Science.gov

Sample records for organic azeotropic mixtures

  1. Separation of organic azeotropic mixtures by pervaporation

    SciTech Connect

    Baker, R.W.

    1991-12-01

    Distillation is a commonly used separation technique in the petroleum refining and chemical processing industries. However, there are a number of potential separations involving azetropic and close-boiling organic mixtures that cannot be separated efficiently by distillation. Pervaporation is a membrane-based process that uses selective permeation through membranes to separate liquid mixtures. Because the separation process is not affected by the relative volatility of the mixture components being separated, pervaporation can be used to separate azetropes and close-boiling mixtures. Our results showed that pervaporation membranes can be used to separate azeotropic mixtures efficiently, a result that is not achievable with simple distillation. The membranes were 5--10 times more permeable to one of the components of the mixture, concentrating it in the permeate stream. For example, the membrane was 10 times more permeable to ethanol than methyl ethyl ketone, producing 60% ethanol permeate from an azeotropic mixture of ethanol and methyl ethyl ketone containing 18% ethanol. For the ethyl acetate/water mixture, the membranes showed a very high selectivity to water (> 300) and the permeate was 50--100 times enriched in water relative to the feed. The membranes had permeate fluxes on the order of 0.1--1 kg/m{sup 2}{center dot}h in the operating range of 55--70{degrees}C. Higher fluxes were obtained by increasing the operating temperature.

  2. Separation of organic azeotropic mixtures by pervaporation. Final technical report

    SciTech Connect

    Baker, R.W.

    1991-12-01

    Distillation is a commonly used separation technique in the petroleum refining and chemical processing industries. However, there are a number of potential separations involving azetropic and close-boiling organic mixtures that cannot be separated efficiently by distillation. Pervaporation is a membrane-based process that uses selective permeation through membranes to separate liquid mixtures. Because the separation process is not affected by the relative volatility of the mixture components being separated, pervaporation can be used to separate azetropes and close-boiling mixtures. Our results showed that pervaporation membranes can be used to separate azeotropic mixtures efficiently, a result that is not achievable with simple distillation. The membranes were 5--10 times more permeable to one of the components of the mixture, concentrating it in the permeate stream. For example, the membrane was 10 times more permeable to ethanol than methyl ethyl ketone, producing 60% ethanol permeate from an azeotropic mixture of ethanol and methyl ethyl ketone containing 18% ethanol. For the ethyl acetate/water mixture, the membranes showed a very high selectivity to water (> 300) and the permeate was 50--100 times enriched in water relative to the feed. The membranes had permeate fluxes on the order of 0.1--1 kg/m{sup 2}{center_dot}h in the operating range of 55--70{degrees}C. Higher fluxes were obtained by increasing the operating temperature.

  3. Anthracene + Pyrene Solid Mixtures: Eutectic and Azeotropic Character

    PubMed Central

    Rice, James W.; Fu, Jinxia; Suuberg, Eric M.

    2010-01-01

    To better characterize the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the anthracene (1) + pyrene (2) system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at 404 K at x1 = 0.22. A model based on eutectic formation can be used to predict the enthalpy of fusion associated with the mixture. For mixtures that contain x1 < 0.90, the enthalpy of fusion is near that of pure pyrene. This and X-ray diffraction results indicate that mixtures of anthracene and pyrene have pyrene-like crystal structures and energetics until the composition nears that of pure anthracene. Solid-vapor equilibrium studies show that mixtures of anthracene and pyrene form solid azeotropes at x1 of 0.03 and 0.14. Additionally, mixtures at x1 = 0.99 sublime at the vapor pressure of pure anthracene, suggesting that anthracene behavior is not significantly influenced by x2 = 0.01 in the crystal structure. PMID:21116474

  4. Anthracene + Pyrene Solid Mixtures: Eutectic and Azeotropic Character.

    PubMed

    Rice, James W; Fu, Jinxia; Suuberg, Eric M

    2010-09-01

    To better characterize the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the anthracene (1) + pyrene (2) system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at 404 K at x(1) = 0.22. A model based on eutectic formation can be used to predict the enthalpy of fusion associated with the mixture. For mixtures that contain x(1) < 0.90, the enthalpy of fusion is near that of pure pyrene. This and X-ray diffraction results indicate that mixtures of anthracene and pyrene have pyrene-like crystal structures and energetics until the composition nears that of pure anthracene. Solid-vapor equilibrium studies show that mixtures of anthracene and pyrene form solid azeotropes at x(1) of 0.03 and 0.14. Additionally, mixtures at x(1) = 0.99 sublime at the vapor pressure of pure anthracene, suggesting that anthracene behavior is not significantly influenced by x(2) = 0.01 in the crystal structure.

  5. A PROCESS FOR SEPARATING AZEOTROPIC MIXTURES BY EXTRACTIVE AND CONVECTIVE DISTILLATION

    DOEpatents

    Frazer, J.W.

    1961-12-19

    A method is described for separating an azeotrope of carbon tetrachloride and 1,1,2,2-tetrafluorodinitroethane boiling at 60 deg C. The ndethod comnprises, specifically, feeding azeotrope vapors admixed with a non- reactive gas into an extractive distillation column heated to a temperature preferably somewhat above the boiling point of the constant boiling mixture. A solvent, di-n-butylphthalate, is metered into the column above the gas inlet and permitted to flow downward, earrying with it the higher bomling fraction, while the constituent having the lower boiling point passes out of the top of the column with the non-reactive gas and is collected in a nitrogen cold trap. Other solvents which alter the vapor pressure relationship may be substituted. The method is generally applicable to azeotropic mixtures. A number of specific mixtures whicb may be separated are disclosed. (AEC)

  6. Gas viscosities of azeotropic mixtures of the halogenated hydrocarbons R500, R502, and R503

    SciTech Connect

    Takahashi, M.; Yokoyama, C.; Takahashi, S.

    1988-07-01

    Gas viscosities of azeotropic mixtures R500 (dichlorodifluoromethane (R12)-1, 1-difluoroethane (R152a)), R 502 (chlorodifluoromethane (R22)-chloropentafluoroethane (R115)), and R503 (chlorotrifluoromethane (R13)-trifluoromethane (R23)) were measured with an oscillating disk viscometer of the Maxwell type at 273.15-423.15 K up to 7.5 MPa. Two empirical equations for the viscosities were obtained; one is for the atmospheric viscosities as a function of temperature, and the other is for the viscosities in the whole range of the present measurement as a function of temperature and density.

  7. Observation of vapor bubble of non-azeotropic binary mixture in microgravity with a two-wavelength interferometer

    SciTech Connect

    Abe, Yoshiyuki; Iwasaki, Akira

    1999-07-01

    Although non-azeotropic mixtures are considered to be promising working fluids in advanced energy conversion systems, the primary technical problems in the heat transfer degradation in phase change processes cause economical handicap to wide-spread applications. The boiling behavior of mixtures still remains a number of basic questions being not answered yet, and the present authors believe that the most essential information for the boiling process in non-azeotropic mixtures is how temperature and concentration profiles are developed around the bubbles. The present study attempts at understanding fundamental heat and mass transfer mechanisms in nucleate pool boiling of non-azeotropic binary mixtures, and with the knowledge to develop a passive boiling heat transfer enhancement eventually. To this end, the authors have employed microgravity environment for rather detailed observation around vapor bubbles in the course of boiling inception and bubble growth. A two-wavelength Mach-Zehnder interferometer has been developed, which withstands mechanical shock caused by gravity change from very low gravity of the order of 10{sup {minus}5} g to relatively high gravity of approximately 8 g exposed during deceleration period. A series of experiments on single vapor bubbles for CFC113 single component and CFC12/CFC112 non-azeotropic binary mixture have been conducted under a high quality microgravity conditions available in 10-second free-fall facility of Japan Microgravity Center (JAMIC). The results for single component liquid showed a strong influence due to Marangoni effect caused by the temperature profile around the bubble. The results for non-azeotropic binary mixture showed, however, considerably different behavior from single component liquid. Both temperature and concentration profiles around a single vapor bubble were evaluated from the interferograms. The temperature and concentration layers established around the bubbles were nearly one order of magnitude larger

  8. SIMULATION OF NON-AZEOTROPIC REFRIGERANT MIXTURES FOR USE IN A DUAL-CIRCUIT REFRIGERATOR/FREEZER WITH COUNTERCURRENT HEAT EXCHANGES

    EPA Science Inventory

    The paper discusses a refrigerator/freezer (RF) system that has two complete and independent refrigeration cycles for the two compartments. It uses a non-azeotropic refrigerant mixture (NARM) in each cycle and countercurrent heat exchangers throughout. This RF is housed in a stan...

  9. Adsorption isotherm of non-azeotropic solution onto porous adsorbents

    NASA Astrophysics Data System (ADS)

    Bono, A.; Ramlan, N. A.; Anisuzzaman, S. M.; Chu, C. M.; Farm, Y. Y.

