on water extracts using pH, dissolved organic carbon (DOC), major ions, and total dissolved Al, Ca, Cu, Mg, and Zn concentrations as input data. Four scenarios representing the composition of dissolved organic substances using fulvic, humic, and acetic acids were derived from the literature and used in the modeling exercise. Different scenarios were used to contrast soil components (rhizosphere vs bulk) and soil pH levels (acidic vs neutral to alkaline). Reference Cu2+ activity values measured by an ion-selective electrode varied between 0.39 and 41 nM. The model MINEQL+ 4.5 provided good predictions of Cu2+ activities [root-mean-square residual (RMSR)= 0.37], while predictions from WHAM 6 were poor (RMSR = 1.74) because they overestimated Cu complexation with DOC. Modeling with WHAM 6 could be improved by adjusting the proportion of inert DOC and the composition of DOC (RMSR = 0.94), but it remained weaker than predictions with MINEQL+ 4.5. These results suggested that the discrepancies between speciation models were attributed to differences in the binding capacity of humic substances with Cu, where WHAM 6 appeared to be too aggressive. Therefore, we concluded that chemical interactions occurring between Cu and DOC were key factors for an accurate simulation of Cu speciation, especially in rhizospheric forest soils, where high variation of the DOC concentration and composition are observed.

Nighttime Ozone Chemical Equilibrium in the Mesopause Region

NASA Astrophysics Data System (ADS)

Kulikov, M. Yu.; Belikovich, M. V.; Grygalashvyly, M.; Sonnemann, G. R.; Ermakova, T. S.; Nechaev, A. A.; Feigin, A. M.

2018-03-01

We examine the applicability of the assumption that nighttime ozone is in photochemical equilibrium. The analysis is based on calculations with a 3-D chemical transport model. These data are used to determine the ratio of correct (calculated) O3 density to its equilibrium value for the conditions of the nighttime mesosphere depending on the altitude, latitude, and month in the annual cycle. The results obtained demonstrate that the retrieval of O and H distributions using the assumption of photochemical ozone equilibrium may lead to a significant error below 81-87 km depending on season. Possible modifications of the currently used approach that allow improving the quality of retrieval of O and H mesospheric distributions from satellite-based observations are discussed.

Improved Simulation of the Pre-equilibrium Triton Emission in Nuclear Reactions Induced by Nucleons

NASA Astrophysics Data System (ADS)

Konobeyev, A. Yu.; Fischer, U.; Pereslavtsev, P. E.; Blann, M.

2014-04-01

A new approach is proposed for the calculation of non-equilibrium triton energy distributions in nuclear reactions induced by nucleons of intermediate energies. It combines models describing the nucleon pick-up, the coalescence and the triton knock-out processes. Emission and absorption rates for excited particles are represented by the pre-equilibrium hybrid model. The model of Sato, Iwamoto, Harada is used to describe the nucleon pick-up and the coalescence of nucleons from exciton configurations starting from (2p,1h) states. The contribution of the direct nucleon pick-up is described phenomenologically. Multiple pre-equilibrium emission of tritons is accounted for. The calculated triton energy distributions are compared with available experimental data.

Sorption, desorption, and speciation of Cd, Ni, and Fe by four calcareous soils as affected by pH.

PubMed

Tahervand, Samaneh; Jalali, Mohsen

2016-06-01

The sorption, desorption, and speciation of cadmium (Cd), nickel (Ni), and iron (Fe) in four calcareous soils were investigated at the pH range of 2-9. The results indicated that sorption of Fe by four soils was higher than 80 % at pH 2, while in the case of Cd and Ni was less than 30 %. The most common sequence of metal sorption at pH 2-9 for four soils was in the order of Fe ≫ Ni > Cd. Cadmium and Ni sorption as a function of pH showed the predictable trend of increasing metal sorption with increase in equilibrium pH, while the Fe sorption trend was different and characterized by three phases. With regard to the order of Cd, Ni, and Fe sorption on soils, Cd and Ni showed high affinity for organic matter (OM), whereas Fe had high tendency for calcium carbonate (CaCO3). Results of metal desorption using 0.01 M NaCl demonstrated that metal sorption on soils containing high amounts of CaCO3 was less reversible in comparison to soils containing high OM. In general, Cd and Ni desorption curves were characterized by three phases; (1) the greatest desorption at pH 2, (2) the low desorption at pH 3-7, and (3) the least desorption at pH > 7. The MINTEQ speciation solubility program showed that the percentage of free metals declined markedly with increase of pH, while the percentage of carbonate and hydroxyl species increased. Furthermore, MINTEQ predicted that saturation index (SI) of metals increased with increasing pH.

Aluminum and Fenton reaction: how can the reaction be modulated by speciation? A computational study using citrate as a test case.

PubMed

Mujika, Jon I; Dalla Torre, Gabriele; Lopez, Xabier

2018-06-13

The pro-oxidant ability of aluminum is behind many of the potential toxic effects of this exogenous element in the human organism. Although the overall process is still far from being understood at the molecular level, the well known ability of aluminum to promote the Fenton reaction is mediated through the formation of stable aluminum-superoxide radical complexes. However, the properties of metal complexes are highly influenced by the speciation of the metal. In this paper, we investigate the effect that speciation could have on the pro-oxidant activity of aluminum. We choose citrate as a test case, because it is the main low-molecular-mass chelator of aluminum in blood serum, forming very stable aluminum-citrate complexes. The influence of citrate in the interaction of aluminum with the superoxide radical is investigated, determining how the formation of aluminum-citrate complexes affects the promotion of the Fenton reaction. The results indicate that citrate increases the stability of the aluminum-superoxide complexes through the formation of ternary compounds, and that the Fenton reaction is even more favorable when aluminum is chelated to citrate. Nevertheless, our results demonstrate that overall, citrate may prevent the pro-oxidant activity of aluminum: on one hand, in an excess of citrate, the formation of 1 : 2 aluminum-citrate complexes is expected. On the other hand, the chelation of iron by citrate makes the reduction of iron thermodynamically unfavorable. In summary, the results suggest that citrate can have both a promotion and protective role, depending on subtle factors, such as initial concentration, non-equilibrium behavior and the exchange rate of ligands in the first shell of the metals.

Austenite grain growth simulation considering the solute-drag effect and pinning effect.

PubMed

Fujiyama, Naoto; Nishibata, Toshinobu; Seki, Akira; Hirata, Hiroyuki; Kojima, Kazuhiro; Ogawa, Kazuhiro

2017-01-01

The pinning effect is useful for restraining austenite grain growth in low alloy steel and improving heat affected zone toughness in welded joints. We propose a new calculation model for predicting austenite grain growth behavior. The model is mainly comprised of two theories: the solute-drag effect and the pinning effect of TiN precipitates. The calculation of the solute-drag effect is based on the hypothesis that the width of each austenite grain boundary is constant and that the element content maintains equilibrium segregation at the austenite grain boundaries. We used Hillert's law under the assumption that the austenite grain boundary phase is a liquid so that we could estimate the equilibrium solute concentration at the austenite grain boundaries. The equilibrium solute concentration was calculated using the Thermo-Calc software. Pinning effect was estimated by Nishizawa's equation. The calculated austenite grain growth at 1473-1673 K showed excellent correspondence with the experimental results.

Effects of elastic strain energy on the antisite defect of D0 22-Ni 3V phase

NASA Astrophysics Data System (ADS)

Zhang, Jing; Chen, Zheng; Wang, Yong Xin; Lu, Yan Li

2010-01-01

A time-dependent phase field microelasticity model of an elastically anisotropic Ni-Al-V solid is employed for a D0 22-Ni 3V antisite defect application. The elastic strain energy (ESE), caused by a coherent misfit, changes the behavior of the temporal evolution occupancy probability (OP), slows down the phase transformation, and eventually leads to directional coarsening of coherent microstructures. In particular, for the antisite defects (Ni V, V Ni) and ternary alloying elements (Al Ni, Al V), ESE is responsible for the decrease in the calculated equilibrium values of Ni V, Al Ni, and Al V, as well as the increase in the equilibrium value of V Ni. The gap between Ni V and V Ni and Al Ni and Al V is narrowed in the system involving ESE, but the calculated equilibrium magnitude of Ni V is still greater than that of V Ni. The calculated equilibrium magnitude of Al Ni was always greater than Al V in this study.

Pb(II) adsorption by a novel activated carbon - alginate composite material. A kinetic and equilibrium study.

PubMed

Cataldo, Salvatore; Gianguzza, Antonio; Milea, Demetrio; Muratore, Nicola; Pettignano, Alberto

2016-11-01

The adsorption capacity of an activated carbon - calcium alginate composite material (ACAA-Ca) has been tested with the aim of developing a new and more efficient adsorbent material to remove Pb(II) ion from aqueous solution. The study was carried out at pH=5, in NaCl medium and in the ionic strength range 0.1-0.75molL -1 . Differential Pulse Anodic Stripping Voltammetry (DP-ASV) technique was used to check the amount of Pb(II) ion removed during kinetic and equilibrium experiments. Different kinetic (pseudo first order, pseudo second order and Vermuelen) and equilibrium (Langmuir and Freundlich) models were used to fit experimental data, and were statistically compared. Calcium alginate (AA-Ca) improves the adsorption capacity (q m ) of active carbon (AC) in the ACAA-Ca adsorbent material (e.g., q m =15.7 and 10.5mgg -1 at I=0.25molL -1 , for ACAA-Ca and AC, respectively). SEM-EDX and thermogravimetric (TGA) measurements were carried out in order to characterize the composite material. The results of the speciation study on the Pb(II) solution and of the characterization of the ACAA-Ca and of the pristine AA-Ca and AC were evaluated in order to explain the specific contribution of AC and AA-Ca to the adsorption of the metal ion. Copyright © 2016 Elsevier B.V. All rights reserved.

Charging Properties of Cassiterite (alpha-SnO2) Surfaces in NaCl and RbCl Ionic Media.

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite ({alpha}-SnO{sub 2}) surfaces at 10-50 C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH{sub 2} group is more acidic than the bridging Sn{sub 2}OH group, with protonation constants (log K{sub H}) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural {alpha}-TiO{sub 2} (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na{sup +} and Rb{sup +}, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na{sup +} between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb{sup +} is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na{sup +}/Rb{sup +} was formulated. According to the SCM, the deprotonated terminal group (SnOH{sup -0.40}) and the protonated bridging group (Sn{sub 2}OH{sup +0.36}) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with increasing negative surface charge, and at pH 10, roughly 40% of the terminal sites are predicted to form cation complexes, whereas anion complexation is minor throughout the studied pH range.« less

Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected Shocks, and Chapman-Jouguet Detonations. Interim Revision, March 1976

NASA Technical Reports Server (NTRS)

Gordon, S.; Mcbride, B. J.

1976-01-01

A detailed description of the equations and computer program for computations involving chemical equilibria in complex systems is given. A free-energy minimization technique is used. The program permits calculations such as (1) chemical equilibrium for assigned thermodynamic states (T,P), (H,P), (S,P), (T,V), (U,V), or (S,V), (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. The program considers condensed species as well as gaseous species.

Determination of successive complexation constants in an ionic liquid: complexation of UO(2)(2+) with NO(3)(-) in C(4)-mimTf(2)N studied by UV-Vis spectroscopy.

PubMed

Georg, Sylvia; Billard, Isabelle; Ouadi, Ali; Gaillard, Clotilde; Petitjean, Laetitia; Picquet, Michel; Solov'ev, Vitaly

2010-04-01

The complexation of UO(2)(2+) with NO(3)(-) has been investigated in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide by UV-vis spectroscopy at T = 18.5 degrees C. The complexation is evidenced through the appearance of four peaks at 425, 438, 453, and 467 nm. EXAFS data indicate that the trinitrato complex, UO(2)(NO(3))(3)(-), is dominating the speciation for a reagent ratio of [NO(3)(-)]/[UO(2)(2+)] > 3. Assuming three successive complexation steps, the conditional stability constants are calculated, the individual absorption spectra are derived, and a speciation plot is presented.

Arsenic speciation in biological samples using XAS and mixed oxidation state calibration standards of inorganic arsenic.

PubMed

Parsons, J G; Lopez, M L; Castillo-Michel, H; Peralta-Videa, J R; Gardea-Torresdey, J L

2009-08-01

The speciation of elements without pre-edge features preformed with X-ray absorption near edge structure (XANES) can lead to problems when the energy difference between two species is small. The speciation of arsenic (As) in plant samples was investigated using the mixtures As2S3/As2O5, As2S3/As2O3, or As2O3/As2O5. The data showed that the energy separation (eV) between As2O5 and As2S3 was 5.8, between As2O3 and As2O5 was 3.6, and between As2S3 and As2O3 was 2.1. From the intensity of the white-line feature and the concentration of As species, calibration curves showing a limit of detection of approximately 10% were generated. In addition, an error of +/-10% was determined for the linear combination-XANES (LC-XANES) fitting technique. The difference between the LC-XANES fittings and calculations from the calibration curves was <10%. The data also showed that the speciation of As in a sample can be determined using EXAFS (extended X-ray absorption fine structure). Finally, it was also shown that both EXAFS and XANES of the sample should be examined to determine the true speciation of an element. Even though there is a difference of 2 eV between As(III) bound to O and As(III) bound to S, in the EXAFS region the As(III)-S and As(III)-O ligands are clearly visible. However, distinction between the As(III)-O and As(V)-O ligands in the EXAFS spectra was not clearly visible in this study.

Flow Injection Photochemical Vapor Generation Coupled with Miniaturized Solution-Cathode Glow Discharge Atomic Emission Spectrometry for Determination and Speciation Analysis of Mercury.

PubMed

Mo, Jiamei; Li, Qing; Guo, Xiaohong; Zhang, Guoxia; Wang, Zheng

2017-10-03

A novel, compact, and green method was developed for the determination and speciation analysis of mercury, based on flow injection photochemical vapor generation (PVG) coupled with miniaturized solution cathode glow discharge-atomic emission spectroscopy (SCGD-AES). The SCGD was generated between a miniature hollow titanium tube and a solution emerging from a glass capillary. Cold mercury vapor (Hg(0)) was generated by PVG and subsequently delivered to the SCGD for excitation, and finally the emission signals were recorded by a miniaturized spectrograph. The detection limits (DLs) of Hg(II) and methylmercury (MeHg) were both determined to be 0.2 μg L -1 . Moreover, mercury speciation analysis could also be performed by using different wavelengths and powers from the UV lamp and irradiation times. Both Hg(II) and MeHg can be converted to Hg(0) for the determination of total mercury (T-Hg) with 8 W/254 nm UV lamp and 60 s irradiation time; while only Hg(II) can be reduced to Hg(0) and determined selectively with 4 W/365 nm UV lamp and 20 s irradiation time. Then, the concentration of MeHg can be calculated by subtracting the Hg(II) from the T-Hg. Because of its similar sensitivity and DL at 8 W/254 nm, the simpler and less toxic Hg(II) was used successfully as a primary standard for the quantification of T-Hg. The novel PVG-SCGD-AES system provides not only a 365-fold improvement in the DL for Hg(II) but also a nonchromatographic method for the speciation analysis of mercury. After validating its accuracy, this method was successfully used for mercury speciation analysis of water and biological samples.

Rare earth element variations resulting from inversion of pigeonite and subsolidus reequilibration in lunar ferroan anorthosites

USGS Publications Warehouse

James, O.B.; Floss, C.; McGee, J.J.

2002-01-01

We present results of a secondary ion mass spectrometry study of the rare earth elements (REEs) in the minerals of two samples of lunar ferroan anorthosite, and the results are applicable to studies of REEs in all igneous rocks, no matter what their planet of origin. Our pyroxene analyses are used to determine solid-solid REE distribution coefficients (D = CREE in low-Ca pyroxene/CREE in augite) in orthopyroxene-augite pairs derived by inversion of pigeonite. Our data and predictions from crystal-chemical considerations indicate that as primary pigeonite inverts to orthopyroxene plus augite and subsolidus reequilibration proceeds, the solid-solid Ds for orthopyroxene-augite pairs progressively decrease for all REEs; the decrease is greatest for the LREEs. The REE pattern of solid-solid Ds for inversion-derived pyroxene pairs is close to a straight line for Sm-Lu and turns upward for REEs lighter than Sm; the shape of this pattern is predicted by the shapes of the REE patterns for the individual minerals. Equilibrium liquids calculated for one sample from the compositions of primary phases, using measured or experimentally determined solid-liquid Ds, have chondrite-normalized REE patterns that are very slightly enriched in LREEs. The plagioclase equilibrium liquid is overall less rich in REEs than pyroxene equilibrium liquids, and the discrepancy probably arises because the calculated plagioclase equilibrium liquid represents a liquid earlier in the fractionation sequence than the pyroxene equilibrium liquids. "Equilibrium" liquids calculated from the compositions of inversion-derived pyroxenes or orthopyroxene derived by reaction of olivine are LREE depleted (in some cases substantially) in comparison with equilibrium liquids calculated from the compositions of primary phases. These discrepancies arise because the inversion-derived and reaction-derived pyroxenes did not crystallize directly from liquid, and the use of solid-liquid Ds is inappropriate. The LREE depletion of the calculated liquids is a relic of formation of these phases from primary LREE-depleted minerals. Thus, if one attempts to calculate the compositions of equilibrium liquids from pyroxene compositions, it is important to establish that the pyroxenes are primary. In addition, our data suggest that experimental studies have underestimated solid-liquid Ds for REEs in pigeonite and that REE contents of liquids calculated using these Ds are overestimates. Our results have implications for Sm-Nd age studies. Our work shows that if pigeonite inversion and/or subsolidus reequilibration between augite and orthopyroxene occured significantly after crystallization, and if pyroxene separates isolated for Sm-Nd studies do not have the bulk composition of the primary pyroxenes, then the Sm-Nd isochron age and ??Nd will be in error. Copyright ?? 2002 Elsevier Science Ltd.

A gel probe equilibrium sampler for measuring arsenic porewater profiles and sorption gradients in sediments: I. Laboratory development

USGS Publications Warehouse

Campbell, K.M.; Root, R.; O'Day, P. A.; Hering, J.G.

2008-01-01

A gel probe equilibrium sampler has been developed to study arsenic (As) geochemistry and sorption behavior in sediment porewater. The gels consist of a hydrated polyacrylamide polymer, which has a 92% water content. Two types of gels were used in this study. Undoped (clear) gels were used to measure concentrations of As and other elements in sediment porewater. The polyacrylamide gel was also doped with hydrous ferric oxide (HFO), an amorphous iron (Fe) oxyhydroxide. When deployed in the field, HFO-doped gels introduce a fresh sorbent into the subsurface thus allowing assessment of in situ sorption. In this study, clear and HFO-doped gels were tested under laboratory conditions to constrain the gel behavior prior to field deployment. Both types of gels were allowed to equilibrate with solutions of varying composition and re-equilibrated in acid for analysis. Clear gels accurately measured solution concentrations (??1%), and As was completely recovered from HFO-doped gels (??4%). Arsenic speciation was determined in clear gels through chromatographic separation of the re-equilibrated solution. For comparison to speciation in solution, mixtures of As(III) and As(V) adsorbed on HFO embedded in gel were measured in situ using X-ray absorption spectroscopy (XAS). Sorption densities for As(III) and As(V) on HFO embedded in gel were obtained from sorption isotherms at pH 7.1. When As and phosphate were simultaneously equilibrated (in up to 50-fold excess of As) with HFO-doped gels, phosphate inhibited As sorption by up to 85% and had a stronger inhibitory effect on As(V) than As(III). Natural organic matter (>200 ppm) decreased As adsorption by up to 50%, and had similar effects on As(V) and As(III). The laboratory results provide a basis for interpreting results obtained by deploying the gel probe in the field and elucidating the mechanisms controlling As partitioning between solid and dissolved phases in the environment. ?? 2008 American Chemical Society.

The Lewis Chemical Equilibrium Program with parametric study capability

NASA Technical Reports Server (NTRS)

Sevigny, R.

1981-01-01

The program was developed to determine chemical equilibrium in complex systems. Using a free energy minimization technique, the program permits calculations such as: chemical equilibrium for assigned thermodynamic states; theoretical rocket performance for both equilibrium and frozen compositions during expansion; incident and reflected shock properties; and Chapman-Jouget detonation properties. It is shown that the same program can handle solid coal in an entrained flow coal gasification problem.

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

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.

Here, the controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn 1–yMnyTe 1–xSe x phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y < 0.05 that are in good agreement with results obtained from bulk equilibrium synthesis experiments andmore » predict significantly higher spinodal limits. An experimental screening using sputtered combinatorial thin film sample libraries showed a remarkable increase in non-equilibrium solubility for x,y > 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn 1–yMn yTe 1–xSe x indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.« less

Recovery of copper from PVC multiwire cable waste by steam gasification.

PubMed

Zabłocka-Malicka, Monika; Rutkowski, Piotr; Szczepaniak, Włodzimierz

2015-12-01

Screened multiwire, PVC insulated tinned copper cable was gasified with steam at high temperature (HTSG) under atmospheric pressure for recovery of cooper. Gases from the process were additionally equilibrated at 850°C on the bed of calcined clay granules and more than 98% of C+H content in the cable was transformed to non-condensing species. Granules prepared from local clay were generally resistant for chlorination, there was also almost no deposition of metals, Cu and Sn, on the catalytic bed. It was found that 28% of chlorine reacted to form CaCl2, 71% was retained in aqueous condensate and only 0.6% was absorbed in alkaline scrubber. More than 99% of calcium existed in the process solid residue as a mixture of calcium chloride and calcium oxide/hydroxide. PVC and other hydrocarbon constituents were completely removed from the cable sample. Copper was preserved in original form and volatilization of copper species appeared insignificant. Tin was alloying with copper and its volatilization was less than 1%. Fractionation and speciation of metals, chlorine and calcium were discussed on the basis of equilibrium model calculated with HSC Chemistry software. High temperature steam gasification prevents direct use of the air and steam/water is in the process simultaneously gaseous carrier and reagent, which may be recycled together with hydrocarbon condensates. Copyright © 2015 Elsevier Ltd. All rights reserved.

Landscape control on the hydrogeochemistry of As, Co and Pb in a boreal stream network

NASA Astrophysics Data System (ADS)

Wällstedt, Teresia; Björkvald, Louise; Laudon, Hjalmar; Borg, Hans; Mörth, Carl-Magnus

2017-08-01

In a boreal stream network, stream water concentrations of As, Co and Pb (filtered, <0.4 μm) of 10 nested streams were studied during two consecutive years in order to evaluate the influence of land cover on the temporal and spatial variability of metal concentrations and speciation. Mean concentrations of Co and Pb showed significant but contrasting relationship to landscape type, while As concentrations were not related to landscape type. Highest concentrations of Pb were found in the wetland dominated streams (>30% wetland), which was suggested to be controlled by atmospheric deposition in combination with high DOC release from the wetlands. For Co, the highest concentrations were found in the forest dominated sites (>98% forest), which were attributed to the weathering of minerogenic sources. Contrasting response to runoff events could also be related to landscape type; during the spring flood, decreasing concentrations of As, Co and Pb were observed in the wetland dominated catchments due to dilution, while increasing concentrations during spring flood were observed in the mixed catchments (2-30% wetland) and to some degree in the forested catchments, probably due to flushing of the organic-rich riparian sources. Further, metal speciation was calculated using the geochemical equilibrium model Visual MINTEQ. This suggests that dissolved inorganic species of As and Co dominated in headwater streams with low pH while DOC had a major influencing role for Pb. In the larger mixed streams where pH was higher and precipitation of e.g. colloidal Fe and Mn (hydr)oxides was favoured, the major influencing factor was instead adsorption to colloidal Fe for As and Pb, while association to organic matter and colloids of e.g. Mn influenced the concentrations of Co. We thus conclude that landscape type and the magnitude of the runoff events are of great importance for the spatial and temporal variations of As, Co and Pb in this boreal stream network. Projected climate change, with increasing runoff, may therefore influence riverine concentrations and fluxes differently, depending on the prevailing landscape type.

Solubility and Speciation in the Water-Carbon Dioxide System

NASA Astrophysics Data System (ADS)

Abramson, E.; Bollengier, O.; Brown, J. M.

2016-12-01

The fluid-fluid miscibility surface of the water-carbon dioxide system contains broad regions (in pressure-composition space) exhibiting gradual variations in the temperature of miscibility; this is as expected. However, there is additionally a line of pressure, extending from roughly 2 GPa and 20 mole% CO2 to 6 GPa and 40 mole%, above which the temperature necessary to complete miscibility falls precipitously. This line, which closely approximates a hard limit, is hypothesized to demark a shift in speciation of dissolved CO2. In the same region of pressure the equilibrium limits of a new solid phase, composed of both water and CO2, have been determined. This new phase, the IR and Raman spectra of which led Wang et al.* to ascribe it to carbonic acid, has an observed associated aqueous form which must, in addition to the well-known bicarbonate and carbonate ions, affect the miscibilities of the system. Since zones of rapid subduction are expected to experience the regions of temperatures and pressures at which these equilibria are observed to shift, the chemical nature of these fluids is expected to undergo significant changes during the subduction process. * Wang H., Zeuschner J., Eremets M., Troyan I. and Willams J. (2016) Sci. Rep. 6, 19902-1-8

Insights on Chemistry of Mercury Species in Clouds over Northern China: Complexation and Adsorption.

PubMed

Li, Tao; Wang, Yan; Mao, Huiting; Wang, Shuxiao; Talbot, Robert W; Zhou, Ying; Wang, Zhe; Nie, Xiaoling; Qie, Guanghao

2018-05-01

Cloud effects on heterogeneous reactions of atmospheric mercury (Hg) are poorly understood due to limited knowledge of cloudwater Hg chemistry. Here we quantified Hg species in cloudwater at the summit of Mt. Tai in northern China. Total mercury (THg) and methylmercury (MeHg) in cloudwater were on average 70.5 and 0.15 ng L -1 , respectively, and particulate Hg (PHg) contributed two-thirds of THg. Chemical equilibrium modeling simulations suggested that Hg complexes by dissolved organic matter (DOM) dominated dissolved Hg (DHg) speciation, which was highly pH dependent. Hg concentrations and speciation were altered by cloud processing, during which significant positive correlations of PHg and MeHg with cloud droplet number concentration ( N d ) were observed. Unlike direct contribution to PHg from cloud scavenging of aerosol particles, abiotic DHg methylation was the most likely source of MeHg. Hg adsorption coefficients K ad (5.9-362.7 L g -1 ) exhibited an inverse-power relationship with cloud residues content. Morphology analyses indicated that compared to mineral particles, fly ash particles could enhance Hg adsorption due to more abundant carbon binding sites on the surface. Severe particulate air pollution in northern China may bring substantial Hg into cloud droplets and impact atmospheric Hg geochemical cycling by aerosol-cloud interactions.

Detailed Modelling of Kinetic Biodegradation Processes in a Laboratory Mmicrocosm

NASA Astrophysics Data System (ADS)

Watson, I.; Oswald, S.; Banwart, S.; Mayer, U.

2003-04-01

Biodegradation of organic contaminants in soil and groundwater usually takes places via different redox processes happening sequentially as well as simultaneously. We used numerical modelling of a long-term lab microcosm experiment to simulate the dynamic behaviour of fermentation and respiration in the aqueous phase in contact with the sandstone material, and to develop a conceptual model describing these processes. Aqueous speciation, surface complexation, mineral dissolution and precipitation were taken into account also. Fermentation can be the first step of the degradation process producing intermediate species, which are subsequently consumed by TEAPs. Microbial growth and substrate utilisation kinetics are coupled via a formulation that also includes aqueous speciation and other geochemical reactions including surface complexation, mineral dissolution and precipitation. Competitive exclusion between TEAPs is integral to the conceptual model of the simulation, and the results indicate that exclusion is not complete, but some overlap is found between TEAPs. The model was used to test approaches like the partial equilibrium approach that currently make use of hydrogen levels to diagnose prevalent TEAPs in groundwater. The observed pattern of hydrogen and acetate concentrations were reproduced well by the simulations, and the results show the relevance of kinetics, lag times and inhibition, and especially that intermediate products play a key role.

Numerical Experiments Based on the Catastrophe Model of Solar Eruptions

NASA Astrophysics Data System (ADS)

Xie, X. Y.; Ziegler, U.; Mei, Z. X.; Wu, N.; Lin, J.

2017-11-01

On the basis of the catastrophe model developed by Isenberg et al., we use the NIRVANA code to perform the magnetohydrodynamics (MHD) numerical experiments to look into various behaviors of the coronal magnetic configuration that includes a current-carrying flux rope used to model the prominence levitating in the corona. These behaviors include the evolution in equilibrium heights of the flux rope versus the change in the background magnetic field, the corresponding internal equilibrium of the flux rope, dynamic properties of the flux rope after the system loses equilibrium, as well as the impact of the referential radius on the equilibrium heights of the flux rope. In our calculations, an empirical model of the coronal density distribution given by Sittler & Guhathakurta is used, and the physical diffusion is included. Our experiments show that the deviation of simulations in the equilibrium heights from the theoretical results exists, but is not apparent, and the evolutionary features of the two results are similar. If the flux rope is initially locate at the stable branch of the theoretical equilibrium curve, the flux rope will quickly reach the equilibrium position in the simulation after several rounds of oscillations as a result of the self-adjustment of the system; and the flux rope lose the equilibrium if the initial location of the flux rope is set at the critical point on the theoretical equilibrium curve. Correspondingly, the internal equilibrium of the flux rope can be reached as well, and the deviation from the theoretical results is somewhat apparent since the approximation of the small radius of the flux rope is lifted in our experiments, but such deviation does not affect the global equilibrium in the system. The impact of the referential radius on the equilibrium heights of the flux rope is consistent with the prediction of the theory. Our calculations indicate that the motion of the flux rope after the loss of equilibrium is consistent with which is predicted by the Lin-Forbes model and observations. Formation of the fast mode shock ahead of the flux rope is observed in our experiments. Outward motions of the flux rope are smooth, and magnetic energy is continuously converted into the other types of energy because both the diffusions are considered in calculations, and magnetic reconnection is allowed to occur successively in the current sheet behind the flux rope.

Tearing Mode Stability of Evolving Toroidal Equilibria

NASA Astrophysics Data System (ADS)

Pletzer, A.; McCune, D.; Manickam, J.; Jardin, S. C.

2000-10-01

There are a number of toroidal equilibrium (such as JSOLVER, ESC, EFIT, and VMEC) and transport codes (such as TRANSP, BALDUR, and TSC) in our community that utilize differing equilibrium representations. There are also many heating and current drive (LSC and TORRAY), and stability (PEST1-3, GATO, NOVA, MARS, DCON, M3D) codes that require this equilibrium information. In an effort to provide seamless compatibility between the codes that produce and need these equilibria, we have developed two Fortran 90 modules, MEQ and XPLASMA, that serve as common interfaces between these two classes of codes. XPLASMA provides a common equilibrium representation for the heating and current drive applications while MEQ provides common equilibrium and associated metric information needed by MHD stability codes. We illustrate the utility of this approach by presenting results of PEST-3 tearing stability calculations of an NSTX discharge performed on profiles provided by the TRANSP code. Using the MEQ module, the TRANSP equilibrium data are stored in a Fortran 90 derived type and passed to PEST3 as a subroutine argument. All calculations are performed on the fly, as the profiles evolve.

The Hydrothermal Chemistry of Gold, Arsenic, Antimony, Mercury and Silver

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

Bessinger, Brad; Apps, John A.

2003-03-23

A comprehensive thermodynamic database based on the Helgeson-Kirkham-Flowers (HKF) equation of state was developed for metal complexes in hydrothermal systems. Because this equation of state has been shown to accurately predict standard partial molal thermodynamic properties of aqueous species at elevated temperatures and pressures, this study provides the necessary foundation for future exploration into transport and depositional processes in polymetallic ore deposits. The HKF equation of state parameters for gold, arsenic, antimony, mercury, and silver sulfide and hydroxide complexes were derived from experimental equilibrium constants using nonlinear regression calculations. In order to ensure that the resulting parameters were internally consistent,more » those experiments utilizing incompatible thermodynamic data were re-speciated prior to regression. Because new experimental studies were used to revise the HKF parameters for H2S0 and HS-1, those metal complexes for which HKF parameters had been previously derived were also updated. It was found that predicted thermodynamic properties of metal complexes are consistent with linear correlations between standard partial molal thermodynamic properties. This result allowed assessment of several complexes for which experimental data necessary to perform regression calculations was limited. Oxygen fugacity-temperature diagrams were calculated to illustrate how thermodynamic data improves our understanding of depositional processes. Predicted thermodynamic properties were used to investigate metal transport in Carlin-type gold deposits. Assuming a linear relationship between temperature and pressure, metals are predicted to predominantly be transported as sulfide complexes at a total aqueous sulfur concentration of 0.05 m. Also, the presence of arsenic and antimony mineral phases in the deposits are shown to restrict mineralization within a limited range of chemical conditions. Finally, at a lesser aqueous sulfur concentration of 0.01 m, host rock sulfidation can explain the origin of arsenic and antimony minerals within the paragenetic sequence.« less

Equilibrium time correlation functions and the dynamics of fluctuations

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

Luban, Marshall; Luscombe, James H.

1999-12-01

Equilibrium time correlation functions are of great importance because they probe the equilibrium dynamical response to external perturbations. We discuss the properties of time correlation functions for several systems that are simple enough to illustrate the calculational steps involved. The discussion underscores the need for avoiding language which misleadingly suggests that thermal equilibrium is associated with a quiescent or moribund state of the system. (c) 1999 American Association of Physics Teachers.

Equilibrium Droplets on Deformable Substrates: Equilibrium Conditions.

PubMed

Koursari, Nektaria; Ahmed, Gulraiz; Starov, Victor M

2018-05-15

Equilibrium conditions of droplets on deformable substrates are investigated, and it is proven using Jacobi's sufficient condition that the obtained solutions really provide equilibrium profiles of both the droplet and the deformed support. At the equilibrium, the excess free energy of the system should have a minimum value, which means that both necessary and sufficient conditions of the minimum should be fulfilled. Only in this case, the obtained profiles provide the minimum of the excess free energy. The necessary condition of the equilibrium means that the first variation of the excess free energy should vanish, and the second variation should be positive. Unfortunately, the mentioned two conditions are not the proof that the obtained profiles correspond to the minimum of the excess free energy and they could not be. It is necessary to check whether the sufficient condition of the equilibrium (Jacobi's condition) is satisfied. To the best of our knowledge Jacobi's condition has never been verified for any already published equilibrium profiles of both the droplet and the deformable substrate. A simple model of the equilibrium droplet on the deformable substrate is considered, and it is shown that the deduced profiles of the equilibrium droplet and deformable substrate satisfy the Jacobi's condition, that is, really provide the minimum to the excess free energy of the system. To simplify calculations, a simplified linear disjoining/conjoining pressure isotherm is adopted for the calculations. It is shown that both necessary and sufficient conditions for equilibrium are satisfied. For the first time, validity of the Jacobi's condition is verified. The latter proves that the developed model really provides (i) the minimum of the excess free energy of the system droplet/deformable substrate and (ii) equilibrium profiles of both the droplet and the deformable substrate.

Non-equilibrium dynamics from RPMD and CMD.

PubMed

Welsch, Ralph; Song, Kai; Shi, Qiang; Althorpe, Stuart C; Miller, Thomas F

2016-11-28

We investigate the calculation of approximate non-equilibrium quantum time correlation functions (TCFs) using two popular path-integral-based molecular dynamics methods, ring-polymer molecular dynamics (RPMD) and centroid molecular dynamics (CMD). It is shown that for the cases of a sudden vertical excitation and an initial momentum impulse, both RPMD and CMD yield non-equilibrium TCFs for linear operators that are exact for high temperatures, in the t = 0 limit, and for harmonic potentials; the subset of these conditions that are preserved for non-equilibrium TCFs of non-linear operators is also discussed. Furthermore, it is shown that for these non-equilibrium initial conditions, both methods retain the connection to Matsubara dynamics that has previously been established for equilibrium initial conditions. Comparison of non-equilibrium TCFs from RPMD and CMD to Matsubara dynamics at short times reveals the orders in time to which the methods agree. Specifically, for the position-autocorrelation function associated with sudden vertical excitation, RPMD and CMD agree with Matsubara dynamics up to O(t 4 ) and O(t 1 ), respectively; for the position-autocorrelation function associated with an initial momentum impulse, RPMD and CMD agree with Matsubara dynamics up to O(t 5 ) and O(t 2 ), respectively. Numerical tests using model potentials for a wide range of non-equilibrium initial conditions show that RPMD and CMD yield non-equilibrium TCFs with an accuracy that is comparable to that for equilibrium TCFs. RPMD is also used to investigate excited-state proton transfer in a system-bath model, and it is compared to numerically exact calculations performed using a recently developed version of the Liouville space hierarchical equation of motion approach; again, similar accuracy is observed for non-equilibrium and equilibrium initial conditions.

SPECIATE 4.3: Addendum to SPECIATE 4.2--Speciation database development documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

SPECIATE 4.0: SPECIATION DATABASE DEVELOPMENT DOCUMENTATION--FINAL REPORT

EPA Science Inventory

SPECIATE is the U.S. EPA's repository of total organic compounds (TOC) and particulate matter (PM) speciation profiles of air pollution sources. This report documents how EPA developed the SPECIATE 4.0 database that replaces the prior version, SPECIATE 3.2. SPECIATE 4.0 includes ...

Aqueous solubility calculation for petroleum mixtures in soil using comprehensive two-dimensional gas chromatography analysis data.

PubMed

Mao, Debin; Lookman, Richard; Van De Weghe, Hendrik; Vanermen, Guido; De Brucker, Nicole; Diels, Ludo

2009-04-03

An assessment of aqueous solubility (leaching potential) of soil contaminations with petroleum hydrocarbons (TPH) is important in the context of the evaluation of (migration) risks and soil/groundwater remediation. Field measurements using monitoring wells often overestimate real TPH concentrations in case of presence of pure oil in the screened interval of the well. This paper presents a method to calculate TPH equilibrium concentrations in groundwater using soil analysis by high-performance liquid chromatography followed by comprehensive two-dimensional gas chromatography (HPLC-GCXGC). The oil in the soil sample is divided into 79 defined hydrocarbon fractions on two GCXGC color plots. To each of these fractions a representative water solubility is assigned. Overall equilibrium water solubility of the non-aqueous phase liquid (NAPL) present in the sample and the water phase's chemical composition (in terms of the 79 fractions defined) are then calculated using Raoult's law. The calculation method was validated using soil spiked with 13 different TPH mixtures and 1 field-contaminated soil. Measured water solubilities using a column recirculation equilibration experiment agreed well to calculated equilibrium concentrations and water phase TPH composition.

Dust formation in LBV envelopes

NASA Astrophysics Data System (ADS)

Gail, H.-P.; Duschl, W. J.; Ferrarotti, A. S.; Weis, K.