    2016-06-01

    Adsorption isotherm is essential component in the understanding of the adsorption process. Several methods of the measurements, analysis and interpretation of adsorption from solution have been reported in the literature. Most of the measurements of adsorption isotherm from solution were involved the measurement of excess isotherm conducted at low region of sorbates concentration. Direct interpretation of excess adsorption isotherm as adsorption isotherm is always been practice. Therefore, in this work a study on the measurement of the adsorption isotherm from solution of non-azeotropic organic solvent mixture onto porous adsorbents for whole range of liquid concentration was conducted. The study included the measurement of excess adsorption isotherm using conventional technique. Theoretical analysis and interpretation of adsorption isotherm from the excess isotherm were conducted using Pseudo Ideal Adsorption, Gibbs Dividing Plane Model and Langmuir-Fruendlich binary isotherm model. For organic solvents, acetone and propanol were chosen as the adsorbates due to the non-azeotropic properties in the mixture. Activated carbon and silicalite were chosen as adsorbents due to the different in their porosity such as macro porous and micro porous structure. The result of the study has revealed that the adsorption isotherm of non-azeotropic mixture onto activated carbon and silicalite can be interpreted as monolayer type of adsorption.

  10. Variation of Azeotropic Composition and Temperature with Pressure

    ERIC Educational Resources Information Center

    Gibbard, H. Frank; Emptage, Michael R.

    1975-01-01

    Describes an undergraduate physical chemistry experiment in which an azeotropic mixture is studied using the vapor pressures of the components as functions of temperature and the azeotropic composition and temperature at one pressure. Discusses in detail the mathematical treatment of obtained thermodynamic data. (MLH)

  11. Understanding the azeotropic diethyl carbonate-water mixture by structural and energetic characterization of DEC(H2O)(n) heteroclusters.

    PubMed

    Ripoll, Juan D; Mejía, Sol M; Mills, Matthew J L; Villa, Aída L

    2015-04-01

    Diethyl carbonate (DEC) is an oxygenated fuel additive. During its synthesis through a promising green process, a DEC-water azeotrope is formed, which decreases DEC production efficiency in the gas phase. Molecular information about this system is scarce but could be of benefit in understanding (and potentially improving) the synthetic process. Therefore, we report a detailed computational study of the conformers of DEC, and their microsolvation with up to four water molecules, with the goal of understanding the observed 1:3 DEC:H2O molar ratio. The most stable DEC conformers (with mutual energy differences < 1.5 kcal mol(-1)) contribute to the energetic and structural properties of the complexes. An exhaustive stochastic exploration of each potential energy surface of DEC-(H2O)n, (where n = 1, 2, 3, 4) heteroclusters discovered 3, 8, 7, and 4 heterodimers, heterotrimers, heterotetramers, and heteropentamers, respectively, at the MP2/6-311++G(d,p) level of theory. DEC conformers and energies of the most stable structures at each heterocluster size were refined using CCSD(T)/6-311++G(d,p). Energy decomposition, electron density topology, and cooperative effects analyses were carried out to determine the relationship between the geometrical features of the heteroclusters and the non-covalent interaction types responsible for their stabilization. Our findings show that electrostatic and exchange energies are responsible for heterocluster stabilization, and also suggest a mutual weakening among hydrogen bonds when more than three water molecules are present. All described results are complementary and suggest a structural and energetic explanation at the molecular level for the experimental molar ratio of 1:3 (DEC:H2O) for the DEC-water azeotrope. PMID:25786831

  12. Study to determine the existence of an azeotropic R-22 `drop-in` substitute

    SciTech Connect

    Kim, M.S.; Morrison, G.; Mulroy, W.J.; Didion, D.A.

    1996-03-01

    The reduction in chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) production and the scheduled phase-out of these ozone depleting refrigerants requires the development and determination of environmentally safe refrigerants for use in heat pumps, water chillers, air conditioners, and refrigerators. Azeotropic mixtures are attractive as alternative refrigerants because they behave very nearly as pure materials. A simple correlative scheme that allows one to judge whether or not an azeotrope is likely in a binary refrigerant mixture is discussed. This paper presents laboratory and computer simulation model evaluation of two of the azeotropic refrigerant mixtures which are identified, HFC-134a (1,1,1,2-tetrafluoroethane) with R-C290 (Propane) and HFC-134a with R-600a (Isobutane), in a generic heat pump apparatus. A third azeotropes mixture, HFC-134a with R-C290 (Cyclopropane) is examined by computer simulation only.

  13. Synthesis of azeotropic batch distillation separation systems

    SciTech Connect

    Safrit, B.T.; Westerberg, A.W.

    1997-05-01

    The sequencing of batch distillation systems, in particular batch distillation columns, can be complicated by the existence of azeotropes in the mixture. These azeotropes can form batch distillation regions where, depending on the initial feed to the batch column, the types of feasible products and separations are limited. It is very important that these distillation regions are known while attempting to synthesize sequences of batch columns so infeasible designs can be eliminated early on in the design phase. The distillation regions also give information regarding the feasible products that can be obtained when the mixture is separated by using a variety of batch column configurations. The authors will show how a tool for finding the batch distillation regions of a particular mixture can be used in the synthesis of batch distillation column sequences. These sequences are determined by the initial feed composition to the separation network. The network of all possible sequences will be generated by using state-task networks when batch rectifying, stripping, middle vessel, and extractive middle vessel columns are allowed. The authors do not determine which sequence is the best, as the best sequence will depend on the particular application to which one is applying the algorithms. They show an example problem for illustration of this technique.

  14. Microstructures of negative and positive azeotropes.

    PubMed

    Shephard, J J; Callear, S K; Imberti, S; Evans, J S O; Salzmann, C G

    2016-07-28

    Azeotropes famously impose fundamental restrictions on distillation processes, yet their special thermodynamic properties make them highly desirable for a diverse range of industrial and technological applications. Using neutron diffraction, we investigate the structures of two prototypical azeotropes, the negative acetone-chloroform and the positive benzene-methanol azeotrope. C-HO hydrogen bonding is the dominating interaction in the negative azeotrope but C-ClO halogen bonding contributes as well. Hydrogen-bonded chains of methanol molecules, which are on average longer than in pure methanol, are the defining structural feature of the positive azeotrope illustrating the fundamentally different local mixing in the two kinds of azeotropes. The emerging trend for both azeotropes is that the more volatile components experience the more pronounced structural changes in their local environments as the azeotropes form. The mixing of the acetone-chloroform azeotrope is essentially random above 20 Å, where the running Kirkwood-Buff integrals of our structural model converge closely to the ones expected from thermodynamic data. The benzene-methanol azeotrope on the other hand displays extended methanol-rich regions and consequently the running Kirkwood-Buff integrals oscillate up to at least 60 Å. Our study provides the first experimental insights into the microstructures of azeotropes and a direct link with their thermodynamic properties. Ultimately, this will provide a route for creating tailored molecular environments in azeotropes to improve and fine-tune their performances. PMID:27367534

  15. Azeotropic Preparation of a "C"-Phenyl "N"-Aryl Imine: An Introductory Undergraduate Organic Chemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Silverberg, Lee J.; Coyle, David J.; Cannon, Kevin C.; Mathers, Robert T.; Richards, Jeffrey A.; Tierney, John

    2016-01-01

    Imines are important in biological chemistry and as intermediates in organic synthesis. An experiment for introductory undergraduate organic chemistry is presented in which benzaldehyde was condensed with "p"-methoxyaniline in toluene to give 4-methoxy-"N"-(phenylmethylene)benzenamine. Water was removed by azeotropic…

  16. Simulation, design, and analysis of azeotropic distillation operations

    SciTech Connect

    Bossen, B.S.; Joergensen, S.B.; Gani, R. )

    1993-04-01

    The computational tools needed for simulation, design, and analysis of azeotropic distillation operations are described. These tools include simple methods to identify the existence of binary and ternary azeotropes and to classify ternary mixtures as homogeneous or heterogeneous. The tools also include more complex methods to compute the phase diagram (or a heterogeneous liquid boiling surface), predict liquid-vapor phase equilibrium, and/or predict liquid-liquid-vapor phase equilibrium for simulations of batch and continuous distillation column operations. Important new features of these tools are the incorporation of a fast and efficient method for test of phase stability in simulation of distillation operations, the ability to handle a large range of mixtures (including mixtures with supercritical compounds), and the ability for computations covering wide ranges of temperature and pressure. On the basis of these tools, simple and consistent design algorithms are developed. The applicability of the design algorithms is verified through process simulation and analysis of the predicted behavior and data from the open literature. Conditions are given for examples illustrating (when and how possible distillation boundaries can be crossed) how multiple steady states can be obtained. Finally, the effect of changes in operating on the dynamic behavior of the azeotropic distillation columns and the sensitivity of design to the prediction of phase equilibria are presented.

  17. Solidification phenomena of binary organic mixtures

    NASA Technical Reports Server (NTRS)

    Chang, K.

    1982-01-01

    The coalescence rates and motion of liquid bubbles in binary organic mixtures were studied. Several factors such as temperature gradient, composition gradient, interfacial tension, and densities of the two phases play important roles in separation of phases of immiscible liquids. An attempt was made to study the effect of initial compositions on separation rates of well-dispersed organic mixtures at different temperatures and, ultimately, on the homogeneity of solidification of the immiscible binary organic liquids. These organic mixtures serve as models for metallic pseudo binary systems under study. Two specific systems were investigated: ethyl salicylate - diethyl glycol and succinonitrile - water.

  18. Supercritical separation process for complex organic mixtures

    DOEpatents

    Chum, Helena L.; Filardo, Giuseppe

    1990-01-01

    A process is disclosed for separating low molecular weight components from complex aqueous organic mixtures. The process includes preparing a separation solution of supercritical carbon dioxide with an effective amount of an entrainer to modify the solvation power of the supercritical carbon dioxide and extract preselected low molecular weight components. The separation solution is maintained at a temperature of at least about 70.degree. C. and a pressure of at least about 1,500 psi. The separation solution is then contacted with the organic mixtures while maintaining the temperature and pressure as above until the mixtures and solution reach equilibrium to extract the preselected low molecular weight components from the organic mixtures. Finally, the entrainer/extracted components portion of the equilibrium mixture is isolated from the separation solution.

  19. Supercritical separation process for complex organic mixtures

    DOEpatents

    Chum, H.L.; Filardo, G.

    1990-10-23

    A process is disclosed for separating low molecular weight components from complex aqueous organic mixtures. The process includes preparing a separation solution of supercritical carbon dioxide with an effective amount of an entrainer to modify the solvation power of the supercritical carbon dioxide and extract preselected low molecular weight components. The separation solution is maintained at a temperature of at least about 70 C and a pressure of at least about 1,500 psi. The separation solution is then contacted with the organic mixtures while maintaining the temperature and pressure as above until the mixtures and solution reach equilibrium to extract the preselected low molecular weight components from the organic mixtures. Finally, the entrainer/extracted components portion of the equilibrium mixture is isolated from the separation solution. 1 fig.

  20. Azeotropic distillation in a middle vessel batch column. 2: Nonlinear separation boundaries

    SciTech Connect

    Cheong, W.; Barton, P.I.

    1999-04-01

    On the basis of the analytical tools developed for the middle vessel column (MVC) operated under limiting conditions, analysis of the qualitative dynamics of the MVC in separating an azeotropic mixture is extended to the more realistic case in which the separation boundaries are nonlinear. The differences between batch stripper pot composition boundaries and batch rectifier pot composition being able to cross these pot composition boundaries. On the basis of these insights, operating procedures are developed in which ternary azeotropic mixtures of acetone, benzene, and chloroform can be separated into their constituent pure components, a separation not achievable with either the batch stripper or the batch rectifier. The operating procedures suggested for separating the ternary azeotropic mixture of acetone, benzene, and chloroform in the MVC are then shown to be the time analogues of sequences of continuous distillation columns that achieve the same separation. On the basis of this space-time analogy, further analogies are developed between the MVC and a continuous column, and it is postulated that many complex separations currently achieved with sequences of continuous columns can also be achieved with a single MVC. Thus, the MVC represents the ultimate multipurpose solvent recovery technology, as it can handle, in a batch multipurpose mode. separations that will otherwise require a dedicated continuous distillation sequence. Finally, the characteristics of perfect MVC batch entrainers, which allow the complete separation of any azeotrope into its constituent pure components in a single MVC, are discussed.

  1. Secondary organic aerosol from biogenic volatile organic compound mixtures

    NASA Astrophysics Data System (ADS)

    Hatfield, Meagan L.; Huff Hartz, Kara E.

    2011-04-01

    The secondary organic aerosol (SOA) yields from the ozonolysis of a Siberian fir needle oil (SFNO), a Canadian fir needle oil (CFNO), and several SOA precursor mixtures containing reactive and non-reactive volatile organic compounds (VOCs) were investigated. The use of precursor mixtures more completely describes the atmosphere where many VOCs exist. The addition of non-reactive VOCs such as bornyl acetate, camphene, and borneol had very little to no effect on SOA yields. The oxidation of VOC mixtures with VOC mass percentages similar to the SFNO produced SOA yields that became more similar to the SOA yield from SFNO as the complexity and concentration of VOCs within the mixture became more similar to overall SFNO composition. The SOA yield produced by the oxidation of CFNO was within the error of the SOA yield produced by the oxidation of SFNO at a similar VOC concentration. The SOA yields from SFNO were modeled using the volatility basis set (VBS), which predicts the SOA yields for a given mass concentration of mixtures containing similar VOCs.

  2. RELIABLE COMPUTATION OF HOMOGENEOUS AZEOTROPES. (R824731)

    EPA Science Inventory

    Abstract

    It is important to determine the existence and composition of homogeneous azeotropes in the analysis of phase behavior and in the synthesis and design of separation systems, from both theoretical and practical standpoints. A new method for reliably locating an...

  3. Activation of aqueous hydrogen peroxide for non-catalyzed dihydroperoxidation of ketones by azeotropic removal of water.

    PubMed

    Starkl Renar, K; Pečar, S; Iskra, J

    2015-09-28

    Cyclic and acyclic ketones were selectively converted to gem-dihydroperoxides in 72-99% yield with 30% aq. hydrogen peroxide by azeotropic distillation of water from the reaction mixture without any catalyst. The reactions were more selective than with 100% H2O2 and due to neutral conditions also less stable products could be obtained. PMID:26289229

  4. Activation of aqueous hydrogen peroxide for non-catalyzed dihydroperoxidation of ketones by azeotropic removal of water.

    PubMed

    Starkl Renar, K; Pečar, S; Iskra, J

    2015-09-28

    Cyclic and acyclic ketones were selectively converted to gem-dihydroperoxides in 72-99% yield with 30% aq. hydrogen peroxide by azeotropic distillation of water from the reaction mixture without any catalyst. The reactions were more selective than with 100% H2O2 and due to neutral conditions also less stable products could be obtained.

  5. 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.

  6. Predicting microbial toxicity of nonuniform multicomponent mixtures of organic chemicals

    SciTech Connect

    Peace, J.; Daniel, D.; Nirmalakhandan, N.; Egemen, E.

    1997-04-01

    Three schemes proposed in the literature for analyzing joint toxic effects of multicomponent mixtures on fish, namely the additivity index (AI), the mixture toxicity index (MTI), and the similarity parameter ({lambda}) are evaluated in this study for microbial toxicity. A new approach is proposed to establish acceptance limits for the similarity parameter, {lambda}, based on experimental errors and uncertainties. Quantitative structure activity relationship (QSAR) techniques are then used to develop a model to predict the concentrations of components in mixtures that would jointly cause 50% inhibition of microbial respiration. The application of this approach is demonstrated on the experimental toxicity data of six eight-component organic chemical mixtures on microorganisms.

  7. Lateral organization of complex lipid mixtures from multiscale modeling

    PubMed Central

    Tumaneng, Paul W.; Pandit, Sagar A.; Zhao, Guijun; Scott, H. L.

    2010-01-01

    The organizational properties of complex lipid mixtures can give rise to functionally important structures in cell membranes. In model membranes, ternary lipid-cholesterol (CHOL) mixtures are often used as representative systems to investigate the formation and stabilization of localized structural domains (“rafts”). In this work, we describe a self-consistent mean-field model that builds on molecular dynamics simulations to incorporate multiple lipid components and to investigate the lateral organization of such mixtures. The model predictions reveal regions of bimodal order on ternary plots that are in good agreement with experiment. Specifically, we have applied the model to ternary mixtures composed of dioleoylphosphatidylcholine:18:0 sphingomyelin:CHOL. This work provides insight into the specific intermolecular interactions that drive the formation of localized domains in these mixtures. The model makes use of molecular dynamics simulations to extract interaction parameters and to provide chain configuration order parameter libraries. PMID:20151760

  8. Acoustic properties of organic acid mixtures in water

    NASA Technical Reports Server (NTRS)

    Macavei, I.; Petrisor, V.; Auslaender, D.

    1974-01-01

    The variation of the rate of propagation of ultrasounds in organic acid mixtures in water points to structural changes caused by interactions that take place under conditions of thermal agitation, at different acid concentrations. At the same time, a difference is found in the changes in velocity as a function of the length of the carbon chain of the acids in the mixture as a result of their effect on the groups of water molecules associated by hydrogen bonds.

  9. Dehydration of an ethanol/water azeotrope through alginate-DNA membranes cross-linked with metal ions by pervaporation.