2005-09-01

The condensation process for the peculiar element mixture of CNO cycle processed material in the pre-SN ejecta of massive stars is investigated. From thermodynamic equilibrium calculations it is shown that the most likely solids to be formed in CNO process equilibrated materials are solid FeSi, metallic Fe, and small quantities of forsterite (Mg2SiO4). Nucleation may be triggered by TiC. Some SiC may be formed by non-equilibrium condensation. As a case study for these substances the non-equilibrium dust condensation in the outflow is calculated for a simple stationary wind model which shows, that these dust species indeed can be formed in the ejecta.

Equilibrium of molybdenum in selected extraction systems

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

Tkac, Peter; Paulenova, Alena

2007-07-01

The concentration of molybdenum(VI) in dissolved irradiated nuclear fuel is comparable with the concentrations of Tc, Am and Np. Therefore it is of big interest to understand its behavior under conditions related to the UREX/TRUEX process. The effect of the poly-speciation of molybdenum in aqueous solution on its extraction by neutral solvents TBP and CMPO/TBP was studied. Extraction yields of molybdenum decreased significantly when AHA was added to aqueous phase. Our investigation confirmed a strong ability of the aceto-hydroxamic acid to form complexes with Mo in high acidic solutions. Spectroscopic data (UV-Vis) confirmed that a fraction of the Mo(VI)-AHA complexmore » is present in the organic phase after extraction. (authors)« less

Molecular simulations of Crussard curves of detonation product mixtures at chemical equilibrium: Microscopic calculation of the Chapman-Jouguet state

NASA Astrophysics Data System (ADS)

Bourasseau, Emeric; Dubois, Vincent; Desbiens, Nicolas; Maillet, Jean-Bernard

2007-06-01

The simultaneous use of the Reaction Ensemble Monte Carlo (ReMC) method and the Adaptative Erpenbeck EOS (AE-EOS) method allows us to calculate direclty the thermodynamical and chemical equilibrium of a mixture on the hugoniot curve. The ReMC method allow to reach chemical equilibrium of detonation products and the AE-EOS method constraints ths system to satisfy the Hugoniot relation. Once the Crussard curve of detonation products has been established, CJ state properties may be calculated. An additional NPT simulation is performed at CJ conditions in order to compute derivative thermodynamic quantities like Cp, Cv, Gruneisen gama, sound velocity, and compressibility factor. Several explosives has been studied, of which PETN, nitromethane, tetranitromethane, and hexanitroethane. In these first simulations, solid carbon is eventually treated using an EOS.

Austenite grain growth simulation considering the solute-drag effect and pinning effect

PubMed Central

Fujiyama, Naoto; Nishibata, Toshinobu; Seki, Akira; Hirata, Hiroyuki; Kojima, Kazuhiro; Ogawa, Kazuhiro

2017-01-01

Abstract The pinning effect is useful for restraining austenite grain growth in low alloy steel and improving heat affected zone toughness in welded joints. We propose a new calculation model for predicting austenite grain growth behavior. The model is mainly comprised of two theories: the solute-drag effect and the pinning effect of TiN precipitates. The calculation of the solute-drag effect is based on the hypothesis that the width of each austenite grain boundary is constant and that the element content maintains equilibrium segregation at the austenite grain boundaries. We used Hillert’s law under the assumption that the austenite grain boundary phase is a liquid so that we could estimate the equilibrium solute concentration at the austenite grain boundaries. The equilibrium solute concentration was calculated using the Thermo-Calc software. Pinning effect was estimated by Nishizawa’s equation. The calculated austenite grain growth at 1473–1673 K showed excellent correspondence with the experimental results. PMID:28179962

Modelling Equilibrium and Fractional Crystallization in the System MgO-FeO-CaO-Al2O3-SiO2

NASA Technical Reports Server (NTRS)

Herbert, F.

1985-01-01

A mathematical modelling technique for use in petrogenesis calculations in the system MgO-FeO-CaO-Al2O3-SiO2 is reported. Semiempirical phase boundary and elemental distribution information was combined with mass balance to compute approximate equilibrium crystallization paths for arbitrary system compositions. The calculation is applicable to a range of system compositions and fractionation calculations are possible. The goal of the calculation is the computation of the composition and quantity of each phase present as a function of the degree of solidification. The degree of solidification is parameterized by the heat released by the solidifying phases. The mathematical requirement for the solution of this problem is: (1) An equation constraining the composition of the magma for each solid phase in equilibrium with the liquidus phase, and (2) an equation for each solid phase and each component giving the distribution of that element between that phase and the magma.

Many-Body Spectral Functions from Steady State Density Functional Theory.

PubMed

Jacob, David; Kurth, Stefan

2018-03-14

We propose a scheme to extract the many-body spectral function of an interacting many-electron system from an equilibrium density functional theory (DFT) calculation. To this end we devise an ideal scanning tunneling microscope (STM) setup and employ the recently proposed steady-state DFT formalism (i-DFT) which allows one to calculate the steady current through a nanoscopic region coupled to two biased electrodes. In our setup, one of the electrodes serves as a probe ("STM tip"), which is weakly coupled to the system we want to measure. In the ideal STM limit of vanishing coupling to the tip, the system is restored to quasi-equilibrium and the normalized differential conductance yields the exact equilibrium many-body spectral function. Calculating this quantity from i-DFT, we derive an exact relation expressing the interacting spectral function in terms of the Kohn-Sham one. As illustrative examples, we apply our scheme to calculate the spectral functions of two nontrivial model systems, namely the single Anderson impurity model and the Constant Interaction Model.

Reconstruction of equilibrium trajectories during whole-body movements.

PubMed

Domen, K; Latash, M L; Zatsiorsky, V M

1999-03-01

The framework of the equilibrium-point hypothesis was used to reconstruct equilibrium trajectories (ETs) of the ankle, hip and body center of mass during quick voluntary hip flexions ('Japanese courtesy bow') by standing subjects. Different spring loads applied to the subject's back were used to introduce smooth perturbations that are necessary to reconstruct ETs based on a series of trials at the same task. Time patterns of muscle torques were calculated using inverse dynamics techniques. A second-order linear model was employed to calculate the instantaneous position of the spring-like joint or center of mass characteristic at different times during the movement. ETs of the joints and of the center of mass had significantly different shapes from the actual trajectories. Integral measures of electromyographic bursts of activity in postural muscles demonstrated a relation to muscle length corresponding to the equilibrium-point hypothesis.

A note on AB INITIO semiconductor band structures

NASA Astrophysics Data System (ADS)

Fiorentini, Vincenzo

1992-09-01

We point out that only the internal features of the DFT ab initio theoretical picture of a crystal should be used in a consistent ab initio calculation of the band structure. As a consequence, we show that ground-state band structure calculations should be performed for the system in equilibrium at zero pressure, i.e. at the computed equilibrium cell volume ω th. Examples of consequences of this attitude are considered.

Application of cause-and-effect analysis to potentiometric titration.

PubMed

Kufelnicki, A; Lis, S; Meinrath, G

2005-08-01

A first attempt has been made to interpret physicochemical data from potentiometric titration analysis in accordance with the complete measurement-uncertainty budget approach (bottom-up) of ISO and Eurachem. A cause-and-effect diagram is established and discussed. Titration data for arsenazo III are used as a basis for this discussion. The commercial software Superquad is used and applied within a computer-intensive resampling framework. The cause-and-effect diagram is applied to evaluation of seven protonation constants of arsenazo III in the pH range 2-10.7. The data interpretation is based on empirical probability distributions and their analysis by second-order correct confidence estimates. The evaluated data are applied in the calculation of a speciation diagram including uncertainty estimates using the probabilistic speciation software Ljungskile.

A world-wide perspective on crucifer speciation and evolution: phylogenetics, biogeography and trait evolution in tribe Arabideae

PubMed Central

Karl, Robert; Koch, Marcus A.

2013-01-01

Background and Aims Tribe Arabideae are the most species-rich monophyletic lineage in Brassicaceae. More than 500 species are distributed in the majority of mountain and alpine regions worldwide. This study provides the first comprehensive phylogenetic analysis for the species assemblage and tests for association of trait and characters, providing the first explanations for the enormous species radiation since the mid Miocene. Methods Phylogenetic analyses of DNA sequence variation of nuclear encoded loci and plastid DNA are used to unravel a reliable phylogenetic tree. Trait and ancestral area reconstructions were performed and lineage-specific diversification rates were calculated to explain various radiations in the last 15 Myr in space and time. Key Results A well-resolved phylogenetic tree demonstrates the paraphyly of the genus Arabis and a new systematic concept is established. Initially, multiple radiations involved a split between lowland annuals and mountain/alpine perennial sister species. Subsequently, increased speciation rates occur in the perennial lineages. The centre of origin of tribe Arabideae is most likely the Irano-Turanian region from which the various clades colonized the temperate mountain and alpine regions of the world. Conclusions Mid Miocene early diversification started with increased speciation rates due to the emergence of various annual lineages. Subsequent radiations were mostly driven by diversification within perennial species during the Pliocene, but increased speciation rates also occurred during that epoch. Taxonomic concepts in Arabis are still in need of a major taxonomic revision to define monophyletic groups. PMID:23904444

Monoterpene chemical speciation in a tropical rainforest:variation with season, height, and time of dayat the Amazon Tall Tower Observatory (ATTO)

NASA Astrophysics Data System (ADS)

María Yáñez-Serrano, Ana; Nölscher, Anke Christine; Bourtsoukidis, Efstratios; Gomes Alves, Eliane; Ganzeveld, Laurens; Bonn, Boris; Wolff, Stefan; Sa, Marta; Yamasoe, Marcia; Williams, Jonathan; Andreae, Meinrat O.; Kesselmeier, Jürgen

2018-03-01

Speciated monoterpene measurements in rainforest air are scarce, but they are essential for understanding the contribution of these compounds to the overall reactivity of volatile organic compound (VOC) emissions towards the main atmospheric oxidants, such as hydroxyl radicals (OH), ozone (O3) and nitrate radicals (NO3). In this study, we present the chemical speciation of gas-phase monoterpenes measured in the tropical rainforest at the Amazon Tall Tower Observatory (ATTO, Amazonas, Brazil). Samples of VOCs were collected by two automated sampling systems positioned on a tower at 12 and 24 m height and analysed using gas chromatography-flame ionization detection. The samples were collected in October 2015, representing the dry season, and compared with previous wet and dry season studies at the site. In addition, vertical profile measurements (at 12 and 24 m) of total monoterpene mixing ratios were made using proton-transfer-reaction mass spectrometry. The results showed a distinctly different chemical speciation between day and night. For instance, α-pinene was more abundant during the day, whereas limonene was more abundant at night. Reactivity calculations showed that higher abundance does not generally imply higher reactivity. Furthermore, inter- and intra-annual results demonstrate similar chemodiversity during the dry seasons analysed. Simulations with a canopy exchange modelling system show simulated monoterpene mixing ratios that compare relatively well with the observed mixing ratios but also indicate the necessity of more experiments to enhance our understanding of in-canopy sinks of these compounds.

The Role of microRNAs in the Repeated Parallel Diversification of Lineages of Midas Cichlid Fish from Nicaragua

PubMed Central

Franchini, Paolo; Xiong, Peiwen; Fruciano, Carmelo; Meyer, Axel

2016-01-01

Cichlid fishes are an ideal model system for studying biological diversification because they provide textbook examples of rapid speciation. To date, there has been little focus on the role of gene regulation during cichlid speciation. However, in recent years, gene regulation has been recognized as a powerful force linking diversification in gene function to speciation. Here, we investigated the potential role of miRNA regulation in the diversification of six cichlid species of the Midas cichlid lineage (Amphilophus spp.) inhabiting the Nicaraguan crater lakes. Using several genomic resources, we inferred 236 Midas miRNA genes that were used to predict the miRNA target sites on 8,232 Midas 3′-UTRs. Using population genomic calculations of SNP diversity, we found the miRNA genes to be more conserved than protein coding genes. In contrast to what has been observed in other cichlid fish, but similar to what has been typically found in other groups, we observed genomic signatures of purifying selection on the miRNA targets by comparing these sites with the less conserved nontarget portion of the 3′-UTRs. However, in one species pair that has putatively speciated sympatrically in crater Lake Apoyo, we recovered a different pattern of relaxed purifying selection and high genetic divergence at miRNA targets. Our results suggest that sequence evolution at miRNA binding sites could be a critical genomic mechanism contributing to the rapid phenotypic evolution of Midas cichlids. PMID:27189980

Orbital stability close to asteroid 624 Hektor using the polyhedral model

NASA Astrophysics Data System (ADS)

Jiang, Yu; Baoyin, Hexi; Li, Hengnian

2018-03-01

We investigate the orbital stability close to the unique L4-point Jupiter binary Trojan asteroid 624 Hektor. The gravitational potential of 624 Hektor is calculated using the polyhedron model with observational data of 2038 faces and 1021 vertexes. Previous studies have presented three different density values for 624 Hektor. The equilibrium points in the gravitational potential of 624 Hektor with different density values have been studied in detail. There are five equilibrium points in the gravitational potential of 624 Hektor no matter the density value. The positions, Jacobian, eigenvalues, topological cases, stability, as well as the Hessian matrix of the equilibrium points are investigated. For the three different density values the number, topological cases, and the stability of the equilibrium points with different density values are the same. However, the positions of the equilibrium points vary with the density value of the asteroid 624 Hektor. The outer equilibrium points move away from the asteroid's mass center when the density increases, and the inner equilibrium point moves close to the asteroid's mass center when the density increases. There exist unstable periodic orbits near the surface of 624 Hektor. We calculated an orbit near the primary's equatorial plane of this binary Trojan asteroid; the results indicate that the orbit remains stable after 28.8375 d.

Calculations of Excitation Functions of Some Structural Fusion Materials for ( n, t) Reactions up to 50 MeV Energy

NASA Astrophysics Data System (ADS)

Tel, E.; Durgu, C.; Aktı, N. N.; Okuducu, Ş.

2010-06-01

Fusion serves an inexhaustible energy for humankind. Although there have been significant research and development studies on the inertial and magnetic fusion reactor technology, there is still a long way to go to penetrate commercial fusion reactors to the energy market. Tritium self-sufficiency must be maintained for a commercial power plant. For self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. So, the working out the systematics of ( n, t) reaction cross sections is of great importance for the definition of the excitation function character for the given reaction taking place on various nuclei at different energies. In this study, ( n, t) reactions for some structural fusion materials such as 27Al, 51V, 52Cr, 55Mn, and 56Fe have been investigated. The new calculations on the excitation functions of 27Al( n, t)25Mg, 51V( n, t)49Ti, 52Cr( n, t)50V, 55Mn( n, t)53Cr and 56Fe( n, t)54Mn reactions have been carried out up to 50 MeV incident neutron energy. In these calculations, the pre-equilibrium and equilibrium effects have been investigated. The pre-equilibrium calculations involve the new evaluated the geometry dependent hybrid model, hybrid model and the cascade exciton model. Equilibrium effects are calculated according to the Weisskopf-Ewing model. Also in the present work, we have calculated ( n, t) reaction cross-sections by using new evaluated semi-empirical formulas developed by Tel et al. at 14-15 MeV energy. The calculated results are discussed and compared with the experimental data taken from the literature.

SPECIATE and using the Speciation Tool to prepare VOC and PM chemical speciation profiles for air quality modeling

EPA Science Inventory

This product provides training to air pollution inventory and modeling professionals to understand the US EPA's SPECIATE database base and Speciation Tool and their use to develop speciated emission inventories.

SPECIATE's VOC and PM Speciation Profiles and Their use to Prepare for Air quality Modeling (2017 EIC)

EPA Pesticide Factsheets

This training provides general concepts on chemical speciation, the SPECIATE database and browser, and how to use the Speciation Tool to create model ready speciation inputs for a photochemical air quality model.

SPECIATE 4.2: speciation Database Development Documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

An unexpectedly long history of sexual selection in birds-of-paradise

PubMed Central

Irestedt, Martin; Jønsson, Knud A; Fjeldså, Jon; Christidis, Les; Ericson, Per GP

2009-01-01

Background The birds-of-paradise (Paradisaeidae) form one of the most prominent avian examples of sexual selection and show a complex biogeographical distribution. The family has accordingly been used as a case-study in several significant evolutionary and biogeographical syntheses. As a robust phylogeny of the birds-of-paradise has been lacking, these hypotheses have been tentative and difficult to assess. Here we present a well supported species phylogeny with divergence time estimates of the birds-of-paradise. We use this to assess if the rates of the evolution of sexually selected traits and speciation have been excessively high within the birds-of-paradise, as well as to re-interpret biogeographical patterns in the group. Results The phylogenetic results confirm some traditionally recognized relationships but also suggest novel ones. Furthermore, we find that species pairs are geographically more closely linked than previously assumed. The divergence time estimates suggest that speciation within the birds-of-paradise mainly took place during the Miocene and the Pliocene, and that several polygynous and morphologically homogeneous genera are several million years old. Diversification rates further suggest that the speciation rate within birds-of-paradise is comparable to that of the enitre core Corvoidea. Conclusion The estimated ages of morphologically homogeneous and polygynous genera within the birds-of-paradise suggest that there is no need to postulate a particularly rapid evolution of sexually selected morphological traits. The calculated divergence rates further suggest that the speciation rate in birds-of-paradise has not been excessively high. Thus the idea that sexual selection could generate high speciation rates and rapid changes in sexual ornamentations is not supported by our birds-of-paradise data. Potentially, hybridization and long generation times in polygynous male birds-of-paradise have constrained morphological diversification and speciation, but external ecological factors on New Guinea may also have allowed the birds-of-paradise to develop and maintain magnificent male plumages. We further propose that the restricted but geographically complex distributions of birds-of-paradise species may be a consequence of the promiscuous breeding system. PMID:19758445

Temperature-Dependent Estimation of Gibbs Energies Using an Updated Group-Contribution Method.

PubMed

Du, Bin; Zhang, Zhen; Grubner, Sharon; Yurkovich, James T; Palsson, Bernhard O; Zielinski, Daniel C

2018-06-05

Reaction-equilibrium constants determine the metabolite concentrations necessary to drive flux through metabolic pathways. Group-contribution methods offer a way to estimate reaction-equilibrium constants at wide coverage across the metabolic network. Here, we present an updated group-contribution method with 1) additional curated thermodynamic data used in fitting and 2) capabilities to calculate equilibrium constants as a function of temperature. We first collected and curated aqueous thermodynamic data, including reaction-equilibrium constants, enthalpies of reaction, Gibbs free energies of formation, enthalpies of formation, entropy changes of formation of compounds, and proton- and metal-ion-binding constants. Next, we formulated the calculation of equilibrium constants as a function of temperature and calculated the standard entropy change of formation (Δ f S ∘ ) using a model based on molecular properties. The median absolute error in estimating Δ f S ∘ was 0.013 kJ/K/mol. We also estimated magnesium binding constants for 618 compounds using a linear regression model validated against measured data. We demonstrate the improved performance of the current method (8.17 kJ/mol in median absolute residual) over the current state-of-the-art method (11.47 kJ/mol) in estimating the 185 new reactions added in this work. The efforts here fill in gaps for thermodynamic calculations under various conditions, specifically different temperatures and metal-ion concentrations. These, to our knowledge, new capabilities empower the study of thermodynamic driving forces underlying the metabolic function of organisms living under diverse conditions. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

40 CFR Appendix Xvii to Part 86 - Procedure for Determining Vehicle Emission Control Technology Category/Fuel Reactivity Adjustment...

Code of Federal Regulations, 2011 CFR

2011-07-01

... profiles shall be obtained from a statistically valid number of TLEVs, LEVs, and ULEVs. (3) The speciated... methanol or liquefied petroleum gas, the quotient calculated above shall be multiplied by 1.1. The resulting value shall constitute the “reactivity adjustment factor” for the methanol or liquefied petroleum...

40 CFR Appendix Xvii to Part 86 - Procedure for Determining Vehicle Emission Control Technology Category/Fuel Reactivity Adjustment...

Code of Federal Regulations, 2010 CFR

2010-07-01

... profiles shall be obtained from a statistically valid number of TLEVs, LEVs, and ULEVs. (3) The speciated... methanol or liquefied petroleum gas, the quotient calculated above shall be multiplied by 1.1. The resulting value shall constitute the “reactivity adjustment factor” for the methanol or liquefied petroleum...

Quantification of metabotropic glutamate subtype 5 receptors in the brain by an equilibrium method using 18F-SP203.

PubMed

Kimura, Yasuyuki; Siméon, Fabrice G; Zoghbi, Sami S; Zhang, Yi; Hatazawa, Jun; Pike, Victor W; Innis, Robert B; Fujita, Masahiro

2012-02-01

A new PET ligand, 3-fluoro-5-(2-(2-(18)F-(fluoromethyl)-thiazol-4-yl)ethynyl)benzonitrile (18F-SP203) can quantify metabotropic glutamate subtype 5 receptors (mGluR5) in human brain by a bolus injection and kinetic modeling. As an alternative approach to a bolus injection, binding can simply be measured as a ratio of tissue to metabolite-corrected plasma at a single time point under equilibrium conditions achieved by administering the radioligand with a bolus injection followed by a constant infusion. The purpose of this study was to validate the equilibrium method as an alternative to the standard kinetic method for measuring 18F-SP203 binding in the brain. Nine healthy subjects were injected with 18F-SP203 using a bolus plus constant infusion for 300 min. A single ratio of bolus-to-constant infusion (the activity of bolus equaled to that of infusion over 219 min) was applied to all subjects to achieve equilibrium in approximately 120 min. As a measure of ligand binding, we compared total distribution volume (VT) calculated by the equilibrium and kinetic methods in each scan. The equilibrium method calculated VT by the ratio of radioactivity in the brain to the concentration of 18F-SP203 in arterial plasma at 120 min, and the kinetic method calculated VT by a two-tissue compartment model using brain and plasma dynamic data from 0 to 120 min. VT obtained via the equilibrium method was highly correlated with VT obtained via kinetic modeling. Inter-subject variability of VT obtained via the equilibrium method was slightly smaller than VT obtained via the kinetic method. VT obtained via the equilibrium method was ~10% higher than VT obtained via the kinetic method, indicating a small difference between the measurements. Taken together, the results of this study show that using the equilibrium method is an acceptable alternative to the standard kinetic method when using 18F-SP203 to measure mGluR5. Although small differences in the measurements obtained via the equilibrium and kinetic methods exist, both methods consistently measured mGluR5 as indicated by the highly correlated VT values; the equilibrium method was slightly more precise, as indirectly measured by the smaller coefficient of variability across subjects. In addition, when using 18F-SP203, the equilibrium method is more efficient because it requires much less data. Copyright © 2011. Published by Elsevier Inc.

Effects of sorbate speciation on sorption of selected sulfonamides in three loamy soils

USGS Publications Warehouse

Kurwadkar , Sudarshan T.; Adams, Craig D.; Meyer, Michael T.; Kolpin, Dana W.

2007-01-01

Sorption of sulfamethazine (SMN) and sulfathiazole (STZ) was investigated in three soils, a North Carolina loamy sand, an Iowa sandy loam, and a Missouri loam, under various pH conditions. A significant increase in the sorption coefficient (KD) was observed in all three soils, as the sulfonamides converted from an anionic form at higher pH to a neutral/cationic form at lower pH. Above pH 7.5, sulfonamides exist primarily in anionic form and have higher aqueous solubility and no cationic character, thereby consequently leading to lower sorption to soils. The effect of speciation on sorption is not the same for all sulfonamides; it is a function of the pH of the soil and the pKa of the sulfonamides. The results indicate that, for the soils under investigation, SMN has comparatively lower KD values than STZ. The pH-dependent sorption of sulfonamides was observed to be consistent in all three soils investigated. The KD values for each speciated formcationic, neutral, and anionicwere calculated using an empirical model in which the species-specific sorption coefficients (KD0, KD1, and KD2) were weighted with their respective fractions present at any given pH.

One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A Reactive Transport Model for Streams and Rivers

USGS Publications Warehouse

Runkel, Robert L.

2010-01-01

OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (waterborne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at http://water.usgs.gov/software/OTEQ.

Finite-Difference Solution for Laminar or Turbulent Boundary Layer Flow over Axisymmetric Bodies with Ideal Gas, CF4, or Equilibrium Air Chemistry

NASA Technical Reports Server (NTRS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-01-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Finite-difference solution for laminar or turbulent boundary layer flow over axisymmetric bodies with ideal gas, CF4, or equilibrium air chemistry

NASA Astrophysics Data System (ADS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-12-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Equilibrium Spline Interface (ESI) for magnetic confinement codes

NASA Astrophysics Data System (ADS)

Li, Xujing; Zakharov, Leonid E.

2017-12-01

A compact and comprehensive interface between magneto-hydrodynamic (MHD) equilibrium codes and gyro-kinetic, particle orbit, MHD stability, and transport codes is presented. Its irreducible set of equilibrium data consists of three (in the 2-D case with occasionally one extra in the 3-D case) functions of coordinates and four 1-D radial profiles together with their first and mixed derivatives. The C reconstruction routines, accessible also from FORTRAN, allow the calculation of basis functions and their first derivatives at any position inside the plasma and in its vicinity. After this all vector fields and geometric coefficients, required for the above mentioned types of codes, can be calculated using only algebraic operations with no further interpolation or differentiation.

First-principles atomistic Wulff constructions for an equilibrium rutile TiO2 shape modeling

NASA Astrophysics Data System (ADS)

Jiang, Fengzhou; Yang, Lei; Zhou, Dali; He, Gang; Zhou, Jiabei; Wang, Fanhou; Chen, Zhi-Gang

2018-04-01

Identifying the exposed surfaces of rutile TiO2 crystal is crucial for its industry application and surface engineering. In this study, the shape of the rutile TiO2 was constructed by applying equilibrium thermodynamics of TiO2 crystals via first-principles density functional theory (DFT) and Wulff principles. From the DFT calculations, the surface energies of six low-index stoichiometric facets of TiO2 are determined after the calibrations of crystal structure. And then, combined surface energy calculations and Wulff principles, a geometric model of equilibrium rutile TiO2 is built up, which is coherent with the typical morphology of fully-developed equilibrium TiO2 crystal. This study provides fundamental theoretical guidance for the surface analysis and surface modification of the rutile TiO2-based materials from experimental research to industry manufacturing.

Grain formation in astronomical systems: A critical review of condensation processes

NASA Technical Reports Server (NTRS)

Donn, B.

1978-01-01

An analysis is presented of the assumption and the applicability of the three theoretical methods for calculating condensations in cosmic clouds where no pre-existing nuclei exist. The three procedures are: thermodynamic equilibrium calculations, nucleation theory, and a kinetic treatment which would take into account the characteristics of each individual collision. Thermodynamics provide detailed results on the composition temperature and composition of the condensate provided the system attains equilibrium. Because of the cosmic abundance mixture of elements, large supersaturations in some cases and low pressures, equilibrium is not expected in astronomical clouds. Nucleation theory, a combination of thermodynamics and kinetics, has the limitations of each scheme. Kinetics, not requiring equilibrium, avoids nearly all the thermodynamics difficulties but requires detailed knowledge of many reactions which thermodynamics avoids. It appears to be the only valid way to treat grain formation in space. A review of experimental studies is given.

A new method of calculating electrical conductivity with applications to natural waters

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ryan, Joseph N.; Ball, James W.

2012-01-01

A new method is presented for calculating the electrical conductivity of natural waters that is accurate over a large range of effective ionic strength (0.0004–0.7 mol kg-1), temperature (0–95 °C), pH (1–10), and conductivity (30–70,000 μS cm-1). The method incorporates a reliable set of equations to calculate the ionic molal conductivities of cations and anions (H+, Li+, Na+, K+, Cs+, NH4+, Mg2+, Ca2+, Sr2+, Ba2+, F-, Cl-, Br-, SO42-, HCO3-, CO32-, NO3-, and OH-), environmentally important trace metals (Al3+, Cu2+, Fe2+, Fe3+, Mn2+, and Zn2+), and ion pairs (HSO4-, NaSO4-, NaCO3-, and KSO4-). These equations are based on new electrical conductivity measurements for electrolytes found in a wide range of natural waters. In addition, the method is coupled to a geochemical speciation model that is used to calculate the speciated concentrations required for accurate conductivity calculations. The method was thoroughly tested by calculating the conductivities of 1593 natural water samples and the mean difference between the calculated and measured conductivities was -0.7 ± 5%. Many of the samples tested were selected to determine the limits of the method and include acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water impacted by municipal waste water. Transport numbers were calculated and H+, Na+, Ca2+, Mg2+, NH4+, K+, Cl-, SO42-, HCO3-, CO32-, F-, Al3+, Fe2+, NO3-, and HSO4- substantially contributed (>10%) to the conductivity of at least one of the samples. Conductivity imbalance in conjunction with charge imbalance can be used to identify whether a cation or an anion measurement is likely in error, thereby providing an additional quality assurance/quality control constraint on water analyses.

A new method of calculating electrical conductivity with applications to natural waters

NASA Astrophysics Data System (ADS)

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ryan, Joseph N.; Ball, James W.

2012-01-01

A new method is presented for calculating the electrical conductivity of natural waters that is accurate over a large range of effective ionic strength (0.0004-0.7 mol kg-1), temperature (0-95 °C), pH (1-10), and conductivity (30-70,000 μS cm-1). The method incorporates a reliable set of equations to calculate the ionic molal conductivities of cations and anions (H+, Li+, Na+, K+, Cs+, NH4+, Mg2+, Ca2+, Sr2+, Ba2+, F-, Cl-, Br-, SO42-, HCO3-, CO32-, NO3-, and OH-), environmentally important trace metals (Al3+, Cu2+, Fe2+, Fe3+, Mn2+, and Zn2+), and ion pairs (HSO4-, NaSO4-, NaCO3-, and KSO4-). These equations are based on new electrical conductivity measurements for electrolytes found in a wide range of natural waters. In addition, the method is coupled to a geochemical speciation model that is used to calculate the speciated concentrations required for accurate conductivity calculations. The method was thoroughly tested by calculating the conductivities of 1593 natural water samples and the mean difference between the calculated and measured conductivities was -0.7 ± 5%. Many of the samples tested were selected to determine the limits of the method and include acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water impacted by municipal waste water. Transport numbers were calculated and H+, Na+, Ca2+, Mg2+, NH4+, K+, Cl-, SO42-, HCO3-, CO32-, F-, Al3+, Fe2+, NO3-, and HSO4-substantially contributed (>10%) to the conductivity of at least one of the samples. Conductivity imbalance in conjunction with charge imbalance can be used to identify whether a cation or an anion measurement is likely in error, thereby providing an additional quality assurance/quality control constraint on water analyses.

Nucleon matter equation of state, particle number fluctuations, and shear viscosity within UrQMD box calculations

NASA Astrophysics Data System (ADS)

Motornenko, A.; Bravina, L.; Gorenstein, M. I.; Magner, A. G.; Zabrodin, E.

2018-03-01

Properties of equilibrated nucleon system are studied within the ultra-relativistic quantum molecular dynamics (UrQMD) transport model. The UrQMD calculations are done within a finite box with periodic boundary conditions. The system achieves thermal equilibrium due to nucleon-nucleon elastic scattering. For the UrQMD-equilibrium state, nucleon energy spectra, equation of state, particle number fluctuations, and shear viscosity η are calculated. The UrQMD results are compared with both, statistical mechanics and Chapman-Enskog kinetic theory, for a classical system of nucleons with hard-core repulsion.

Quantum statistical mechanics of dense partially ionized hydrogen

NASA Technical Reports Server (NTRS)

Dewitt, H. E.; Rogers, F. J.

1972-01-01

The theory of dense hydrogen plasmas beginning with the two component quantum grand partition function is reviewed. It is shown that ionization equilibrium and molecular dissociation equilibrium can be treated in the same manner with proper consideration of all two-body states. A quantum perturbation expansion is used to give an accurate calculation of the equation of state of the gas for any degree of dissociation and ionization. The statistical mechanical calculation of the plasma equation of state is intended for stellar interiors. The general approach is extended to the calculation of the equation of state of the outer layers of large planets.

Group Contribution Methods for Phase Equilibrium Calculations.

PubMed

Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

2015-01-01

The development and design of chemical processes are carried out by solving the balance equations of a mathematical model for sections of or the whole chemical plant with the help of process simulators. For process simulation, besides kinetic data for the chemical reaction, various pure component and mixture properties are required. Because of the great importance of separation processes for a chemical plant in particular, a reliable knowledge of the phase equilibrium behavior is required. The phase equilibrium behavior can be calculated with the help of modern equations of state or g(E)-models using only binary parameters. But unfortunately, only a very small part of the experimental data for fitting the required binary model parameters is available, so very often these models cannot be applied directly. To solve this problem, powerful predictive thermodynamic models have been developed. Group contribution methods allow the prediction of the required phase equilibrium data using only a limited number of group interaction parameters. A prerequisite for fitting the required group interaction parameters is a comprehensive database. That is why for the development of powerful group contribution methods almost all published pure component properties, phase equilibrium data, excess properties, etc., were stored in computerized form in the Dortmund Data Bank. In this review, the present status, weaknesses, advantages and disadvantages, possible applications, and typical results of the different group contribution methods for the calculation of phase equilibria are presented.

NMVOCs speciated emissions from mobile sources and their effect on air quality and human health in the metropolitan area of Buenos Aires, Argentina

NASA Astrophysics Data System (ADS)

D'Angiola, Ariela; Dawidowski, Laura; Gomez, Dario; Granier, Claire

2014-05-01

Since 2007, more than half of the world's population live in urban areas. Urban atmospheres are dominated by pollutants associated with vehicular emissions. Transport emissions are an important source of non-methane volatile organic compounds (NMVOCs) emissions, species of high interest because of their negative health effects and their contribution to the formation of secondary pollutants responsible for photochemical smog. NMVOCs emissions are generally not very well represented in emission inventories and their speciation presents a high level of uncertainty. In general, emissions from South American countries are still quite unknown for the international community, and usually present a high degree of uncertainty due to the lack of available data to compile emission inventories. Within the Inter-American Institute for Global Change Research (IAI, www.iai.int) projects, UMESAM (Urban Mobile Emissions in South American Megacities) and SAEMC (South American Emissions, Megacities and Climate, http://saemc.cmm.uchile.cl/), the effort was made to compute on-road transport emission inventories for South American megacities, namely Bogota, Buenos Aires, Lima, Sao Paulo and Santiago de Chile, considering megacities as urban agglomerations with more than 5 million inhabitants. The present work is a continuation of these projects, with the aim to extend the calculated NMVOCs emissions inventory into the individual species required by CTMs. The on-road mobile sector of the metropolitan area of Buenos Aires (MABA), Argentina, accounted for 70 Gg of NMVOCs emissions for 2006, without considering two-wheelers. Gasoline light-duty vehicles were responsible for 64% of NMVOCs emissions, followed by compressed natural gas (CNG) light-duty vehicles (22%), diesel heavy-duty vehicles (11%) and diesel light-duty vehicles (7%). NMVOCs emissions were speciated according to fuel and technology, employing the European COPERT (Ntziachristos & Samaras, 2000) VOCs speciation scheme for gasoline and diesel vehicles and the USEPA SPECIATE (Simon et al., 2010) profile for CNG vehicles. NMVOCs emissions were composed of 31% aromatic compounds, 29% linear alkanes, 20% olefins, 12% ramified alkanes, 7% aldehydes and negligible contributions from cycloalkanes, ketones, Polycyclic Aromatic Hydrocarbons (PAHs) and other NMVOCs. Aromatic compounds dominated gasoline light-duty vehicles' emissions (~45%), while linear alkanes those of CNG light-duty vehicles (~80%). Aldehydes' contributions increased for diesel light and heavy-duty vehicles. VOCs speciation schemes for transport emissions were collected from the literature from Europe, USA, Asia, Oceania and Latin America with the aim to account for the associated uncertainty by compound for each fuel and technology type. The resulting individual NMVOCs emissions were used to calculate the corresponding tropospheric ozone formation (Carter, 1994), as well as the human toxicity potential in terms of 1.4 dichlorobenzene. Olefins and aromatic compounds in terms of species, and gasoline in terms of fuels, were found to impose the highest risk in urban environments regarding air quality and human health.

Solubility limits in quaternary SnTe-based alloys [Metastability and solubility limits in quaternary SnTe-based alloys guided by combinatorial sputtering

DOE PAGES

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.; ...

2017-05-09

Here, the controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn 1–yMnyTe 1–xSe x phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y < 0.05 that are in good agreement with results obtained from bulk equilibrium synthesis experiments andmore » predict significantly higher spinodal limits. An experimental screening using sputtered combinatorial thin film sample libraries showed a remarkable increase in non-equilibrium solubility for x,y > 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn 1–yMn yTe 1–xSe x indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.« less

Calculation of a double reactive azeotrope using stochastic optimization approaches

NASA Astrophysics Data System (ADS)

Mendes Platt, Gustavo; Pinheiro Domingos, Roberto; Oliveira de Andrade, Matheus

2013-02-01

An homogeneous reactive azeotrope is a thermodynamic coexistence condition of two phases under chemical and phase equilibrium, where compositions of both phases (in the Ung-Doherty sense) are equal. This kind of nonlinear phenomenon arises from real world situations and has applications in chemical and petrochemical industries. The modeling of reactive azeotrope calculation is represented by a nonlinear algebraic system with phase equilibrium, chemical equilibrium and azeotropy equations. This nonlinear system can exhibit more than one solution, corresponding to a double reactive azeotrope. The robust calculation of reactive azeotropes can be conducted by several approaches, such as interval-Newton/generalized bisection algorithms and hybrid stochastic-deterministic frameworks. In this paper, we investigate the numerical aspects of the calculation of reactive azeotropes using two metaheuristics: the Luus-Jaakola adaptive random search and the Firefly algorithm. Moreover, we present results for a system (with industrial interest) with more than one azeotrope, the system isobutene/methanol/methyl-tert-butyl-ether (MTBE). We present convergence patterns for both algorithms, illustrating - in a bidimensional subdomain - the identification of reactive azeotropes. A strategy for calculation of multiple roots in nonlinear systems is also applied. The results indicate that both algorithms are suitable and robust when applied to reactive azeotrope calculations for this "challenging" nonlinear system.

Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium

NASA Technical Reports Server (NTRS)

Hunt, J. L.; Boney, L. R.

1973-01-01

Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.

Equilibrium Phase Behavior of the Square-Well Linear Microphase-Forming Model.

PubMed

Zhuang, Yuan; Charbonneau, Patrick

2016-07-07

We have recently developed a simulation approach to calculate the equilibrium phase diagram of particle-based microphase formers. Here, this approach is used to calculate the phase behavior of the square-well linear model for different strengths and ranges of the linear long-range repulsive component. The results are compared with various theoretical predictions for microphase formation. The analysis further allows us to better understand the mechanism for microphase formation in colloidal suspensions.

User's guide for vectorized code EQUIL for calculating equilibrium chemistry on Control Data STAR-100 computer

NASA Technical Reports Server (NTRS)

Kumar, A.; Graves, R. A., Jr.; Weilmuenster, K. J.