    PubMed

    Uragami, Tadashi; Banno, Masashi; Miyata, Takashi

    2015-12-10

    To obtain high dehydration membranes for an ethanol/water azeotrope, dried blend membranes prepared from mixtures of sodium alginate (Alg-Na) and sodium deoxyribonucleate (DNA-Na) were cross-linked by immersing in a methanol solution of CaCl2 or MaCl2. In the dehydration of an ethanol/water azeotropic mixture by pervaporation, the effects of immersion time in methanol solution of CaCl2 or MaCl2 on the permeation rate and water/ethanol selectivity through Alg-DNA/Ca(2+) and Alg-DNA/Mg(2+) cross-linked membranes were investigated. Alg-DNA/Mg(2+) cross-linked membrane immersed for 12h in methanol solution of MaCl2 exhibited the highest water/ethanol selectivity. This results from depressed swelling of the membranes by formation of a cross-linked structure. However, excess immersion in solution containing cross-linker led to an increase in the hydrophobicity of cross-linked membrane. Therefore, the water/ethanol selectivity of Alg-DNA/Mg(2+) cross-linked membranes with an excess immersion in cross-linking solution was lowered. The relationship between the structure of Alg-DNA/Ca(2+) and Alg-DNA/Mg(2+) cross-linked membranes and their permeation and separation characteristics during pervaporation of an ethanol/water azeotropic mixture is discussed in detail.

  10. Estimation of Interfacial Tension between Organic Liquid Mixtures and Water

    SciTech Connect

    Yoon, Hongkyu; Oostrom, Martinus; Werth, Charles J.

    2009-10-15

    Knowledge of IFT values for chemical mixtures helps guide the design and analysis of various processes, including NAPL remediation with surfactants or alcohol flushing, enhanced oil recovery, and chemical separation technologies, yet available literature values are sparse. A comprehensive comparison of thermodynamic and empirical models for estimating interfacial tension (IFT) of organic chemical mixtures with water is conducted, mainly focusing on chlorinated organic compounds for 14 ternary, three quaternary, and one quinary systems. Emphasis is placed on novel results for systems with three and four organic chemical compounds, and for systems with composite organic compounds like lard oil and mineral oil. Seven models are evaluated: the ideal and nonideal monolayer models (MLID and MLNID), the ideal and nonideal mutual solubility models (MSID and MSNID), an empirical model for ternary systems (EM), a linear mixing model based on mole fractions (LMMM), and a newly developed linear mixing model based on volume fractions of organic mixtures (LMMV) for higher order systems. The two ideal models (MLID and MSID) fit ternary systems of chlorinated organic compounds without surface active compounds relatively well. However, both ideal models did not perform well for the mixtures containing a surface active compound. However, for these systems, both the MLNID and MSNID models matched the IFT data well. It is shown that the MLNID model with a surface coverage value (0.00341 mmol/m2) obtained in this study can practically be used for chlorinated organic compounds. The LMMM results in poorer estimates of the IFT as the difference in IFT values of individual organic compounds in a mixture increases. The EM, with two fitting parameters, provided accurate results for all 14 ternary systems including composite organic compounds. The new LMMV method for quaternary and higher component systems was successfully tested. This study shows that the LMMV may be able to be used for

  11. Separation of polar compounds using a flexible metal-organic framework

    SciTech Connect

    Motkuri, Radha K.; Thallapally, Praveen K.; Annapureddy, Harsha V.; Dang, Liem X.; Krishna, Rajamani; Nune, Satish K.; Fernandez, Carlos A.; Liu, Jian; McGrail, B. Peter

    2015-01-01

    A flexible metal-organic framework constructed from a flexible linker is shown to possess the capability of separating mixtures of polar compounds by exploiting the differences in the saturation capacities of the constituents. The separation possibilities with the flexible MOF include mixtures of propanol isomers, and various azeotropes. Transient breakthrough simulations show that these sorption-based separations are in favor of the component with higher saturation capacity.

  12. Multiple steady states in heterogeneous azeotropic distillation

    SciTech Connect

    Bekiaris, N.; Meski, G.A.; Morari, M.

    1996-01-01

    In this article, the authors study multiple steady states in ternary heterogeneous azeotropic distillation. They show that in the case of infinite reflux and an infinite number of trays, one can construct bifurcation diagrams on physical grounds with the distillate flow as the bifurcation parameter. Multiple steady states exist when the distillate flow varies nonmonotonically along the continuation path of the bifurcation diagram. The authors show how the distillate and bottom product paths can be located for tray or packed columns, with or without decanter and with different types of condenser and reboiler. They derive a necessary and sufficient condition for the existence of these multiple steady states based on the geometry of the product paths. They also locate in the composition triangle the feed compositions that lead to these multiple steady states. They show that the prediction of the existence of multiple steady states in the case of infinite reflux and an infinite number of trays has relevant implications for columns operating at finite reflux and with a finite number of trays.

  13. Azeotropic distillation in a middle vessel batch column. 3: Model validation

    SciTech Connect

    Cheong, W.; Barton, P.I.

    1999-04-01

    A dimensional time model of the middle vessel batch distillation column (MVC) is developed in the ABACUSS process modeling environment, and simulations are conducted to validate the theoretical insights developed for the operation of the MVC based on a warped time model of the MVC. The qualitative dynamics of the MVC operated in the presence of linear separation boundaries are validated via simulations conducted on the ternary azeotropic mixture of acetone, chloroform, and methanol. It is also shown via simulation that the separation results obtained from a column with significant but reasonable amounts of holdup on the trays are not significantly different from a column in which holdup in the trays is assumed to be negligible. Theoretical operating policies for separating the azeotrope of acetone and chloroform using benzene as a batch entrainer are also validated using the ABACUSS model. Finally, the authors explore the advantages and disadvantages of different feasible operating policies for separating a mixture of acetone, benzene, and chloroform completely into its constituent pure components.

  14. Efficient water removal in lipase-catalyzed esterifications using a low-boiling-point azeotrope.

    PubMed

    Yan, Youchun; Bornscheuer, Uwe T; Schmid, Rolf D

    2002-04-01

    High conversions in lipase-catalyzed syntheses of esters from free acyl donors and an alcohol requires efficient removal of water preferentially at temperatures compatible to enzyme activity. Using a lipase B from Candida antarctica (CAL-B)-mediated synthesis of sugar fatty-acid esters, we show that a mixture of ethyl methylketone (EMK) and hexane (best ratio: 4:1, vo/vo) allows efficient removal of water generated during esterification. Azeotropic distillation of the solvent mixture (composition: 26% EMK, 55% hexane, 19% water) takes place at 59 degrees C, which closely matches the optimum temperature reported for CAL-B. Water is then removed from the azeotrope by membrane vapor permeation. In case of glucose stearate, 93% yield was achieved after 48 h using an equimolar ratio of glucose and stearic acid. CAL-B could be reused for seven reaction cycles, with 86% residual activity after 14 d total reaction time at 59 degrees C. A decrease in fatty-acid chain length as well as increasing temperatures (75 degrees C) resulted in lower conversions. In addition, immobilization of CAL-B on a magnetic polypropylene carrier (EP 100) facilitated separation of the biocatalyst.

  15. Method for removing organic liquids from aqueous solutions and mixtures

    DOEpatents

    Hrubesh, Lawrence W.; Coronado, Paul R.; Dow, Jerome P.

    2004-03-23

    A method for removing organic liquids from aqueous solutions and mixtures. The method employs any porous material preferably in granular form and having small pores and a large specific surface area, that is hydrophobic so that liquid water does not readily wet its surface. In this method, organics, especially organic solvents that mix with and are more volatile than water, are separated from aqueous solution by preferentially evaporating across the liquid/solid boundary formed at the surfaces of the hydrophobic porous materials. Also, organic solvents that are immiscible with water, preferentially wet the surfaces of the hydrophobic material and are drawn within the porous materials by capillary action.

  16. ATR spectra on boundary with mixture containing organic substances

    NASA Astrophysics Data System (ADS)

    Schelokov, R. V.; Yatsishen, V. V.

    2005-02-01

    The problem of not destroying diagnostics and dosing of radiation at laser therapy is one of important in medicine. Therefore the purpose of our work is development of method ATR for diagnostics and researches in biomedicine. In this work as objects of consideration were: a mixture of nicotine with water, a mixture of an ascorbic acid with water and surface lesions of an eye cornea by a herpes virus. Results of our consideration are the ATR spectra defined at different concentration of organic substances and virions.

  17. Solubility of organic solutes in ethanol-water mixtures

    SciTech Connect

    Li, A.; Yalkowsky, S.H.

    1994-12-31

    The log-linear solubilization model was applied to experimental solubility data of 109 organic compounds in ethanol/water mixtures. It is found that the extent of solubilization strongly depends on the solute hydrophobicity and the ethanol concentration in the solvent mixture. Patterns of deviation from the log-linear model are related to the structure and hydrophobicity of the solutes. Predictive equations were obtained by regression of the experimental data with solute octanol-water partition coefficient (log K{sub ow}). The logarithms of the solubilization and the solute log K{sub ow} range over eleven orders of magnitude. The solubilities of chrysene, perylene, benzo(a)pyrene, pentachlorobenzene, and hexachlorobenzene in ethanol/water mixtures were experimentally determined, and the results fit well into the model.