1980-01-01

A vectorized code, EQUIL, was developed for calculating the equilibrium chemistry of a reacting gas mixture on the Control Data STAR-100 computer. The code provides species mole fractions, mass fractions, and thermodynamic and transport properties of the mixture for given temperature, pressure, and elemental mass fractions. The code is set up for the electrons H, He, C, O, N system of elements. In all, 24 chemical species are included.

"Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

PubMed

Nagarajan, Ramanathan

2015-07-01

Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to obtain different micelle sizes for the same block copolymer, by the choices we can make of the common solvent and the mode of solvent substitution. Published by Elsevier Inc.

The NATA code: Theory and analysis, volume 1. [user manuals (computer programming) - gas dynamics, wind tunnels

NASA Technical Reports Server (NTRS)

Bade, W. L.; Yos, J. M.

1975-01-01

A computer program for calculating quasi-one-dimensional gas flow in axisymmetric and two-dimensional nozzles and rectangular channels is presented. Flow is assumed to start from a state of thermochemical equilibrium at a high temperature in an upstream reservoir. The program provides solutions based on frozen chemistry, chemical equilibrium, and nonequilibrium flow with finite reaction rates. Electronic nonequilibrium effects can be included using a two-temperature model. An approximate laminar boundary layer calculation is given for the shear and heat flux on the nozzle wall. Boundary layer displacement effects on the inviscid flow are considered also. Chemical equilibrium and transport property calculations are provided by subroutines. The code contains precoded thermochemical, chemical kinetic, and transport cross section data for high-temperature air, CO2-N2-Ar mixtures, helium, and argon. It provides calculations of the stagnation conditions on axisymmetric or two-dimensional models, and of the conditions on the flat surface of a blunt wedge. The primary purpose of the code is to describe the flow conditions and test conditions in electric arc heated wind tunnels.

Combining MOSCED with molecular simulation free energy calculations or electronic structure calculations to develop an efficient tool for solvent formulation and selection

NASA Astrophysics Data System (ADS)

Cox, Courtney E.; Phifer, Jeremy R.; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T.; O'Loughlin, Elizabeth J.; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T.; Paluch, Andrew S.

2017-02-01

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

Combining MOSCED with molecular simulation free energy calculations or electronic structure calculations to develop an efficient tool for solvent formulation and selection.

PubMed

Cox, Courtney E; Phifer, Jeremy R; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T; O'Loughlin, Elizabeth J; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T; Paluch, Andrew S

2017-02-01

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

The mutual influence of speciation and combination of Cu and Pb on the photodegradation of dimethyl o-phthalate.

PubMed

Jiang, Xinshu; Wang, Zhe; Zhang, Yiyue; Wang, Fei; Zhu, Mijia; Yao, Jun

2016-12-01

Specific industrial application of dimethyl o-phthalate (DMP) in ore flotation has led to DMP-heavy metals combined pollution, which causes the abiotic degradation of DMP in the environment more complex. This study focused on the effect of Cu and Pb on photodegradation of DMP. The major mechanism of inhibiting effect of Cu and Pb on degradation of DMP involved their speciation and combination. It was found that the Cu (5 mg/L, I = 95.4%) and Pb (5 mg/L, I = 100%) could inhibit the photodegradation of DMP. The main species that inhibit the DMP degradation were Cu(OH) + and Pb(OH) + , respectively. The intensity of the UV-Vis absorbance of DMP was obviously related to the concentration of Cu 2+ (R 2  = 0.8655) or Pb 2+ (R 2  = 0.9019) ions. Fluorescence quenching effect of Cu 2+ (R 2  > 0.9946), Pb 2+ (R 2  > 0.6879) on DMP is strongly correlated with the concentration of ions. And the equilibrium membrane dialysis experiment has also verified the combination of DMP and Cu, Pb. These results are useful to understand the effect mechanism of metal species on the photodegradation of organic chemicals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Computer program determines chemical equilibria in complex systems

NASA Technical Reports Server (NTRS)

Gordon, S.; Zeleznik, F. J.

1966-01-01

Computer program numerically solves nonlinear algebraic equations for chemical equilibrium based on iteration equations independent of choice of components. This program calculates theoretical performance for frozen and equilibrium composition during expansion and Chapman-Jouguet flame properties, studies combustion, and designs hardware.

Rumsey and Walker_AMT_2016_Figure 1.xlsx

EPA Pesticide Factsheets

Figure summarizes diurnal profiles of uncertainty in the chemical gradient and transfer velocity measurements from which fluxes are calculated. This dataset is associated with the following publication:Rumsey, I. Application of an online ion chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur. ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, USA, 9(6): 2581-2592, (2016).

The Role of microRNAs in the Repeated Parallel Diversification of Lineages of Midas Cichlid Fish from Nicaragua.

PubMed

Franchini, Paolo; Xiong, Peiwen; Fruciano, Carmelo; Meyer, Axel

2016-06-03

Cichlid fishes are an ideal model system for studying biological diversification because they provide textbook examples of rapid speciation. To date, there has been little focus on the role of gene regulation during cichlid speciation. However, in recent years, gene regulation has been recognized as a powerful force linking diversification in gene function to speciation. Here, we investigated the potential role of miRNA regulation in the diversification of six cichlid species of the Midas cichlid lineage (Amphilophus spp.) inhabiting the Nicaraguan crater lakes. Using several genomic resources, we inferred 236 Midas miRNA genes that were used to predict the miRNA target sites on 8,232 Midas 3'-UTRs. Using population genomic calculations of SNP diversity, we found the miRNA genes to be more conserved than protein coding genes. In contrast to what has been observed in other cichlid fish, but similar to what has been typically found in other groups, we observed genomic signatures of purifying selection on the miRNA targets by comparing these sites with the less conserved nontarget portion of the 3'-UTRs. However, in one species pair that has putatively speciated sympatrically in crater Lake Apoyo, we recovered a different pattern of relaxed purifying selection and high genetic divergence at miRNA targets. Our results suggest that sequence evolution at miRNA binding sites could be a critical genomic mechanism contributing to the rapid phenotypic evolution of Midas cichlids. © The Author 2016. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Evaluation of mineral-aqueous chemical equilibria of felsic reservoirs with low-medium temperature: A comparative study in Yangbajing geothermal field and Guangdong geothermal fields

NASA Astrophysics Data System (ADS)

Li, Jiexiang; Sagoe, Gideon; Yang, Guang; Lu, Guoping

2018-02-01

Classical geothermometers are useful tools for estimating reservoir temperatures of geothermal systems. However, their application to low-medium temperature reservoirs is limited because large variations of temperatures calculated by different classical geothermometers are usually observed. In order to help choose the most appropriate classical geothermometer for calculating the temperatures of low-medium temperature reservoirs, this study evaluated the mineral-aqueous equilibria of typical low-medium temperature felsic reservoirs in the Yangbajing geothermal field and Guangdong geothermal fields. The findings of this study support that reservoirs in the Guangdong geothermal fields have no direct magma influence. Also, natural reservoirs may represent the intermediate steady state before reaching full equilibrium, which rarely occurs. For the low-medium temperature geothermal systems without the influence of magma, even with seawater intrusion, the process of minerals reaching mineral-aqueous equilibrium is sequential: chlorite and chalcedony are the first, then followed by K-feldspar, kaolinite and K-mica. Chlorite may reach equilibrium at varying activity values, and the equilibrium between K-feldspar and kaolinite or K-feldspar and K-mica can fix the contents of K and Al in the solutions. Although the SiO2 and Al attain equilibrium state, albite and laumontite remain unsaturated and thus may affect low-medium temperature calculations. In this study, the chalcedony geothermometer was found to be the most suitable geothermometer for low-medium temperature reservoirs. The results of K-Mg geothermometer may be useful to complement that of the chalcedony geothermometer in low-medium temperature reservoir systems. Na-K geothermometer will give unreliable results at low-medium temperatures; and Na-K-Ca will also be unsuitable to calculate reservoir temperatures lower than 180 °C, probably caused by the chemical imbalance of laumontite.

Influence of soil pH on the sorption of ionizable chemicals: modeling advances.

PubMed

Franco, Antonio; Fu, Wenjing; Trapp, Stefan

2009-03-01

The soil-water distribution coefficient of ionizable chemicals (K(d)) depends on the soil acidity, mainly because the pH governs speciation. Using pH-specific K(d) values normalized to organic carbon (K(OC)) from the literature, a method was developed to estimate the K(OC) of monovalent organic acids and bases. The regression considers pH-dependent speciation and species-specific partition coefficients, calculated from the dissociation constant (pK(a)) and the octanol-water partition coefficient of the neutral molecule (log P(n)). Probably because of the lower pH near the organic colloid-water interface, the optimal pH to model dissociation was lower than the bulk soil pH. The knowledge of the soil pH allows calculation of the fractions of neutral and ionic molecules in the system, thus improving the existing regression for acids. The same approach was not successful with bases, for which the impact of pH on the total sorption is contrasting. In fact, the shortcomings of the model assumptions affect the predictive power for acids and for bases differently. We evaluated accuracy and limitations of the regressions for their use in the environmental fate assessment of ionizable chemicals.

Shock tube and chemical kinetic modeling study of the oxidation of 2,5-dimethylfuran.

PubMed

Sirjean, Baptiste; Fournet, René; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; Wang, Weijing; Oehlschlaeger, Matthew A

2013-02-21

A detailed kinetic model describing the oxidation of 2,5-dimethylfuran (DMF), a potential second-generation biofuel, is proposed. The kinetic model is based upon quantum chemical calculations for the initial DMF consumption reactions and important reactions of intermediates. The model is validated by comparison to new DMF shock tube ignition delay time measurements (over the temperature range 1300-1831 K and at nominal pressures of 1 and 4 bar) and the DMF pyrolysis speciation measurements of Lifshitz et al. [ J. Phys. Chem. A 1998 , 102 ( 52 ), 10655 - 10670 ]. Globally, modeling predictions are in good agreement with the considered experimental targets. In particular, ignition delay times are predicted well by the new model, with model-experiment deviations of at most a factor of 2, and DMF pyrolysis conversion is predicted well, to within experimental scatter of the Lifshitz et al. data. Additionally, comparisons of measured and model predicted pyrolysis speciation provides validation of theoretically calculated channels for the oxidation of DMF. Sensitivity and reaction flux analyses highlight important reactions as well as the primary reaction pathways responsible for the decomposition of DMF and formation and destruction of key intermediate and product species.

Synthesis of hexavalent molybdenum formo- and aceto-hydroxamates and deferoxamine via liquid-liquid metal partitioning

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

Breshears, Andrew T.; Brown, M. Alex; Bloom, Ira

We report a new method of crystal growth and synthesis based on liquid-liquid partitioning that allows for isolation and in-depth characterization of molybdenyl bis(formohydroxamate), Mo-FHA, molybdenyl bis(acetohydroxamate), Mo-AHA, and molybdenyl deferoxamine, Mo-DFO, for the first time. This novel approach affords shorter crystal growth time (hourly timeframe) without sacrificing crystal size or integrity when other methods of crystallization were unsuccessful. All three Mo complexes are characterized in solution via FTIR, NMR, UV-vis, and EXAFS spectroscopy. Mo-AHA and Mo-FHA structures are resolved by single crystal X-ray diffraction. Using the molybdenyl hydroxamate structural information, the speciation of Mo in a siderophore complex (Mo-DFO)more » is determined via complimentary spectroscopic methods and confirmed by DFT calculations. ESI-MS verifies that a complex of 1:1 molybdenum to deferoxamine is present in solution. Additionally, the Mo solution speciation in the precursor organic phase, MoO2(NO3)2HEH[EHP]2 (where HEH[EHP] is 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester), is characterized by FTIR and EXAFS spectroscopy as well as DFT calculations.« less

FY06 L2C2 HE program report Zaug et al.

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

Zaug, J M; Crowhurst, J C; Howard, W M

2008-08-01

The purpose of this project is to advance the improvement of LLNL thermochemical computational models that form the underlying basis or input for laboratory hydrodynamic simulations. Our general work approach utilizes, by design, tight experimental-theoretical research interactions that allow us to not empirically, but rather more scientifically improve LLNL computational results. The ultimate goal here is to confidently predict through computer models, the performance and safety parameters of currently maintained, modified, and newly designed stockpile systems. To attain our goal we make relevant experimental measurements on candidate detonation products constrained under static high-pressure and temperature conditions. The reduced information frommore » these measurements is then used to construct analytical forms that describe the potential surface (repulsive energy as a function of interatomic separation distance) of single and mixed fluid or detonation product species. These potential surface shapes are also constructed using input from well-trusted shock wave physics and assorted thermodynamic data available in the open literature. Our potential surfaces permit one to determine the equations of state (P,V,T), the equilibrium chemistry, phase, and chemical interactions of detonation products under a very wide range of extreme pressure temperature conditions. Using our foundation of experimentally refined potential surfaces we are in a position to calculate, with confidence, the energetic output and chemical speciation occurring from a specific combustion and/or detonation reaction. The thermochemical model we developed and use for calculating the equilibrium chemistry, kinetics, and energy from ultrafast processes is named 'Cheetah'. Computational results from our Cheetah code are coupled to laboratory ALE3D hydrodynamic simulation codes where the complete response behavior of an existing or proposed system is ultimately predicted. The Cheetah thermochemical code is also used by well over 500 U.S. government DoD and DOE community users who calculate the chemical properties of detonated high explosives, propellants, and pyrotechnics. To satisfy the growing needs of LLNL and the general user community we continue to improve the robustness of our Cheetah code. The P-T range of current speed of sound experiments will soon be extended by a factor of four and our recently developed technological advancements permit us to, for the first time, study any chemical specie or fluid mixture. New experiments will focus on determining the miscibility or coexistence curves of detonation product mixtures. Our newly constructed ultrafast laser diagnostics will permit us to determine what chemical species exist under conditions approaching Chapman-Jouguet (CJ) detonation states. Furthermore we will measure the time evolution of candidate species and use our chemical kinetics data to develop new and validate existing rate laws employed in future versions of our Cheetah thermochemical code.« less

Fugacity and concentration gradients in a gravity field

NASA Technical Reports Server (NTRS)

May, C. E.

1986-01-01

Equations are reviewed which show that at equilibrium fugacity and concentration gradients can exist in gravitational fields. At equilibrium, the logarithm of the ratio of the fugacities of a species at two different locations in a gravitational field is proportional to the difference in the heights of the two locations and the molecular weight of the species. An analogous relation holds for the concentration ratios in a multicomponent system. The ratio is calculated for a variety of examples. The kinetics for the general process are derived, and the time required to approach equilibrium is calculated for several systems. The following special topics are discussed: ionic solutions, polymers, multiphase systems, hydrostatic pressure, osmotic pressure, and solubility gradients in a gravity field.

Recommendations for terminology and databases for biochemical thermodynamics.

PubMed

Alberty, Robert A; Cornish-Bowden, Athel; Goldberg, Robert N; Hammes, Gordon G; Tipton, Keith; Westerhoff, Hans V

2011-05-01

Chemical equations are normally written in terms of specific ionic and elemental species and balance atoms of elements and electric charge. However, in a biochemical context it is usually better to write them with ionic reactants expressed as totals of species in equilibrium with each other. This implies that atoms of elements assumed to be at fixed concentrations, such as hydrogen at a specified pH, should not be balanced in a biochemical equation used for thermodynamic analysis. However, both kinds of equations are needed in biochemistry. The apparent equilibrium constant K' for a biochemical reaction is written in terms of such sums of species and can be used to calculate standard transformed Gibbs energies of reaction Δ(r)G'°. This property for a biochemical reaction can be calculated from the standard transformed Gibbs energies of formation Δ(f)G(i)'° of reactants, which can be calculated from the standard Gibbs energies of formation of species Δ(f)G(j)° and measured apparent equilibrium constants of enzyme-catalyzed reactions. Tables of Δ(r)G'° of reactions and Δ(f)G(i)'° of reactants as functions of pH and temperature are available on the web, as are functions for calculating these properties. Biochemical thermodynamics is also important in enzyme kinetics because apparent equilibrium constant K' can be calculated from experimentally determined kinetic parameters when initial velocities have been determined for both forward and reverse reactions. Specific recommendations are made for reporting experimental results in the literature. Copyright © 2011 Elsevier B.V. All rights reserved.

Calculating the mean time to capture for tethered ligands and its effect on the chemical equilibrium of bound ligand pairs.

PubMed

Shen, Lu; Decker, Caitlin G; Maynard, Heather D; Levine, Alex J

2016-09-01

We present here the calculation of the mean time to capture of a tethered ligand to the receptor. This calculation is then used to determine the shift in the partitioning between (1) free, (2) singly bound, and (3) doubly bound ligands in chemical equilibrium as a function of the length of the tether. These calculations are used in the research article Fibroblast Growth Factor 2 Dimer with Superagonist in vitro Activity Improves Granulation Tissue Formation During Wound Healing (Decker et al., in press [1]) to explain quantitatively how changes in polymeric linker length in the ligand dimers modifies the efficacy of these molecules relative to that of free ligands.

Dynamics of a gravity-gradient stabilized flexible spacecraft

NASA Technical Reports Server (NTRS)

Meirovitch, L.; Juang, J. N.

1974-01-01

The dynamics of gravity-gradient stabilized flexible satellite in the neighborhood of a deformed equilibrium configuration are discussed. First the equilibrium configuration was determined by solving a set of nonlinear differential equations. Then stability of motion about the deformed equilibrium was tested by means of the Liapunov direct method. The natural frequencies of oscillation of the complete structure were calculated. The analysis is applicable to the RAE/B satellite.

Computing Equilibrium Chemical Compositions

NASA Technical Reports Server (NTRS)

Mcbride, Bonnie J.; Gordon, Sanford

1995-01-01

Chemical Equilibrium With Transport Properties, 1993 (CET93) computer program provides data on chemical-equilibrium compositions. Aids calculation of thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93/PC is version of CET93 specifically designed to run within 640K memory limit of MS-DOS operating system. CET93/PC written in FORTRAN.

Calculation of the equilibrium distribution for a deleterious gene by the finite Fourier transform.

PubMed

Lange, K

1982-03-01

In a population of constant size every deleterious gene eventually attains a stochastic equilibrium between mutation and selection. The individual probabilities of this equilibrium distribution can be computed by an application of the finite Fourier transform to an appropriate branching process formula. Specific numerical examples are discussed for the autosomal dominants, Huntington's chorea and chondrodystrophy, and for the X-linked recessive, Becker's muscular dystrophy.

Chemical bonding and the equilibrium composition of Grignard reagents in ethereal solutions.

PubMed

Henriques, André M; Barbosa, André G H

2011-11-10

A thorough analysis of the electronic structure and thermodynamic aspects of Grignard reagents and its associated equilibrium composition in ethereal solutions is performed. Considering methylmagnesium halides containing fluorine, chlorine, and bromine, we studied the neutral, charged, and radical species associated with their chemical equilibrium in solution. The ethereal solvents considered, tetrahydrofuran (THF) and ethyl ether (Et(2)O), were modeled using the polarizable continuum model (PCM) and also by explicit coordination to the Mg atoms in a cluster. The chemical bonding of the species that constitute the Grignard reagent is analyzed in detail with generalized valence bond (GVB) wave functions. Equilibrium constants were calculated with the DFT/M06 functional and GVB wave functions, yielding similar results. According to our calculations and existing kinetic and electrochemical evidence, the species R(•), R(-), (•)MgX, and RMgX(2)(-) must be present in low concentration in the equilibrium. We conclude that depending on the halogen, a different route must be followed to produce the relevant equilibrium species in each case. Chloride and bromide must preferably follow a "radical-based" pathway, and fluoride must follow a "carbanionic-based" pathway. These different mechanisms are contrasted against the available experimental results and are proven to be consistent with the existing thermodynamic data on the Grignard reagent equilibria.

Human calprotectin affects the redox speciation of iron.

PubMed

Nakashige, Toshiki G; Nolan, Elizabeth M

2017-08-16

We report that the metal-sequestering human host-defense protein calprotectin (CP, S100A8/S100A9 oligomer) affects the redox speciation of iron (Fe) in bacterial growth media and buffered aqueous solution. Under aerobic conditions and in the absence of an exogenous reducing agent, CP-Ser (S100A8(C42S)/S100A9(C3S) oligomer) depletes Fe from three different bacterial growth media preparations over a 48 h timeframe (T = 30 °C). The presence of the reducing agent β-mercaptoethanol accelerates this process and allows CP-Ser to deplete Fe over a ≈1 h timeframe. Fe-depletion assays performed with metal-binding-site variants of CP-Ser show that the hexahistidine (His 6 ) site, which coordinates Fe(ii) with high affinity, is required for Fe depletion. An analysis of Fe redox speciation in buffer containing Fe(iii) citrate performed under aerobic conditions demonstrates that CP-Ser causes a time-dependent increase in the [Fe(ii)]/[Fe(iii)] ratio. Taken together, these results indicate that the hexahistidine site of CP stabilizes Fe(ii) and thereby shifts the redox equilibrium of Fe to the reduced ferrous state under aerobic conditions. We also report that the presence of bacterial metabolites affects the Fe-depleting activity of CP-Ser. Supplementation of bacterial growth media with an Fe(iii)-scavenging siderophore (enterobactin, staphyloferrin B, or desferrioxamine B) attenuates the Fe-depleting activity of CP-Ser. This result indicates that formation of Fe(iii)-siderophore complexes blocks CP-mediated reduction of Fe(iii) and hence the ability of CP to coordinate Fe(ii). In contrast, the presence of pyocyanin (PYO), a redox-cycling phenazine produced by Pseudomonas aeruginosa that reduces Fe(iii) to Fe(ii), accelerates Fe depletion by CP-Ser under aerobic conditions. These findings indicate that the presence of microbial metabolites that contribute to metal homeostasis at the host/pathogen interface can affect the metal-sequestering function of CP.

The procedure and results of calculations of the equilibrium isotopic composition of a demonstration subcritical molten salt reactor

NASA Astrophysics Data System (ADS)

Nevinitsa, V. A.; Dudnikov, A. A.; Blandinskiy, V. Yu.; Balanin, A. L.; Alekseev, P. N.; Titarenko, Yu. E.; Batyaev, V. F.; Pavlov, K. V.; Titarenko, A. Yu.

2015-12-01

A subcritical molten salt reactor with an external neutron source is studied computationally as a facility for incineration and transmutation of minor actinides from spent nuclear fuel of reactors of VVER-1000 type and for producing 233U from 232Th. The reactor configuration is chosen, the requirements to be imposed on the external neutron source are formulated, and the equilibrium isotopic composition of heavy nuclides and the key parameters of the fuel cycle are calculated.

TMAP: Tübingen NLTE Model-Atmosphere Package

NASA Astrophysics Data System (ADS)

Werner, Klaus; Dreizler, Stefan; Rauch, Thomas

2012-12-01

The Tübingen NLTE Model-Atmosphere Package (TMAP) is a tool to calculate stellar atmospheres in spherical or plane-parallel geometry in hydrostatic and radiative equilibrium allowing departures from local thermodynamic equilibrium (LTE) for the population of atomic levels. It is based on the Accelerated Lambda Iteration (ALI) method and is able to account for line blanketing by metals. All elements from hydrogen to nickel may be included in the calculation with model atoms which are tailored for the aims of the user.

Calculation of the acid-base equilibrium constants at the alumina/electrolyte interface from the ph dependence of the adsorption of singly charged ions (Na+, Cl-)

NASA Astrophysics Data System (ADS)

Gololobova, E. G.; Gorichev, I. G.; Lainer, Yu. A.; Skvortsova, I. V.

2011-05-01

A procedure was proposed for the calculation of the acid-base equilibrium constants at an alumina/electrolyte interface from experimental data on the adsorption of singly charged ions (Na+, Cl-) at various pH values. The calculated constants (p K {1/0}= 4.1, p K {2/0}= 11.9, p K {3/0}= 8.3, and p K {4/0}= 7.7) are shown to agree with the values obtained from an experimental pH dependence of the electrokinetic potential and the results of potentiometric titration of Al2O3 suspensions.

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

Wolery, Thomas J.; Tayne, Andrew; Jove-Colon, Carlos F.

Thermodynamic data are essential for understanding and evaluating geochemical processes, as by speciation-solubility calculations, reaction -path modeling, or reactive transport simulation. These data are required to evaluate both equilibrium states and the kinetic approach to such states (via the affinity term in rate laws). The development of thermodynamic databases for these purposes has a long history in geochemistry (e.g., Garrels and Christ, 1965; Helgeson et al., 1969; Helgeson et al., 1978, Johnson et al., 1992; Robie and Hemingway, 1995), paralleled by related and applicable work in the larger scientific community (e.g., Wagman et al., 1982, 1989; Cox et al., 1989;more » Barin and Platzki, 1995; Binneweis and Milke, 1999). The Yucca Mountain Project developed two qualified thermodynamic databases for to model geochemical processes, including ones involving repository components such as spent fuel. The first of the two (BSC, 2007a) was for systems containing dilute aqueous solutions only, the other (BSC, 2007b) for systems involving concentrated aqueous solutions and incorporating a model for such based on Pitzer’s (1991) equations . A 25°C-only database with similarities to the latter was also developed for WIPP (cf. Xiong, 2005). The YMP dilute systems database is widely used in the geochemistry community for a variety of applications involving rock/water interactions. The purpose of the present task is to improve these databases for work on the Used Fuel Disposition Project and maintain some semblance of order that will support qualification in support of the development of future underground high level nuclear waste disposal.« less

46 CFR 28.515 - Submergence test as an alternative to stability calculations.

Code of Federal Regulations, 2011 CFR

2011-10-01

... float in calm water after being submerged for 18 hours so that— (1) The vessel has an equilibrium heel... in paragraph (c) of this section, except that the equilibrium heel angle must not exceed 30° and the...

Structural determination of individual chemical species in a mixed system by iterative transformation factor analysis-based X-ray absorption spectroscopy combined with UV-visible absorption and quantum chemical calculation.

PubMed

Ikeda, Atsushi; Hennig, Christoph; Rossberg, André; Tsushima, Satoru; Scheinost, Andreas C; Bernhard, Gert

2008-02-15

A multitechnique approach using extended X-ray absorption fine structure (EXAFS) spectroscopy based on iterative transformation factor analysis (ITFA), UV-visible absorption spectroscopy, and density functional theory (DFT) calculations has been performed in order to investigate the speciation of uranium(VI) nitrate species in acetonitrile and to identify the complex structure of individual species in the system. UV-visible spectral titration suggests that there are four different species in the system, that is, pure solvated species, mono-, di-, and trinitrate species. The pure EXAFS spectra of these individual species are extracted by ITFA from the measured spectral mixtures on the basis of the speciation distribution profile calculated from the UV-visible data. Data analysis of the extracted EXAFS spectra, with the help of DFT calculations, reveals the most probable complex structures of the individual species. The pure solvated species corresponds to a uranyl hydrate complex with an equatorial coordination number (CNeq) of 5, [UO2(H2O)5]2+. Nitrate ions tend to coordinate to the uranyl(VI) ion in a bidentate fashion rather than a unidentate one in acetonitrile for all the nitrate species. The mononitrate species forms the complex of [UO2(H2O)3NO3]+ with a CNeq value of 5, while the di- and trinitrate species have a CNeq value of 6, corresponding to [UO2(H2O)2(NO3)2]0 (D2h) and [UO2(NO3)3]- (D3h), respectively.

Collisional Ionization Equilibrium for Optically Thin Plasmas

NASA Technical Reports Server (NTRS)

Bryans, P.; Mitthumsiri, W.; Savin, D. W.; Badnell, N. R.; Gorczyca, T. W.; Laming, J. M.

2006-01-01

Reliably interpreting spectra from electron-ionized cosmic plasmas requires accurate ionization balance calculations for the plasma in question. However, much of the atomic data needed for these calculations have not been generated using modern theoretical methods and their reliability are often highly suspect. We have utilized state-of-the-art calculations of dielectronic recombination (DR) rate coefficients for the hydrogenic through Na-like ions of all elements from He to Zn. We have also utilized state-of-the-art radiative recombination (RR) rate coefficient calculations for the bare through Na-like ions of all elements from H to Zn. Using our data and the recommended electron impact ionization data of Mazzotta et al. (1998), we have calculated improved collisional ionization equilibrium calculations. We compare our calculated fractional ionic abundances using these data with those presented by Mazzotta et al. (1998) for all elements from H to Ni, and with the fractional abundances derived from the modern DR and RR calculations of Gu (2003a,b, 2004) for Mg, Si, S, Ar, Ca, Fe, and Ni.

Visualizing speciation in artificial cichlid fish.

PubMed

Clement, Ross

2006-01-01

The Cichlid Speciation Project (CSP) is an ALife simulation system for investigating open problems in the speciation of African cichlid fish. The CSP can be used to perform a wide range of experiments that show that speciation is a natural consequence of certain biological systems. A visualization system capable of extracting the history of speciation from low-level trace data and creating a phylogenetic tree has been implemented. Unlike previous approaches, this visualization system presents a concrete trace of speciation, rather than a summary of low-level information from which the viewer can make subjective decisions on how speciation progressed. The phylogenetic trees are a more objective visualization of speciation, and enable automated collection and summarization of the results of experiments. The visualization system is used to create a phylogenetic tree from an experiment that models sympatric speciation.

Comparative tests of the role of dewlap size in Anolis lizard speciation

PubMed Central

Harrison, Alexis; Mahler, D. Luke; Castañeda, María del Rosario; Glor, Richard E.; Herrel, Anthony; Stuart, Yoel E.; Losos, Jonathan B.

2016-01-01

Phenotypic traits may be linked to speciation in two distinct ways: character values may influence the rate of speciation or diversification in the trait may be associated with speciation events. Traits involved in signal transmission, such as the dewlap of Anolis lizards, are often involved in the speciation process. The dewlap is an important visual signal with roles in species recognition and sexual selection, and dewlaps vary among species in relative size as well as colour and pattern. We compile a dataset of relative dewlap size digitized from photographs of 184 anole species from across the genus' geographical range. We use phylogenetic comparative methods to test two hypotheses: that larger dewlaps are associated with higher speciation rates, and that relative dewlap area diversifies according to a speciational model of evolution. We find no evidence of trait-dependent speciation, indicating that larger signals do not enhance any role the dewlap has in promoting speciation. Instead, we find a signal of mixed speciational and gradual trait evolution, with a particularly strong signal of speciational change in the dewlaps of mainland lineages. This indicates that dewlap size diversifies in association with the speciation process, suggesting that divergent selection may play a role in the macroevolution of this signalling trait. PMID:28003450

EPA’s SPECIATE 4.4 Database:Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

EPA’s SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

Ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure

NASA Astrophysics Data System (ADS)

Sucipto, Retno Kumala Hesti; Kuswandi, Wibawa, Gede

2017-05-01

The objective of this study was to determine ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure. Using 25 mL equilibrium cell equipped jacketted water connected to water bath to maintain equilibrium temperature constant. The procedure of this experiment was conducted by inserting mixture of eugenol + tert-butanol + water system at certain composition into equilibrium cell. The solution was stirred for 4 hours and then was allowed for 20 hours in order to separate aqueous and organic phases completely. The temperature equilibrium cell of and the atmosphere pressure were recorded as equilibrium temperature and pressure for each measurenment. The equilibrium compositions of each phase were analyzed using Gas Chromatography. The experimental data obtained in this work were correlated with NRTL and UNIQUAC models with root mean square deviation between esperimental and calculated equilibrium compositions of 0.03% and 0.04% respectively.

Another dimension to metamorphic phase equilibria: the power of interactive movies for understanding complex phase diagram sections

NASA Astrophysics Data System (ADS)

Moulas, E.; Caddick, M. J.; Tisato, N.; Burg, J.-P.

2012-04-01

The investigation of metamorphic phase equilibria, using software packages that perform thermodynamic calculations, involves a series of important assumptions whose validity can often be questioned but are difficult to test. For example, potential influences of deformation on phase relations, and modification of effective reactant composition (X) at successive stages of equilibrium may both introduce significant uncertainty into phase diagram calculations. This is generally difficult to model with currently available techniques, and is typically not well quantified. We present here a method to investigate such phenomena along pre-defined Pressure-Temperature (P-T) paths, calculating local equilibrium via Gibbs energy minimization. An automated strategy to investigate complex changes in the effective equilibration composition has been developed. This demonstrates the consequences of specified X modification and, more importantly, permits automated calculation of X changes that are likely along the requested path if considering several specified processes. Here we describe calculations considering two such processes and show an additional example of a metamorphic texture that is difficult to model with current techniques. Firstly, we explore the assumption that although water saturation and bulk-rock equilibrium are generally considered to be valid assumptions in the calculation of phase equilibria, the saturation of thermodynamic components ignores mechanical effects that the fluid/melt phase can impose on the rock, which in turn can modify the effective equilibrium composition. Secondly, we examine how mass fractionation caused by porphyroblast growth at low temperatures or progressive melt extraction at high temperatures successively modifies X out of the plane of the initial diagram, complicating the process of determining best-fit P-T paths for natural samples. In particular, retrograde processes are poorly modeled without careful consideration of prograde fractionation processes. Finally we show how, although the effective composition of symplectite growth is not easy to determine and quantify, it is possible to successfully model by constructing a series of phase equilibria calculations.

Solar heating of common lunar minerals for the production of oxygen

NASA Technical Reports Server (NTRS)

Senior, C. L.

1991-01-01

The purpose of this work was to demonstrate the feasibility of vapor-phase reduction (pyrolysis) of lunar materials to produce oxygen. Solar furnace experiments were conducted on two common lunar minerals, ilmenite and anorthite. Thermodynamic equilibrium calculations predicted that ilmenite should show a larger pressure increase than anorthite under conditions of the experiments and this was confirmed by the experiments. The measured mass loss of the ilmenite sample was consistent with loss of oxygen by reduction of iron in the liquid phase; this result was also predicted from equilibrium calculations. Based on preliminary experiments and equilibrium calculations, the temperatures needed for pyrolysis are expected to be in the range of 2000 to 2500 K, giving total gas pressures of 0.01 to 1 torr. Bulk regolith can be used as a feedstock without extensive beneficiation. Further, selective condensation of metal-containing species from the gas phase may yield metallic iron and silicon as byproducts from the process.

Pollutant threshold concentration determination in marine ecosystems using an ecological interaction endpoint.

PubMed

Wang, Changyou; Liang, Shengkang; Guo, Wenting; Yu, Hua; Xing, Wenhui

2015-09-01

The threshold concentrations of pollutants are determined by extrapolating single-species effect data to community-level effects. This assumes the most sensitive endpoint of the life cycle of individuals and the species sensitivity distribution from single-species toxic effect tests, thus, ignoring the ecological interactions. The uncertainties due to this extrapolation can be partially overcome using the equilibrium point of a customized ecosystem. This method incorporates ecological interactions and integrates the effects on growth, survival, and ingestion into a single effect measure, the equilibrium point excursion in the customized ecosystem, in order to describe the toxic effects on plankton. A case study showed that the threshold concentration of copper calculated with the endpoint of the equilibrium point was 10 μg L(-1), which is significantly different from the threshold calculated with a single-species endpoint. The endpoint calculated using this method provides a more relevant measure of the ecological impact than any single individual-level endpoint. Copyright © 2015 Elsevier Ltd. All rights reserved.

Predicting the equilibrium solubility of solid polycyclic aromatic hydrocarbons and dibenzothiophene using a combination of MOSCED plus molecular simulation or electronic structure calculations

NASA Astrophysics Data System (ADS)

Phifer, Jeremy R.; Cox, Courtney E.; da Silva, Larissa Ferreira; Nogueira, Gabriel Gonçalves; Barbosa, Ana Karolyne Pereira; Ley, Ryan T.; Bozada, Samantha M.; O'Loughlin, Elizabeth J.; Paluch, Andrew S.

2017-06-01

Methods to predict the equilibrium solubility of non-electrolyte solids are important for the design of novel separation processes. Here we demonstrate how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here SMD or SM8, can be used to predict parameters for the MOdified Separation of Cohesive Energy Density (MOSCED) method. The method is applied to the solutes naphthalene, anthracene, phenanthrene, pyrene and dibenzothiophene, compounds of interested to the petroleum industry and for environmental remediation. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. Comparing to a total of 422 non-aqueous and 193 aqueous experimental solubilities, we find the proposed method is able to well correlate the data. The use of MOSCED is additionally advantageous as it is a solubility parameter-based method useful for intuitive solvent selection and formulation.

US EPA's SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, volatile o...

EPA’s SPECIATE 4.4 Database: Bridging Data Sources and Data Users

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

The Equilibrium and Pre-equilibrium Triton Emission Spectra of Some Target Nuclei for ( n, xt) Reactions up to 45 MeV Energy

NASA Astrophysics Data System (ADS)

Tel, E.; Kaplan, A.; Aydın, A.; Özkorucuklu, S.; Büyükuslu, H.; Yıldırım, G.

2010-08-01

Although there have been significant research and development studies on the inertial and magnetic fusion reactor technology, there is still a long way to go to penetrate commercial fusion reactors to the energy market. Tritium self-sufficiency must be maintained for a commercial power plant. For self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. So, working out the systematics of ( n,t) reaction cross sections and triton emission differential data are important for the given reaction taking place on various nuclei at different energies. In this study, ( n,xt) reactions for some target nuclei as 16O, 27Al, 59Co and 209Bi have been investigated up to 45 MeV incident neutron energy. In the calculations of the triton emission spectra, the pre-equilibrium and equilibrium effects have been used. The calculated results have been compared with the experimental data taken from the literature.

Gallium isotope fractionation during Ga adsorption on calcite and goethite

NASA Astrophysics Data System (ADS)

Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques

2018-02-01

Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its geochemical analog aluminum.

On the ortho-para equilibrium of H2 in the atmospheres of the Jovian planets

NASA Technical Reports Server (NTRS)

Smith, W. H.

1978-01-01

The ratio for the equivalent widths for the unsaturated H2 quadrupole transitions observed in the Jovian planets is calculated and compared with a large number of observations. The comparison indicates that equilibrium hydrogen may be present in Jupiter and Saturn, while Uranus and Neptune exhibit ratios not in accord with equilibrium hydrogen. Observations which can differentiate among the possible states of H2 are proposed.

Statistical equilibrium in cometary C2. II - Swan/Phillips band ratios

NASA Technical Reports Server (NTRS)

Swamy, K. S. K.; Odell, C. R.

1979-01-01

Statistical equilibrium calculations have been made for both the triplet and ground state singlets for C2 in comets, using the exchange rate as a free parameter. The predictions of the results are consistent with optical observations and may be tested definitively by accurate observations of the Phillips and Swan band ratios. Comparison with the one reported observation indicates compatibility with a low exchange rate and resonance fluorescence statistical equilibrium.

Multilocus resolution of phylogeny and timescale in the extant adaptive radiation of Hawaiian honeycreepers.

PubMed

Lerner, Heather R L; Meyer, Matthias; James, Helen F; Hofreiter, Michael; Fleischer, Robert C

2011-11-08

Evolutionary theory has gained tremendous insight from studies of adaptive radiations. High rates of speciation, morphological divergence, and hybridization, combined with low sequence variability, however, have prevented phylogenetic reconstruction for many radiations. The Hawaiian honeycreepers are an exceptional adaptive radiation, with high phenotypic diversity and speciation that occurred within the geologically constrained setting of the Hawaiian Islands. Here we analyze a new data set of 13 nuclear loci and pyrosequencing of mitochondrial genomes that resolves the Hawaiian honeycreeper phylogeny. We show that they are a sister taxon to Eurasian rosefinches (Carpodacus) and probably came to Hawaii from Asia. We use island ages to calibrate DNA substitution rates, which vary substantially among gene regions, and calculate divergence times, showing that the radiation began roughly when the oldest of the current large Hawaiian Islands (Kauai and Niihau) formed, ~5.7 million years ago (mya). We show that most of the lineages that gave rise to distinctive morphologies diverged after Oahu emerged (4.0-3.7 mya) but before the formation of Maui and adjacent islands (2.4-1.9 mya). Thus, the formation of Oahu, and subsequent cycles of colonization and speciation between Kauai and Oahu, played key roles in generating the morphological diversity of the extant honeycreepers. Copyright © 2011 Elsevier Ltd. All rights reserved.

Selective speciation and determination of inorganic arsenic in water, food and biological samples.

PubMed

Tuzen, Mustafa; Saygi, Kadriye Ozlem; Karaman, Isa; Soylak, Mustafa

2010-01-01

A procedure for the speciation of arsenic(III) and arsenic(V) in natural water samples has been established in the presented work. Arsenic(III) ions were quantitatively recovered on Alternaria solani coated Diaion HP-2MG resin at pH 7, while the recoveries of arsenic(V) was below 10%. Arsenic(V) in the mixing solution containing As(III) and As(V) was reduced by using KI and L(+) ascorbic acid solution, then the procedure was applied to determination of total arsenic. Arsenic(V) was calculated as the difference between the total arsenic content and As(III) content. The determination of arsenic was performed by using hydride generation atomic absorption spectrometry. The influences of some alkali, earth alkali and transition metals on the biosorption of arsenic(III) were investigated. The preconcentration factor was 35. The detection limits for As(III) (N=20, k=3) was found as 11 ng L(-1). The relative standard deviation and relative error of the determinations were found to be lower than 7% and 4%, respectively. The accuracy of the method was confirmed with certified reference materials. The method was successively applied for the determination and speciation of inorganic arsenic in water, food and biological samples. Copyright 2009 Elsevier Ltd. All rights reserved.

Hawking radiation and nonequilibrium quantum critical current noise.

PubMed

Sonner, Julian; Green, A G

2012-08-31

The dynamical scaling of quantum critical systems in thermal equilibrium may be inherited in the driven steady state, leading to universal out-of-equilibrium behavior. This attractive notion has been demonstrated in just a few cases. We demonstrate how holography-a mapping between the quantum critical system and a gravity dual-provides an illuminating perspective and new results. Nontrivial out-of-equilibrium universality is particularly apparent in current noise, which is dual to Hawking radiation in the gravitational system. We calculate this in a two-dimensional system driven by a strong in-plane electric field and deduce a universal scaling function interpolating between previously established equilibrium and far-from-equilibrium current noise. Since this applies at all fields, out-of-equilibrium experiments no longer require very high fields for comparison with theory.

Free energy landscape from path-sampling: application to the structural transition in LJ38

NASA Astrophysics Data System (ADS)

Adjanor, G.; Athènes, M.; Calvo, F.

2006-09-01

We introduce a path-sampling scheme that allows equilibrium state-ensemble averages to be computed by means of a biased distribution of non-equilibrium paths. This non-equilibrium method is applied to the case of the 38-atom Lennard-Jones atomic cluster, which has a double-funnel energy landscape. We calculate the free energy profile along the Q4 bond orientational order parameter. At high or moderate temperature the results obtained using the non-equilibrium approach are consistent with those obtained using conventional equilibrium methods, including parallel tempering and Wang-Landau Monte Carlo simulations. At lower temperatures, the non-equilibrium approach becomes more efficient in exploring the relevant inherent structures. In particular, the free energy agrees with the predictions of the harmonic superposition approximation.

Speciation of High-Pressure Carbon-Saturated COH Fluids at Buffered fO2 Conditions: An Experimental Approach

NASA Astrophysics Data System (ADS)

Tumiati, S.; Tiraboschi, C.; Recchia, S.; Poli, S.

2014-12-01

The quantitative assessment of species in COH fluids is crucial in modelling mantle processes. For instance, H2O/CO2 ratio in the fluid phase influences the location of the solidus and of carbonation/decarbonation reactions in peridotitic systems . In the scientific literature, the speciation of COH fluids has been generally assumed on the basis of thermodynamic calculations using equations of state of simple H2O-non-polar gas systems (e.g., H2O-CO2-CH4). Only few authors dealt with the experimental determination of high-pressure COH fluid species at different conditions, using diverse experimental and analytical approaches (e.g., piston cylinder+capsule-piercing+gas-chromatography/mass-spectrometry; cold-seal+silica glass capsules+Raman). We performed experiments on COH fluids using a capsule-piercing device coupled with a quadrupole mass spectrometry. This type of analyzer ensures superior performances in terms of selectivity of molecules to be detected, high acquisition rates and extended linear response range. Experiments were carried out in a rocking piston cylinder apparatus at pressure of 1 GPa and temperatures from 800 to 900°C. Carbon-saturated fluids were generated through the addition of oxalic acid dihydrate and graphite. Single/double capsules and different packing materials (BN and MgO) were used to evaluate the divergence from the thermodynamic speciation model. Moreover, to assess the effect of solutes on COH fluid speciation we also performed a set of experiments adding synthetic forsterite to the charge. To determine the speciation we assembled a capsule-piercing device that allows to puncture the capsule in a gas-tight vessel at 80°C. The extraction Teflon vessel is composed of a base part, where the capsule is allocated on a steel support, and a top part where a steel drill is mounted. To release the quenched fluids from the capsule, the base part of vessel is hand-tighten to the top part, allowing the steel pointer to pierce the capsule. The evolved gases are then convoyed to a quadrupole mass spectrometer through a heated line to avoid the condensation of water. Our results suggest that fluid speciation can diverge considerably compared to the thermodynamic model depending on the experimental strategies adopted and on the presence of solutes in complex COH systems.

Bounded energy states in homogeneous turbulent shear flow: An alternative view

NASA Technical Reports Server (NTRS)

Bernard, Peter S.; Speziale, Charles G.

1990-01-01

The equilibrium structure of homogeneous turbulent shear flow is investigated from a theoretical standpoint. Existing turbulence models, in apparent agreement with physical and numerical experiments, predict an unbounded exponential time growth of the turbulent kinetic energy and dissipation rate; only the anisotropy tensor and turbulent time scale reach a structural equilibrium. It is shown that if vortex stretching is accounted for in the dissipation rate transport equation, then there can exist equilibrium solutions, with bounded energy states, where the turbulence production is balanced by its dissipation. Illustrative calculations are present for a k-epsilon model modified to account for vortex stretching. The calculations indicate an initial exponential time growth of the turbulent kinetic energy and dissipation rate for elapsed times that are as large as those considered in any of the previously conducted physical or numerical experiments on homogeneous shear flow. However, vortex stretching eventually takes over and forces a production-equals-dissipation equilibrium with bounded energy states. The validity of this result is further supported by an independent theoretical argument. It is concluded that the generally accepted structural equilibrium for homogeneous shear flow with unbounded component energies is in need of re-examination.

Determination of chemical speciations of cerium in nuclear waste glasses

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

Gong, Meiling; Li, Hong

1996-12-31

Cerium oxides have been widely used as a surrogate for plutonium in the investigation of the melt and durability behavior of simulated nuclear waste glasses. It is well known that there is a cerous-ceric equilibrium in silicate glasses under normal melting conditions. The position of this equilibrium depends on glass composition, melting temperature, furnace atmosphere, and possibly the total amounts of cerium in glass. The oxidation state of cerium affects total solubility of cerium in glass, solubilities of other components in glass, viscosities and liquidus temperatures of the melts, and the chemical durability of the glasses. A procedure was developedmore » for the determination of the ceric and cerous distribution. The glass was ground to small particles of less than 300 meshes and was dissolved in mixture of HF and H{sub 2}SO{sub 4}. The ceric oxide was graduately reduced to cerous species in the presence of HF acid during the dissolution. To compensate the change of the equilibrium during the dissolution, a calibration curve is made with a mixture of standard solution of ceric sulphate and one gram of glass of the same composition containing no cerium. Boric acid was added to complex the fluoride ions, and the resultant solution was titrated potentiometrically with 0.01 N ferrous ammonium sulphate solution. The corrected ceric concentration was obtained on the calibration curve. The total cerium content in the above solution was analyzed using ICP-AES and the cerous content was the difference between the total Ce and Ce(+4).« less

The Navy/NASA Engine Program (NNEP89): Interfacing the program for the calculation of complex Chemical Equilibrium Compositions (CEC)

NASA Technical Reports Server (NTRS)

Gordon, Sanford

1991-01-01

The NNEP is a general computer program for calculating aircraft engine performance. NNEP has been used extensively to calculate the design and off-design (matched) performance of a broad range of turbine engines, ranging from subsonic turboprops to variable cycle engines for supersonic transports. Recently, however, there has been increased interest in applications for which NNEP is not capable of simulating, such as the use of alternate fuels including cryogenic fuels and the inclusion of chemical dissociation effects at high temperatures. To overcome these limitations, NNEP was extended by including a general chemical equilibrium method. This permits consideration of any propellant system and the calculation of performance with dissociation effects. The new extended program is referred to as NNEP89.

Zirconium-nickel crystals—hydrogen accumulators: Dissolution and penetration of hydrogen atoms in alloys

NASA Astrophysics Data System (ADS)

Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.; Kamenetskaya, E. A.

2016-07-01

The calculation of the free energy, thermodynamic equilibrium equations, and kinetic equations of the intermetallic compound Zr2NiH x has been carried out based on molecular-kinetic concepts. The equilibrium hydrogen concentration depending on the temperature, pressure, and energy parameters has been calculated. The absorption-desorption of hydrogen has been studied, and the possibility of the realization of the hysteresis effect has been revealed. The kinetics of the dissolution and permeability of hydrogen is considered, the time dependence of these values has been found, and conditions for the extremum character of their time dependence have been determined. Relaxation times of the dissolution and permeability of hydrogen into the alloy have been calculated. The calculation results are compared with the experimental data available in the literature.

Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

NASA Technical Reports Server (NTRS)

1976-01-01

The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

Theoretical estimates of equilibrium 13C-18O clumping in carbonates and organic acids

NASA Astrophysics Data System (ADS)

Schauble, E. A.; Eiler, J. M.

2004-12-01

The development of techniques for measuring small gas-phase molecules containing more than one rare stable isotope (e.g., 13C18O16O) at natural, ppm-level abundances1,2 has made it possible to track sources and sinks of atmospheric gases from a new perspective. Similar measurements of 13C-18O clumping in ancient samples could improve our understanding of ancient climates, if the abundances of `clumped' rare stable isotopes in materials that retain isotopic signatures over geologic time can be measured with sufficient precision. This theoretical study estimates the abundances of such 13C-18O `clumps' in carbonates and organic acids and discusses their potential applications. Accompanying abstracts by Eiler et al. and Ghosh et al. will present the analytical methods and some initial data for carbonate minerals to examine the applicability of our theoretical models. Equilibrium isotopic speciations in carbonate minerals and organic acids are calculated from the reduced partition function ratios of isotopically substituted crystals and molecules. Vibrational frequencies used as input for these calculations come from ab initio force fields, determined using density functional theory. Our calculations indicate that carbonate minerals, including calcite, dolomite, and aragonite, when equilibrated at earth-surface temperatures, will have a slight overabundance of CO32- groups containing both 13C and 18O (i.e., 13C18O16O22-) relative to what would be expected if carbon and oxygen isotopes were distributed randomly in the crystal lattice. Calcite and dolomite crystals are predicted to have 0.4‰ excesses of 13C18O16O22- at 298 K; in aragonite the excess will be about 0.05‰ larger. The excesses are smaller for crystals formed or equilibrated at higher temperatures, decreasing by 0.003\\permil/oC at room temperature and essentially disappearing at temperatures of 1000 K or higher. Similarly, there is an excess of both 13C18O16OH and 13C16O18OH groups in organic acids like formic acid (HCOOH) and pyruvic acid (CH3COCOOH) that equilibrate at low temperatures. For gas-phase carboxylic acids, 13C-18O clumping in the COOH group is strongest at the C=O double bond, with an 1.0-1.1‰ excess at room temperature. The C-O-H subgroup has an ~0.4‰ 13C-18O excess, and thus the average anomaly for the whole COOH group is 0.7-0.8\\permil. As with carbonate minerals, these excesses decrease at higher temperatures. The magnitude of 13C-18O clumping in carboxylic acid is similar to gas-phase CO2 1,2,3, while in carbonate minerals the effect is about one-half as large. The temperature sensitivity of these isotopic clumping effects suggests that measurements of abundances of 13C-18O bonds in carbonates and organic acids could be useful for paleothermometry. The clumping equilibrium is an internal property of each phase, so temperature information can be obtained even when the isotopic composition of the fluid phase from which a sample precipitated is unknown. Clumping effects may also be able to distinguish pristine, unaltered sedimentary and biogenic carbonates and organic deposits from those that have undergone post-depositional diagenesis or metamorphism, even in samples that have not suffered extensive open-system exchange. Refs: 1Eiler et al. 2004, GCA in press; 2Schauble et al. in prep.; 3Wang et al. 2004, GCA in press.

First-principles investigations of equilibrium Ca, Mg, Si and O isotope fractionations between silicate melts and minerals

NASA Astrophysics Data System (ADS)

Qi, Y.; Liu, X.; Kang, J.; He, L.

2017-12-01

Equilibrium isotope fractionation factors are essential for using stable isotope data to study many geosciences processes such as planetary differentiation and mantle evolution. The mass-dependent equilibrium isotope fractionation is primarily controlled by the difference in bond energies triggered by the isotope substitution. With the recent advances in computational capabilities, first-principles calculation has become a reliable tool to investigate equilibrium isotopic fractionations, greatly improving our understanding of the factors controlling isotope fractionations. It is important to understand the isotope fractionation between melts and minerals because magmatism is critical for creating and shaping the Earth. However, because isotope fractionation between melts and minerals is small at high temperature, it is difficult to experimentally calibrate such small signature. Due to the disordered and dynamic character of melts, calculations of equilibrium isotope fractionation of melts are more challenging than that for gaseous molecules or minerals. Here, we apply first-principles molecular dynamics method to calculate equilibrium Ca, Mg, Si, and O isotope fractionations between silicate melts and minerals. Our results show that equilibrium Mg, Si, and O isotope fractionations between olivine and pure Mg2SiO4 melt are close to zero at high temperature (e.g. δ26Mgmelt-ol = 0.03 ± 0.04‰, δ30Simelt-ol = -0.06 ± 0.07‰, δ18Omelt-ol = 0.07‰ ± 0.08 at 1500 K). Equilibrium Ca, Mg, Si, and O isotope fractionations between diopside and basalt melt (67% CaMgSi2O6 + 33% CaAl2Si2O8) are also negligible at high temperature (e.g. δ44/40Camelt-cpx = -0.01 ± 0.02‰, δ26Mgmelt-cpx = -0.05 ± 0.14‰, δ30Simelt-cpx = 0.04 ± 0.04‰, δ18Omelt-cpx = 0.03 ± 0.07‰ at 1500 K). These results are consistent with the observations in natural samples that there is no significant Ca, Mg, Si, and O isotope fractionation during mantle partial melting, demonstrating the reliability of our methods. Thus, our results can be used to understand stable isotope fractionation during partial melting of mantle peridotite or fractional crystallization during magmatic differentiation. The first-principles molecular dynamics method is a promising tool to obtain equilibrium fractionation of more isotope systems for complicate liquids.

Microwave spectra and molecular structures of (Z)-pent-2-en-4-ynenitrile and maleonitrile.

PubMed

Halter, R J; Fimmen, R L; McMahon, R J; Peebles, S A; Kuczkowski, R L; Stanton, J F

2001-12-12

Accurate equilibrium structures have been determined for (Z)-pent-2-en-4-ynenitrile (8) and maleonitrile (9) by combining microwave spectroscopy data and ab initio quantum chemistry calculations. The microwave spectra of 10 isotopomers of 8 and 5 isotopomers of 9 were obtained using a pulsed nozzle Fourier transform microwave spectrometer. The ground-state rotational constants were adjusted for vibration-rotation interaction effects calculated from force fields obtained from ab initio calculations. The resultant equilibrium rotational constants were used to determine structures that are in very good agreement with those obtained from high-level ab initio calculations (CCSD(T)/cc-pVTZ). The geometric parameters in 8 and 9 are very similar; they also do not differ significantly from the all-carbon analogue, (Z)-hex-3-ene-1,5-diyne (7), the parent molecule for the Bergman cyclization. A small deviation from linearity about the alkyne and cyano linkages is observed for 7-9 and several related species where accurate equilibrium parameters are available. The data on 7-9 should be of interest to radioastronomy and may provide insights on the formation and interstellar chemistry of unsaturated species such as the cyanopolyynes.

Assessment of two-temperature kinetic model for dissociating and weakly-ionizing nitrogen

NASA Technical Reports Server (NTRS)

Park, C.

1986-01-01

The validity of the author's two-temperature, chemical/kinetic model which the author has recently improved is assessed by comparing the calculated results with the existing experimental data for nitrogen in the dissociating and weakly ionizing regime produced behind a normal shock wave. The computer program Shock Tube Radiation Program (STRAP) based on the two-temperature model is used in calculating the flow properties behind the shock wave and the Nonequilibrium Air Radiation (NEQAIR) program, in determining the radiative characteristics of the flow. Both programs were developed earlier. Comparison is made between the calculated and the existing shock tube data on (1) spectra in the equilibrium region, (2) rotational temperature of the N2(+) B state, (3) vibrational temperature of the N2(+) B state, (4) electronic excitation temperature of the N2 B state, (5) the shape of time-variation of radiation intensities, (6) the times to reach the peak in radiation intensity and equilibrium, and (7) the ratio of nonequilibrium to equilibrium radiative heat fluxes. Good agreement is seen between the experimental data and the present calculation except for the vibrational temperature. A possible reason for the discrepancy is given.

A thermochemical model of radiation damage and annealing applied to GaAs solar cells

NASA Technical Reports Server (NTRS)

Conway, E. J.; Walker, G. H.; Heinbockel, J. H.

1981-01-01

Calculations of the equilibrium conditions for continuous radiation damage and thermal annealing are reported. The calculations are based on a thermochemical model developed to analyze the incorporation of point imperfections in GaAs, and modified by introducing the radiation to produce native lattice defects rather than high-temperature and arsenic atmospheric pressure. The concentration of a set of defects, including vacancies, divacancies, and impurity vacancy complexes, are calculated as a function of temperature. Minority carrier lifetimes, short circuit current, and efficiency are deduced for a range of equilibrium temperatures. The results indicate that GaAs solar cells could have a mission life which is not greatly limited by radiation damage.

High-accuracy calculations of the ground, 1 1A1', and the 2 1A1', 2 3A1', and 1 1E' excited states of H3+.

PubMed

Pavanello, Michele; Adamowicz, Ludwik

2009-01-21

Accurate variational Born-Oppenheimer calculations of the 1 (1)A(1) ('), 2 (1)A(1) ('), 2 (3)A(1) ('), and 1 (1)E(') states of the H(3) (+) ion at the ground-state equilibrium geometry are reported. The wave functions of the states are expanded in terms of explicitly correlated spherical Gaussian functions with shifted centers. In the variational optimization the analytical gradient of the energy with respect to the nonlinear exponential parameters of the Gaussians has been employed. The energies obtained in the calculations are the best variational estimates ever calculated for the four states. One-electron densities for the states, as well as a D(3h)-restricted potential energy surface of the ground state calculated around the equilibrium geometry, are also presented and discussed.

A comparison of three algebraic stress closures for combustor flow calculations

NASA Technical Reports Server (NTRS)

Nikjooy, M.; So, R. M. C.; Hwang, B. C.

1985-01-01

A comparison is made of the performance of two locally nonequilibrium and one equilibrium algebraic stress closures in calculating combustor flows. Effects of four different pressure-strain models on these closure models are also analyzed. The results show that the pressure-strain models have a much greater influence on the calculated mean velocity and turbulence field than the algebraic stress closures, and that the best mean strain model for the pressure-strain terms is that proposed by Launder, Reece and Rodi (1975). However, the equilibrium algebraic stress closure with the Rotta return-to-isotropy model (1951) for the pressure-strain terms gives as good a correlation with measurements as when the Launder et al. mean strain model is included in the pressure-strain model. Finally, comparison of the calculations with the standard k-epsilon closure results show that the algebraic stress closures are better suited for simple turbulent flow calculations.

Arsenic Speciation in Groundwater: Role of Thioanions

EPA Science Inventory

The behavior of arsenic in groundwater environments is fundamentally linked to its speciation. Understanding arsenic speciation is important because chemical speciation impacts reactivity, bioavailability, toxicity, and transport and fate processes. In aerobic environments arsen...

Chromium speciation in environmental samples using a solid phase spectrophotometric method

NASA Astrophysics Data System (ADS)

Amin, Alaa S.; Kassem, Mohammed A.

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H2SO4 and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11 × 107 and 3.90 × 107 L mol-1 cm-1 for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L-1 with RSD of <1.85% (n = 8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L-1 for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L-1, respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested.

Estimation of speciated and total mercury dry deposition at monitoring locations in eastern and central North America

USGS Publications Warehouse

Zhang, L.; Blanchard, P.; Gay, D.A.; Prestbo, E.M.; Risch, M.R.; Johnson, D.; Narayan, J.; Zsolway, R.; Holsen, T.M.; Miller, E.K.; Castro, M.S.; Graydon, J.A.; St. Louis, V.L.; Dalziel, J.

2012-01-01

Dry deposition of speciated mercury, i.e., gaseous oxidized mercury (GOM), particulate-bound mercury (PBM), and gaseous elemental mercury (GEM), was estimated for the year 2008–2009 at 19 monitoring locations in eastern and central North America. Dry deposition estimates were obtained by combining monitored two- to four-hourly speciated ambient concentrations with modeled hourly dry deposition velocities (Vd) calculated using forecasted meteorology. Annual dry deposition of GOM+PBM was estimated to be in the range of 0.4 to 8.1 μg m−2 at these locations with GOM deposition being mostly five to ten times higher than PBM deposition, due to their different modeled Vd values. Net annual GEM dry deposition was estimated to be in the range of 5 to 26 μg m−2 at 18 sites and 33 μg m−2 at one site. The estimated dry deposition agrees very well with limited surrogate-surface dry deposition measurements of GOM and PBM, and also agrees with litterfall mercury measurements conducted at multiple locations in eastern and central North America. This study suggests that GEM contributes much more than GOM+PBM to the total dry deposition at the majority of the sites considered here; the only exception is at locations close to significant point sources where GEM and GOM+PBM contribute equally to the total dry deposition. The relative magnitude of the speciated dry deposition and their good comparisons with litterfall deposition suggest that mercury in litterfall originates primarily from GEM, which is consistent with the limited number of previous field studies. The study also supports previous analyses suggesting that total dry deposition of mercury is equal to, if not more important than, wet deposition of mercury on a regional scale in eastern North America.

Linearized theory of inhomogeneous multiple 'water-bag' plasmas

NASA Technical Reports Server (NTRS)

Bloomberg, H. W.; Berk, H. L.

1973-01-01

Equations are derived for describing the inhomogeneous equilibrium and small deviations from the equilibrium, giving particular attention to systems with trapped particles. An investigation is conducted of periodic systems with a single trapped-particle water bag, taking into account the behavior of the perturbation equations at the turning points. An outline is provided concerning a procedure for obtaining the eigenvalues. The results of stability calculations connected with the sideband effects are considered along with questions regarding the general applicability of the multiple water-bag approach in stability calculations.

The procedure and results of calculations of the equilibrium isotopic composition of a demonstration subcritical molten salt reactor

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

Nevinitsa, V. A., E-mail: Neviniza-VA@nrcki.ru; Dudnikov, A. A.; Blandinskiy, V. Yu.

2015-12-15

A subcritical molten salt reactor with an external neutron source is studied computationally as a facility for incineration and transmutation of minor actinides from spent nuclear fuel of reactors of VVER-1000 type and for producing {sup 233}U from {sup 232}Th. The reactor configuration is chosen, the requirements to be imposed on the external neutron source are formulated, and the equilibrium isotopic composition of heavy nuclides and the key parameters of the fuel cycle are calculated.

Thermodynamic equilibrium-air correlations for flowfield applications

NASA Technical Reports Server (NTRS)

Zoby, E. V.; Moss, J. N.

1981-01-01

Equilibrium-air thermodynamic correlations have been developed for flowfield calculation procedures. A comparison between the postshock results computed by the correlation equations and detailed chemistry calculations is very good. The thermodynamic correlations are incorporated in an approximate inviscid flowfield code with a convective heating capability for the purpose of defining the thermodynamic environment through the shock layer. Comparisons of heating rates computed by the approximate code and a viscous-shock-layer method are good. In addition to presenting the thermodynamic correlations, the impact of several viscosity models on the convective heat transfer is demonstrated.

Applications of Programmable Calculators in Chemistry Classes

ERIC Educational Resources Information Center

Holdsworth, David

1977-01-01

Described is the use of calculators in two experiments. In the first, students determine the relative atomic mass of magnesium. In the second, students use a calculator to determine a constant for gaseous concentrations of two reactants and the product at equilibrium. (AJ)

Sulfur diffusion in dacitic melt at various oxidation states: Implications for volcanic degassing

NASA Astrophysics Data System (ADS)

Lierenfeld, Matthias Bernhard; Zajacz, Zoltán; Bachmann, Olivier; Ulmer, Peter

2018-04-01

The diffusivity of S in a hydrous dacitic melt (4.5-6.0 wt.% H2O) has been investigated in the temperature (T) and pressure (P) range of 950 °C to 1100 °C and 200 to 250 MPa, respectively. Three series of experiments were conducted at relatively low oxygen fugacity (fO2) conditions [0.8 log units below fayalite-magnetite-quartz equilibrium (FMQ -0.8); referred to as "low fO2"] and high fO2 conditions (FMQ +2.5; referred to as "high fO2") to determine if the diffusivity of S is affected by its oxidation state and speciation. Sulfur concentration profiles were measured by electron microprobe and the diffusion coefficient (D) was calculated by fitting these profiles. Sulfur diffusion is approximately one order of magnitude faster when S is dominantly present as sulfide species (low fO2) in comparison to the sulfate dominated experiments (high fO2). The following Arrhenian equations were obtained for high and low fO2 conditions at 200 MPa: high fO2: D = 10-5.92±0.86 * exp ({-137.3±21.5 kJ/mol}/{RT}) low fO2: D = 10-5.18±1.39 * exp ({-125.7±34.4 kJ/mol}/{RT}) where D is the average diffusion coefficient in m2 s-1, R is the gas constant in 8.3144 J mol-1 K-1 and T is the temperature in K. Our results demonstrate for the first time in natural melts that S diffusion is strongly sensitive to fO2. Our S diffusivities under low fO2 conditions are only slightly slower of those found for H2O, suggesting that S can be rather efficiently purged from reduced dacitic melts during volcanic eruptions. However, for more oxidized systems (e.g. subduction zones), S diffusion will be much slower and will hinder equilibrium syn-eruptive degassing during rapid decompression. Therefore, we conclude that the "excess" measured during many explosive volcanic eruptions in arcs is dominantly derived from S-rich bubble accumulation in the eruptible portion of the magma reservoir.

Effect of adsorbed metals ions on the transport of Zn- and Ni-EDTA complexes in a sand and gravel aquifer

USGS Publications Warehouse

Kent, D.B.; Davis, J.A.; Anderson, L.C.D.; Rea, B.A.; Coston, J.A.

2002-01-01

Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales. Copyright ?? 2002 Elsevier Science Ltd.

Calculations of critical misfit and thickness: An overview

NASA Technical Reports Server (NTRS)

Vandermerwe, Jan H.; Jesser, W. A.

1988-01-01

This overview stresses the equilibrium/nonequilibrium nature of the physical properties, as well as the basic properties of the models, used to calculate critical misfit and critical thickness in epitaxy.

Islands as model systems in ecology and evolution: prospects fifty years after MacArthur-Wilson.

PubMed

Warren, Ben H; Simberloff, Daniel; Ricklefs, Robert E; Aguilée, Robin; Condamine, Fabien L; Gravel, Dominique; Morlon, Hélène; Mouquet, Nicolas; Rosindell, James; Casquet, Juliane; Conti, Elena; Cornuault, Josselin; Fernández-Palacios, José María; Hengl, Tomislav; Norder, Sietze J; Rijsdijk, Kenneth F; Sanmartín, Isabel; Strasberg, Dominique; Triantis, Kostas A; Valente, Luis M; Whittaker, Robert J; Gillespie, Rosemary G; Emerson, Brent C; Thébaud, Christophe

2015-02-01

The study of islands as model systems has played an important role in the development of evolutionary and ecological theory. The 50th anniversary of MacArthur and Wilson's (December 1963) article, 'An equilibrium theory of insular zoogeography', was a recent milestone for this theme. Since 1963, island systems have provided new insights into the formation of ecological communities. Here, building on such developments, we highlight prospects for research on islands to improve our understanding of the ecology and evolution of communities in general. Throughout, we emphasise how attributes of islands combine to provide unusual research opportunities, the implications of which stretch far beyond islands. Molecular tools and increasing data acquisition now permit re-assessment of some fundamental issues that interested MacArthur and Wilson. These include the formation of ecological networks, species abundance distributions, and the contribution of evolution to community assembly. We also extend our prospects to other fields of ecology and evolution - understanding ecosystem functioning, speciation and diversification - frequently employing assets of oceanic islands in inferring the geographic area within which evolution has occurred, and potential barriers to gene flow. Although island-based theory is continually being enriched, incorporating non-equilibrium dynamics is identified as a major challenge for the future. © 2014 John Wiley & Sons Ltd/CNRS.

Adsorption behavior of sulfamethazine in an activated sludge process treating swine wastewater.

PubMed

Ben, Weiwei; Qiang, Zhimin; Yin, Xiaowei; Qu, Jiuhui; Pan, Xun

2014-08-01

Swine wastewater is an important pollution source of antibiotics entering the aquatic environment. In this work, the adsorption behavior of sulfamethazine (SMN), a commonly-used sulfonamide antibiotic, on activated sludge from a sequencing batch reactor treating swine wastewater was investigated. The results show that the adsorption of SMN on activated sludge was an initially rapid process and reached equilibrium after 6hr. The removal efficiency of SMN from the water phase increased with an increasing concentration of mixed liquor suspended solids, while the adsorbed concentration of SMN decreased. Solution pH influenced both the speciation of SMN and the surface properties of activated sludge, thus significantly impacting the adsorption process. A linear partition model could give a good fit for the equilibrium concentrations of SMN at the test temperatures (i.e., 10, 20 and 30°C). The partition coefficient (Kd) was determined to be 100.5L/kg at 20°C, indicating a quite high adsorption capacity for SMN. Thermodynamic analysis revealed that SMN adsorption on activated sludge was an exothermic process. This study could help to clarify the fate and behavior of sulfonamide antibiotics in the activated sludge process and assess consequent environmental risks arising from sludge disposal as well. Copyright © 2014. Published by Elsevier B.V.

Interfacial free energy and stiffness of aluminum during rapid solidification

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

Brown, Nicholas T.; Martinez, Enrique; Qu, Jianmin

Using molecular dynamics simulations and the capillary fluctuation method, we have calculated the anisotropic crystal-melt interfacial free energy and stiffness of aluminum in a rapid solidification system where a temperature gradient is applied to enforce thermal non-equilibrium. To calculate these material properties, the standard capillary fluctuation method typically used for systems in equilibrium has been modified to incorporate a second-order Taylor expansion of the interfacial free energy term. The result is a robust method for calculating interfacial energy, stiffness and anisotropy as a function of temperature gradient using the fluctuations in the defined interface height. This work includes the calculationmore » of interface characteristics for temperature gradients ranging from 11 to 34 K/nm. The captured results are compared to a thermal equilibrium case using the same model and simulation technique with a zero gradient definition. We define the temperature gradient as the change in temperature over height perpendicular to the crystal-melt interface. The gradients are applied in MD simulations using defined thermostat regions on a stable solid-liquid interface initially in thermal equilibrium. The results of this work show that the interfacial stiffness and free energy for aluminum are dependent on the magnitude of the temperature gradient, however the anisotropic parameters remain independent of the non-equilibrium conditions applied in this analysis. As a result, the relationships of the interfacial free energy/stiffness are determined to be linearly related to the thermal gradient, and can be interpolated to find material characteristics at additional temperature gradients.« less

Interfacial free energy and stiffness of aluminum during rapid solidification

DOE PAGES

Brown, Nicholas T.; Martinez, Enrique; Qu, Jianmin

2017-05-01

Using molecular dynamics simulations and the capillary fluctuation method, we have calculated the anisotropic crystal-melt interfacial free energy and stiffness of aluminum in a rapid solidification system where a temperature gradient is applied to enforce thermal non-equilibrium. To calculate these material properties, the standard capillary fluctuation method typically used for systems in equilibrium has been modified to incorporate a second-order Taylor expansion of the interfacial free energy term. The result is a robust method for calculating interfacial energy, stiffness and anisotropy as a function of temperature gradient using the fluctuations in the defined interface height. This work includes the calculationmore » of interface characteristics for temperature gradients ranging from 11 to 34 K/nm. The captured results are compared to a thermal equilibrium case using the same model and simulation technique with a zero gradient definition. We define the temperature gradient as the change in temperature over height perpendicular to the crystal-melt interface. The gradients are applied in MD simulations using defined thermostat regions on a stable solid-liquid interface initially in thermal equilibrium. The results of this work show that the interfacial stiffness and free energy for aluminum are dependent on the magnitude of the temperature gradient, however the anisotropic parameters remain independent of the non-equilibrium conditions applied in this analysis. As a result, the relationships of the interfacial free energy/stiffness are determined to be linearly related to the thermal gradient, and can be interpolated to find material characteristics at additional temperature gradients.« less

Bats (Chiroptera: Noctilionoidea) Challenge a Recent Origin of Extant Neotropical Diversity.

PubMed

Rojas, Danny; Warsi, Omar M; Dávalos, Liliana M

2016-05-01

The mechanisms underlying the high extant biodiversity in the Neotropics have been controversial since the 19th century. Support for the influence of period-specific changes on diversification often rests on detecting more speciation events during a particular period. The timing of speciation events may reflect the influence of incomplete taxon sampling, protracted speciation, and null processes of lineage accumulation. Here we assess the influence of these factors on the timing of speciation with new multilocus data for New World noctilionoid bats (Chiroptera: Noctilionoidea). Biogeographic analyses revealed the importance of the Neotropics in noctilionoid diversification, and the critical role of dispersal. We detected no shift in speciation rate associated with the Quaternary or pre-Quaternary periods, and instead found an increase in speciation linked to the evolution of the subfamily Stenodermatinae (∼18 Ma). Simulations modeling constant speciation and extinction rates for the phylogeny systematically showed more speciation events in the Quaternary. Since recording more divergence events in the Quaternary can result from lineage accumulation, the age of extant sister species cannot be interpreted as supporting higher speciation rates during this period. Instead, analyzing the factors that influence speciation requires modeling lineage-specific traits and environmental, spatial, and ecological drivers of speciation. © The Author(s) 2016. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Frequency-dependent selection predicts patterns of radiations and biodiversity.

PubMed

Melián, Carlos J; Alonso, David; Vázquez, Diego P; Regetz, James; Allesina, Stefano

2010-08-26

Most empirical studies support a decline in speciation rates through time, although evidence for constant speciation rates also exists. Declining rates have been explained by invoking pre-existing niches, whereas constant rates have been attributed to non-adaptive processes such as sexual selection and mutation. Trends in speciation rate and the processes underlying it remain unclear, representing a critical information gap in understanding patterns of global diversity. Here we show that the temporal trend in the speciation rate can also be explained by frequency-dependent selection. We construct a frequency-dependent and DNA sequence-based model of speciation. We compare our model to empirical diversity patterns observed for cichlid fish and Darwin's finches, two classic systems for which speciation rates and richness data exist. Negative frequency-dependent selection predicts well both the declining speciation rate found in cichlid fish and explains their species richness. For groups like the Darwin's finches, in which speciation rates are constant and diversity is lower, speciation rate is better explained by a model without frequency-dependent selection. Our analysis shows that differences in diversity may be driven by incipient species abundance with frequency-dependent selection. Our results demonstrate that genetic-distance-based speciation and frequency-dependent selection are sufficient to explain the high diversity observed in natural systems and, importantly, predict decay through time in speciation rate in the absence of pre-existing niches.

An Excel-based tool for evaluating and visualizing geothermobarometry data

NASA Astrophysics Data System (ADS)

Hora, John Milan; Kronz, Andreas; Möller-McNett, Stefan; Wörner, Gerhard

2013-07-01

Application of geothermobarometry based on equilibrium exchange of chemical components between two mineral phases in natural samples frequently leads to the dilemma of either: (1) relying on relatively few measurements where there is a high likelihood of equilibrium, or (2) using many analysis pairs, where a significant proportion may not be useful and must be filtered out. The second approach leads to the challenges of (1) evaluation of equilibrium for large numbers of analysis pairs, (2) finding patterns in the dataset where multiple populations exist, and (3) visualizing relationships between calculated temperatures and compositional and textural parameters. Given the limitations of currently-used thermobarometry spreadsheets, we redesign them in a way that eliminates tedium by automating data importing, quality control and calculations, while making all results visible in a single view. Rather than using a traditional spreadsheet layout, we array the calculations in a grid. Each color-coded grid node contains the calculated temperature result corresponding to the intersection of two analyses given in the corresponding column and row. We provide Microsoft Excel templates for some commonly-used thermometers, that can be modified for use with any geothermometer or geobarometer involving two phases. Conditional formatting and ability to sort according to any chosen parameter simplifies pattern recognition, while tests for equilibrium can be incorporated into grid calculations. A case study of rhyodacite domes at Parinacota volcano, Chile, indicates a single population of Fe-Ti oxide temperatures, despite Mg-Mn compositional variability. Crystal zoning and differing thermal histories are, however, evident as a bimodal population of plagioclase-amphibole temperatures. Our approach aids in identification of suspect analyses and xenocrysts and visualization of links between temperature and phase composition. This facilitates interpretation of whether heat transfer was accompanied by bulk mass transfer, and to what degree diffusion has homogenized calculated temperature results in hybrid magmas.