  18. Adsorbate shape selectivity: Separation of the HF/134a azeotrope over carbogenic molecular sieve

    SciTech Connect

    Hong, A.; Mariwala, R.K.; Kane, M.S.; Foley, H.C.

    1995-03-01

    Experimental evidence is provided for adsorptive shape selectivity in the separation of the azeotrope between HF and 1,1,1,2-tetrafluoroethane (134a) over pyrolyzed poly(furfuryl alcohol)-derived carbogenic molecular sieve (PPFA-CMS). The separation can be accomplished over coconut charcoal or Carbosieve G on the basis of the differences in the extent of equilibrium adsorption of HF and 134a. On these adsorbents 134a is more strongly bound than HF, thus it elutes much more slowly from the bed. The heat of adsorption for 134a in the vicinity of 200 C on Carbosieve G is {approximately}8.8 kcal/mol. In contrast, when the same azeotropic mixture is separated over PPFA-CMS prepared at 500 C, 134a is not adsorbed. As a result 134a elutes from the bed first, followed by HF. The reversal is brought about by the narrower pore size and pore size distribution of the PPFA-CMS versus that for Carbosieve G. Thus the separation over PPFA-CMS is an example of adsorbate shape selectivity and represents a limiting case of kinetic separation.

  19. Ultrasonic study on organic liquid and binary organic liquid mixtures by using Schaaffs' collision factor theory

    NASA Astrophysics Data System (ADS)

    Lu, Yi-Gang; Dong, Yan-Wu

    2006-09-01

    Based on Schaaffs' collision factor theory (CFT) in liquids, the equations for nonlinear ultrasonic parameters in both organic liquid and binary organic liquid mixtures are deduced. The nonlinear ultrasonic parameters, including pressure coefficient, temperature coefficients of ultrasonic velocity, and nonlinear acoustic parameter B/A in both organic liquid and binary organic liquid mixtures, are evaluated for comparison with the measured results and data from other sources. The equations show that the coefficient of ultrasonic velocity and nonlinear acoustic parameter B/A are closely related to molecular interactions. These nonlinear ultrasonic parameters reflect some information of internal structure and outside status of the medium or mixtures. From the exponent of repulsive forces of the molecules, several thermodynamic parameters, pressure and temperature of the medium, the nonlinear ultrasonic parameters and ultrasonic nature of the medium can be evaluated. When evaluating and studying nonlinear acoustic parameter B/A of binary organic liquid mixtures, there is no need to know the nonlinear acoustic parameter B/A of the components. Obviously, the equation reveals the connection between the nonlinear ultrasonic nature and internal structure and outside status of the mixtures more directly and distinctly than traditional mixture law for B/A, e.g. Apfel's and Sehgal's laws for liquid binary mixtures.

  20. Exposure of humans to a volatile organic mixture. 2. Sensory

    SciTech Connect

    Hudnell, H.K.; Otto, D.A.; House, D.E.; Molhave, L.

    1992-01-01

    Time-course functions for symptoms of the sick building syndrome were derived from 66 healthy males exposed to clean air and a volatile organic compound (VOC) mixture in separate sessions. The mixture contained 22 VOCs (25 mg/cu m total concentration) commonly found air-borne in new or recently renovated buildings. Subjects rated the intensity of perceived irritation, odor, and other variables before and twice during 2.75 hr exposure periods. Eye and throat irritation, headache, and drowsiness increased or showed no evidence of adaptation during exposure, whereas odor intensity decreased by 30%. These results indicate that irritation intensity and other symptoms are not related in any simple fashion to odor intensity, suggesting that the symptoms may not be a psychosomatic response to detection of an aversive odor. Instead, subthreshold levels of VOCs may interact additively or hyperadditively and stimulate trigeminal nerve receptors.

  1. Mixture interlayer for high performance organic-inorganic perovskite photodetectors

    NASA Astrophysics Data System (ADS)

    Tang, Feng; Chen, Qi; Chen, Lei; Ye, Fengye; Cai, Jinhua; Chen, Liwei

    2016-09-01

    Organic-inorganic perovskites are promising light absorbing active materials for photodetectors; however, the performance of current organic-inorganic perovskite-based photodetectors are limited by the high dark current due to hole injection at the cathode interlayer typically composed of fullerene derivatives. We have developed a mixture interlayer by simply blending polymethyl methacrylate (PMMA) with [6,6]-phenyl-C61-butyric acidmethyl ester (PCBM). Scanning Kelvin probe microscopy imaging reveals that the presence of PMMA reduced the work function of the PCBM:PMMA interlayer, which leads to increased energy barrier for hole injection and better hole-blocking property. Optimized perovskite photodetector with PCBM:PMMA hole-blocking interlayer exhibits a high detectivity of 1.1 × 1013 Jones, a broad linear dynamic range of 112 dB, and a fast response time of 2.2 μs.

  2. Self-organized pattern formation in motor-microtubule mixtures

    NASA Astrophysics Data System (ADS)

    Sankararaman, Sumithra; Menon, Gautam I.; Sunil Kumar, P. B.

    2004-09-01

    We model the stable self-organized patterns obtained in the nonequilibrium steady states of mixtures of molecular motors and microtubules. In experiments [Nédélec , Nature (London) 389, 305 (1997); Surrey , Science 292, 1167 (2001)] performed in a quasi-two-dimensional geometry, microtubules are oriented by complexes of motor proteins. This interaction yields a variety of patterns, including arrangements of asters, vortices, and disordered configurations. We model this system via a two-dimensional vector field describing the local coarse-grained microtubule orientation and two scalar density fields associated to molecular motors. These scalar fields describe motors which either attach to and move along microtubules or diffuse freely within the solvent. Transitions between single aster, spiral, and vortex states are obtained as a consequence of confinement, as parameters in our model are varied. For systems in which the effects of confinement can be neglected, we present a map of nonequilibrium steady states, which includes arrangements of asters and vortices separately as well as aster-vortex mixtures and fully disordered states. We calculate the steady state distribution of bound and free motors in aster and vortex configurations of microtubules and compare these to our simulation results, providing qualitative arguments for the stability of different patterns in various regimes of parameter space. We study the role of crowding or “saturation” effects on the density profiles of motors in asters, discussing the role of such effects in stabilizing single asters. We also comment on the implications of our results for experiments.

  3. Hydrothermal oxidation of ammonia/organic waste mixtures

    SciTech Connect

    Luan, Li; Proesmans, P.I.; Buelow, S.J.

    1997-05-01

    Hydrothermal oxidation is a promising new technology for the treatment of radioactive contaminated hazardous organic wastes. Los Alamos National Laboratory is currently evaluating this technology for the U. S. Department of Energy. In this paper, we present experimental results from the study of the hydrothermal oxidation of an ammonia/alcohol/uranium waste mixture. The use of a co-oxidant system consisting of hydrogen peroxide combined with nitrate is discussed. Experiments demonstrate near complete destruction of ammonia and organic compounds at 500{degrees} C, 38 MPa, and 50 seconds reaction time. The ammonia and total organic carbon (TOC) concentrations in a waste simulant is reduced from 8,500 mg/L of ammonia and 12,500 mg/L TOC to 30 mg/L ammonia and less than 10 mg/L TOC. The major reaction products are CO{sub 2}, N{sub 2}, and a small amount of N{sub 2}O. Comparison experiments with nitrate and hydrogen peroxide used individually show the advantage of the co-oxidant system.

  4. Control of Meloidogyne incognita Using Mixtures of Organic Acids.

    PubMed

    Seo, Yunhee; Kim, Young Ho

    2014-12-01

    This study sought to control the root-knot nematode (RKN) Meloidogyne incognita using benign organo-chemicals. Second-stage juveniles (J2) of RKN were exposed to dilutions (1.0%, 0.5%, 0.2%, and 0.1%) of acetic acid (AA), lactic acid (LA), and their mixtures (MX). The nematode bodies were disrupted severely and moderately by vacuolations in 0.5% of MX and single organic acids, respectively, suggesting toxicity of MX may be higher than AA and LA. The mortality of J2 was 100% at all concentrations of AA and MX and only at 1.0% and 0.5% of LA, which lowered slightly at 0.2% and greatly at 0.1% of LA. This suggests the nematicidal activity of MX may be mostly derived from AA together with supplementary LA toxicity. MX was applied to chili pepper plants inoculated with about 1,000 J2, for which root-knot gall formations and plant growths were examined 4 weeks after inoculation. The root gall formation was completely inhibited by 0.5% MX and standard and double concentrations of fosthiazate; and inhibited 92.9% and 57.1% by 0.2% and 0.1% MX, respectively. Shoot height, shoot weight, and root weight were not significantly (P ≤ 0.05) different among all treatments and the untreated and non-inoculated controls. All of these results suggest that the mixture of the organic acids may have a potential to be developed as an eco-friendly nematode control agent that needs to be supported by the more nematode control experiments in fields. PMID:25506312