Observations and Thermochemical Calculations for Hot-Jupiter Atmospheres

NASA Astrophysics Data System (ADS)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver; Cubillos, Patricio; Stemm, Madison

2015-01-01

I present Spitzer eclipse observations for WASP-14b and WASP-43b, an open source tool for thermochemical equilibrium calculations, and components of an open source tool for atmospheric parameter retrieval from spectroscopic data. WASP-14b is a planet that receives high irradiation from its host star, yet, although theory does not predict it, the planet hosts a thermal inversion. The WASP-43b eclipses have signal-to-noise ratios of ~25, one of the largest among exoplanets. To assess these planets' atmospheric composition and thermal structure, we developed an open-source Bayesian Atmospheric Radiative Transfer (BART) code. My dissertation tasks included developing a Thermochemical Equilibrium Abundances (TEA) code, implementing the eclipse geometry calculation in BART's radiative transfer module, and generating parameterized pressure and temperature profiles so the radiative-transfer module can be driven by the statistical module.To initialize the radiative-transfer calculation in BART, TEA calculates the equilibrium abundances of gaseous molecular species at a given temperature and pressure. It uses the Gibbs-free-energy minimization method with an iterative Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. The code is tested against the original method developed by White at al. (1958), the analytic method developed by Burrows and Sharp (1999), and the Newton-Raphson method implemented in the open-source Chemical Equilibrium with Applications (CEA) code. TEA, written in Python, is modular, documented, and available to the community via the open-source development site GitHub.com.Support for this work was provided by NASA Headquarters under the NASA Earth and Space Science Fellowship Program, grant NNX12AL83H, by NASA through an award issued by JPL/Caltech, and through the Science Mission Directorate's Planetary Atmospheres Program, grant NNX12AI69G.

An experimental and theoretical method for determination of standard electrode potential for the redox couple diphenyl sulfone/diphenyl sulfide

NASA Astrophysics Data System (ADS)

Song, Y. Z.; Wei, K. X.; Lv, J. S.

2013-12-01

DFT calculations were performed for diphenyl sulfide and diphenyl sulfone. The electrochemistry of diphenyl sulfide on the gold electrode was investigated by cyclic voltammety and the results show that standard electrode potential for redox couple diphenyl sulfone/diphenyl sulfide is 1.058 V, which is consistent with that of 1.057 calculated at B3LYP/6-31++G( d, p)-IEFPCM level. The front orbit theory and Mulliken charges of molecular explain well on the oxidation of diphenyl sulfide in oxidative desulfurization. According to equilibrium theory the experimental equilibrium constant in the oxidative desulfurization of H2O2, is 1.17 × 1048, which is consistent with the theoretical equilibrium constant is 2.18 × 1048 at B3LYP/6-31++G( d, p)-IEFPCM level.

A computer program for two-dimensional and axisymmetric nonreacting perfect gas and equilibrium chemically reacting laminar, transitional and-or turbulent boundary layer flows

NASA Technical Reports Server (NTRS)

Miner, E. W.; Anderson, E. C.; Lewis, C. H.

1971-01-01

A computer program is described in detail for laminar, transitional, and/or turbulent boundary-layer flows of non-reacting (perfect gas) and reacting gas mixtures in chemical equilibrium. An implicit finite difference scheme was developed for both two dimensional and axisymmetric flows over bodies, and in rocket nozzles and hypervelocity wind tunnel nozzles. The program, program subroutines, variables, and input and output data are described. Also included is the output from a sample calculation of fully developed turbulent, perfect gas flow over a flat plate. Input data coding forms and a FORTRAN source listing of the program are included. A method is discussed for obtaining thermodynamic and transport property data which are required to perform boundary-layer calculations for reacting gases in chemical equilibrium.

A theoretical DFT study on the structural parameters and azide-tetrazole equilibrium in substituted azidothiazole systems.

PubMed

Abu-Eittah, Rafie H; El-Kelany, Khaled E

2012-12-01

Azido-tetrazole equilibrium is sensitive to: substitution, solvent, temperature and phase. In this work, the effects of the type and position of substitution on the thiazole ring of azidothiazoles on its structural parameters and on the azido-tetrazole equilibrium have been theoretically investigated using the density functional procedures at the B3LYP/6-311G(∗∗) level of theory. This study includes the investigation of the equilibrium geometry, the transformation of the trans-conformer to the cis one then the ring closure to the tetrazole isomer. The transition states of the two steps were located, confirmed and the structural parameters were calculated. In all the steps of calculations, geometry optimization was considered. The results obtained indicate that substitution by: -NO(2) and -CN group shifts the equilibrium to the azide side and in some cases the tetrazole isomer is not obtained. On the other hand, substitution by: -NH(2) and -OH groups shifts the equilibrium to the tetrazole side and in some cases the azide isomer is not obtained and if formed changes spontaneously to the tetrazole isomer. The decisive parameters which determine the position of the equilibrium are: charge density on atoms N3 and N8, rearrangement of bond length and bond angles during the process of cyclization and variation of dipole moment as a result of cyclization. Results of this work indicate that substitution on C5 is more efficient than substitution on C4 of the thiazole ring. Copyright © 2012 Elsevier B.V. All rights reserved.

Advanced methods for preparation and characterization of infrared detector materials. [mercury cadmium telluride alloys

NASA Technical Reports Server (NTRS)

Lehoczky, S. L.; Szofran, F. R.

1981-01-01

Differential thermal analysis data were obtained on mercury cadmium telluride alloys in order to establish the liquidus temperatures for the various alloy compositions. Preliminary theoretical analyses was performed to establish the ternary phase equilibrium parameters for the metal rich region of the phase diagram. Liquid-solid equilibrium parameters were determined for the pseudobinary alloy system. Phase equilibrium was calculated and Hg(l-x) Cd(x) Te alloys were directionally solidified from pseudobinary melts. Electrical resistivity and Hall coefficient measurements were obtained.

Aqueous fluid composition in CI chondritic materials: Chemical equilibrium assessments in closed systems

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Yu.

2012-08-01

Solids of nearly solar composition have interacted with aqueous fluids on carbonaceous asteroids, icy moons, and trans-neptunian objects. These processes altered mineralogy of accreted materials together with compositions of aqueous and gaseous phases. We evaluated chemistry of aqueous solutions coexisted with CI-type chondritic solids through calculations of chemical equilibria in closed water-rock-gas systems at different compositions of initial fluids, water/rock mass ratios (0.1-1000), temperatures (<350 °C), and pressures (<2 kbars). The calculations show that fluid compositions are mainly affected by solubilities of solids, the speciation of chlorine in initial water-rock mixtures, and the occurrence of Na-bearing secondary minerals such as saponite. The major species in modeled alkaline solutions are Na+, Cl-, CO32-,HCO3-, K+, OH-, H2, and CO2. Aqueous species of Mg, Fe, Ca, Mn, Al, Ni, Cr, S, and P are not abundant in these fluids owing to low solubility of corresponding solids. Typical NaCl type alkaline fluids coexist with saponite-bearing mineralogy that usually present in aqueously altered chondrites. A common occurrence of these fluids is consistent with the composition of grains emitted from Enceladus. Na-rich fluids with abundant CO32-,HCO3-, and OH- anions coexist with secondary mineralogy depleted in Na. The Na2CO3 and NaHCO3 type fluids could form via accretion of cometary ices. NaOH type fluids form in reduced environments and may locally occur on parent bodies of CR carbonaceous chondrites. Supposed melting of accreted HCl-bearing ices leads to early acidic fluids enriched in Mg, Fe and other metals, consistent with signs of low-pH alteration in chondrites. Neutralization of these solutions leads to alkaline Na-rich fluids. Sulfate species have negligible concentrations in closed systems, which remain reduced, especially at elevated pressures created by forming H2 gas. Hydrogen, CO2, and H2O dominate in the gaseous phase, though the abundance of methane cannot be fairly estimated.

Carbon dioxide sequestration induced mineral precipitation healing of fractured reservoir seals

NASA Astrophysics Data System (ADS)

Welch, N.; Crawshaw, J.

2017-12-01

Initial experiments and the thermodynaic basis for carbon dioxide sequestration induced mineral precipitation healing of fractures through reservoir seals will be presented. The basis of this work is the potential exists for the dissolution of reservoir host rock formation carbonate minerals in the acidified injection front of CO2 during sequestration or EOR. This enriched brine and the bulk CO2 phase will then flow through the reservoir until contact with the reservoir seal. At this point any fractures present in the reservoir seal will be the preferential flow path for the bulk CO2 phase as well as the acidified brine front. These fractures would currently be filled with non-acidified brine saturated in seal formation brine. When the acidifeid brine from the host formation and the cap rock brine mix there is the potential for minerals to fall out of solution, and for these precipitated minerals to decrease or entirely cut off the fluid flow through the fractures present in a reservoir seal. Initial equilibrium simulations performed using the PHREEQC1 database drived from the PHREEQE2 database are used to show the favorable conditions under which this mineral precipitation can occurs. Bench scale fluid mixing experiments were then performed to determine the kinetics of the mineral precipitation process, and determine the progress of future experiemnts involving fluid flow within fractured anhydrite reservoir seal samples. 1Parkhurst, D.L., and Appelo, C.A.J., 2013, Description of input and examples for PHREEQC version 3—A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations: U.S. Geological Survey Techniques and Methods, book 6, chap. A43, 497 p., available only at https://pubs.usgs.gov/tm/06/a43/. 2Parkhurst, David L., Donald C. Thorstenson, and L. Niel Plummer. PHREEQE: a computer program for geochemical calculations. No. 80-96. US Geological Survey, Water Resources Division,, 1980.

On the Future of Thermochemical Databases, the Development of Solution Models and the Practical Use of Computational Thermodynamics in Volcanology, Geochemistry and Petrology: Can Innovations of Modern Data Science Democratize an Oligarchy?

NASA Astrophysics Data System (ADS)

Ghiorso, M. S.

2014-12-01

Computational thermodynamics (CT) has now become an essential tool of petrologic and geochemical research. CT is the basis for the construction of phase diagrams, the application of geothermometers and geobarometers, the equilibrium speciation of solutions, the construction of pseudosections, calculations of mass transfer between minerals, melts and fluids, and, it provides a means of estimating materials properties for the evaluation of constitutive relations in fluid dynamical simulations. The practical application of CT to Earth science problems requires data. Data on the thermochemical properties and the equation of state of relevant materials, and data on the relative stability and partitioning of chemical elements between phases as a function of temperature and pressure. These data must be evaluated and synthesized into a self consistent collection of theoretical models and model parameters that is colloquially known as a thermodynamic database. Quantitative outcomes derived from CT reply on the existence, maintenance and integrity of thermodynamic databases. Unfortunately, the community is reliant on too few such databases, developed by a small number of research groups, and mostly under circumstances where refinement and updates to the database lag behind or are unresponsive to need. Given the increasing level of reliance on CT calculations, what is required is a paradigm shift in the way thermodynamic databases are developed, maintained and disseminated. They must become community resources, with flexible and assessable software interfaces that permit easy modification, while at the same time maintaining theoretical integrity and fidelity to the underlying experimental observations. Advances in computational and data science give us the tools and resources to address this problem, allowing CT results to be obtained at the speed of thought, and permitting geochemical and petrological intuition to play a key role in model development and calibration.

EPAs SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of source category-specific particulate matter (PM), volatile organic gas, and other gas speciation profiles of air pollutant emissions. Abt Associates, Inc. developed SPECIATE 4.4 through a collaborat...

SPECIATE Version 4.4 Database Development Documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Some of the many uses of these source profiles include: (1) creating speciated emissions inventories for regi...

SPECIATE - EPA'S DATABASE OF SPECIATED EMISSION PROFILES

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of total organic compound (TOC) and particulate matter (PM) speciation profiles for emissions from air pollution sources. The data base has recently been updated and an associated report has recently been re...

Speciation has a spatial scale that depends on levels of gene flow.

PubMed

Kisel, Yael; Barraclough, Timothy G

2010-03-01

Area is generally assumed to affect speciation rates, but work on the spatial context of speciation has focused mostly on patterns of range overlap between emerging species rather than on questions of geographical scale. A variety of geographical theories of speciation predict that the probability of speciation occurring within a given region should (1) increase with the size of the region and (2) increase as the spatial extent of intraspecific gene flow becomes smaller. Using a survey of speciation events on isolated oceanic islands for a broad range of taxa, we find evidence for both predictions. The probability of in situ speciation scales with island area in bats, carnivorous mammals, birds, flowering plants, lizards, butterflies and moths, and snails. Ferns are an exception to these findings, but they exhibit high frequencies of polyploid and hybrid speciation, which are expected to be scale independent. Furthermore, the minimum island size for speciation correlates across groups with the strength of intraspecific gene flow, as is estimated from a meta-analysis of published population genetic studies. These results indicate a general geographical model of speciation rates that are dependent on both area and gene flow. The spatial scale of population divergence is an important but neglected determinant of broad-scale diversity patterns.

Application of the Firefly and Luus-Jaakola algorithms in the calculation of a double reactive azeotrope

NASA Astrophysics Data System (ADS)

Mendes Platt, Gustavo; Pinheiro Domingos, Roberto; Oliveira de Andrade, Matheus

2014-01-01

The calculation of reactive azeotropes is an important task in the preliminary design and simulation of reactive distillation columns. Classically, homogeneous nonreactive azeotropes are vapor-liquid coexistence conditions where phase compositions are equal. For homogeneous reactive azeotropes, simultaneous phase and chemical equilibria occur concomitantly with equality of compositions (in the Ung-Doherty transformed space). The modeling of reactive azeotrope calculation is represented by a nonlinear algebraic system with phase equilibrium, chemical equilibrium and azeotropy equations. This nonlinear system can exhibit more than one solution, corresponding to a double reactive azeotrope. In a previous paper (Platt et al 2013 J. Phys.: Conf. Ser. 410 012020), we investigated some numerical aspects of the calculation of reactive azeotropes in the isobutene + methanol + methyl-tert-butyl-ether (with two reactive azeotropes) system using two metaheuristics: the Luus-Jaakola adaptive random search and the Firefly algorithm. Here, we use a hybrid structure (stochastic + deterministic) in order to produce accurate results for both azeotropes. After identifying the neighborhood of the reactive azeotrope, the nonlinear algebraic system is solved using Newton's method. The results indicate that using metaheuristics and some techniques devoted to the calculation of multiple minima allows both azeotropic coordinates in this reactive system to be obtains. In this sense, we provide a comprehensive analysis of a useful framework devoted to solving nonlinear systems, particularly in phase equilibrium problems.

Reduced Equations for Calculating the Combustion Rates of Jet-A and Methane Fuel

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2003-01-01

Simplified kinetic schemes for Jet-A and methane fuels were developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) that is being developed at Glenn. These kinetic schemes presented here result in a correlation that gives the chemical kinetic time as a function of initial overall cell fuel/air ratio, pressure, and temperature. The correlations would then be used with the turbulent mixing times to determine the limiting properties and progress of the reaction. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentration of carbon monoxide as a function of fuel air ratio, pressure, and temperature. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates and the values obtained from the equilibrium correlations were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide, and NOx were obtained for both Jet-A fuel and methane.

Bayesian Atmospheric Radiative Transfer (BART)Thermochemical Equilibrium Abundance (TEA) Code and Application to WASP-43b

NASA Astrophysics Data System (ADS)

Blecic, Jasmina; Harrington, Joseph; Bowman, Matthew O.; Cubillos, Patricio E.; Stemm, Madison; Foster, Andrew

2014-11-01

We present a new, open-source, Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. TEA uses the Gibbs-free-energy minimization method with an iterative Lagrangian optimization scheme. It initializes the radiative-transfer calculation in our Bayesian Atmospheric Radiative Transfer (BART) code. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. The code is tested against the original method developed by White at al. (1958), the analytic method developed by Burrows and Sharp (1999), and the Newton-Raphson method implemented in the open-source Chemical Equilibrium with Applications (CEA) code. TEA is written in Python and is available to the community via the open-source development site GitHub.com. We also present BART applied to eclipse depths of WASP-43b exoplanet, constraining atmospheric thermal and chemical parameters. This work was supported by NASA Planetary Atmospheres grant NNX12AI69G and NASA Astrophysics Data Analysis Program grant NNX13AF38G. JB holds a NASA Earth and Space Science Fellowship.

Thermodynamic properties and transport coefficients of air thermal plasmas mixed with ablated vapors of Cu and polytetrafluoroethylene

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

Zhang, JunMin, E-mail: jmzhang@buaa.edu.cn, E-mail: guanyg@tsinghua.edu.cn; Lu, ChunRong; Guan, YongGang, E-mail: jmzhang@buaa.edu.cn, E-mail: guanyg@tsinghua.edu.cn

2015-10-15

Because the fault arc in aircraft electrical system often causes a fire, it is particularly important to analyze its energy and transfer for aircraft safety. The calculation of arc energy requires the basic parameters of the arc. This paper is mainly devoted to the calculations of equilibrium composition, thermodynamic properties (density, molar weight, enthalpy, and specific heat at constant pressure) and transport coefficients (thermal conductivity, electrical conductivity, and viscosity) of plasmas produced by a mixture of air, Cu, and polytetrafluoroethylene under the condition of local thermodynamic equilibrium. The equilibrium composition is determined by solving a system of equations around themore » number densities of each species. The thermodynamic properties are obtained according to the standard thermodynamic relationships. The transport coefficients are calculated using the Chapman-Enskog approximations. Results are presented in the temperature range from 3000 to 30 000 K for pressures of 0.08 and 0.1 MPa, respectively. The results are more accurate and are reliable reference data for theoretical analysis and computational simulation of the behavior of fault arc.« less

Tautomerism, molecular structure, intramolecular hydrogen bond, and enol-enol equilibrium of para halo substituted 4,4,4-trifluoro-1-phenyl-1,3-butanedione; Experimental and theoretical studies

NASA Astrophysics Data System (ADS)

Darugar, V. R.; Vakili, M.; Nekoei, A. R.; Tayyari, S. F.; Afzali, R.

2017-12-01

Para halo, X = F, Cl, and Br, substitution effect on tautomerism, keto-enol content, molecular structure, intramolecular hydrogen bonding, and enol-enol equilibrium constants of 4,4,4-trifluoro-1-phenyl-1,3-butanedione, known as trifluorobenzoylacetone (TFBA), have been investigated by means of density functional theory calculations and NMR, IR, and UV-Vis spectroscopic methods. Comparing the calculated and experimental results suggests coexisting of two stable cis-enol forms of titled molecules in comparable proportions in the sample. The theoretical and experimental results show that the equilibrium constants between both stable cis-enol forms of the studied molecules are similar, about 1.1-1.2. According to the AIM calculated results performed at the B3LYP/6-311++G∗∗ level, the target para halo molecules have a hydrogen bond strength of about 18.6 kcal/mol, as a medium hydrogen bond, similar to that of TFBA. The theoretical and experimental results indicate that there is no considerable difference between the hydrogen bond strength of the X-substituted titled molecules.

Study of evaporating the irradiated graphite in equilibrium low-temperature plasma

NASA Astrophysics Data System (ADS)

Bespala, E. V.; Novoselov, I. Yu.; Pavlyuk, A. O.; Kotlyarevskiy, S. G.

2018-01-01

The paper describes a problem of accumulation of irradiated graphite due to operation of uranium-graphite nuclear reactors. The main noncarbon contaminants that contribute to the overall activity of graphite elements are iso-topes 137Cs, 60Co, 90Sr, 36Cl, and 3H. A method was developed for processing of irradiated graphite ensuring the volu-metric decontamination of samples. The calculation results are presented for equilibrium composition of plasma-chemical reactions in systems "irradiated graphite-argon" and "irradiated graphite-helium" for a wide range of tem-peratures. The paper describes a developed mathematical model for the process of purification of a porous graphite surface treated by equilibrium low-temperature plasma. The simulation results are presented for the rate of sublimation of radioactive contaminants as a function of plasma temperature and plasma flow velocity when different plasma-forming gases are used. The extraction coefficient for the contaminant 137Cs from the outer side of graphite pores was calculated. The calculations demonstrated the advantages of using a lighter plasma forming gas, i.e., helium.

Recovery of oil from oil-in-water emulsion using biopolymers by adsorptive method.

PubMed

Elanchezhiyan, S Sd; Sivasurian, N; Meenakshi, Sankaran

2014-09-01

In the present study, it is aimed to identify, a low cost sorbent for the recovery of oil from oil-in-water emulsion using biopolymers such as chitin and chitosan. Chitin has the greater adsorption capacity than chitosan due to its hydrophobic nature. The characterizations of chitin and chitosan were done using FTIR, SEM, EDAX, XRD, TGA and DSC techniques. Under batch equilibrium mode, a systematic study was performed to optimize the various equilibrium parameters viz., contact time, pH, dosage, initial concentration of oil, and temperature. The adsorption process reached equilibrium at 40 min of contact time and the percentage removal of oil was found to be higher (90%) in the acidic medium. The Freundlich and Langmuir models were applied to describe the equilibrium isotherms and the isotherm constants were calculated. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated to find out the nature of the sorption mechanism. The kinetic studies were investigated with reaction-based and diffusion-based models. The suitable mechanism for the removal of oil has been established. Copyright © 2014 Elsevier B.V. All rights reserved.

Non-equilibrium transport in the quantum dot: quench dynamics and non-equilibrium steady state

NASA Astrophysics Data System (ADS)

Culver, Adrian; Andrei, Natan

We calculate the non-equilibrium current driven by a voltage drop across a quantum dot. The system is described by the two lead Anderson model at zero temperature with on-site Coulomb repulsion and non-interacting, linearized leads. We prepare the system in an initial state consisting of a free Fermi sea in each lead with the voltage drop given as the difference between the two Fermi levels. We quench the system by coupling the dot to the leads at t =0 and following the time evolution of the wavefunction. In the long time limit a new type of Bethe Ansatz wavefunction emerges, which satisfies the Lippmann-Schwinger equation with the two Fermi seas serving as the boundary conditions. The solution describes the non-equilibrium steady state of the system. We use this solution to compute the infinite time limit of the expectation value of the current operator at a given voltage, yielding the I-V characteristic. The calculation is non-perturbative and exact. Research supported by NSF Grant DMR 1410583.

An improved correlation to predict molecular weight between crosslinks based on equilibrium degree of swelling of hydrogel networks.

PubMed

Jimenez-Vergara, Andrea C; Lewis, John; Hahn, Mariah S; Munoz-Pinto, Dany J

2018-04-01

Accurate characterization of hydrogel diffusional properties is of substantial importance for a range of biotechnological applications. The diffusional capacity of hydrogels has commonly been estimated using the average molecular weight between crosslinks (M c ), which is calculated based on the equilibrium degree of swelling. However, the existing correlation linking M c and equilibrium swelling fails to accurately reflect the diffusional properties of highly crosslinked hydrogel networks. Also, as demonstrated herein, the current model fails to accurately predict the diffusional properties of hydrogels when polymer concentration and molecular weight are varied simultaneously. To address these limitations, we evaluated the diffusional properties of 48 distinct hydrogel formulations using two different photoinitiator systems, employing molecular size exclusion as an alternative methodology to calculate average hydrogel mesh size. The resulting data were then utilized to develop a revised correlation between M c and hydrogel equilibrium swelling that substantially reduces the limitations associated with the current correlation. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1339-1348, 2018. © 2017 Wiley Periodicals, Inc.

SPECIATE--EPA'S DATABASE OF SPECIATED EMISSION PROFILES

EPA Science Inventory

SPECIATE is EPA's repository of Total Organic Compound and Particulate Matter speciated profiles for a wide variety of sources. The profiles in this system are provided for air quality dispersion modeling and as a library for source-receptor and source apportionment type models. ...

SPECIATE 4.4: The Bridge Between Emissions Characterization and Modeling

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Some of the many uses of these source profiles include: (1) creating speciated emissions inventories for...

Venusian atmospheric equilibrium chemistry at the Pioneer Venus anomalous event altitude

NASA Technical Reports Server (NTRS)

Craig, Roger A.

1994-01-01

No convincing explanation for the anomalous behavior of the Atmospheric Structure Experiment temperature sensors at approximately 13 km altitude has been found. It occurred on all of the widely-spaced probes, in a similar fashion. A preliminary effort has been made to determine atmospheric chemical species which might be present at 13 km. The purpose of this effort is to initiate suggestions of possible chemical interactions and to explore the effects of the presence of possible metal reactants including condensation. Equilibrium fractions of chemical species were calculated at a variety of conditions. Baseline calculations were made for the altitudes near 13 km. For comparison calculations were also made at 13 km but with the introduction of plausible metal atoms.

Effects of Dissolved Carbonate on Arsenate Adsorption and Surface Speciation at the Hematite-Water Interface

USGS Publications Warehouse

Arai, Y.; Sparks, D.L.; Davis, J.A.

2004-01-01

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite-water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [PCO2 = 10 -3.5 atm and ???0; CO2-free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L -1, [As(V)]0 = 1.5 mM and / = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L-1, [As(V)] 0 = 0.5 mM and / = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems (PCO2 = 10-3.5 atm)than in the CO2-free argon system at pH 4-7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (???2.8 A??) and bidentate binuclear (???3.3 A??) bonding at pH 4.5-8 and loading levels of 0.46-3.10 ??M m-2. Using the results of the pseudoequilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the PCO2 = 10-3.5 atm and the CO2-free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO2(g).

The importance of trace element speciation in biomedical science.

PubMed

Templeton, Douglas M

2003-04-01

According to IUPAC terminology, trace element speciation reflects differences in chemical composition at multiple levels from nuclear and electronic structure to macromolecular complexation. In the medical sciences, all levels of composition are important in various circumstances, and each can affect the bioavailability, distribution, physiological function, toxicity, diagnostic utility, and therapeutic potential of an element. Here we discuss, with specific examples, three biological principles in the intimate relation between speciation and biological behavior: i) the kinetics of interconversion of species determines distribution within the organism, ii) speciation governs transport across various biological barriers, and iii) speciation can limit potentially undesirable interactions between physiologically essential elements. We will also describe differences in the speciation of iron in states of iron overload, to illustrate how speciation analysis can provide insight into cellular processes in human disease.

Near-equilibrium dumb-bell-shaped figures for cohesionless small bodies

NASA Astrophysics Data System (ADS)

Descamps, Pascal

2016-02-01

In a previous paper (Descamps, P. [2015]. Icarus 245, 64-79), we developed a specific method aimed to retrieve the main physical characteristics (shape, density, surface scattering properties) of highly elongated bodies from their rotational lightcurves through the use of dumb-bell-shaped equilibrium figures. The present work is a test of this method. For that purpose we introduce near-equilibrium dumb-bell-shaped figures which are base dumb-bell equilibrium shapes modulated by lognormal statistics. Such synthetic irregular models are used to generate lightcurves from which our method is successfully applied. Shape statistical parameters of such near-equilibrium dumb-bell-shaped objects are in good agreement with those calculated for example for the Asteroid (216) Kleopatra from its dog-bone radar model. It may suggest that such bilobed and elongated asteroids can be approached by equilibrium figures perturbed be the interplay with a substantial internal friction modeled by a Gaussian random sphere.

Model-based analysis of coupled equilibrium-kinetic processes: indirect kinetic studies of thermodynamic parameters using the dynamic data.

PubMed

Emami, Fereshteh; Maeder, Marcel; Abdollahi, Hamid

2015-05-07

Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.

Auxiliary principle technique and iterative algorithm for a perturbed system of generalized multi-valued mixed quasi-equilibrium-like problems.

PubMed

Rahaman, Mijanur; Pang, Chin-Tzong; Ishtyak, Mohd; Ahmad, Rais

2017-01-01

In this article, we introduce a perturbed system of generalized mixed quasi-equilibrium-like problems involving multi-valued mappings in Hilbert spaces. To calculate the approximate solutions of the perturbed system of generalized multi-valued mixed quasi-equilibrium-like problems, firstly we develop a perturbed system of auxiliary generalized multi-valued mixed quasi-equilibrium-like problems, and then by using the celebrated Fan-KKM technique, we establish the existence and uniqueness of solutions of the perturbed system of auxiliary generalized multi-valued mixed quasi-equilibrium-like problems. By deploying an auxiliary principle technique and an existence result, we formulate an iterative algorithm for solving the perturbed system of generalized multi-valued mixed quasi-equilibrium-like problems. Lastly, we study the strong convergence analysis of the proposed iterative sequences under monotonicity and some mild conditions. These results are new and generalize some known results in this field.

Ozone chemical equilibrium in the extended mesopause under the nighttime conditions

NASA Astrophysics Data System (ADS)

Belikovich, M. V.; Kulikov, M. Yu.; Grygalashvyly, M.; Sonnemann, G. R.; Ermakova, T. S.; Nechaev, A. A.; Feigin, A. M.

2018-01-01

For retrieval of atomic oxygen and atomic hydrogen via ozone observations in the extended mesopause region (∼70-100 km) under nighttime conditions, an assumption on photochemical equilibrium of ozone is often used in research. In this work, an assumption on chemical equilibrium of ozone near mesopause region during nighttime is proofed. We examine 3D chemistry-transport model (CTM) annual calculations and determine the ratio between the correct (modeled) distributions of the O3 density and its equilibrium values depending on the altitude, latitude, and season. The results show that the retrieval of atomic oxygen and atomic hydrogen distributions using an assumption on ozone chemical equilibrium may lead to large errors below ∼81-87 km. We give simple and clear semi-empirical criterion for practical utilization of the lower boundary of the area with ozone's chemical equilibrium near mesopause.

Examination of Arsenic Speciation in Sulfidic Solutions Using X-ray Absorption Spectroscopy

EPA Science Inventory

The chemical speciation of arsenic in sulfidic waters is complicated by the existence of thioarsenic species. The purpose of this research was to use advanced spectroscopy techniques along with speciation modeling and chromatography to elucidate the chemical speciation of As in ...

Computational methods for reactive transport modeling: An extended law of mass-action, xLMA, method for multiphase equilibrium calculations

NASA Astrophysics Data System (ADS)

Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg; Saar, Martin O.

2016-10-01

We present an extended law of mass-action (xLMA) method for multiphase equilibrium calculations and apply it in the context of reactive transport modeling. This extended LMA formulation differs from its conventional counterpart in that (i) it is directly derived from the Gibbs energy minimization (GEM) problem (i.e., the fundamental problem that describes the state of equilibrium of a chemical system under constant temperature and pressure); and (ii) it extends the conventional mass-action equations with Lagrange multipliers from the Gibbs energy minimization problem, which can be interpreted as stability indices of the chemical species. Accounting for these multipliers enables the method to determine all stable phases without presuming their types (e.g., aqueous, gaseous) or their presence in the equilibrium state. Therefore, the here proposed xLMA method inherits traits of Gibbs energy minimization algorithms that allow it to naturally detect the phases present in equilibrium, which can be single-component phases (e.g., pure solids or liquids) or non-ideal multi-component phases (e.g., aqueous, melts, gaseous, solid solutions, adsorption, or ion exchange). Moreover, our xLMA method requires no technique that tentatively adds or removes reactions based on phase stability indices (e.g., saturation indices for minerals), since the extended mass-action equations are valid even when their corresponding reactions involve unstable species. We successfully apply the proposed method to a reactive transport modeling problem in which we use PHREEQC and GEMS as alternative backends for the calculation of thermodynamic properties such as equilibrium constants of reactions, standard chemical potentials of species, and activity coefficients. Our tests show that our algorithm is efficient and robust for demanding applications, such as reactive transport modeling, where it converges within 1-3 iterations in most cases. The proposed xLMA method is implemented in Reaktoro, a unified open-source framework for modeling chemically reactive systems.

On exchange rate misalignments in the Eurozone's peripheral countries

NASA Astrophysics Data System (ADS)

Grochová, Ladislava; Plecitá, Klára

2013-10-01

In this paper we model equilibrium exchange rates for the Eurozone's countries on the basis of the Behavioural Equilibrium Exchange Rate approach, which assumes, that equilibrium exchange rates are in the long run affected by economic fundamentals. To assess the degree of exchange rate misalignment for the Eurozone's peripheral countries - Portugal, Ireland, Greece and Spain - the gap between the actual and the modelled equilibrium exchange rate value is calculated. Our results show that Spain, Portugal and Ireland had their real exchange rates in equilibrium when they joined the Eurozone; however their real exchange rates have been persistently overvalued since the beginning of the 2000s. Greece, on the other hand, has experienced diminishing undervaluation at the beginning of its membership in the Eurozone and since 2009 has exhibited an overvalued real exchange rate.

Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge.

PubMed

Hung, Nguyen Viet; Tateda, Masafumi; Ike, Michihiko; Fujita, Masanori; Tsunoi, Shinji; Tanaka, Minoru

2004-01-01

Nonylphenol(NP), nonylphenoxy acetic acid (NP1EC), nonylphenol monoethoxy acetic acid (NP2EC), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) are biodegradation end products (BEPs) of nonionic surfactant nonylphenolpolyethoxylates (NPnEO). In this research, sorption of these compounds onto model activated sludge was characterized. Sorption equilibrium experiments showed that NP, NP1EO and NP2EO reached equilibrium in about 12 h, while equilibrium of NP1EC and NP2EC were reached earlier, in about 4 h. In sorption isotherm experiments, obtained equilibrium data at 28 degrees C fitted well to Freundlich sorption model for all investigated compounds. For NP1EC, in addition to Freundlich, equilibrium data also fitted well to Langmuir model. Linear sorption model was also tried, and equilibrium data of all NP, NP1EO, NP2EO and NP2EC except NP1EC fitted well to this model. Calculated Freundlich coefficient (K(F)) and linear sorption coefficient (K(D)) showed that sorption capacity of the investigated compounds were in order NP > NP2EO > NP1EO > NP1EC approximately NP2EC. For NP, NP1EO and NP2EO, high values of calculated K(F) and K(D) indicated an easy uptake of these compounds from aqueous phase onto activated sludge. Whereas, NP1EC and NP2EC with low values of K(F) and K(D) absorbed weakly to activated sludge and tended to preferably remain in aqueous phase.

Speciation genetics: current status and evolving approaches

PubMed Central

Wolf, Jochen B. W.; Lindell, Johan; Backström, Niclas

2010-01-01

The view of species as entities subjected to natural selection and amenable to change put forth by Charles Darwin and Alfred Wallace laid the conceptual foundation for understanding speciation. Initially marred by a rudimental understanding of hereditary principles, evolutionists gained appreciation of the mechanistic underpinnings of speciation following the merger of Mendelian genetic principles with Darwinian evolution. Only recently have we entered an era where deciphering the molecular basis of speciation is within reach. Much focus has been devoted to the genetic basis of intrinsic postzygotic isolation in model organisms and several hybrid incompatibility genes have been successfully identified. However, concomitant with the recent technological advancements in genome analysis and a newfound interest in the role of ecology in the differentiation process, speciation genetic research is becoming increasingly open to non-model organisms. This development will expand speciation research beyond the traditional boundaries and unveil the genetic basis of speciation from manifold perspectives and at various stages of the splitting process. This review aims at providing an extensive overview of speciation genetics. Starting from key historical developments and core concepts of speciation genetics, we focus much of our attention on evolving approaches and introduce promising methodological approaches for future research venues. PMID:20439277

NLTE steady-state response matrix method.

NASA Astrophysics Data System (ADS)

Faussurier, G.; More, R. M.

2000-05-01

A connection between atomic kinetics and non-equilibrium thermodynamics has been recently established by using a collisional-radiative model modified to include line absorption. The calculated net emission can be expressed as a non-local thermodynamic equilibrium (NLTE) symmetric response matrix. In the paper, this connection is extended to both cases of the average-atom model and the Busquet's model (RAdiative-Dependent IOnization Model, RADIOM). The main properties of the response matrix still remain valid. The RADIOM source function found in the literature leads to a diagonal response matrix, stressing the absence of any frequency redistribution among the frequency groups at this order of calculation.

Double simple-harmonic-oscillator formulation of the thermal equilibrium of a fluid interacting with a coherent source of phonons

NASA Technical Reports Server (NTRS)

Defacio, B.; Vannevel, Alan; Brander, O.

1993-01-01

A formulation is given for a collection of phonons (sound) in a fluid at a non-zero temperature which uses the simple harmonic oscillator twice; one to give a stochastic thermal 'noise' process and the other which generates a coherent Glauber state of phonons. Simple thermodynamic observables are calculated and the acoustic two point function, 'contrast' is presented. The role of 'coherence' in an equilibrium system is clarified by these results and the simple harmonic oscillator is a key structure in both the formulation and the calculations.

Theoretical and experimental investigation of the destruction of graphites in a flow of dissociated air

NASA Technical Reports Server (NTRS)

Bovina, T. A.; Zviagin, Y. V.; Markelov, N. V.; Chudetskiy, Y. V.

1986-01-01

A method is presented for calculating the heating and erosion of blunt bodies made of graphite in a high-enthalpy flow of dissociated air, assuming chemical equilibrium on the surface and taking account of the thermal effects of combustion and sublimation of graphite. The analysis involves the use of a finite difference scheme to solve an equation of unsteady heat conduction. Attention is given to the equilibrium vaporization of C, C2 and C3 molecules. The calculations agree well with experimental data for a wide range of temperatures and stagnation pressures.

An interactive computer code for calculation of gas-phase chemical equilibrium (EQLBRM)

NASA Technical Reports Server (NTRS)

Pratt, B. S.; Pratt, D. T.

1984-01-01

A user friendly, menu driven, interactive computer program known as EQLBRM which calculates the adiabatic equilibrium temperature and product composition resulting from the combustion of hydrocarbon fuels with air, at specified constant pressure and enthalpy is discussed. The program is developed primarily as an instructional tool to be run on small computers to allow the user to economically and efficiency explore the effects of varying fuel type, air/fuel ratio, inlet air and/or fuel temperature, and operating pressure on the performance of continuous combustion devices such as gas turbine combustors, Stirling engine burners, and power generation furnaces.

Calculating Equilibrium Constants in the SnCl2-H2O-NaOH System According to Potentiometric Titration Data

NASA Astrophysics Data System (ADS)

Maskaeva, L. N.; Fedorova, E. A.; Yusupov, R. A.; Markov, V. F.

2018-05-01

The potentiometric titration of tin chloride SnCl2 is performed in the concentration range of 0.00009-1.1 mol/L with a solution of sodium hydroxide NaOH. According to potentiometric titration data based on modeling equilibria in the SnCl2-H2O-NaOH system, basic equations are generated for the main processes, and instability constants are calculated for the resulting hydroxo complexes and equilibrium constants of low-soluble tin(II) compounds. The data will be of interest for specialists in the field of theory of solutions.

Electron-Impact Excitation Cross Sections for Modeling Non-Equilibrium Gas

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Liu, Yen; Panesi, Marco; Munafo, Alessandro; Wray, Alan; Carbon, Duane F.

2015-01-01

In order to provide a database for modeling hypersonic entry in a partially ionized gas under non-equilibrium, the electron-impact excitation cross sections of atoms have been calculated using perturbation theory. The energy levels covered in the calculation are retrieved from the level list in the HyperRad code. The downstream flow-field is determined by solving a set of continuity equations for each component. The individual structure of each energy level is included. These equations are then complemented by the Euler system of equations. Finally, the radiation field is modeled by solving the radiative transfer equation.

Phase stability in nanoscale material systems: extension from bulk phase diagrams

NASA Astrophysics Data System (ADS)

Bajaj, Saurabh; Haverty, Michael G.; Arróyave, Raymundo; Goddard Frsc, William A., III; Shankar, Sadasivan

2015-05-01

Phase diagrams of multi-component systems are critical for the development and engineering of material alloys for all technological applications. At nano dimensions, surfaces (and interfaces) play a significant role in changing equilibrium thermodynamics and phase stability. In this work, it is shown that these surfaces at small dimensions affect the relative equilibrium thermodynamics of the different phases. The CALPHAD approach for material surfaces (also termed ``nano-CALPHAD'') is employed to investigate these changes in three binary systems by calculating their phase diagrams at nano dimensions and comparing them with their bulk counterparts. The surface energy contribution, which is the dominant factor in causing these changes, is evaluated using the spherical particle approximation. It is first validated with the Au-Si system for which experimental data on phase stability of spherical nano-sized particles is available, and then extended to calculate phase diagrams of similarly sized particles of Ge-Si and Al-Cu. Additionally, the surface energies of the associated compounds are calculated using DFT, and integrated into the thermodynamic model of the respective binary systems. In this work we found changes in miscibilities, reaction compositions of about 5 at%, and solubility temperatures ranging from 100-200 K for particles of sizes 5 nm, indicating the importance of phase equilibrium analysis at nano dimensions.Phase diagrams of multi-component systems are critical for the development and engineering of material alloys for all technological applications. At nano dimensions, surfaces (and interfaces) play a significant role in changing equilibrium thermodynamics and phase stability. In this work, it is shown that these surfaces at small dimensions affect the relative equilibrium thermodynamics of the different phases. The CALPHAD approach for material surfaces (also termed ``nano-CALPHAD'') is employed to investigate these changes in three binary systems by calculating their phase diagrams at nano dimensions and comparing them with their bulk counterparts. The surface energy contribution, which is the dominant factor in causing these changes, is evaluated using the spherical particle approximation. It is first validated with the Au-Si system for which experimental data on phase stability of spherical nano-sized particles is available, and then extended to calculate phase diagrams of similarly sized particles of Ge-Si and Al-Cu. Additionally, the surface energies of the associated compounds are calculated using DFT, and integrated into the thermodynamic model of the respective binary systems. In this work we found changes in miscibilities, reaction compositions of about 5 at%, and solubility temperatures ranging from 100-200 K for particles of sizes 5 nm, indicating the importance of phase equilibrium analysis at nano dimensions. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01535a

Assessment of Important SPECIATE Profiles in EPA’s Emissions Modeling Platform and Current Data Gaps

EPA Science Inventory

The US Environmental Protection Agency (EPA)’s SPECIATE database contains speciation profiles for both particulate matter (PM) and volatile organic compounds (VOCs) that are key inputs for creating speciated emission inventories for air quality modeling. The objective of th...

Modeling Anaerobic Soil Organic Carbon Decomposition in Arctic Polygon Tundra: Insights into Soil Geochemical Influences on Carbon Mineralization: Modeling Archive

DOE Data Explorer

Zheng, Jianqiu; Thornton, Peter; Painter, Scott; Gu, Baohua; Wullschleger, Stan; Graham, David

2018-06-13

This anaerobic carbon decomposition model is developed with explicit representation of fermentation, methanogenesis and iron reduction by combining three well-known modeling approaches developed in different disciplines. A pool-based model to represent upstream carbon transformations and replenishment of DOC pool, a thermodynamically-based model to calculate rate kinetics and biomass growth for methanogenesis and Fe(III) reduction, and a humic ion-binding model for aqueous phase speciation and pH calculation are implemented into the open source geochemical model PHREEQC (V3.0). Installation of PHREEQC is required to run this model.

Extraordinarily rapid speciation in a marine fish

PubMed Central

Momigliano, Paolo; Jokinen, Henri; Fraimout, Antoine; Florin, Ann-Britt; Norkko, Alf; Merilä, Juha

2017-01-01

Divergent selection may initiate ecological speciation extremely rapidly. How often and at what pace ecological speciation proceeds to yield strong reproductive isolation is more uncertain. Here, we document a case of extraordinarily rapid speciation associated with ecological selection in the postglacial Baltic Sea. European flounders (Platichthys flesus) in the Baltic exhibit two contrasting reproductive behaviors: pelagic and demersal spawning. Demersal spawning enables flounders to thrive in the low salinity of the Northern Baltic, where eggs cannot achieve neutral buoyancy. We show that demersal and pelagic flounders are a species pair arising from a recent event of speciation. Despite having a parapatric distribution with extensive overlap, the two species are reciprocally monophyletic and show strongly bimodal genotypic clustering and no evidence of contemporary migration, suggesting strong reproductive isolation. Divergence across the genome is weak but shows strong signatures of selection, a pattern suggestive of a recent ecological speciation event. We propose that spawning behavior in Baltic flounders is the trait under ecologically based selection causing reproductive isolation, directly implicating a process of ecological speciation. We evaluated different possible evolutionary scenarios under the approximate Bayesian computation framework and estimate that the speciation process started in allopatry ∼2,400 generations ago, following the colonization of the Baltic by the demersal lineage. This is faster than most known cases of ecological speciation and represents the most rapid event of speciation ever reported for any marine vertebrate. PMID:28533412

Iron Speciation in the Subtropical Waters East of New Zealand using Multi Detection Window CLE-AdCSV Titrations.

NASA Astrophysics Data System (ADS)

Chandrasekhar, Anoop; Sander, Sylvia; Milnes, Angie; Boyd, Philip

2015-04-01

Iron plays a significant role in the ocean productivity as a micro nutrient that facilitates the growth of marine phytoplankton and microbes. The bioavailability of iron in the ocean depends on it speciation. Iron is bio available in its dissolved form and about 99.9% of dissolved iron in seawater is organically complexed with natural ligands. The competitive ligand equilibration - adsorptive cathodic stripping voltammetry (CLE-AdCSV) is the widely used technique to examine Fe speciation. The method has its own limitations. The analytical window employed in this technique has a distinct impact on Fe speciation results (Buck, Moffett et al. 2012). Recently, (Pizeta, Sander et al. in preparation) have shown that the accuracy of complexometric titrations improve if multiple analytical windows (MAW) are solved as a united dataset. Several programs are now available that enable this approach with the KMS (Kineteql.xls , Hudson 2014), which is based on an Excel application based on speciation calculation (Hudson, Rue et al. 2003, Sander, Hunter et al. 2011), being one of them. In the present work, the unified MAW data analysis method is applied to determine iron speciation by CLE-AdCSV with salicyl aldoxime (SA) (Abualhaija and van den Berg 2014) in real seawater samples from the Spring bloom FeCycle III voyage, which took place in an anticyclonic eddy in subtropical waters east of New Zealand in spring 2012. Two different analytical windows (5 and 15µM SA) were applied to samples from depth profiles taken during this cruise. The data obtained was analysed using the program KMS (Kineteql.xls). Most samples only returned one Fe-binding ligands class. Higher ligand concentrations were observed in the upper water column and the stability constants were above 22 (e.g. 22.25 ± 0.21 for station 63). Our results will be discussed in the context of microbial community distribution as well as other biogeochemical parameters. Abualhaija, M. M. and C. M. G. van den Berg (2014). "Chemical speciation of iron in seawater using catalytic cathodic stripping voltammetry with ligand competition against salicylaldoxime." Marine Chemistry 164(0): 60-74. Buck, K. N., J. Moffett, K. A. Barbeau, R. M. Bundy, Y. Kondo and J. Wu (2012). "The organic complexation of iron and copper: an intercomparison of competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) techniques " Limnology and Oceanography: Methods 10: 496-515. Hudson, R. J. M., E. L. Rue and K. W. Bruland (2003). "Modeling Complexometric Titrations of Natural Water Samples." Environ. Sci. Tech. 37: 1553-1562. Pizeta, I., S. G. Sander, O. Baars, K. Buck, R. Bundy, G. Carrasco, P. Croot, C. Garnier, L. Gerringa, M. Gledhill, K. Hirose, D. R. Hudson, Y. Kondo-Jacquot, L. Laglera, D. Omanovic, M. Rijkenberg, B. Twining and M. Wells (in preparation). "Intercomparison of estimating metal binding ligand parameters from simulated titration data using different fitting approaches." for Limnology and Oceanography: Methods. Sander, S. G., K. A. Hunter, H. Harms and M. Wells (2011). "Numerical approach to speciation and estimation of parameters used in modeling trace metal bioavailability." Environmental Science and Technology 45(15): 6388-6395.

On the Effectiveness of Nature-Inspired Metaheuristic Algorithms for Performing Phase Equilibrium Thermodynamic Calculations

PubMed Central

Fateen, Seif-Eddeen K.; Bonilla-Petriciolet, Adrian

2014-01-01

The search for reliable and efficient global optimization algorithms for solving phase stability and phase equilibrium problems in applied thermodynamics is an ongoing area of research. In this study, we evaluated and compared the reliability and efficiency of eight selected nature-inspired metaheuristic algorithms for solving difficult phase stability and phase equilibrium problems. These algorithms are the cuckoo search (CS), intelligent firefly (IFA), bat (BA), artificial bee colony (ABC), MAKHA, a hybrid between monkey algorithm and krill herd algorithm, covariance matrix adaptation evolution strategy (CMAES), magnetic charged system search (MCSS), and bare bones particle swarm optimization (BBPSO). The results clearly showed that CS is the most reliable of all methods as it successfully solved all thermodynamic problems tested in this study. CS proved to be a promising nature-inspired optimization method to perform applied thermodynamic calculations for process design. PMID:24967430

On the effectiveness of nature-inspired metaheuristic algorithms for performing phase equilibrium thermodynamic calculations.

PubMed

Fateen, Seif-Eddeen K; Bonilla-Petriciolet, Adrian

2014-01-01

The search for reliable and efficient global optimization algorithms for solving phase stability and phase equilibrium problems in applied thermodynamics is an ongoing area of research. In this study, we evaluated and compared the reliability and efficiency of eight selected nature-inspired metaheuristic algorithms for solving difficult phase stability and phase equilibrium problems. These algorithms are the cuckoo search (CS), intelligent firefly (IFA), bat (BA), artificial bee colony (ABC), MAKHA, a hybrid between monkey algorithm and krill herd algorithm, covariance matrix adaptation evolution strategy (CMAES), magnetic charged system search (MCSS), and bare bones particle swarm optimization (BBPSO). The results clearly showed that CS is the most reliable of all methods as it successfully solved all thermodynamic problems tested in this study. CS proved to be a promising nature-inspired optimization method to perform applied thermodynamic calculations for process design.

General equilibrium second-order hydrodynamic coefficients for free quantum fields

NASA Astrophysics Data System (ADS)

Buzzegoli, M.; Grossi, E.; Becattini, F.

2017-10-01

We present a systematic calculation of the corrections of the stress-energy tensor and currents of the free boson and Dirac fields up to second order in thermal vorticity, which is relevant for relativistic hydrodynamics. These corrections are non-dissipative because they survive at general thermodynamic equilibrium with non vanishing mean values of the conserved generators of the Lorentz group, i.e. angular momenta and boosts. Their equilibrium nature makes it possible to express the relevant coefficients by means of correlators of the angular-momentum and boost operators with stress-energy tensor and current, thus making simpler to determine their so-called "Kubo formulae". We show that, at least for free fields, the corrections are of quantum origin and we study several limiting cases and compare our results with previous calculations. We find that the axial current of the free Dirac field receives corrections proportional to the vorticity independently of the anomalous term.

Thermal Behavior of Cd During Sludge Incineration: Experiments and Thermodynamic Equilibrium Model.

PubMed

Liu, Jingyong; Zhuo, Zhongxu; Sun, Shuiyu; Xie, Wuming; Lu, Shaoyou; Sun, Jian; Kuo, Jiahong; Yujie, Wang

2016-12-01

  Experiments and thermodynamic equilibrium calculations were performed to investigate the behavior of Cd during sewage sludge incineration. The chemical equilibrium calculations indicated that chlorine significantly increased the volatilization of Cd in the form of CdCl2. In addition, SiO2-containing materials can function as sorbents for stabilizing Cd. The effect of PVC added to the sludge on the migration of Cd in the sludge was greater than that of NaCl. As the temperature increased, both organic and inorganic chlorides reduced the Cd distribution in the bottom ash. The chloride concentration, and the incineration time exhibited insignificant changes in Cd emission. With the addition of either NaCl or PVC into the sludge, the phases of Cd present in the bottom slag were primarily present in the form of silica-alumina oxides or multi-metal oxide, which could inhabit the Cd volatilization.

Calculation of open and closed system elastic coefficients for multicomponent solids

NASA Astrophysics Data System (ADS)

Mishin, Y.

2015-06-01

Thermodynamic equilibrium in multicomponent solids subject to mechanical stresses is a complex nonlinear problem whose exact solution requires extensive computations. A few decades ago, Larché and Cahn proposed a linearized solution of the mechanochemical equilibrium problem by introducing the concept of open system elastic coefficients [Acta Metall. 21, 1051 (1973), 10.1016/0001-6160(73)90021-7]. Using the Ni-Al solid solution as a model system, we demonstrate that open system elastic coefficients can be readily computed by semigrand canonical Monte Carlo simulations in conjunction with the shape fluctuation approach. Such coefficients can be derived from a single simulation run, together with other thermodynamic properties needed for prediction of compositional fields in solid solutions containing defects. The proposed calculation approach enables streamlined solutions of mechanochemical equilibrium problems in complex alloys. Second order corrections to the linear theory are extended to multicomponent systems.

First principles calculations of thermal conductivity with out of equilibrium molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Puligheddu, Marcello; Gygi, Francois; Galli, Giulia

The prediction of the thermal properties of solids and liquids is central to numerous problems in condensed matter physics and materials science, including the study of thermal management of opto-electronic and energy conversion devices. We present a method to compute the thermal conductivity of solids by performing ab initio molecular dynamics at non equilibrium conditions. Our formulation is based on a generalization of the approach to equilibrium technique, using sinusoidal temperature gradients, and it only requires calculations of first principles trajectories and atomic forces. We discuss results and computational requirements for a representative, simple oxide, MgO, and compare with experiments and data obtained with classical potentials. This work was supported by MICCoM as part of the Computational Materials Science Program funded by the U.S. Department of Energy (DOE), Office of Science , Basic Energy Sciences (BES), Materials Sciences and Engineering Division under Grant DOE/BES 5J-30.

The equilibrium of the reaction catalysed by citrate oxaloacetate-lyase

PubMed Central

Tate, S. S.; Datta, S. P.

1965-01-01

1. A method of preparation and purification of citrate oxaloacetate-lyase (EC 4.1.3.6) from Aerobacter aerogenes is described. 2. The equilibrium of this reaction has been determined at pH 8·4 and 25°. It has been shown that K, i.e. [citrate3−]/[oxaloacetateketo2−][acetate −], is 3·08±0·72, but that Kapp., i.e. [total citrate]/[total oxaloacetate][total acetate], is markedly affected by the initial concentrations of the reactants and magnesium. 3. The free-energy change during the cleavage of citrate has been calculated and compared with data from other sources. 4. The free energy of hydrolysis of acetyl-CoA has been evaluated from the present data. 5. A detailed knowledge of the interactions of the reactants with metal ions has been shown to be important in the calculation of the equilibrium constant and related thermodynamic functions. PMID:14348207

Geochemistry of rare earth elements within waste rocks from the Montviel carbonatite deposit, Québec, Canada.

PubMed

Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Pelletier, Mia

2018-04-01

Several rare earth element (REE) mine projects around the world are currently at the feasibility stage. Unfortunately, few studies have evaluated the contamination potential of REE and their effects on the environment. In this project, the waste rocks from the carbonatites within the Montviel proterozoic alkaline intrusion (near Lebel-sur-Quévillon, Quebec, Canada) are assessed in this research. The mineralization is mainly constituted by light REE (LREE) fluorocarbonates (qaqarssukite-Ce, kukharenkoite-Ce), LREE carbonates (burbankite, Sr-Ba-Ca-REE, barytocalcite, strontianite, Ba-REE-carbonates), and phosphates (apatite, monazite). The gangue minerals are biotites, chlorite, albite, ankerite, siderite, and calcite. The SEM-EDS analyses show that (i) the majority of REE are associated with the fine fraction (< 106 μm), (ii) REE are mainly associated with carbonates, (iii) all analyzed minerals preferably contain LREE (La, Ce, Pr, Nd, Sm, Eu), (iv) the sum of LREE in each analyzed mineral varies between ~ 3 and 10 wt%, (v) the heavy REE (HREE) identified are Gd and Yb at < 0.4 wt%, and (vi) three groups of carbonate minerals were observed containing variable concentrations of Ca, Na, and F. Furthermore, the mineralogical composition of REE-bearing minerals, REE mobility, and REE speciation was investigated. The leachability and geochemical behavior of these REE-bearing mine wastes were tested using normalized kinetic testing (humidity cells). Leachate results displayed higher LREE concentrations, with decreasing shale-normalized patterns. Thermodynamical equilibrium calculations suggest that the precipitation of secondary REE minerals may control the REE mobility.

Speciation and distribution of cadmium and lead in salinized horizons of antrosols

NASA Astrophysics Data System (ADS)

Bulgariu, D.; Bulgariu, L.; Astefanei, D.

2009-04-01

The utilization of intensive technologies for the vegetable cultivation in glass houses by the administration of high doses of organic fertilizes, the supra-dimensional irrigation and the maintaining of soil at high humidity state, in special in case of vicious drainage have as result the rapid degradation of morphological, chemical and physical characteristics of soils, concretized by: (i) decrease of structural aggregates stability; (ii) more dense packing of soil; (iii) accumulation of easy soluble salts (in special at superior horizons level); (iv) limitation of organic compounds and micro-elements biodisponibility. All these determined a significant reduction of productivity and of exploitation duration of soils from glass houses. These phenomena modified continuously the dynamic of speciation processes and inter-phases distribution, of heavy metals in soils from glass houses, and can determined a non-controlled accumulation of heavy metals, in special as mobile forms with high biodisponibility. Ours studied have been performed using soil profiles drawing from Copou-glass house, Iasi (Romania). Has been followed the modification of distribution for speciation forms of cadmium and lead (two heavy metals with high toxicity degree), between hortic antrosol horizons, and between chemical-mineralogical components of this, with the progressive salinization of superior horizons, in 2007-2008 period. The separation, differentiation and determination of cadmium and lead speciation forms was done by combined solid-liquid sequential extraction (SPE) and extraction in aqueous polymer-inorganic salt two-phase systems (ABS) procedure, presented in some of ours previous studies. After extraction, the total contents of the two heavy metals and fractions from these differential bonded by mineral and organic components of hortic antrosol have been determined by atomic absorption spectrometry. The specific interaction mechanisms of Cd and Pb with organic-mineral components of soils have been estimated on the basis of Raman and FT-IR spectra, recorded for fractions obtained after each extraction step. These data were correlated with those obtained by chemical analysis and UV-VIS spectrometry, and were used for to establish the type and weight of Cd and Pb speciation forms in studied antrosol. Our studies have been show that in medium and inferior horizons of hortic antrosols, the heavy metals have a general accumulation tendency, preferential by binding on organic matter and organic-mineral complexes, components with higher abundance in such type of soils. The selectivity and complexation mechanisms are controlled by speciation forms of the two metals. This phenomenon has two important consequences, the strong fixation of heavy metals in hortic antrosol and significant modification of structure and conformation of organic macromolecules. A specific phenomenon of hortic antrosols is that the accumulation rate of heavy metals is higher than levigation rate, and the mobile forms of these have a higher biodisponibility, being relative easy assimilated by plants. The progressive salinization of superior horizons of soils from glass houses, determined a sever perturbation of equilibrium between Cd and Pb speciation forms. In consequence these will have an accentuated migration tendency in superior horizons, as complexes with inorganic ligands, with a high mobility and biodsiponibility. The accumulation of soluble salts in superior horizons, and the formation of frangipane horizon (horizon of geochemical segregation of hortic antrosols) modified the ionic strength from soil solution and the thermodynamic activity of cadmium and lead species. Under these conditions, the levigation rate of cadmium and lead is higher than the accumulation rate, which means that the migration of these metals in soil solution occurs fast and in high concentrations. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07 an Project PNCDI 2-D5 no. 52141 / 08).

Crystal structure optimisation using an auxiliary equation of state

NASA Astrophysics Data System (ADS)

Jackson, Adam J.; Skelton, Jonathan M.; Hendon, Christopher H.; Butler, Keith T.; Walsh, Aron

2015-11-01

Standard procedures for local crystal-structure optimisation involve numerous energy and force calculations. It is common to calculate an energy-volume curve, fitting an equation of state around the equilibrium cell volume. This is a computationally intensive process, in particular, for low-symmetry crystal structures where each isochoric optimisation involves energy minimisation over many degrees of freedom. Such procedures can be prohibitive for non-local exchange-correlation functionals or other "beyond" density functional theory electronic structure techniques, particularly where analytical gradients are not available. We present a simple approach for efficient optimisation of crystal structures based on a known equation of state. The equilibrium volume can be predicted from one single-point calculation and refined with successive calculations if required. The approach is validated for PbS, PbTe, ZnS, and ZnTe using nine density functionals and applied to the quaternary semiconductor Cu2ZnSnS4 and the magnetic metal-organic framework HKUST-1.

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

USGS Publications Warehouse

Burns, Douglas A.

1989-01-01

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

Application of a single model to study the adsorption equilibrium of prednisolone on six carbonaceous materials.

PubMed

Valenzuela-Calahorro, C; Cuerda-Correa, E; Navarrete-Guijosa, A; Gonzalez-Pradas, E

2002-06-01

The knowledge of sorption processes of nonelectrolytes in solution by solid adsorbents implies the study of kinetics, equilibrium, and thermodynamic functions. However, quite frequently the equilibrium isotherms are studied by comparing them with those corresponding to the Giles et al. classification (1); these isotherms are also analyzed by fitting them to equations based on thermodynamic or kinetic criteria, and even to empirical equations. Nevertheless, information obtained is more coherent and satisfactory if the adsorption isotherms are fitted by using an equation describing the equilibrium isotherms according to the kinetic laws. These mentioned laws would determine each one of the unitary processes (one or more) which condition the global process. In this paper, an adsorption process of prednisolone in solution by six carbonaceous materials is explained according to a previously proposed single model, which allows to establish a kinetic law which fits satisfactorily most of C vs t isotherms (2). According to the above-mentioned kinetic law, equations describing sorption equilibrium processes have been deducted, and experimental data points have been fitted to these equations; such a fitting yields to different values of adsorption capacity and kinetic equilibrium constants for the different processes at several temperatures. However, in spite of their practical interest, these constants have no thermodynamic signification. Thus, the thermodynamic equilibrium constant (K) has been calculated by using a modified expression of the Gaines et al. equation (3). Global average values of the thermodynamic functions have also been calculated from the K values. Information related to variations of DeltaH and DeltaS with the surface coverage fraction was obtained by using the corresponding Clausius-Clapeyron equations.

Evaluation of Magnetic Diagnostics for MHD Equilibrium Reconstruction of LHD Discharges

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

Sontag, Aaron C; Hanson, James D.; Lazerson, Sam

2011-01-01

Equilibrium reconstruction is the process of determining the set of parameters of an MHD equilibrium that minimize the difference between expected and experimentally observed signals. This is routinely performed in axisymmetric devices, such as tokamaks, and the reconstructed equilibrium solution is then the basis for analysis of stability and transport properties. The V3FIT code [1] has been developed to perform equilibrium reconstruction in cases where axisymmetry cannot be assumed, such as in stellarators. The present work is focused on using V3FIT to analyze plasmas in the Large Helical Device (LHD) [2], a superconducting, heliotron type device with over 25 MWmore » of heating power that is capable of achieving both high-beta ({approx}5%) and high density (>1 x 10{sup 21}/m{sup 3}). This high performance as well as the ability to drive tens of kiloamperes of toroidal plasma current leads to deviations in the equilibrium state from the vacuum flux surfaces. This initial study examines the effectiveness of using magnetic diagnostics as the observed signals in reconstructing experimental plasma parameters for LHD discharges. V3FIT uses the VMEC [3] 3D equilibrium solver to calculate an initial equilibrium solution with closed, nested flux surfaces based on user specified plasma parameters. This equilibrium solution is then used to calculate the expected signals for specified diagnostics. The differences between these expected signal values and the observed values provides a starting {chi}{sup 2} value. V3FIT then varies all of the fit parameters independently, calculating a new equilibrium and corresponding {chi}{sup 2} for each variation. A quasi-Newton algorithm [1] is used to find the path in parameter space that leads to a minimum in {chi}{sup 2}. Effective diagnostic signals must vary in a predictable manner with the variations of the plasma parameters and this signal variation must be of sufficient amplitude to be resolved from the signal noise. Signal effectiveness can be defined for a specific signal and specific reconstruction parameter as the dimensionless fractional reduction in the posterior parameter variance with respect to the signal variance. Here, {sigma}{sub i}{sup sig} is the variance of the ith signal and {sigma}{sub j}{sup param} param is the posterior variance of the jth fit parameter. The sum of all signal effectiveness values for a given reconstruction parameter is normalized to one. This quantity will be used to determine signal effectiveness for various reconstruction cases. The next section will examine the variation of the expected signals with changes in plasma pressure and the following section will show results for reconstructing model plasmas using these signals.« less

Semiconductor material and method for enhancing solubility of a dopant therein

DOEpatents

Sadigh, Babak; Lenosky, Thomas J.; Rubia, Tomas Diaz; Giles, Martin; Caturla, Maria-Jose; Ozolins, Vidvuds; Asta, Mark; Theiss, Silva; Foad, Majeed; Quong, Andrew

2003-09-09

A method for enhancing the equilibrium solubility of boron and indium in silicon. The method involves first-principles quantum mechanical calculations to determine the temperature dependence of the equilibrium solubility of two important p-type dopants in silicon, namely boron and indium, under various strain conditions. The equilibrium thermodynamic solubility of size-mismatched impurities, such as boron and indium in silicon, can be raised significantly if the silicon substrate is strained appropriately. For example, for boron, a 1% compressive strain raises the equilibrium solubility by 100% at 1100.degree. C.; and for indium, a 1% tensile strain at 1100.degree. C., corresponds to an enhancement of the solubility by 200%.

Bioconcentration of lipophilic compounds by some aquatic organisms

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

Hawker, D.W.; Connell, D.W.

1986-04-01

With nondegradable, lipophilic compounds having log P values ranging from 2 to 6, direct linear relationships have been found between the logarithms of the equilibrium bioconcentration factors, and also reciprocal clearance rate constants, with log P for daphnids and molluscs. These relationships permit calculation of the times required for equilibrium and significant bioconcentration of lipophilic chemicals. Compared with fish, these time periods are successively shorter for molluscs, then daphnids. The equilibrium biotic concentration was found to decrease with increasing chemical hydrophobicity for both molluscs and daphnids. Also, new linear relationships between the logarithm of the bioconcentration factor and log Pmore » were found for compounds not attaining equilibrium within finite exposure times.« less

A Semiconductor Material And Method For Enhancing Solubility Of A Dopant Therein

DOEpatents

Sadigh, Babak; Lenosky, Thomas J.; Diaz de la Rubia, Tomas; Giles, Martin; Caturla, Maria-Jose; Ozolins, Vidvuds; Asta, Mark; Theiss, Silva; Foad, Majeed; Quong, Andrew

2005-03-29

A method for enhancing the equilibrium solubility of boron ad indium in silicon. The method involves first-principles quantum mechanical calculations to determine the temperature dependence of the equilibrium solubility of two important p-type dopants in silicon, namely boron and indium, under various strain conditions. The equilibrium thermodynamic solubility of size-mismatched impurities, such as boron and indium in silicon, can be raised significantly if the silicon substrate is strained appropriately. For example, for boron, a 1% compressive strain raises the equilibrium solubility by 100% at 1100.degree. C.; and for indium, a 1% tensile strain at 1100.degree. C., corresponds to an enhancement of the solubility by 200%.

Method for enhancing the solubility of boron and indium in silicon

DOEpatents

Sadigh, Babak; Lenosky, Thomas J.; Diaz de la Rubia, Tomas; Giles, Martin; Caturla, Maria-Jose; Ozolins, Vidvuds; Asta, Mark; Theiss, Silva; Foad, Majeed; Quong, Andrew

2002-01-01

A method for enhancing the equilibrium solubility of boron and indium in silicon. The method involves first-principles quantum mechanical calculations to determine the temperature dependence of the equilibrium solubility of two important p-type dopants in silicon, namely boron and indium, under various strain conditions. The equilibrium thermodynamic solubility of size-mismatched impurities, such as boron and indium in silicon, can be raised significantly if the silicon substrate is strained appropriately. For example, for boron, a 1% compressive strain raises the equilibrium solubility by 100% at 1100.degree. C.; and for indium, a 1% tensile strain at 1100.degree. C., corresponds to an enhancement of the solubility by 200%.

Raman spectra of thiolated arsenicals with biological importance.

PubMed

Yang, Mingwei; Sun, Yuzhen; Zhang, Xiaobin; McCord, Bruce; McGoron, Anthony J; Mebel, Alexander; Cai, Yong

2018-03-01

Surface enhanced Raman scattering (SERS) has great potential as an alternative tool for arsenic speciation in biological matrices. SERS measurements have advantages over other techniques due to its ability to maintain the integrity of arsenic species and its minimal requirements for sample preparation. Up to now, very few Raman spectra of arsenic compounds have been reported. This is particularly true for thiolated arsenicals, which have recently been found to be widely present in humans. The lack of data for Raman spectra in arsenic speciation hampers the development of new tools using SERS. Herein, we report the results of a study combining the analysis of experimental Raman spectra with that obtained from density functional calculations for some important arsenic metabolites. The results were obtained with a hybrid functional B3LYP approach using different basis sets to calculate Raman spectra of the selected arsenicals. By comparing experimental and calculated spectra of dimethylarsinic acid (DMA V ), the basis set 6-311++G** was found to provide computational efficiency and precision in vibrational frequency prediction. The Raman frequencies for the rest of organoarsenicals were studied using this basis set, including monomethylarsonous acid (MMA III ), dimethylarsinous acid (DMA III ), dimethylmonothioarinic acid (DMMTA V ), dimethyldithioarsinic acid (DMDTA V ), S-(Dimethylarsenic) cysteine (DMA III (Cys)) and dimethylarsinous glutathione (DMA III GS). The results were compared with fingerprint Raman frequencies from As─O, As─C, and As─S obtained under different chemical environments. These fingerprint vibrational frequencies should prove useful in future measurements of different species of arsenic using SERS. Copyright © 2017 Elsevier B.V. All rights reserved.

Sensitivity of equilibrium profile reconstruction to motional Stark effect measurements

NASA Astrophysics Data System (ADS)

Batha, S. H.; Levinton, F. M.; Hirshman, S. P.; Bell, M. G.; Wieland, R. M.

1996-09-01

The magnetic-field pitch-angle profile, gamma p(R) identical to tan-1(Bpol/Btor), is measured on TFTR using a motional Stark effect (MSE) polarimeter. Measured pitch angle profiles, along with kinetic profiles and external magnetic measurements, are used to compute a self-consistent equilibrium using the free-boundary variational moments equilibrium code VMEC. Uncertainties in the q profile due to uncertainties in gamma P(R), magnetic measurements and kinetic measurements are found to be small. Subsequent uncertainties in the VMEC-calculated current density and shear profiles are also small

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

PubMed Central

Wills, Lindsay A.; Qu, Xiaohui; Chang, I-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-01-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions. PMID:28643782

Complexation of copper by aquatic humic substances from different environments

USGS Publications Warehouse

McKnight, Diane M.; Feder, Gerald L.; Thurman, E. Michael; Wershaw, Robert L.

1983-01-01

The copper-complexing properties of aquatic humic substances isolated from eighteen different environments were characterized by potentiometric titration, using a cupric ion selective electrode. Potentiometric data were analyzed using FITEQL, a computer program for the determination of chemical equilibrium constants from experimental data. All the aquatic humic substances could be modelled as having two types of Cu(II)-binding sites: one with K equal to about 106 and a concentration of 1.0 ± 0.4 × 10−6 M(mg C)−1 and another with K equal to about 108 and a concentration of 2.6 ± 1.6 × 10−7 M(mg C)−1.A method is described for estimating the Cu(II)-binding sites associated with dissolved humic substances in natural water based on a measurement of dissolved organic carbon, which may be helpful in evaluating chemical processes controlling speciation of Cu and bioavailability of Cu to aquatic organisms.

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

Zhang, Fan; Parker, Jack C.; Watson, David B

This study investigates uranium and technetium sorption onto aluminum and iron hydroxides during titration of acidic groundwater. The contaminated groundwater exhibits oxic conditions with high concentrations of NO{sub 3}{sup -}, SO{sub 4}{sup 2-}, U, Tc, and various metal cations. More than 90% of U and Tc was removed from the aqueous phase as Al and Fe precipitated above pH 5.5, but was partially resolublized at higher pH values. An equilibrium hydrolysis and precipitation reaction model adequately described variations in aqueous concentrations of metal cations. An anion exchange reaction model was incorporated to simulate sulfate, U and Tc sorption onto variablymore » charged (pH-dependent) Al and Fe hydroxides. Modeling results indicate that competitive sorption/desorption on mixed mineral phases needs to be considered to adequately predict U and Tc mobility. The model could be useful for future studies of the speciation of U, Tc and co-existing ions during pre- and post-groundwater treatment practices.« less

Chapter A6. Section 6.5. Reduction-Oxidation Potential (Electrode Method)

USGS Publications Warehouse

Nordstrom, D. Kirk; Wilde, Franceska D.

2005-01-01

Reduction-oxidation (redox) potential--also referred to as Eh--is a measure of the equilibrium potential, relative to the standard hydrogen electrode, developed at the interface between a noble metal electrode and an aqueous solution containing electroactive chemical species. Measurements of Eh are used to evaluate geochemical speciation models, and Eh data can provide insights on the evolution and status of water chemistry in an aqueous system. Nevertheless, the measurement is fraught with inherent interferences and limitations that must be understood and considered to determine applicability to the aqueous system being studied. For this reason, Eh determination is not one of the field parameters routinely measured by the U.S. Geological Survey (USGS). This section of the National Field Manual (NFM) describes the equipment and procedures needed to measure Eh in water using a platinum electrode. Guidance as to the limitations and interpretation of Eh measurement also is included.

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

NASA Astrophysics Data System (ADS)

Wills, Lindsay A.; Qu, Xiaohui; Chang, I.-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-06-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions.

Reactive extraction at liquid-liquid systems

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina

2018-01-01

The chapter summarizes the state of knowledge about a metal transport in two-phase system. The first part of this review focuses on the distribution law and main factors determination in classical solvent extraction (solubility and polarity of the solute, as well as inter- and intramolecules interaction. Next part of the chapter is devoted to the reactive solvent extraction and the molecular modeling requiring knowledge on type of extractants, complexation mechanisms, metals ions speciation and oxidation during complexes forming, and other parameters that enable to understand the extraction process. Also the kinetic data that is needed for proper modeling, simulation and design of processes needed for critical separations are discussed. Extraction at liquid-solid system using solvent impregnated resins is partially identical as in the case of the corresponding solvent extraction, therefore this subject was also presented in all aspects of separation process (equilibrium, mechanism, kinetics).

Assessment of important SPECIATE Profiles in EPA’s Emissions Modeling Platform and Current Data Gaps (US EPA 2017 International Emissions Inventory Conference)

EPA Science Inventory

The US Environmental Protection Agency (EPA)’s SPECIATE database contains speciation profiles for both particulate matter (PM) and volatile organic compounds (VOCs) that are key inputs for creating speciated emission inventories for air quality modeling. The objective of th...

A complex speciation–richness relationship in a simple neutral model

PubMed Central

Desjardins-Proulx, Philippe; Gravel, Dominique

2012-01-01

Speciation is the “elephant in the room” of community ecology. As the ultimate source of biodiversity, its integration in ecology's theoretical corpus is necessary to understand community assembly. Yet, speciation is often completely ignored or stripped of its spatial dimension. Recent approaches based on network theory have allowed ecologists to effectively model complex landscapes. In this study, we use this framework to model allopatric and parapatric speciation in networks of communities. We focus on the relationship between speciation, richness, and the spatial structure of communities. We find a strong opposition between speciation and local richness, with speciation being more common in isolated communities and local richness being higher in more connected communities. Unlike previous models, we also find a transition to a positive relationship between speciation and local richness when dispersal is low and the number of communities is small. We use several measures of centrality to characterize the effect of network structure on diversity. The degree, the simplest measure of centrality, is the best predictor of local richness and speciation, although it loses some of its predictive power as connectivity grows. Our framework shows how a simple neutral model can be combined with network theory to reveal complex relationships between speciation, richness, and the spatial organization of populations. PMID:22957181

Divergence with gene flow across a speciation continuum of Heliconius butterflies.

PubMed

Supple, Megan A; Papa, Riccardo; Hines, Heather M; McMillan, W Owen; Counterman, Brian A

2015-09-24

A key to understanding the origins of species is determining the evolutionary processes that drive the patterns of genomic divergence during speciation. New genomic technologies enable the study of high-resolution genomic patterns of divergence across natural speciation continua, where taxa pairs with different levels of reproductive isolation can be used as proxies for different stages of speciation. Empirical studies of these speciation continua can provide valuable insights into how genomes diverge during speciation. We examine variation across a handful of genomic regions in parapatric and allopatric populations of Heliconius butterflies with varying levels of reproductive isolation. Genome sequences were mapped to 2.2-Mb of the H. erato genome, including 1-Mb across the red color pattern locus and multiple regions unlinked to color pattern variation. Phylogenetic analyses reveal a speciation continuum of pairs of hybridizing races and incipient species in the Heliconius erato clade. Comparisons of hybridizing pairs of divergently colored races and incipient species reveal that genomic divergence increases with ecological and reproductive isolation, not only across the locus responsible for adaptive variation in red wing coloration, but also at genomic regions unlinked to color pattern. We observe high levels of divergence between the incipient species H. erato and H. himera, suggesting that divergence may accumulate early in the speciation process. Comparisons of genomic divergence between the incipient species and allopatric races suggest that limited gene flow cannot account for the observed high levels of divergence between the incipient species. Our results provide a reconstruction of the speciation continuum across the H. erato clade and provide insights into the processes that drive genomic divergence during speciation, establishing the H. erato clade as a powerful framework for the study of speciation.