  5. Control of Meloidogyne incognita Using Mixtures of Organic Acids

    PubMed Central

    Seo, Yunhee; Kim, Young Ho

    2014-01-01

    This study sought to control the root-knot nematode (RKN) Meloidogyne incognita using benign organo-chemicals. Second-stage juveniles (J2) of RKN were exposed to dilutions (1.0%, 0.5%, 0.2%, and 0.1%) of acetic acid (AA), lactic acid (LA), and their mixtures (MX). The nematode bodies were disrupted severely and moderately by vacuolations in 0.5% of MX and single organic acids, respectively, suggesting toxicity of MX may be higher than AA and LA. The mortality of J2 was 100% at all concentrations of AA and MX and only at 1.0% and 0.5% of LA, which lowered slightly at 0.2% and greatly at 0.1% of LA. This suggests the nematicidal activity of MX may be mostly derived from AA together with supplementary LA toxicity. MX was applied to chili pepper plants inoculated with about 1,000 J2, for which root-knot gall formations and plant growths were examined 4 weeks after inoculation. The root gall formation was completely inhibited by 0.5% MX and standard and double concentrations of fosthiazate; and inhibited 92.9% and 57.1% by 0.2% and 0.1% MX, respectively. Shoot height, shoot weight, and root weight were not significantly (P ≤ 0.05) different among all treatments and the untreated and non-inoculated controls. All of these results suggest that the mixture of the organic acids may have a potential to be developed as an eco-friendly nematode control agent that needs to be supported by the more nematode control experiments in fields. PMID:25506312

  6. Dynamic self-organization of microwell-aggregated cellular mixtures.

    PubMed

    Song, Wei; Tung, Chih-Kuan; Lu, Yen-Chun; Pardo, Yehudah; Wu, Mingming; Das, Moumita; Kao, Der-I; Chen, Shuibing; Ma, Minglin

    2016-06-29

    Cells with different cohesive properties self-assemble in a spatiotemporal and context-dependent manner. Previous studies on cell self-organization mainly focused on the spontaneous structural development within a short period of time during which the cell numbers remained constant. However the effect of cell proliferation over time on the self-organization of cells is largely unexplored. Here, we studied the spatiotemporal dynamics of self-organization of a co-culture of MDA-MB-231 and MCF10A cells seeded in a well defined space (i.e. non-adherent microfabricated wells). When cell-growth was chemically inhibited, high cohesive MCF10A cells formed a core surrounded by low cohesive MDA-MB-231 cells on the periphery, consistent with the differential adhesion hypothesis (DAH). Interestingly, this aggregate morphology was completely inverted when the cells were free to grow. At an initial seeding ratio of 1 : 1 (MDA-MB-231 : MCF10A), the fast growing MCF10A cells segregated in the periphery while the slow growing MDA-MB-231 cells stayed in the core. Another morphology developed at an inequal seeding ratio (4 : 1), that is, the cell mixtures developed a side-by-side aggregate morphology. We conclude that the cell self-organization depends not only on the cell cohesive properties but also on the cell seeding ratio and proliferation. Furthermore, by taking advantage of the cell self-organization, we purified human embryonic stem cells-derived pancreatic progenitors (hESCs-PPs) from co-cultured feeder cells without using any additional tools or labels. PMID:27275624

  7. Flammability limits of fuel/fluorocarbon azeotropes

    SciTech Connect

    Alvares, N.J.; Hammond, P.R.; Foote, K.; Ford, H.W. Jr.

    1981-02-10

    Both Dehn and Thorne have intimated that flash point (FP) measurements could be used to define the gas-phase flammability limits of fire and retardant vapor mixtures above the surface of heated retardant containing flammable liquids. However, it was found that ignitable mixtures exist above the liquid surface, where the concentration of the agent in the fluid is well beyond the limiting concentrating for inerting of alcohol fires. Clearly this anomaly results from diffusion competition of air and liquid vapor mixture at the position of the ignitor, as influenced by the design of the experimental apparatus. The authors are skeptical about the need or worth of attempting to define flammability limits using FP data, especially since unknown variables control the response. More important is to define the concentration of liquid phase retardant that will affect gas phase inerting. Thus, it is necessary to continue practical testing of retardant-containing liquids for their effectiveness in mitigating possible accidents, e.g., the next phase of this work will assess the effectiveness of halocarbons to inert high-pressure alcohol/agent leaks impinging on both electrical and flame ignition sources.

  8. Process for separating a fluid feed mixture containing hydrocarbon oil and an organic solvent

    SciTech Connect

    Bitter, J.G.A.; Haan, J.P.

    1989-03-07

    This patent describes a process for separating a fluid feed mixture containing a hydrocarbon lubricating base oil and an organic solvent selected from furfural and mixture of toluene and methyl ethyl ketone which process comprises subjecting the fluid feed mixture to reverse osmosis in a reverse osmosis zone with a membrane comprising a layer of a silicone polymer. The process provides a retentate stream having an organic solvent content higher than the feed mixture, and a permeate stream having an organic solvent content less than the amount of solvent in the feed mixture, and permits recovering hydrocarbon oil from the permeate stream.

  9. The effect of azeotropism on combustion characteristics of blended fuel pool fire.

    PubMed

    Ding, Yanming; Wang, Changjian; Lu, Shouxiang

    2014-04-30

    The effect of azeotropism on combustion characteristics of blended fuel pool fire was experimentally studied in an open fire test space of State Key Laboratory of Fire Science. A 30 cm × 30 cm square pool filled with n-heptane and ethanol blended fuel was employed. Flame images, burning rate and temperature distribution were collected and recorded in the whole combustion process. Results show that azeotropism obviously dominates the combustion behavior of n-heptane/ethanol blended fuel pool fire. The combustion process after ignition exhibits four typical stages: initial development, azeotropic burning, single-component burning and decay stage. Azeotropism appears when temperature of fuel surface reaches azeotropic point and blended fuel burns at azeotropic ratio. Compared with individual pure fuel, the effect of azeotropism on main fire parameters, such as flame height, burning rate, flame puffing frequency and centerline temperature were analyzed. Burning rate and centerline temperature of blended fuel are higher than that of individual pure fuel respectively at azeotropic burning stage, and flame puffing frequency follows the empirical formula between Strouhal and Froude number for pure fuel.

  10. 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.

  11. Membrane permeation process for dehydration of organic liquid mixtures using sulfonated ion-exchange polyalkene membranes

    DOEpatents

    Cabasso, Israel; Korngold, Emmanuel

    1988-01-01

    A membrane permeation process for dehydrating a mixture of organic liquids, such as alcohols or close boiling, heat sensitive mixtures. The process comprises causing a component of the mixture to selectively sorb into one side of sulfonated ion-exchange polyalkene (e.g., polyethylene) membranes and selectively diffuse or flow therethrough, and then desorbing the component into a gas or liquid phase on the other side of the membranes.

  12. SOIL SORPTION OF VOLATILE AND SEMIVOLATILE ORGANIC COMPOUNDS IN A MIXTURE

    EPA Science Inventory

    Studies were conducted to evaluate lipophilicity as a predictor sorption for a mixture of organic compounds with high vapor pressures commonly present at hazardous waste sites. Sorption partition coefficients (Kp) for the mixture of 16 volatile and semivolatile ...

  13. Azeotropic distillation in a middle vessel batch column. 1: Model formulation and linear separation boundaries

    SciTech Connect

    Cheong, W.; Barton, P.I.

    1999-04-01

    A mathematical model for the middle vessel batch distillation column (MVC) is developed using the concept of warped time analysis and used to study the qualitative dynamics of the MVC when it is used to separate multicomponent azeotropic mixtures. A limiting analysis is then developed for a MVC with an infinite number of trays, operated under infinite reflux/reboil ratios, under the assumption of linear separation boundaries. It is determined that, under limiting conditions, the distillate product drawn from the MVC is given by the {alpha} limit set of the MVC still pot composition, while the bottoms product drawn from the MVC is given by the {omega} limit set of the MVC still pot composition. The net product composition is determined by taking a convex combination of the two products. The notions of steering the still pot composition, the vector cone of possible motion for the still pot composition, and the equivalency of the MVC to the combined operation of a batch rectifier and a stripper are also explored. The definition of batch distillation regions for the MVC operated at a given value of the middle vessel parameter {lambda}, and the bifurcation of these regions with the variation of {lambda}, are investigated. Lastly, a mathematical model incorporating the concept of warped time is developed for a multivessel column. The MVC can be viewed as a specific case of the multivessel column.