Combining the GW formalism with the polarizable continuum model: A state-specific non-equilibrium approach

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

Duchemin, Ivan, E-mail: ivan.duchemin@cea.fr; Jacquemin, Denis; Institut Universitaire de France, 1 rue Descartes, 75005 Paris Cedex 5

We have implemented the polarizable continuum model within the framework of the many-body Green’s function GW formalism for the calculation of electron addition and removal energies in solution. The present formalism includes both ground-state and non-equilibrium polarization effects. In addition, the polarization energies are state-specific, allowing to obtain the bath-induced renormalisation energy of all occupied and virtual energy levels. Our implementation is validated by comparisons with ΔSCF calculations performed at both the density functional theory and coupled-cluster single and double levels for solvated nucleobases. The present study opens the way to GW and Bethe-Salpeter calculations in disordered condensed phases ofmore » interest in organic optoelectronics, wet chemistry, and biology.« less

Quantum statistical mechanics of dense partially ionized hydrogen.

NASA Technical Reports Server (NTRS)

Dewitt, H. E.; Rogers, F. J.

1972-01-01

The theory of dense hydrogenic plasmas beginning with the two component quantum grand partition function is reviewed. It is shown that ionization equilibrium and molecular dissociation equilibrium can be treated in the same manner with proper consideration of all two-body states. A quantum perturbation expansion is used to give an accurate calculation of the equation of state of the gas for any degree of dissociation and ionization. In this theory, the effective interaction between any two charges is the dynamic screened potential obtained from the plasma dielectric function. We make the static approximation; and we carry out detailed numerical calculations with the bound and scattering states of the Debye potential, using the Beth-Uhlenbeck form of the quantum second virial coefficient. We compare our results with calculations from the Saha equation.

Erosive processes after tectonic uplift stimulate vicariant and adaptive speciation: evolution in an Afrotemperate-endemic paper daisy genus

PubMed Central

2014-01-01

Background The role of tectonic uplift in stimulating speciation in South Africa’s only alpine zone, the Drakensberg, has not been explicitly examined. Tectonic processes may influence speciation both through the creation of novel habitats and by physically isolating plant populations. We use the Afrotemperate endemic daisy genus Macowania to explore the timing and mode (geographic versus adaptive) of speciation in this region. Between sister species pairs we expect high morphological divergence where speciation has happened in sympatry (adaptive) while with geographic (vicariant) speciation we may expect to find less morphological divergence and a greater degree of allopatry. A dated molecular phylogenetic hypothesis for Macowania elucidates species’ relationships and is used to address the potential impact of uplift on diversification. Morphological divergence of a small sample of reproductive and vegetative characters, used as a proxy for adaptive divergence, is measured against species’ range distributions to estimate mode of speciation across two subclades in the genus. Results The Macowania crown age is consistent with the hypothesis of post-uplift diversification, and we find evidence for both vicariant and adaptive speciation between the two subclades within Macowania. Both subclades exhibit strong signals of range allopatry, suggesting that geographic isolation was important in speciation. One subclade, associated with dry, rocky environments at high altitudes, shows very little morphological and ecological differentiation but high range allopatry. The other subclade occupies a greater variety of habitats and exhibits far greater morphological differentiation, but contains species with overlapping distribution ranges. Conclusions Species in Macowania are likely to have diversified in response to tectonic uplift, and we invoke uplift and uplift-mediated erosion as the main drivers of speciation. The greater relative morphological divergence in sympatric species of Macowania indicates that speciation in the non-sympatric taxa may not have required obvious adaptive differences, implying that simple geographic isolation was the driving force for speciation (‘neutral speciation’). PMID:24524661

Extensive range overlap between heliconiine sister species: evidence for sympatric speciation in butterflies?

PubMed

Rosser, Neil; Kozak, Krzysztof M; Phillimore, Albert B; Mallet, James

2015-06-30

Sympatric speciation is today generally viewed as plausible, and some well-supported examples exist, but its relative contribution to biodiversity remains to be established. We here quantify geographic overlap of sister species of heliconiine butterflies, and use age-range correlations and spatial simulations of the geography of speciation to infer the frequency of sympatric speciation. We also test whether shifts in mimetic wing colour pattern, host plant use and climate niche play a role in speciation, and whether such shifts are associated with sympatry. Approximately a third of all heliconiine sister species pairs exhibit near complete range overlap, and analyses of the observed patterns of range overlap suggest that sympatric speciation contributes 32%-95% of speciation events. Müllerian mimicry colour patterns and host plant choice are highly labile traits that seem to be associated with speciation, but we find no association between shifts in these traits and range overlap. In contrast, climatic niches of sister species are more conserved. Unlike birds and mammals, sister species of heliconiines are often sympatric and our inferences using the most recent comparative methods suggest that sympatric speciation is common. However, if sister species spread rapidly into sympatry (e.g. due to their similar climatic niches), then assumptions underlying our methods would be violated. Furthermore, although we find some evidence for the role of ecology in speciation, ecological shifts did not show the associations with range overlap expected under sympatric speciation. We delimit species of heliconiines in three different ways, based on "strict and " "relaxed" biological species concepts (BSC), as well as on a surrogate for the widely-used "diagnostic" version of the phylogenetic species concept (PSC). We show that one reason why more sympatric speciation is inferred in heliconiines than in birds may be due to a different culture of species delimitation in the two groups. To establish whether heliconiines are exceptional will require biogeographic comparative studies for a wider range of animal taxa including many more invertebrates.

Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

NASA Astrophysics Data System (ADS)

Filius, Jeroen D.; Meeussen, Johannes C. L.; Lumsdon, David G.; Hiemstra, Tjisse; van Riemsdijk, Willem H.

2003-04-01

Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.

Equilibrium Reconstruction on the Large Helical Device

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

Samuel A. Lazerson, D. Gates, D. Monticello, H. Neilson, N. Pomphrey, A. Reiman S. Sakakibara, and Y. Suzuki

Equilibrium reconstruction is commonly applied to axisymmetric toroidal devices. Recent advances in computational power and equilibrium codes have allowed for reconstructions of three-dimensional fields in stellarators and heliotrons. We present the first reconstructions of finite beta discharges in the Large Helical Device (LHD). The plasma boundary and magnetic axis are constrained by the pressure profile from Thomson scattering. This results in a calculation of plasma beta without a-priori assumptions of the equipartition of energy between species. Saddle loop arrays place additional constraints on the equilibrium. These reconstruction utilize STELLOPT, which calls VMEC. The VMEC equilibrium code assumes good nested fluxmore » surfaces. Reconstructed magnetic fields are fed into the PIES code which relaxes this constraint allowing for the examination of the effect of islands and stochastic regions on the magnetic measurements.« less

Thermodynamic properties of gaseous fluorocarbons and isentropic equilibrium expansions of two binary mixtures of fluorocarbons and argon

NASA Technical Reports Server (NTRS)

Talcott, N. A., Jr.

1977-01-01

Equations and computer code are given for the thermodynamic properties of gaseous fluorocarbons in chemical equilibrium. In addition, isentropic equilibrium expansions of two binary mixtures of fluorocarbons and argon are included. The computer code calculates the equilibrium thermodynamic properties and, in some cases, the transport properties for the following fluorocarbons: CCl2F, CCl2F2, CBrF3, CF4, CHCl2F, CHF3, CCL2F-CCl2F, CCLF2-CClF2, CF3-CF3, and C4F8. Equilibrium thermodynamic properties are tabulated for six of the fluorocarbons(CCl3F, CCL2F2, CBrF3, CF4, CF3-CF3, and C4F8) and pressure-enthalpy diagrams are presented for CBrF3.

Emergence of currents as a transient quantum effect in nonequilibrium systems

NASA Astrophysics Data System (ADS)

Granot, Er'El; Marchewka, Avi

2011-09-01

Most current calculations are based on equilibrium or semi-equilibrium models. However, except for very special scenarios (like ring configuration), the current cannot exist in equilibrium. Moreover, unlike with equilibrium scenarios, there is no generic approach to confront out-of-equilibrium currents. In this paper we used recent studies on transient quantum mechanics to solve the current, which appears in the presence of very high density gradients and fast transients. It shows that the emerging current appears instantaneously, and although the density beyond the discontinuity is initially negligible the currents there have a finite value, and remain constant for a finite period. It is shown that this nonequilibrium effect can be measured in real experiments (such as cooled rubidium atoms), where the discontinuity is replaced with a finite width (hundreds of nanometers) gradient.

Ram Accelerator Performance Calculations Using a Modified Version of the NASA CET89 Equilibrium Chemistry Code

DTIC Science & Technology

1994-12-01

Army Research Laboratory ATTN: AMSRL-WT-PA Aberdeen Proving Ground, MD 21005-5066 9 . SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING...8 1.5 DISTANCE vs. TIME CALCULATION ........................................... 9 2. D ISCU SSIO N...21 Figure 9 : Comparison of calculated thrust curves ..................................... 32 v

Predicting Metal Speciation & Bioavailability via Estimation of Metal-Organic Thermodynamic Properties

NASA Astrophysics Data System (ADS)

Prasad, A.; Howells, A. E.; Shock, E.

2017-12-01

The biological fate of any metal depends on its chemical form in the environment. Arsenic for example, is extremely toxic in the form of inorganic As+3 but completely benign in the organic form of arsenobetaine. Thus, given an exhaustive set of reactions and their equilibrium constants (logK), the bioavailability of any metal can be obtained for blood plasma, hydrothermal fluids or any system of interest. While many data exist for metal-inorganic ligands, logK data covering the temperature range of life for metal-organic complexes are sparse. Hence, we decided to estimate metal-organic logK values from correlations with the commonly available values of ligand pKa. Metal ion specific correlations were made with ligands classified according to their electron donor atoms, denticity and other chemical factors. While this approach has been employed before (Carbonaro et al. 2007, GCA 71, 3958-3968), new correlations were developed that provide estimates even when no metal-organic logK is available. In addition, we have used the same methods to make estimates of metal-organic entropy of association (ΔaS), which can provide logK for any temperature of biological relevance. Our current correlations employ logK and ΔaS data from 30 metal ions (like the biologically relevant Fe+3 & Zn+2) and 74 ligands (like formate and ethylenediamine), which can be expanded to estimate the metal-ligand reaction properties for these 30 metal ions with a possibly limitless number of ligands that may belong to our categories of ligands. With the help of such data, copper speciation was obtained for a defined growth medium for methanotrophs employed by Morton et al. (2000, AEM 66, 1730-1733) that agrees with experimental measurements showing that the free metal ion may not be the bioavailable form in all conditions. These results encourage us to keep filling the gaps in metal-organic logK data and continue finding relationships between biological responses (like metal-accumulation ratios & metal-induced toxicity) and metal speciation.

Speciation of inorganic and organolead compounds by gas chromatography-atomic absorption spectrometry and the determination of lead species after pre-concentration onto diphenylthiocarbazone-anchored polymeric microbeads

NASA Astrophysics Data System (ADS)

Salih, Bekir

2000-07-01

Poly(EGDMA-HEMA) microbeads were prepared by suspension copolymerization of ethyleneglycol dimethacrylate (EGDMA) and hydroxyethylmethacrylate (HEMA) using poly(vinylalcohol), benzoyl peroxide and toluene as the stabilizer, the initiator, and the diluent, respectively. A chelating ligand, diphenylthiocarbazone (dithizone), was then attached. The microbeads were characterized by FT-IR and elemental analysis. The affinity microbeads containing 118.9 μmol dithizone g -1 polymer were used in the adsorption/desorption of some selected lead species, Pb(II), (CH 3) 2PbCl 2, (C 2H 5) 2PbCl 2, (CH 3) 3PbCl, and (C 2H 5) 3PbCl from aqueous media containing different amounts of these species (5-200 mg l -1) at different pH values, 2.0-8.0. Adsorption rates were high, and adsorption equilibrium was reached in approximately 45 min. The detection limits of the lead species onto the dithizone-anchored affinity microbeads from solutions containing a single species was 0.28 ng ml -1 for Pb(II), 0.12 ng ml -1 for (CH 3) 3PbCl, 0.24 ng ml -1 for (C 2H 5) 3PbCl, 0.18 ng ml -1 for (CH 3) 2PbCl 2 and 0.30 ng ml -1 for (C 2H 5) 2PbCl 2 on a weight basis for lead. The same behavior was observed during competitive adsorption that is adsorption from a mixture. The affinity order of the lead species was Pb(II)>(CH 3) 2PbCl 2>(CH 3) 3PbCl>(C 2H 5) 3PbCl>(C 2H 5) 2PbCl 2 for competitive adsorption. Dithizone-anchored microbeads were found to be suitable for repeated use of more than five cycles, without noticeable loss of adsorption capacity. For the speciation of organolead compounds, ionic alkyllead compounds were derivatized by n-butyl Grignard reagent and the speciation was performed using a gas chromatography-atomic absorption spectrometry coupled system. Detection limits were improved at least 180-fold with this preconcentration approach using the dithizone-anchored microbeads.

In-situ Raman spectroscopic study of aluminate speciation in H2O-KOH solutions at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Mookherjee, M.; Keppler, H.; Manning, C. E.

2009-12-01

The solubility of corundum in H2O is low even at high pressure and temperatures. Therefore, it is commonly assumed that alumina remains essentially immobile during fluid-rock interaction. However, field and experimental evidence suggests that alumina solubility is strongly enhanced in the presence of silica as well as in alkaline solutions. In order to understand what controls the alumina solubility and how it is enhanced as a function of fluid composition, we conducted Raman-spectroscopic study of Al speciation in aqueous fluids at high pressure and temperature. Experiments were carried out in an externally heated hydrothermal diamond-anvil cell equipped with low-fluorescence diamonds and iridium gaskets. Raman spectra were collected with a Horiba Jobin-Yvon Labram HR spectrometer using the 514 nm line of an argon laser for excitation. In a first series of experiments, the speciation of alumina was studied in a 1 M KOH solution in equilibrium with corundum up to 700 oC and ~1 GPa. The Raman spectra show a prominent band at 618 cm-1 interpreted to arise from Al-O stretching vibrations associated with the tetrahedral [Al(OH)4]1- species. At higher pressure and temperature, an additional vibrational mode appears in the spectra at 374 cm-1 (full width at half maximum ~ 20 cm-1). This feature is tentatively attributed to [(OH)3Al-O-Al(OH)3]2- (Moolenaar et al. 1970, Jour. Phys. Chem., 74, 3629-3636). No evidence for KAl(OH)4 was observed, consistent with piston cylinder experiments at 700 oC and 1 GPa (Wohlers & Manning, 2009, Chem. Geol., 262, 310). Upon cooling from high-pressure and high temperature, slow kinetics of corundum regrowth lead to oversaturation in the solutions, as evidenced by sharp peaks at 930 and 1066 cm-1 observed upon cooling. These features are probably due to colloidal aluminum hydroxide. The results provide the first evidence for aluminate polymerization at high pressure and temperature, and offer insights into the causes for enhancement of corundum solubility in alkaline solutions.

A Newton method for the magnetohydrodynamic equilibrium equations

NASA Astrophysics Data System (ADS)

Oliver, Hilary James

We have developed and implemented a (J, B) space Newton method to solve the full nonlinear three dimensional magnetohydrodynamic equilibrium equations in toroidal geometry. Various cases have been run successfully, demonstrating significant improvement over Picard iteration, including a 3D stellarator equilibrium at β = 2%. The algorithm first solves the equilibrium force balance equation for the current density J, given a guess for the magnetic field B. This step is taken from the Picard-iterative PIES 3D equilibrium code. Next, we apply Newton's method to Ampere's Law by expansion of the functional J(B), which is defined by the first step. An analytic calculation in magnetic coordinates, of how the Pfirsch-Schlüter currents vary in the plasma in response to a small change in the magnetic field, yields the Newton gradient term (analogous to ∇f . δx in Newton's method for f(x) = 0). The algorithm is computationally feasible because we do this analytically, and because the gradient term is flux surface local when expressed in terms of a vector potential in an Ar=0 gauge. The equations are discretized by a hybrid spectral/offset grid finite difference technique, and leading order radial dependence is factored from Fourier coefficients to improve finite- difference accuracy near the polar-like origin. After calculating the Newton gradient term we transfer the equation from the magnetic grid to a fixed background grid, which greatly improves the code's performance.

Quantifying Na(I)-insulin and K(I)-insulin non-covalent complexes by ESI-MS method and calculation of their equilibrium constants.

PubMed

Gülfen, Mustafa; Özdemir, Abdil; Lin, Jung-Lee; Chen, Chung-Hsuan

2017-10-01

In this study, the dissociation and formation equilibrium constants of Na(I)-insulin and K(I)-insulin complexes have been calculated after the quantifying them on ESI mass spectrometer. The ESI-MS spectra of the complexes were measured by using the solvents as 50% MeOH in water and 100% water. The effect of pH on the Na(I)-insulin and K(I)-insulin complex formation were examined. Serial binding of Na(I) and K(I) ions to the insulin molecule were observed in the ESI-MS measurements. The first formation equilibrium constants were calculated as K f1 : 5.48×10 3 1/M for Na(I)-insulin complex and K f1 : 4.87×10 3 1/M for K(I)-insulin in water. The binding capability of Na(I) ions to insulin molecule is higher than the capability of K(I) ions. In case of a comparison together with Ca(II)-insulin and Mg(II)-insulin, the formation equilibrium constants (K f1 ) are in order of Ca(II)-insulin>Mg(II)-insulin>Na(I)-insulin>K(I)-insulin in water. The results showed that Na(I) and K(I) ions are involved in the formation of the non-covalent complexes with insulin molecule, since high extracellular and intracellular concentrations of them in the body. Copyright © 2017 Elsevier B.V. All rights reserved.

Equilibrium nuclear ensembles taking into account vaporization of hot nuclei in dense stellar matter

NASA Astrophysics Data System (ADS)

Furusawa, Shun; Mishustin, Igor

2018-02-01

We investigate the high-temperature effect on the nuclear matter that consists of mixture of nucleons and all nuclei in the dense and hot stellar environment. The individual nuclei are described within the compressible-liquid-drop model that is based on Skyrme interactions for bulk energies and that takes into account modifications of the surface and Coulomb energies at finite temperatures and densities. The free-energy density is minimized with respect to the individual equilibrium densities of all heavy nuclei and the nuclear composition. We find that their optimized equilibrium densities become smaller and smaller at high temperatures because of the increase in thermal contributions to bulk free energies and the reduction of surface energies. The neutron-rich nuclei become unstable and disappear one after another at given temperatures. The calculations are performed for two sets of model parameters leading to different values of the slope parameter in the nuclear-symmetry energy. It is found that the larger slope parameter reduces the equilibrium densities and the melting temperatures. We also compare the proposed model with some other approaches and find that the mass fractions of heavy nuclei in the previous calculations that omit vaporization are underestimated at T ≲10 MeV and overestimated at T ≳10 MeV. The further sophistication of calculations of nuclear vaporization and of light clusters would be required to construct the equation of state for explosive astrophysical phenomena.

Composition and Thermodynamic Properties of Air in Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Moeckel, W E; Weston, Kenneth C

1958-01-01

Charts have been prepared relating the thermodynamic properties of air in chemical equilibrium for temperatures to 15,000 degrees k and for pressures 10(-5) to 10 (plus 4) atmospheres. Also included are charts showing the composition of air, the isentropic exponent, and the speed of sound. These charts are based on thermodynamic data calculated by the National Bureau of Standards.

Validation of vibration-dissociation coupling models in hypersonic non-equilibrium separated flows

NASA Astrophysics Data System (ADS)

Shoev, G.; Oblapenko, G.; Kunova, O.; Mekhonoshina, M.; Kustova, E.

2018-03-01

The validation of recently developed models of vibration-dissociation coupling is discussed in application to numerical solutions of the Navier-Stokes equations in a two-temperature approximation for a binary N2/N flow. Vibrational-translational relaxation rates are computed using the Landau-Teller formula generalized for strongly non-equilibrium flows obtained in the framework of the Chapman-Enskog method. Dissociation rates are calculated using the modified Treanor-Marrone model taking into account the dependence of the model parameter on the vibrational state. The solutions are compared to those obtained using traditional Landau-Teller and Treanor-Marrone models, and it is shown that for high-enthalpy flows, the traditional and recently developed models can give significantly different results. The computed heat flux and pressure on the surface of a double cone are in a good agreement with experimental data available in the literature on low-enthalpy flow with strong thermal non-equilibrium. The computed heat flux on a double wedge qualitatively agrees with available data for high-enthalpy non-equilibrium flows. Different contributions to the heat flux calculated using rigorous kinetic theory methods are evaluated. Quantitative discrepancy of numerical and experimental data is discussed.

Integrated Force Method Solution to Indeterminate Structural Mechanics Problems

NASA Technical Reports Server (NTRS)

Patnaik, Surya N.; Hopkins, Dale A.; Halford, Gary R.

2004-01-01

Strength of materials problems have been classified into determinate and indeterminate problems. Determinate analysis primarily based on the equilibrium concept is well understood. Solutions of indeterminate problems required additional compatibility conditions, and its comprehension was not exclusive. A solution to indeterminate problem is generated by manipulating the equilibrium concept, either by rewriting in the displacement variables or through the cutting and closing gap technique of the redundant force method. Compatibility improvisation has made analysis cumbersome. The authors have researched and understood the compatibility theory. Solutions can be generated with equal emphasis on the equilibrium and compatibility concepts. This technique is called the Integrated Force Method (IFM). Forces are the primary unknowns of IFM. Displacements are back-calculated from forces. IFM equations are manipulated to obtain the Dual Integrated Force Method (IFMD). Displacement is the primary variable of IFMD and force is back-calculated. The subject is introduced through response variables: force, deformation, displacement; and underlying concepts: equilibrium equation, force deformation relation, deformation displacement relation, and compatibility condition. Mechanical load, temperature variation, and support settling are equally emphasized. The basic theory is discussed. A set of examples illustrate the new concepts. IFM and IFMD based finite element methods are introduced for simple problems.

Monte Carlo calculations of LR115 detector response to 222Rn in the presence of 220Rn.

PubMed

Nikezić, D; Yu, K N

2000-04-01

The sensitivities (in m) of bare LR115 detectors and detectors in diffusion chambers to 222Rn and 220Rn chains are calculated by the Monte Carlo method. The partial sensitivities of bare detectors to the 222Rn chain are larger than those to the 220Rn chain, which is due to the higher energies of alpha particles in the 220Rn chain and the upper energy limit for detection for the LR115 detector. However, the total sensitivities are approximately equal because 220Rn is always in equilibrium with its first progeny, which is not the case for the 222Rn chain. The total sensitivity of bare LR115 detectors to 222Rn chain depends linearly on the equilibrium factor. The overestimation in 222Rn measurements with bare detectors caused by 220Rn in air can reach 10% in normal environmental conditions. An analytical relationship between the equilibrium factor and the ratio between track densities on the bare detector and the detector enclosed in chamber is given in the last part of the paper. This ratio is also affected by 220Rn, which can disturb the determination of the equilibrium factor.

Quasi-equilibria in reduced Liouville spaces.

PubMed

Halse, Meghan E; Dumez, Jean-Nicolas; Emsley, Lyndon

2012-06-14

The quasi-equilibrium behaviour of isolated nuclear spin systems in full and reduced Liouville spaces is discussed. We focus in particular on the reduced Liouville spaces used in the low-order correlations in Liouville space (LCL) simulation method, a restricted-spin-space approach to efficiently modelling the dynamics of large networks of strongly coupled spins. General numerical methods for the calculation of quasi-equilibrium expectation values of observables in Liouville space are presented. In particular, we treat the cases of a time-independent Hamiltonian, a time-periodic Hamiltonian (with and without stroboscopic sampling) and powder averaging. These quasi-equilibrium calculation methods are applied to the example case of spin diffusion in solid-state nuclear magnetic resonance. We show that there are marked differences between the quasi-equilibrium behaviour of spin systems in the full and reduced spaces. These differences are particularly interesting in the time-periodic-Hamiltonian case, where simulations carried out in the reduced space demonstrate ergodic behaviour even for small spins systems (as few as five homonuclei). The implications of this ergodic property on the success of the LCL method in modelling the dynamics of spin diffusion in magic-angle spinning experiments of powders is discussed.

One-dimensional thermohydraulic code THESEUS and its application to chilldown process simulation in two-phase hydrogen flows

NASA Astrophysics Data System (ADS)

Papadimitriou, P.; Skorek, T.

THESUS is a thermohydraulic code for the calculation of steady state and transient processes of two-phase cryogenic flows. The physical model is based on four conservation equations with separate liquid and gas phase mass conservation equations. The thermohydraulic non-equilibrium is calculated by means of evaporation and condensation models. The mechanical non-equilibrium is modeled by a full-range drift-flux model. Also heat conduction in solid structures and heat exchange for the full spectrum of heat transfer regimes can be simulated. Test analyses of two-channel chilldown experiments and comparisons with the measured data have been performed.

Comment on “Hydromagnesite solubility product and growth kinetics in aqueous solution from 25 to 75 °C” by Gautier, Q., Benezeth, P., Mavromatis, V., and Schott, J

DOE PAGES

Xiong, Yongliang

2016-04-16

Here, Gautier et al. (2014) recently published their determination of hydromagnesite solubility constant and hydromagnesite growth kinetics. Although their raw data appear to be of high quality, there is an oversight in their calculations of the hydromagnesite solubility constants given the solution compositions in their experiments. The oversight lies in the fact that they did not consider the constraint of simultaneous equilibrium with brucite. This oversight causes their newly calculated equilibrium constant for hydromagnesite to be discordant with the literature values (Königsberger et al., 1992 and Xiong, 2011).

Influence of condensed species on thermo-physical properties of LTE and non-LTE SF6-Cu mixture

NASA Astrophysics Data System (ADS)

Chen, Zhexin; Wu, Yi; Yang, Fei; Sun, Hao; Rong, Mingzhe; Wang, Chunlin

2017-10-01

SF6-Cu mixture is frequently formed in high-voltage circuit breakers due to the electrode erosion and metal vapor diffusion. During the interruption process, the multiphase effect and deviation from local thermal equilibrium (non-LTE assumption) can both affect the thermo-physical of the arc plasma and further influence the performance of circuit breaker. In this paper, thermo-physical properties, namely composition, thermodynamic properties and transport coefficients are calculated for multiphase SF6-Cu mixture with and without LTE assumption. The composition is confirmed by combining classical two-temperature mass action law with phase equilibrium condition deduced from second law of thermodynamics. The thermodynamic properties and transport coefficients are calculated using the multiphase composition result. The influence of condensed species on thermo-physical properties is discussed at different temperature, pressure (0.1-10 atm), non-equilibrium degrees (1-10), and copper molar proportions (0-50%). It is found that the multiphase effect has significant influence on specific enthalpy, specific heat and heavy species thermal conductivity in both LTE and non-LTE SF6-Cu system. This paper provides a more accurate database for computational fluid dynamic calculation.

Evaluating measurement uncertainty in fluid phase equilibrium calculations

NASA Astrophysics Data System (ADS)

van der Veen, Adriaan M. H.

2018-04-01

The evaluation of measurement uncertainty in accordance with the ‘Guide to the expression of uncertainty in measurement’ (GUM) has not yet become widespread in physical chemistry. With only the law of the propagation of uncertainty from the GUM, many of these uncertainty evaluations would be cumbersome, as models are often non-linear and require iterative calculations. The methods from GUM supplements 1 and 2 enable the propagation of uncertainties under most circumstances. Experimental data in physical chemistry are used, for example, to derive reference property data and support trade—all applications where measurement uncertainty plays an important role. This paper aims to outline how the methods for evaluating and propagating uncertainty can be applied to some specific cases with a wide impact: deriving reference data from vapour pressure data, a flash calculation, and the use of an equation-of-state to predict the properties of both phases in a vapour-liquid equilibrium. The three uncertainty evaluations demonstrate that the methods of GUM and its supplements are a versatile toolbox that enable us to evaluate the measurement uncertainty of physical chemical measurements, including the derivation of reference data, such as the equilibrium thermodynamical properties of fluids.

A Computational Study on the Ground and Excited States of Nickel Silicide.

PubMed

Schoendorff, George; Morris, Alexis R; Hu, Emily D; Wilson, Angela K

2015-09-17

Nickel silicide has been studied with a range of computational methods to determine the nature of the Ni-Si bond. Additionally, the physical effects that need to be addressed within calculations to predict the equilibrium bond length and bond dissociation energy within experimental error have been determined. The ground state is predicted to be a (1)Σ(+) state with a bond order of 2.41 corresponding to a triple bond with weak π bonds. It is shown that calculation of the ground state equilibrium geometry requires a polarized basis set and treatment of dynamic correlation including up to triple excitations with CR-CCSD(T)L resulting in an equilibrium bond length of only 0.012 Å shorter than the experimental bond length. Previous calculations of the bond dissociation energy resulted in energies that were only 34.8% to 76.5% of the experimental bond dissociation energy. It is shown here that use of polarized basis sets, treatment of triple excitations, correlation of the valence and subvalence electrons, and a Λ coupled cluster approach is required to obtain a bond dissociation energy that deviates as little as 1% from experiment.

Calculation of a coaxial microwave torch

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

Gritsinin, S. I.; Kossyi, I. A.; Kulumbaev, E. B.

2006-10-15

Parameters of an equilibrium microwave discharge in an atmospheric-pressure argon flow in a coaxial waveguide with a truncated inner electrode are calculated numerically by using a self-consistent two-dimensional MHD model. The results obtained agree satisfactorily with the experimental data.

Secondary sympatry caused by range expansion informs on the dynamics of microendemism in a biodiversity hotspot.

PubMed

Nattier, Romain; Grandcolas, Philippe; Elias, Marianne; Desutter-Grandcolas, Laure; Jourdan, Hervé; Couloux, Arnaud; Robillard, Tony

2012-01-01

Islands are bounded areas where high endemism is explained either by allopatric speciation through the fragmentation of the limited amount of space available, or by sympatric speciation and accumulation of daughter species. Most empirical evidence point out the dominant action of allopatric speciation. We evaluate this general view by looking at a case study where sympatric speciation is suspected. We analyse the mode, tempo and geography of speciation in Agnotecous, a cricket genus endemic to New Caledonia showing a generalized pattern of sympatry between species making sympatric speciation plausible. We obtained five mitochondrial and five nuclear markers (6.8 kb) from 37 taxa corresponding to 17 of the 21 known extant species of Agnotecous, and including several localities per species, and we conducted phylogenetic and dating analyses. Our results suggest that the diversification of Agnotecous occurred mostly through allopatric speciation in the last 10 Myr. Highly microendemic species are the most recent ones (<2 Myr) and current sympatry is due to secondary range expansion after allopatric speciation. Species distribution should then be viewed as a highly dynamic process and extreme microendemism only as a temporary situation. We discuss these results considering the influence of climatic changes combined with intricate soil diversity and mountain topography. A complex interplay between these factors could have permitted repeated speciation events and range expansion.

Selenium Metabolism in Cancer Cells: The Combined Application of XAS and XFM Techniques to the Problem of Selenium Speciation in Biological Systems

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Finney, Lydia; Vogt, Stefan; Witting, Paul K.; Harris, Hugh H.

2013-01-01

Determining the speciation of selenium in vivo is crucial to understanding the biological activity of this essential element, which is a popular dietary supplement due to its anti-cancer properties. Hyphenated techniques that combine separation and detection methods are traditionally and effectively used in selenium speciation analysis, but require extensive sample preparation that may affect speciation. Synchrotron-based X-ray absorption and fluorescence techniques offer an alternative approach to selenium speciation analysis that requires minimal sample preparation. We present a brief summary of some key HPLC-ICP-MS and ESI-MS/MS studies of the speciation of selenium in cells and rat tissues. We review the results of a top-down approach to selenium speciation in human lung cancer cells that aims to link the speciation and distribution of selenium to its biological activity using a combination of X-ray absorption spectroscopy (XAS) and X-ray fluorescence microscopy (XFM). The results of this approach highlight the distinct fates of selenomethionine, methylselenocysteine and selenite in terms of their speciation and distribution within cells: organic selenium metabolites were widely distributed throughout the cells, whereas inorganic selenium metabolites were compartmentalized and associated with copper. New data from the XFM mapping of electrophoretically-separated cell lysates show the distribution of selenium in the proteins of selenomethionine-treated cells. Future applications of this top-down approach are discussed. PMID:23698165

A comparative analysis of island floras challenges taxonomy-based biogeographical models of speciation.

PubMed

Igea, Javier; Bogarín, Diego; Papadopulos, Alexander S T; Savolainen, Vincent

2015-02-01

Speciation on islands, and particularly the divergence of species in situ, has long been debated. Here, we present one of the first, complete assessments of the geographic modes of speciation for the flora of a small oceanic island. Cocos Island (Costa Rica) is pristine; it is located 550 km off the Pacific coast of Central America. It harbors 189 native plant species, 33 of which are endemic. Using phylogenetic data from insular and mainland congeneric species, we show that all of the endemic species are derived from independent colonization events rather than in situ speciation. This is in sharp contrast to the results of a study carried out in a comparable system, Lord Howe Island (Australia), where as much as 8.2% of the plant species were the product of sympatric speciation. Differences in physiography and age between the islands may be responsible for the contrasting patterns of speciation observed. Importantly, comparing phylogenetic assessments of the modes of speciation with taxonomy-based measures shows that widely used island biogeography approaches overestimate rates of in situ speciation. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.

Biosorption of trivalent chromium on the brown seaweed biomass.

PubMed

Yun, Y S; Park, D; Park, J M; Volesky, B

2001-11-01

Biosorption has attracted attention as a cost-effective means for the treatment of metal-bearing wastewater. However, the mechanism of metal binding is not clearly understood, and consequently, modeling of the biosorption performance is still raising debates. In this study, the biosorption of trivalent chromium was investigated with protonated brown alga Ecklonia biomass as a model system. Titration of the biomass revealed that it contains at least three types of functional groups. The Fourier transform infrared spectrometry showed that the carboxyl group was the chromium-binding site within the pH range (pH 1-5) used in this study, where chromium does not precipitate. The pK value and the number of carboxyl groups were estimated to be 4.6 +/- 0.1 and 2.2 +/- 0.1 mmol/g, respectively. The equilibrium sorption isotherms determined at different solution pH indicated that the uptake of chromium increased significantly with increasing pH. A model for the description of chromium biosorption was developed incorporating the hydrolysis reactions that chromium undergoes in the aquatic phase. The model was able to predict the equilibrium sorption experimental data at different pH values and chromium concentrations. In addition, the speciation of the binding site as a function of the solution pH was predicted using the model in order to visualize the distribution of chromium ionic species on the binding site.

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

USGS Publications Warehouse

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

1987-01-01

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

Sexual selection accounts for the geographic reversal of sexual size dimorphism in the dung fly, sepsis punctum (Diptera: Sepsidae).

PubMed

Puniamoorthy, Nalini; Schäfer, Martin A; Blanckenhorn, Wolf U

2012-07-01

Sexual size dimorphism (SSD) varies widely across and within species. The differential equilibrium model of SSD explains dimorphism as the evolutionary outcome of consistent differences in natural and sexual selection between the sexes. Here, we comprehensively examine a unique cross-continental reversal in SSD in the dung fly, Sepsis punctum. Using common garden laboratory experiments, we establish that SSD is male-biased in Europe and female-biased in North America. When estimating sexual (pairing success) and fecundity selection (clutch size of female partner) on males under three operational sex ratios (OSRs), we find that the intensity of sexual selection is significantly stronger in European versus North American populations, increasing with male body size and OSR in the former only. Fecundity selection on female body size also increases strongly with egg number and weakly with egg volume, however, equally on both continents. Finally, viability selection on body size in terms of intrinsic (physiological) adult life span in the laboratory is overall nil and does not vary significantly across all seven populations. Although it is impossible to prove causality, our results confirm the differential equilibrium model of SSD in that differences in sexual selection intensity account for the reversal in SSD in European versus North American populations, presumably mediating the ongoing speciation process in S. punctum. © 2012 The Author(s).

Divergence times in the termite genus Macrotermes (Isoptera: Termitidae).

PubMed

Brandl, R; Hyodo, F; Korff-Schmising, M von; Maekawa, K; Miura, T; Takematsu, Y; Matsumoto, T; Abe, T; Bagine, R; Kaib, M

2007-10-01

The evolution of fungus-growing termites is supposed to have started in the African rain forests with multiple invasions of semi-arid habitats as well as multiple invasions of the Oriental region. We used sequences of the mitochondrial COII gene and Bayesian dating to investigate the time frame of the evolution of Macrotermes, an important genus of fungus-growing termites. We found that the genus Macrotermes consists of at least 6 distantly related clades. Furthermore, the COII sequences suggested some cryptic diversity within the analysed African Macrotermes species. The dates calculated with the COII data using a fossilized termite mound to calibrate the clock were in good agreement with dates calculated with COI sequences using the split between Locusta and Chortippus as calibration point which supports the consistency of the calibration points. The clades from the Oriental region dated back to the early Tertiary. These estimates of divergence times suggested that Macrotermes invaded Asia during periods with humid climates. For Africa, many speciation events predated the Pleistocene and fall in range of 6-23 million years ago. These estimates suggest that savannah-adapted African clades radiated with the spread of the semi-arid ecosystems during the Miocene. Apparently, events during the Pleistocene were of little importance for speciation within the genus Macrotermes. However, further investigations are necessary to increase the number of taxa for phylogenetic analysis.

Volatile organic compounds speciation and their influence on ozone formation potential in an industrialized urban area in Brazil.

PubMed

Galvão, Elson Silva; Santos, Jane Meri; Reis Junior, Neyval Costa; Stuetz, Richard Michael

2016-09-01

Speciation and the influence on the ozone formation potential (OFP) from volatile organic compounds (VOCs) have been studied between February June 2013 in Vitória, ES, Brazil. Passive samplers were installed at three air-quality monitoring stations and a total of 96 samplings were collected. A total of 78 VOCs were characterized by gas chromatograph-mass spectrometer. The predominant group was organic acids, followed by alcohols and substituted aromatics and 14 precursor species were quantified. An analysis correlating concentrations with wind direction was conducted to identify possible sources. The OFP was calculated applying the scale of maximum incremental reactivity proposed by Carter.[ 23 ] Ozone precursors with the greatest OFP such as undecane, toluene, ethylbenzene and m, p-xylene compounds were the most abundant with means of 0.855, 0.365, 0.259 and 0.289 µg m(-3), respectively. The benzene, toluene, ethylbenzene and xylene (BTEX) group was found below the limits considered harmful to the health of the population living in Vitória. The OFP calculated for the precursors group was 22.55 µg m(-3) for the rainy season and 32.11 µg m(-3) for the dry season. The VOC/NOx ratio in Vitória is approximately 1.71, indicating that the region has a VOC-limiting condition for the production of ozone.

Non-Equilibrium Dynamics with Quantum Monte Carlo

NASA Astrophysics Data System (ADS)

Dong, Qiaoyuan

This work is motivated by the fact that the investigation of non-equilibrium phenomena in strongly correlated electron systems has developed into one of the most active and exciting branches of condensed matter physics as it provides rich new insights that could not be obtained from the study of equilibrium situations. However, a theoretical description of those phenomena is missing. Therefore, in this thesis, we develop a numerical method that can be used to study two minimal models--the Hubbard model and the Anderson impurity model with general parameter range and time dependence. We begin by introducing the theoretical framework and the general features of the Hubbard model. We then describe the dynamical mean field theory (DMFT), which was first invented by Georges in 1992. It provides a feasible way to approach strongly correlated electron systems and reduces the complexity of the calculations via a mapping of lattice models onto quantum impurity models subject to a self-consistency condition. We employ the non-equilibrium extension of DMFT and map the Hubbard model to the single impurity Anderson model (SIAM). Since the fundamental component of the DMFT method is a solver of the single impurity Anderson model, we continue with a description of the formalism to study the real-time dynamics of the impurity model staring at its thermal equilibrium state. We utilize the non-equilibrium strong-coupling perturbation theory and derive semi-analytical approximation methods such as the non-crossing approximation (NCA) and the one-crossing approximation (OCA). We then use the Quantum Monte-Carlo method (QMC) as a numerically exact method and present proper measurements of local observables, current and Green's functions. We perform simulations of the current after a quantum quench from equilibrium by rapidly applying a bias voltage in a wide range of initial temperatures. The current exhibits short equilibrium times and saturates upon the decrease of temperature at all times, indicating Kondo behavior both in the transient regime and in the steady state. However, this bare QMC solver suffers from a dynamical sign problem for long time propagations. To overcome the limitations of this bare treatment, we introduce the "Inchworm algorithm'', based on iteratively reusing the information obtained in previous steps to extend the propagation to longer times and stabilize the calculations. We show that this algorithm greatly reduces the required order for each simulation and re-scales the exponential challenge to quadratic in time. We introduce a method to compute Green's functions, spectral functions, and currents for inchworm Monte Carlo and show how systematic error assessments in real time can be obtained. We illustrate the capabilities of the algorithm with a study of the behavior of quantum impurities after an instantaneous voltage quench from a thermal equilibrium state. We conclude with the applications of the unbiased inchworm impurity solver to DMFT calculations. We employ the methods for a study of the one-band paramagnetic Hubbard model on the Bethe lattice in equilibrium, where the DMFT approximation becomes exact. We begin with a brief introduction of the Mott metal insulator phase diagram. We present the results of both real time Green's functions and spectral functions from our nonequilibrium calculations. We observe the metal-insulator crossover as the on-site interaction is increased and the formation of a quasi-particle peak as the temperature is lowered. We also illustrate the convergence of our algorithms in different aspects.

Siphon flows in isolated magnetic flux tubes. III - The equilibrium path of the flux-tube arch

NASA Technical Reports Server (NTRS)

Thomas, John H.; Montesinos, Benjamin

1990-01-01

It is shown how to calculate the equilibrium path of a thin magnetic flux tube in a stratified, nonmagnetic atmosphere when the flux tube contains a steady siphon flow. The equilbrium path of a static thin flux tube in an infinite stratified atmosphere generally takes the form of a symmetric arch of finite width, with the flux tube becoming vertical at either end of the arch. A siphon flow within the flux tube increases the curvature of the arched equilibrium path in order that the net magnetic tension force can balance the inertial force of the flow, which tries to straighten the flux tube. Thus, a siphon flow reduces the width of the arched equilibrium path, with faster flows producing narrower arches. The effect of the siphon flow on the equilibrium path is generally greater for flux tubes of weaker magnetic field strength. Examples of the equilibrium are shown for both isothemal and adiabatic siphon flows in thin flux tubes in an isothermal external atmosphere.

Radiative heat transfer and nonequilibrium Casimir-Lifshitz force in many-body systems with planar geometry

NASA Astrophysics Data System (ADS)

Latella, Ivan; Ben-Abdallah, Philippe; Biehs, Svend-Age; Antezza, Mauro; Messina, Riccardo

2017-05-01

A general theory of photon-mediated energy and momentum transfer in N -body planar systems out of thermal equilibrium is introduced. It is based on the combination of the scattering theory and the fluctuational-electrodynamics approach in many-body systems. By making a Landauer-like formulation of the heat transfer problem, explicit formulas for the energy transmission coefficients between two distinct slabs as well as the self-coupling coefficients are derived and expressed in terms of the reflection and transmission coefficients of the single bodies. We also show how to calculate local equilibrium temperatures in such systems. An analogous formulation is introduced to quantify momentum transfer coefficients describing Casimir-Lifshitz forces out of thermal equilibrium. Forces at thermal equilibrium are readily obtained as a particular case. As an illustration of this general theoretical framework, we show on three-body systems how the presence of a fourth slab can impact equilibrium temperatures in heat-transfer problems and equilibrium positions resulting from the forces acting on the system.

Chemical equilibria of thermal waters for the application of geothermometers from the Guanzhong basin, China

NASA Astrophysics Data System (ADS)

Xilai, Zheng; Armannsson, Halldor; Yongle, Li; Hanxue, Qiu

2002-03-01

In this study, representative samples from thermal wells and springs were chemically analyzed and geothermometers were used to calculate the deep temperatures of geothermal reservoirs on the basis of water-mineral equilibrium. In some cases, however, the chemical components are not in equilibrium with the minerals in the reservoir. Therefore, log( Q/ K) diagrams are used to study the chemical equilibrium for the minerals that are likely to participate. The Na-K-Mg triangular diagram is also applied to evaluate the equilibrium of water with reservoir rocks. Standard curves at the reference temperatures are prepared to reveal which type of silica geothermometer is appropriate for the specified condition. This study shows that water samples from geothermal wells W9 and W12 are in equilibrium with the selective minerals, and chalcedony may control the fluid-silica equilibrium. It is estimated that there is an exploitable low-temperature reservoir with possible temperatures of 80-90°C in the Guanzhong basin.

Self-consistent approach for neutral community models with speciation

NASA Astrophysics Data System (ADS)

Haegeman, Bart; Etienne, Rampal S.

2010-03-01

Hubbell’s neutral model provides a rich theoretical framework to study ecological communities. By incorporating both ecological and evolutionary time scales, it allows us to investigate how communities are shaped by speciation processes. The speciation model in the basic neutral model is particularly simple, describing speciation as a point-mutation event in a birth of a single individual. The stationary species abundance distribution of the basic model, which can be solved exactly, fits empirical data of distributions of species’ abundances surprisingly well. More realistic speciation models have been proposed such as the random-fission model in which new species appear by splitting up existing species. However, no analytical solution is available for these models, impeding quantitative comparison with data. Here, we present a self-consistent approximation method for neutral community models with various speciation modes, including random fission. We derive explicit formulas for the stationary species abundance distribution, which agree very well with simulations. We expect that our approximation method will be useful to study other speciation processes in neutral community models as well.

Is the Reaction Equilibrium Composition in Non-ideal Mixtures Uniquely Determined by the Initial Composition?

NASA Astrophysics Data System (ADS)

Sefcik, Jan

1998-05-01

Reaction equilibrium can be mathematically described by the equilibrium equation and the reaction equilibrium composition can be calculated by solving this equation. It can be proved by non-elementary thermodynamic arguments that for a generic system with given initial composition, temperature and pressure there is a unique stable equilibrium state corresponding to the global minimum of the Gibbs free energy function. However, when the concept of equilibrium is introduced in undergraduate chemistry and chemical engineering courses, such arguments are generally not accessible. When there is a single reaction equilibrium among mixture components and the components form an ideal mixture, it has been demonstrated by a simple, elegant mathematical argument that there is a unique composition satisfying the equilibrium equation. It has been also suggested that this particular argument extends to non-ideal mixtures by simply incorporating activity coefficients. We show that the argument extension to non-ideal systems is not generally valid. Increasing non-ideality can result in non-monotonicity of the function crucial for the simple uniqueness argument, and only later it leads to non-uniqueness and hence phase separation. The main feature responsible for this is a composition dependence of activity coefficients in non-ideal mixtures.

VALIDATION OF MERCURY CEMS WHEN COFIRING BIOMASS AT MADISON ELECTRIC'S BLOUNT STATION

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

Dennis L. Laudal; Jeffrey S. Thompson

2000-09-30

The state of Wisconsin has been concerned about mercury deposition into its lakes and streams and has been evaluating strategies to reduce mercury emissions. As part of this effort, the Blount Station, owned and operated by Madison Gas and Electric Company (MGE), has undergone a project to evaluate the effects and potential mercury emissions reduction of cofiring preconsumer waste. MGE owns and operates the Blount Generating Station located in central Madison, Wisconsin. At present, Blount operates with nine boilers and six turbine generators. The two largest boilers at Blount produce 400,000 pounds of steam per hour at 950 F andmore » 1250 psi. These larger boilers, MGE's Boiler Nos. 8 and 9, have the capability of cofiring both paper and plastic. MGE's Blount Generating Station was one of the first electric generating stations in the United States to retrofit its existing steam boilers to successfully burn refuse-derived fuel and other alternate fuels including waste paper and wood. It is the No. 9 boiler that was the focus of this project to determine the effect of cofiring PDF (plastic- and paper-derived fuel) on speciated mercury emissions. The project was laid out to compare four different fuel combinations: (1) coal feed only, (2) coal with plastic, (3) coal with paper, and (4) coal with paper and plastic. The design was to run the boiler for 2 days at each condition, thus allowing four samples to be taken at each condition. This plan was aimed at getting at least three representative samples at each condition and allowed for difficulties in sampling and boiler operation. The following objectives were accomplished as part of the project to determine the effects of cofiring PDF on mercury emissions and speciation at MGE Blount Station: Successfully completed all of the mercury sampling for each of the four boiler/PDF conditions using the Ontario Hydro (OH) mercury speciation method; Determined mercury concentrations at the stack location using mercury continuous emission monitors (CEMs) for each of the four boiler/PDF conditions; Calculated the overall mercury mass balance for each of the runs; Determined chlorine concentrations at the stack location using EPA Method 26A for each of the four boiler/PDF conditions; and Calculated speciated mercury flow to determine removal and/or transformations before its exiting the unit at the stack for each of the four boiler/PDF conditions.« less

How does organic matter occurrence set limit onto the use of Ce anomaly as a reliable proxy of redox conditions in shallow groundwaters?

NASA Astrophysics Data System (ADS)

Dia, A.; Gruau, G.; Davranche, M.; Vidy, A.; Henin, O.; Petitjean, P.; Le Coz-Bouhnik, M.

2003-04-01

This study is dedicated to the effects of organic matter on the hydrochemistry of Rare Earth Elements (REE) and the ability of using the Ce anomaly as a reliable proxy of redox conditions in surface waters when organic matter occurs. The data include a : i) two-year survey of SREE and Ce anomalies in organic-rich waters recovered from a catchment located in Brittany (western Europe) and (ii) experimental incubation of organic soils from this catchment set under controlled conditions, as well as, (iii) a REE speciation calculation in both the natural organic-rich waters from the wetlands and the experimental solutions. Field and experimental data appear to be extremely coherent, displaying good correlation between the SREE, the Dissolved Organic Carbon (DOC) contents and the redox state. The field data show a strong increase of the SREE and DOC concentrations in soil waters when the environment becomes more reducing. The onset of DOC and SREE contents is seen to be in phase with the increase of dissolved Fe and Mn. The role of Fe-, Mn-oxyhydroxides is confirmed by the experimental data as the maximum of DOC and SREE content is reached when Fe2+ reaches a maximum in the soil solution, suggesting that reductive dissolution of Fe, Mn-oxyhydroxides happens. Despite the strong redox changes and the known redox sensitive behaviour of Ce as compared to other REE, none Ce anomaly variation is observed during either, the experimental procedure, or the field survey through time. Speciation calculations were performed showing that in both such pH range and moderately oxidizing waters in DOC-rich waters, REE should have an organic speciation. Such an organic speciation prevents the formation of Ce(IV) and therefore the development of any Ce anomaly. However, since the studied waters are highly oxidizing (high nitrate contents), the nitrates impose the redox formation of Ce(IV) and a Ce anomaly should appear. Therefore, Ce(IV) is not formed in these waters either because (i) the reaction kinetic might be so slow that the anomaly has no time to ever happen in the field, or (ii) Ce(IV) might be linked to the organic colloidal fraction. Since the thermodynamic modelling does not help getting information, further experimental kinetics or ultrafiltration studies will be required to clarify these latter points. This has to be fixed to be able to use the Ce anomaly as a reliable proxy of redox conditions in organic-rich environment.

Ionization and excitation in cool giant stars. I - Hydrogen and helium

NASA Technical Reports Server (NTRS)

Luttermoser, Donald G.; Johnson, Hollis R.

1992-01-01

The influence that non-LTE radiative transfer has on the electron density, ionization equilibrium, and excitation equilibrium in model atmospheres representative of both oxygen-rich and carbon-rich red giant stars is demonstrated. The radiative transfer and statistical equilibrium equations are solved self-consistently for H, H(-), H2, He I, C I, C II, Na I, Mg I, Mg II, Ca I, and Ca II in a plane-parallel static medium. Calculations are made for both radiative-equilibrium model photospheres alone and model photospheres with attached chromospheric models as determined semiempirically with IUE spectra of g Her (M6 III) and TX Psc (C6, 2). The excitation and ionization results for hydrogen and helium are reported.

Metal/Silicate Partitioning, Melt Speciation, Accretion, and Core Formation in the Earth

NASA Astrophysics Data System (ADS)

Drake, M. J.; Hillgren, V. J.; Dearo, J. A.; Capobianco, C. J.

1993-07-01

Core formation in terrestrial planets was concomitant with accretion. Siderophile and chalcophile element signatures in the mantles of planets are the result of these processes. For Earth, abundances of most siderophile and chalcophile elements are elevated relative to predictions from simple metal/silicate equilibria at low pressures [1]. This observation has led to three hypotheses for how these abundances were established: heterogeneous accretion [2], inefficient core formation [3], and metal/silicate equilibria at magma ocean pressures and temperatures [4]. Knowledge of speciation of siderophile elements in silicate melts in equilibrium with metal may help distinguish between these hypotheses. But there is some uncertainty regarding speciation. For example, Ni and Co have been reported to be present as 1+ or zero valence species in silicate melts at redox states appropriate to planetary accretion, rather than the expected 2+ state [5-7]. Independent metal/silicate partitioning experiments by three members of this group using two different experimental designs on both synthetic and natural compositions do not show evidence for Ni and Co in valence states other than 2+ over a wide range of redox states. For example, solid metal/silicate melt partition coefficients for Ni at 1260 degrees C obtained by VJH from experiments investigating the partitioning of Ni, Co, Mo, W, and P are indistinguishable from those obtained by JAD in similar experiments investigating the partitioning of Ni, Ge, and Sn. Both datasets define a line with the equation: log D(Ni) = - 0.54log fO2 - 3.14 with r^2 > 0.995. (Note that fO2 was calculated in both studies from thermodynamic data and phase compositions. A small, systematic offset from the true fO2 as measured by a solid electrolyte cell affects both equations similarly, but does not diminish their close agreement.) The valence of Ni in the silicate melt is obtained by multiplying the slope of the line by -4, indicating divalent Ni in both studies. Experiments by [8] between 1300 degrees C and 1550 degrees C and fO2 from air to just below iron-wustite in which Ni and Co are partitioned between Pt metal and CaO-Al2O3-SiO2 silicate melt also show evidence only for 2+ valence. Capobianco et al. [1] have noted that reliable extrapolation from current laboratory temperatures (1190 degrees C-1600 degrees C) to magma ocean temperatures is not possible. The hypothesis that siderophile and chalcophile element abundances in the mantle of Earth were established by metal/silicate equilibria at magma ocean pressures and temperatures needs to be tested using direct experimental measurements at magma ocean temperatures and pressures. Such experiments are currently being conducted. References: [1] Capobianco et al. (1993) J. Geophys. Res., 98, 5433. [2] Wanke (1981) Phil. Trans. R. Soc. London, A303, 287. [3] Jones and Drake (1986) Nature, 322, 221. [4] Murthy (1991) Science, 253, 303. [5] Schmitt et al. (1989) GCA, 53, 173. [6] Ehlers et al. (1993) GCA, 56, 3733. [7] Colson (1992) Nature, 357, 65. [8] Capobianco and Amelin (1993) GCA, 56 (in press).

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

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

Biogeochemical modeling of CO2 and CH4 production in anoxic Arctic soil microcosms

NASA Astrophysics Data System (ADS)

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; Yang, Ziming; Graham, David E.; Gu, Baohua; Painter, Scott L.; Thornton, Peter E.

2016-09-01

Soil organic carbon turnover to CO2 and CH4 is sensitive to soil redox potential and pH conditions. However, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximately describe the observed pH evolution without additional parameterization. Although Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. The equilibrium speciation predicts a substantial increase in CO2 solubility as pH increases, and taking into account CO2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO2 production from closed microcosms can be substantially underestimated based on headspace CO2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.

Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Chen, Xinming; Romaniello, Stephen J.; Anbar, Ariel D.

2017-10-01

Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time. We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

Magnetic solid-phase extraction combined with graphite furnace atomic absorption spectrometry for speciation of Cr(III) and Cr(VI) in environmental waters.

PubMed

Jiang, Hong-mei; Yang, Ting; Wang, Yan-hong; Lian, Hong-zhen; Hu, Xin

2013-11-15

A new approach of magnetic solid phase extraction (MSPE) coupled with graphite furnace atomic absorption spectrometry (GFAAS) has been developed for the speciation of Cr(III) and Cr(VI) using zincon-immobilized silica-coated magnetic Fe3O4 nanoparticles (Zincon-Si-MNPs) as the MSPE absorbent. Cr(III) was quantitatively reserved on the absorbent at pH 9.1 while total Cr was reserved at pH 6.5. The absorbed Cr species were eluted by using 2 mol/L HCl and detected by GFAAS. The concentration of Cr(VI) could be calculated by subtracting Cr(III) from total Cr. All the parameters affecting the separation and extraction efficiency of Cr species such as pH, extraction time, concentration and volume of eluent, sample volume and influence of co-existing ions were systematically examined and the optimized conditions were established accordingly. The detection limit (LOD) of the method was 0.016 and 0.011 ng mL(-1) for Cr(III) and Cr(VI), respectively, with the enrichment factor of 100 and 150. The precisions of this method (Relative standard deviation, RSD, n=7) for Cr(III) and Cr(VI) at 0.1 ng mL(-1) were 6.0% and 6.2%, respectively. In order to validate the proposed method, a certified reference material of environmental water was analyzed, and the result of Cr speciation was in good agreement with the certified value. This MSPE-GFAAS method has been successfully applied for the speciation of Cr(III) and Cr(VI) in lake and tap waters with the recoveries of 88-109% for the spiked samples. Moreover, the MSPE separation mechanism of Cr(III) and Cr(VI) based on their adsorption-desorption on Zincon-Si-MNPs has been explained through various spectroscopic characterization. © 2013 Elsevier B.V. All rights reserved.

Chromium speciation in environmental samples using a solid phase spectrophotometric method.

PubMed

Amin, Alaa S; Kassem, Mohammed A

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H(2)SO(4) and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11×10(7) and 3.90×10(7) L mol(-1)cm(-1) for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L(-1) with RSD of <1.85% (n=8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L(-1) for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L(-1), respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested. Copyright © 2012 Elsevier B.V. All rights reserved.

The Importance of Kinetics and Redox in the Biogeochemical Cycling of Iron in the Surface Ocean

PubMed Central

Croot, Peter L.; Heller, Maija I.

2012-01-01

It is now well established that Iron (Fe) is a limiting element in many regions of the open ocean. Our current understanding of the key processes which control iron distribution in the open ocean have been largely based on thermodynamic measurements performed under the assumption of equilibrium conditions. Using this equilibrium approach, researchers have been able to detect and quantify organic complexing ligands in seawater and examine their role in increasing the overall solubility of iron. Our current knowledge about iron bioavailability to phytoplankton and bacteria is also based heavily on carefully controlled laboratory studies where it is assumed the chemical species are in equilibrium in line with the free ion association model and/or its successor the biotic ligand model. Similarly most field work on iron biogeochemistry generally consists of a single profile which is in essence a “snap-shot” in time of the system under investigation. However it is well known that the surface ocean is an extremely dynamic environment and it is unlikely if thermodynamic equilibrium between all the iron species present is ever truly achieved. In sunlit waters this is mostly due to the daily passage of the sun across the sky leading to photoredox processes which alter Fe speciation by cycling between redox states and between inorganic and organic species. Episodic deposition events, dry and wet, are also important perturbations to iron cycling as they bring in new iron to the system and alter the equilibrium between iron species and phases. Here we utilize new field data collected in the open ocean on the complexation kinetics of iron in the surface ocean to identify the important role of weak iron binding ligands (i.e., those that cannot maintain iron in solution indefinitely at seawater pH: αFeL < αFe′) in allowing transient increases in iron solubility in response to iron deposition events. Experiments with the thermal O2- source SOTS-1 also indicate the short term impact of this species on iron solubility also with relevance to the euphotic zone. This data highlights the roles of kinetics, redox, and weaker iron binding ligands in the biogeochemical cycling of iron in the ocean. PMID:22723797

Price competition and equilibrium analysis in multiple hybrid channel supply chain

NASA Astrophysics Data System (ADS)

Kuang, Guihua; Wang, Aihu; Sha, Jin

2017-06-01

The amazing boom of Internet and logistics industry prompts more and more enterprises to sell commodity through multiple channels. Such market conditions make the participants of multiple hybrid channel supply chain compete each other in traditional and direct channel at the same time. This paper builds a two-echelon supply chain model with a single manufacturer and a single retailer who both can choose different channel or channel combination for their own sales, then, discusses the price competition and calculates the equilibrium price under different sales channel selection combinations. Our analysis shows that no matter the manufacturer and retailer choose same or different channel price to compete, the equilibrium price does not necessarily exist the equilibrium price in the multiple hybrid channel supply chain and wholesale price change is not always able to coordinate supply chain completely. We also present the sufficient and necessary conditions for the existence of equilibrium price and coordination wholesale price.

Coupling of PIES 3-D Equilibrium Code and NIFS Bootstrap Code with Applications to the Computation of Stellarator Equilibria

NASA Astrophysics Data System (ADS)

Monticello, D. A.; Reiman, A. H.; Watanabe, K. Y.; Nakajima, N.; Okamoto, M.

1997-11-01

The existence of bootstrap currents in both tokamaks and stellarators was confirmed, experimentally, more than ten years ago. Such currents can have significant effects on the equilibrium and stability of these MHD devices. In addition, stellarators, with the notable exception of W7-X, are predicted to have such large bootstrap currents that reliable equilibrium calculations require the self-consistent evaluation of bootstrap currents. Modeling of discharges which contain islands requires an algorithm that does not assume good surfaces. Only one of the two 3-D equilibrium codes that exist, PIES( Reiman, A. H., Greenside, H. S., Compt. Phys. Commun. 43), (1986)., can easily be modified to handle bootstrap current. Here we report on the coupling of the PIES 3-D equilibrium code and NIFS bootstrap code(Watanabe, K., et al., Nuclear Fusion 35) (1995), 335.

Thermodynamic derivation of open circuit voltage in vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Pavelka, Michal; Wandschneider, Frank; Mazur, Petr

2015-10-01

Open circuit voltage of vanadium redox flow batteries is carefully calculated using equilibrium thermodynamics. This analysis reveals some terms in the Nernst relation which are usually omitted in literature. Due to the careful thermodynamic treatment, all uncertainties about the form of Nernst relation are removed except for uncertainties in activity coefficients of particular species. Moreover, it is shown (based again on equilibrium thermodynamics) that batteries with anion-exchange membranes follow different Nernst relation than batteries with cation-exchange membranes. The difference is calculated, and it is verified experimentally that the formula for anion-exchange membranes describes experiments with anion-exchange membranes better than the corresponding formula for cation-exchange membranes. In summary, careful thermodynamic calculation of open circuit voltage of vanadium redox flow batteries is presented, and the difference between voltage for anion-exchange and cation-exchange membranes is revealed.

Anharmonic effects in the quantum cluster equilibrium method

NASA Astrophysics Data System (ADS)

von Domaros, Michael; Perlt, Eva

2017-03-01

The well-established quantum cluster equilibrium (QCE) model provides a statistical thermodynamic framework to apply high-level ab initio calculations of finite cluster structures to macroscopic liquid phases using the partition function. So far, the harmonic approximation has been applied throughout the calculations. In this article, we apply an important correction in the evaluation of the one-particle partition function and account for anharmonicity. Therefore, we implemented an analytical approximation to the Morse partition function and the derivatives of its logarithm with respect to temperature, which are required for the evaluation of thermodynamic quantities. This anharmonic QCE approach has been applied to liquid hydrogen chloride and cluster distributions, and the molar volume, the volumetric thermal expansion coefficient, and the isobaric heat capacity have been calculated. An improved description for all properties is observed if anharmonic effects are considered.

MBSSAS: A code for the computation of margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.

1991-01-01

The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henry's law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system. ?? 1991.

CCSDT calculations of molecular equilibrium geometries

NASA Astrophysics Data System (ADS)

Halkier, Asger; Jørgensen, Poul; Gauss, Jürgen; Helgaker, Trygve

1997-08-01

CCSDT equilibrium geometries of CO, CH 2, F 2, HF, H 2O and N 2 have been calculated using the correlation-consistent cc-pVXZ basis sets. Similar calculations have been performed for SCF, CCSD and CCSD(T). In general, bond lengths decrease when improving the basis set and increase when improving the N-electron treatment. CCSD(T) provides an excellent approximation to CCSDT for bond lengths as the largest difference between CCSDT and CCSD(T) is 0.06 pm. At the CCSDT/cc-pVQZ level, basis set deficiencies, neglect of higher-order excitations, and incomplete treatment of core-correlation all give rise to errors of a few tenths of a pm, but to a large extent, these errors cancel. The CCSDT/cc-pVQZ bond lengths deviate on average only by 0.11 pm from experiment.

Equilibrium and nonequilibrium models on Solomon networks

NASA Astrophysics Data System (ADS)

Lima, F. W. S.

2016-05-01

We investigate the critical properties of the equilibrium and nonequilibrium systems on Solomon networks. The equilibrium and nonequilibrium systems studied here are the Ising and Majority-vote models, respectively. These systems are simulated by applying the Monte Carlo method. We calculate the critical points, as well as the critical exponents ratio γ/ν, β/ν and 1/ν. We find that both systems present identical exponents on Solomon networks and are of different universality class as the regular two-dimensional ferromagnetic model. Our results are in agreement with the Grinstein criterion for models with up and down symmetry on regular lattices.

Algorithm For Hypersonic Flow In Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Palmer, Grant

1989-01-01

Implicit, finite-difference, shock-capturing algorithm calculates inviscid, hypersonic flows in chemical equilibrium. Implicit formulation chosen because overcomes limitation on mathematical stability encountered in explicit formulations. For dynamical portion of problem, Euler equations written in conservation-law form in Cartesian coordinate system for two-dimensional or axisymmetric flow. For chemical portion of problem, equilibrium state of gas at each point in computational grid determined by minimizing local Gibbs free energy, subject to local conservation of molecules, atoms, ions, and total enthalpy. Major advantage: resulting algorithm naturally stable and captures strong shocks without help of artificial-dissipation terms to damp out spurious numerical oscillations.

Equivalence of equations describing trace element distribution during equilibrium partial melting

NASA Technical Reports Server (NTRS)

Consolmagno, G. J.; Drake, M. J.

1976-01-01

It is shown that four equations used for calculating the evolution of trace-element abundances during equilibrium partial melting are mathematically equivalent. The equations include those of Hertogen and Gijbels (1976), Shaw (1970), Schilling (1971), and O'Nions and Clarke (1972). The general form to which all these equations reduce is presented, and an analysis is performed to demonstrate their mathematical equivalence. It is noted that the utility of the general equation flows from the nature of equilibrium (i.e., the final state is independent of the path by which that state is attained).

Sediment-water partitioning of inorganic mercury in estuaries.

PubMed

Turner, A; Millward, G E; Le Roux, S M

2001-12-01

The sediment-water partitioning and speciation of inorganic mercury have been studied under simulated estuarine conditions by monitoring the hydrophobicity and uptake of dissolved 203Hg(II) in samples from a variety of estuarine environments. A persistent increase in the distribution coefficientwith increasing salinity is inconsistent with inorganic speciation calculations, which predict an increase in the concentration of the soluble HgCl4(2-) complex (or reduction in sediment-water distribution coefficient) with increasing salinity. Partition data are, however, defined by an empirical equation relating to the salting out of nonelectrolytes via electrostriction and are characterized by salting constants between about 1.4 and 2.0 L mol(-1). Salting out of the neutral, covalent chloro-complex, HgCl2(0), is predicted but cannot account for the magnitude of salting out observed. Since Hg(II) strongly complexes with dissolved (and particulate) organic matter in natural environments, of more significance appears to be the salting out of Hg(II)-organic complexes. Operational measurements of the speciation of dissolved Hg(II) using Sep-Pak C18 columns indicate a reduction in the proportion of hydrophobic (C18-retained) dissolved Hg(II) complexes with increasing salinity, both in the presence and absence of suspended particles. Ratios of hydrophobic Hg(ll) before and after particle addition suggest a coupled salting out-sorption mechanism, with the precise nature of Hg(II) species salted out being determined bythe characteristics and concentrations of dissolved and sediment organic matter.

An area-preserving mapping in natural canonical coordinates for magnetic field line trajectories in the DIII-D tokamak

NASA Astrophysics Data System (ADS)

Punjabi, Alkesh

2009-11-01

The new approach of integrating magnetic field line trajectories in natural canonical coordinates (Punjabi and Ali 2008 Phys. Plasmas 15 122502) in divertor tokamaks is used for the DIII-D tokamak (Luxon and Davis1985 Fusion Technol. 8 441). The equilibrium EFIT data (Evans et al 2004 Phys. Rev. Lett. 92 235003, Lao et al 2005 Fusion Sci. Technol. 48 968) for the DIII-D tokamak shot 115467 at 3000 ms is used to construct the equilibrium generating function (EGF) for the DIII-D in natural canonical coordinates. The EGF gives quite an accurate representation of the closed and open equilibrium magnetic surfaces near the separatrix, the separatrix, the position of the X-point and the poloidal magnetic flux inside the ideal separatrix in the DIII-D. The equilibrium safety factor q from the EGF is somewhat smaller than the DIII-D EFIT q profile. The equilibrium safety factor is calculated from EGF as described in the previous paper (Punjabi and Ali 2008 Phys. Plasmas 15 122502). Here the safety factor for the open surfaces in the DIII-D is calculated. A canonical transformation is used to construct a symplectic mapping for magnetic field line trajectories in the DIII-D in natural canonical coordinates. The map is explored in more detail in this work, and is used to calculate field line trajectories in the DIII-D tokamak. The continuous analogue of the map does not distort the DIII-D magnetic surfaces in different toroidal planes between successive iterations of the map. The map parameter k can represent effects of magnetic asymmetries in the DIII-D. These effects in the DIII-D are illustrated. The DIII-D map is then used to calculate stochastic broadening of the ideal separatrix from the topological noise and field errors, the low mn, the high mn and peeling-ballooning magnetic perturbations in the DIII-D. The width of the stochastic layer scales as 1/2 power of amplitude with a maximum deviation of 6% from the Boozer-Rechester scaling (Boozer and Rechester 1978 Phys. Fluids 21 682). The loss of poloidal flux scales linearly with the amplitude of perturbation with a maximum deviation of 10% from linearity. Perturbations with higher mode numbers result in higher stochasticity. The higher the complexity and coupling in the equilibrium magnetic geometry, the closer is the scaling to the Boozer-Rechester scaling of width. The comparison of the EGF for the simple map (Punjabi et al 1992 Phys. Rev. Lett. 69 3322) with that of the DIII-D shows that the more complex the magnetic geometry and the more coupling of modes in equilibrium, the more robust or resilient is the system against the chaos-inducing, symmetry-breaking perturbations.

The reality and importance of founder speciation in evolution.

PubMed

Templeton, Alan R

2008-05-01

A founder event occurs when a new population is established from a small number of individuals drawn from a large ancestral population. Mayr proposed that genetic drift in an isolated founder population could alter the selective forces in an epistatic system, an observation supported by recent studies. Carson argued that a period of relaxed selection could occur when a founder population is in an open ecological niche, allowing rapid population growth after the founder event. Selectable genetic variation can actually increase during this founder-flush phase due to recombination, enhanced survival of advantageous mutations, and the conversion of non-additive genetic variance into additive variance in an epistatic system, another empirically confirmed prediction. Templeton combined the theories of Mayr and Carson with population genetic models to predict the conditions under which founder events can contribute to speciation, and these predictions are strongly confirmed by the empirical literature. Much of the criticism of founder speciation is based upon equating founder speciation to an adaptive peak shift opposed by selection. However, Mayr, Carson and Templeton all modeled a positive interaction of selection and drift, and Templeton showed that founder speciation is incompatible with peak-shift conditions. Although rare, founder speciation can have a disproportionate importance in adaptive innovation and radiation, and examples are given to show that "rare" does not mean "unimportant" in evolution. Founder speciation also interacts with other speciation mechanisms such that a speciation event is not a one-dimensional process due to either selection alone or drift alone. (c) 2008 Wiley Periodicals, Inc.

Kinetic and equilibrium characteristics of sorption of saponin of Quillaja Saponaria Molina on chitosan

NASA Astrophysics Data System (ADS)

Mironenko, N. V.; Smuseva, S. O.; Brezhneva, T. A.; Selemenev, V. F.

2016-12-01

The equilibrium and kinetic curves of the sorption of saponin of Quillaja saponaria molina on chitosan were analyzed. The inner diffusion was found to be limiting, and its coefficients were calculated. It was found that the form of the curves of the sorption isotherms of saponin is determined by the competing processes of association in solution and absorption by chitosan.

Equilibrium moisture content of wood in outdoor locations in the United States and worldwide

Treesearch

W. T. Simpson

1998-01-01

With relative humidity and temperature data from the National Oceanic and Atmospheric Administration, the average equilibrium moisture content for each month of the year was calculated for 262 locations in the United States and 122 locations outside the United States. As an aid for storage of kiln-dried lumber, a graph is presented for determining the reduction in...

Transport and equilibrium in field-reversed mirrors

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

Boyd, J.K.

Two plasma models relevant to compact torus research have been developed to study transport and equilibrium in field reversed mirrors. In the first model for small Larmor radius and large collision frequency, the plasma is described as an adiabatic hydromagnetic fluid. In the second model for large Larmor radius and small collision frequency, a kinetic theory description has been developed. Various aspects of the two models have been studied in five computer codes ADB, AV, NEO, OHK, RES. The ADB code computes two dimensional equilibrium and one dimensional transport in a flux coordinate. The AV code calculates orbit average integralsmore » in a harmonic oscillator potential. The NEO code follows particle trajectories in a Hill's vortex magnetic field to study stochasticity, invariants of the motion, and orbit average formulas. The OHK code displays analytic psi(r), B/sub Z/(r), phi(r), E/sub r/(r) formulas developed for the kinetic theory description. The RES code calculates resonance curves to consider overlap regions relevant to stochastic orbit behavior.« less

Solutions for Reacting and Nonreacting Viscous Shock Layers with Multicomponent Diffusion and Mass Injection. Ph.D. Thesis - Virginia Polytechnic Inst. and State Univ.

NASA Technical Reports Server (NTRS)

Moss, J. N.

1971-01-01

Numerical solutions are presented for the viscous shocklayer equations where the chemistry is treated as being either frozen, equilibrium, or nonequilibrium. Also the effects of the diffusion model, surface catalyticity, and mass injection on surface transport and flow parameters are considered. The equilibrium calculations for air species using multicomponent: diffusion provide solutions previously unavailable. The viscous shock-layer equations are solved by using an implicit finite-difference scheme. The flow is treated as a mixture of inert and thermally perfect species. Also the flow is assumed to be in vibrational equilibrium. All calculations are for a 45 deg hyperboloid. The flight conditions are those for various altitudes and velocities in the earth's atmosphere. Data are presented showing the effects of the chemical models; diffusion models; surface catalyticity; and mass injection of air, water, and ablation products on heat transfer; skin friction; shock stand-off distance; wall pressure distribution; and tangential velocity, temperature, and species profiles.

Adsorption laboratory experiment for undergraduate chemical engineering: Introducing kinetic, equilibrium and thermodynamic concepts

NASA Astrophysics Data System (ADS)

Muryanto, S.; Djatmiko Hadi, S.

2016-11-01

Adsorption laboratory experiment for undergraduate chemical engineering program is discussed. The experiment demonstrated adsorption of copper ions commonly found in wastewater using bio-sorbent, i.e. agricultural wastes. The adsorption was performed in a batch mode under various parameters: adsorption time (up to 120 min), initial pH (2 to 6), adsorbent dose (2.0 to 12.0 g L-1), adsorbent size (50 to 170 mesh), initial Cu2+ concentration (25 to 100 ppm) and temperatures (room temp to 40°C). The equilibrium and kinetic data of the experiments were calculated using the two commonly used isotherms: Langmuir and Lagergren pseudo-first-order kinetics. The maximum adsorption capacity for Cu2+ was found as 94.34 mg g-1. Thermodynamically, the adsorption process was spontaneous and endothermic. The calculated activation energy for the adsorption was observed as high as 127.94 kJ mol-1. Pedagogically, the experiment was assumed to be important in increasing student understanding of kinetic, equilibrium and thermodynamic concepts.

Computer programs for axial flow compressor design

NASA Technical Reports Server (NTRS)

Carmody, R. H.; Creveling, H. F.

1969-01-01

Four computer programs examine effects of design parameters and indicate areas for research of multistage axial flow compressors. The programs provide information on velocity diagrams and stage-by-stage performance calculation, radial equilibrium of flow, radial distribution of total pressure, and off-design performance calculation.

Temperature dependence of the intensity of the vibration-rotational absorption band ν2 of H2O trapped in an argon matrix

NASA Astrophysics Data System (ADS)

Pitsevich, G.; Doroshenko, I.; Malevich, A..; Shalamberidze, E.; Sapeshko, V.; Pogorelov, V.; Pettersson, L. G. M.

2017-02-01

Using two sets of effective rotational constants for the ground (000) and the excited bending (010) vibrational states the calculation of frequencies and intensities of vibration-rotational transitions for J″ = 0 - 2; and J‧ = 0 - 3; was carried out in frame of the model of a rigid asymmetric top for temperatures from 0 to 40 K. The calculation of the intensities of vibration-rotational absorption bands of H2O in an Ar matrix was carried out both for thermodynamic equilibrium and for the case of non-equilibrium population of para- and ortho-states. For the analysis of possible interaction of vibration-rotational and translational motions of a water molecule in an Ar matrix by 3D Schrödinger equation solving using discrete variable representation (DVR) method, calculations of translational frequencies of H2O in a cage formed after one argon atom deleting were carried out. The results of theoretical calculations were compared to experimental data taken from literature.