  14. Toxicity of natural mixtures of organic pollutants in temperate and polar marine phytoplankton.

    PubMed

    Echeveste, Pedro; Galbán-Malagón, Cristóbal; Dachs, Jordi; Berrojalbiz, Naiara; Agustí, Susana

    2016-11-15

    Semivolatile and persistent organic pollutants (POPs) undergo atmospheric transport before being deposited to the oceans, where they partition to phytoplankton organic matter. The goal of this study was to determine the toxicity of naturally occurring complex mixtures of organic pollutants to temperate and polar phytoplankton communities from the Mediterranean Sea, the North East (NE) Atlantic, and Southern Oceans. The cell abundance of the different phytoplankton groups, chlorophyll a concentrations, viability of the cells, and growth and decay constants were monitored in response to addition of a range of concentrations of mixtures of organic pollutants obtained from seawater extracts. Almost all of the phytoplankton groups were significantly affected by the complex mixtures of non-polar and polar organic pollutants, with toxicity being greater for these mixtures than for single POPs or simple POP mixtures. Cocktails' toxicity arose at concentrations as low as tenfold the field oceanic levels, probably due to a higher chemical activity of the mixture than of simple POPs mixtures. Overall, smaller cells were the most affected, although Mediterranean picophytoplankton was significantly more tolerant to non-polar POPs than picophytoplankton from the Atlantic Ocean or the Bellingshausen Sea microphytoplankton. PMID:27470667

  15. Toxicity of natural mixtures of organic pollutants in temperate and polar marine phytoplankton.

    PubMed

    Echeveste, Pedro; Galbán-Malagón, Cristóbal; Dachs, Jordi; Berrojalbiz, Naiara; Agustí, Susana

    2016-11-15

    Semivolatile and persistent organic pollutants (POPs) undergo atmospheric transport before being deposited to the oceans, where they partition to phytoplankton organic matter. The goal of this study was to determine the toxicity of naturally occurring complex mixtures of organic pollutants to temperate and polar phytoplankton communities from the Mediterranean Sea, the North East (NE) Atlantic, and Southern Oceans. The cell abundance of the different phytoplankton groups, chlorophyll a concentrations, viability of the cells, and growth and decay constants were monitored in response to addition of a range of concentrations of mixtures of organic pollutants obtained from seawater extracts. Almost all of the phytoplankton groups were significantly affected by the complex mixtures of non-polar and polar organic pollutants, with toxicity being greater for these mixtures than for single POPs or simple POP mixtures. Cocktails' toxicity arose at concentrations as low as tenfold the field oceanic levels, probably due to a higher chemical activity of the mixture than of simple POPs mixtures. Overall, smaller cells were the most affected, although Mediterranean picophytoplankton was significantly more tolerant to non-polar POPs than picophytoplankton from the Atlantic Ocean or the Bellingshausen Sea microphytoplankton.

  16. PROCEDURES FOR DERIVING EQUILIBRIUM PARTITIONING BENCHMARKS (ESBS) FOR THE PROTECTION OF BENTHIC ORGANISM: PAH MIXTURES

    EPA Science Inventory

    This equilibrium partitioning sediment benchmark (ESB) document describes procedures to derive concentrations of PAH mixtures in sediment which are protective of the presence of benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it accounts for t...

  17. The solubility of hydrophobic aromatic chemicals in organic solvent/water mixtures

    SciTech Connect

    Dickhut, R.M.

    1989-01-01

    The influence of dissolved organic solvents on the aqueous phase solubility of hydrophobic aromatic chemicals was investigated. To provide a basis for a comprehensive evaluation of the importance of cosolvent properties on solubility, the effects of several different organic cosolvents on the solubility of a model hydrophobic solute, naphthalene, were determined. Naphthalene solubility was measured in binary, ternary, and quaternary alcohol/water (methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol) mixtures, binary ketone/water (acetone, methylethylketone, diethylketone), and aromatic organic solvent/water (benzene, toluene) mixtures. The solubility data were statistically evaluated and used to obtain an estimate of the overall accuracy of solubility measurements of hydrophobic chemicals in organic solvent/water mixtures. An accurate data base for mixed solvent solubility was established by combining the solubility data with additional solubility data obtained experimentally and from the literature. Thermodynamic models for predicting solubility in organic solvent/water mixtures were tested against the experimental data. The effects of organic cosolvent properties and solute hydrophobicity on solubility behavior and model predictive capability were evaluated. The results were used to evaluate the accuracy of existing models for predicting solubility and to explore possible molecular interactions in organic solvent/water mixtures.

  18. Complex mixtures of air pollutants: characterizing the cancer risk of polycyclic organic matter.

    PubMed Central

    Lewtas, J

    1993-01-01

    Complex mixtures of polycyclic organic matter (POM) are used to illustrate the scientific problems and issues associated with characterizing the comparative risk of related complex mixtures. The complexity of mixtures in which the active components are not well characterized present special challenges, which include identifying the critical components of mixtures, their sources, and the appropriate biomarker(s) of exposure and dose; developing the appropriate experimental models for dose-response assessment; species extrapolation; and developing a scientific basis for predicting from one mixture to another. Strategies for addressing these issues include bioassay-directed chemical characterization of bioactive components of complex mixtures, apportionment methods to determine the source of biological activity and risk, DNA adduct methods to determine tissue exposure and target dose of mixtures, and comparative approaches to determining the relative similarity, potency, and risk of complex mixtures. Epidemiological data are available for humans exposed to POM from coke ovens, coal roofing tar, coal smoke, aluminum smelters, and cigarette smoke. These emissions are characterized and compared to POM from automotive emissions (diesel and gasoline), woodstove emissions, residential oil furnace emissions, and ambient air particles. The tumor potency and estimated cancer risks for these POM mixtures ranges over nearly three orders of magnitude. PMID:8354169

  19. DESIGNING FIXED-BED ADSORBERS TO REMOVE MIXTURES OF ORGANICS.

    EPA Science Inventory

    A liquid-phase granular activated carbon (GAC) pilot plant and a full-scale GAC adsorber were designed, built, and operated in order to evaluate their performance for treating a groundwater contaminated with several volatile and synthetic organic chemicals. Several empty bed con...

  20. Designing fixed-bed adsorbers to remove mixtures of organics

    SciTech Connect

    Hand, D.W.; Crittenden, J.C.; Arora, H.; Miller, J.M.; Lykins, B.W.

    1989-01-01

    A liquid-phase granular activated carbon (GAC) pilot plant and a full-scale GAC adsorber were designed, built, and operated in order to evaluate their performance for treating a groundwater contaminated with several volatile and synthetic organic chemicals. Several empty bed contact times (EBCTs) ranging from 1 to 30 min were used during the pilot-plant study, and a simple method for evaluating the GAC use rate as a function of the EBCT was developed and demonstrated for dichloroethene and trichloroethene (TCE). Pilot-plant data were compared with the pore surface diffusion model, which considers external and internal mass transfer mechanisms of pore and surface diffusion. Natural organic matter in the water was found to decrease GAC capacity and kinetics for TCE.

  1. SOLUBILITY, SORPTION AND TRANSPORT OF HYDROPHOBIC ORGANIC CHEMICALS IN COMPLEX MIXTURES

    EPA Science Inventory

    The research summarized in this report focuses on the effects which organic cosolvents have on the sorption and mobility of organic contaminants. This work was initiated In an effort to improve our understanding of the environmental consequences associated with complex mixtur...

  2. Experimental study of multiple steady states in homogeneous azeotropic distillation

    SciTech Connect

    Guettinger, T.E.; Dorn, C.; Morari, M.

    1997-03-01

    Bekiaris et al. (1993) explained the existence of multiple steady states in homogeneous ternary azeotropic distillation, on the basis of the analysis of the case of infinite reflux and infinite column length (infinite number of trays). They showed that the predictions of multiple steady states for such infinite columns have relevant implications for columns of finite length operated at finite reflux. In this article, experiments are described for the ternary homogeneous system methanol-methyl butyrate-toluene which demonstrate the existence of multiple steady states (output multiplicities) caused by the vapor-liquid-equilibrium. The experiments on an industrial pilot column show two stable steady states for the same feed flow rate and composition and the same set of operating parameters. The measurements are in excellent agreement with the predictions obtained for infinite columns using the {infinity}/{infinity} analysis tool as well as with stage-by-stage simulation results. These experiments represent the first published study reporting evidence for the predictions and simulations by various researchers showing that type of output multiplicities in distillation.

  3. Microbial toxicity of mixtures of organic chemicals in soil medium-experimental protocol and modeling

    SciTech Connect

    Arulgnanendran, V.R.J.; Khandan, N.N.

    1995-12-31

    A laboratory procedure was developed to measure the microbial toxicity in soils using respirometric technique. The procedure was tested on 35 organic chemicals and several 8- and 10- component equitoxic mixtures. The chemicals assayed in this study were found to act jointly by simple addition. A modeling approach incorporating partitioning, sorption and Quantitative Structure Activity Relationship (QSAR) techniques was developed to estimate single chemical and mixture toxicity. This modeling approach was validated using an external testing set of data.

  4. ACTION CONCENTRATION FOR MIXTURES OF VOLATILE ORGANIC COMPOUNDS (VOC) & METHANE & HYDROGEN

    SciTech Connect

    MARUSICH, R.M.

    2006-07-10

    Waste containers may contain volatile organic compounds (VOCs), methane, hydrogen and possibly propane. These constituents may occur individually or in mixtures. Determining if a waste container contains a flammable concentration of flammable gases and vapors (from VOCs) is important to the safety of the handling, repackaging and shipping activities. This report provides the basis for determining the flammability of mixtures of flammable gases and vapors. The concentration of a mixture that is at the lowest flammability limit for that mixture is called the action concentration. The action concentration can be determined using total VOC concentrations or actual concentration of each individual VOC. The concentrations of hydrogen and methane are included with the total VOC or individual VOC concentration to determine the action concentration. Concentrations below this point are not flammable. Waste containers with gas/vapor concentrations at or above the action concentration are considered flammable.

  5. Nature of Mesoscopic Organization in Protic Ionic Liquid-Alcohol Mixtures.

    PubMed

    Schroer, Wolffram; Triolo, Alessandro; Russina, Olga

    2016-03-10

    The mesoscopic morphology of mixtures of ethylammonium nitrate, a protic ionic liquid, and n-pentanol is explored for the first time using small angle X-ray scattering as a function of concentration and temperature. Both compounds are amphiphilic and characterized by an extended hydrogen bonding network; however, though macroscopically homogeneous, their mixtures are highly heterogeneous at the mesoscopic spatial scales. Previous structural studies rationalized similar features in related mixtures proposing the existence of large aggregates or micelle- and/or microemulsion-like structures. Here we show that a detailed analysis of the present concentration and temperature resolved experimental data set supports a structural scenario where the mesoscopic heterogeneities are the due to density fluctuations that are precursors of liquid-liquid phase separation. Accordingly no existence of structurally organized aggregates (such as micellar or microemulsion aggregates) is required to account for the mesoscopic heterogeneities detected in this class of binary mixtures. PMID:26895177

  6. Effects of organic acid-surfactant mixtures on levels of bacteria and beef quality traits

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Introduction: Organic acid efficacy as an antimicrobial treatment of beef carcass surfaces may be increased through the addition of surfactants. However, the effects of antimicrobial-surfactant mixtures on beef quality traits such as flavor and color stability may make their use unacceptable. Purp...

  7. Optical Properties of Fluorescent Mixtures: Comparing Quantum Dots to Organic Dyes

    ERIC Educational Resources Information Center

    Hutchins, Benjamin M.; Morgan, Thomas T.; Ucak-Astarlioglu, Mine G.; Wlilliams, Mary Elizabeth

    2007-01-01

    The study describes and compares the size-dependent optical properties of organic dyes with those of semiconductor nanocrystals or quantum dots (QDs). The analysis shows that mixtures of QDs contain emission colors that are sum of the individual QD components.

  8. Molecular identification of organic compounds in atmospheric complex mixtures and relationship to atmospheric chemistry and sources.

    PubMed Central

    Mazurek, Monica A

    2002-01-01

    This article describes a chemical characterization approach for complex organic compound mixtures associated with fine atmospheric particles of diameters less than 2.5 m (PM2.5). It relates molecular- and bulk-level chemical characteristics of the complex mixture to atmospheric chemistry and to emission sources. Overall, the analytical approach describes the organic complex mixtures in terms of a chemical mass balance (CMB). Here, the complex mixture is related to a bulk elemental measurement (total carbon) and is broken down systematically into functional groups and molecular compositions. The CMB and molecular-level information can be used to understand the sources of the atmospheric fine particles through conversion of chromatographic data and by incorporation into receptor-based CMB models. Once described and quantified within a mass balance framework, the chemical profiles for aerosol organic matter can be applied to existing air quality issues. Examples include understanding health effects of PM2.5 and defining and controlling key sources of anthropogenic fine particles. Overall, the organic aerosol compositional data provide chemical information needed for effective PM2.5 management. PMID:12634131

  9. Suppression of Rhizoctonia solani in Potting Mixtures Amended with Compost Made from Organic Household Waste.

    PubMed

    Tuitert, G; Szczech, M; Bollen, G J

    1998-08-01

    ABSTRACT Compost made from organic household and garden waste was used to substitute part of the peat in potting mixtures used for growing woody ornamental nursery stock. The effects of amendment with compost on the colonization of potting mixture by Rhizoctonia solani (AG1) were studied in greenhouse experiments. A bioassay was developed using cucumber as a sensitive herbaceous test plant as a substitute for woody ornamental cuttings. Pathogen growth in the potting mixture was estimated by measuring the distance over which damping-off of seedlings occurred. Compost from two commercial composting facilities suppressed growth of R. solani in potting mixtures with 20% of the product when the compost was fresh (directly after delivery) or long matured (after 5 to 7 months of additional curing). In contrast, short-matured compost (1 month of additional curing) from the same batches stimulated pathogen growth. In vitro mycelial growth of R. solani on mixtures with mature compost was inhibited by microbial antagonism. Compost-amended potting mixtures responded differentially to the addition of cellulose powder; the effect on suppressiveness depended on curing time and origin of the compost. In long-matured compost, suppressiveness to R. solani was associated with high population densities of cellulolytic and oligotrophic actinomycetes. The ratio of the population density of actinomycetes to that of other bacteria was around 200-fold higher in mature suppressive compost than in conducive compost.

  10. Fact or artifact: the representativeness of ESI-MS for complex natural organic mixtures.

    PubMed

    Novotny, Nicole R; Capley, Erin N; Stenson, Alexandra C

    2014-04-01

    Because mass spectrometers provide their own dispersion and resolution of analytes, electrospray ionization mass spectrometry (ESI-MS) has become a workhorse for the characterization of complex mixtures from aerosols to crude oil. Unfortunately, ESI mass spectra commonly contain multimers, adducts and fragments. For the characterization of complex mixtures of unknown initial composition, this presents a significant concern. Mixed-multimer formation could potentially lead to results that bare no resemblance to the original mixture. Conversely, ESI-MS has continually reflected subtle differences between natural organic matter mixtures that are in agreement with prediction or theory. Knowing the real limitations of the technique is therefore critical to avoiding both over-interpretation and unwarranted skepticism. Here, data were collected on four mass spectrometers under a battery of conditions. Results indicate that formation of unrepresentative ions cannot entirely be ruled out, but non-covalent multimers do not appear to make a major contribution to typical natural organic matter spectra based on collision-induced dissociation results. Multimers also appear notably reduced when a cooling gas is present in the accumulation region of the mass spectrometer. For less complex mixtures, the choice of spray solvent can make a difference, but generally spectrum cleanliness (i.e. representativeness) comes at the price of increased selectivity.

  11. Adsorption and desorption of mixtures of organic vapors on beaded activated carbon.

    PubMed

    Wang, Haiyan; Jahandar Lashaki, Masoud; Fayaz, Mohammadreza; Hashisho, Zaher; Philips, John H; Anderson, James E; Nichols, Mark

    2012-08-01

    In this study, adsorption and desorption of mixtures of organic compounds commonly emitted from automotive painting operations were experimentally studied. A mixture of two alkanes and a mixture of eight organic compounds were adsorbed onto beaded activated carbon (BAC) and then thermally desorbed under nitrogen. Following both adsorption and regeneration, samples of the BAC were chemically extracted. Gas chromatography-mass spectrometry (GC-MS) was used to quantify the compounds in the adsorption and desorption gas streams and in the BAC extracts. In general, for both adsorbate mixtures, competitive adsorption resulted in displacing low boiling point compounds by high boiling point compounds during adsorption. In addition to boiling point, adsorbate structure and functionality affected adsorption dynamics. High boiling point compounds such as n-decane and 2,2-dimethylpropylbenzene were not completely desorbed after three hours regeneration at 288 °C indicating that these two compounds contributed to heel accumulation on the BAC. Additional compounds not present in the mixtures were detected in the extract of regenerated BAC possibly due to decomposition or other reactions during regeneration. Closure analysis based on breakthrough curves, solvent extraction of BAC and mass balance on the reactor provided consistent results of the amount of adsorbates on the BAC after adsorption and/or regeneration. PMID:22742925

  12. Water uptake of multicomponent organic mixtures and their influence on hygroscopicity of inorganic salts.

    PubMed

    Wang, Yuanyuan; Jing, Bo; Guo, Yucong; Li, Junling; Tong, Shengrui; Zhang, Yunhong; Ge, Maofa

    2016-07-01

    The hygroscopic behaviors of atmospherically relevant multicomponent water soluble organic compounds (WSOCs) and their effects on ammonium sulfate (AS) and sodium chloride were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA) in the relative humidity (RH) range of 5%-90%. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model (E-AIM) and Zdanovskii-Stokes-Robinson (ZSR) method. The equal mass multicomponent WSOCs mixture containing levoglucosan, succinic acid, phthalic acid and humic acid showed gradual water uptake without obvious phase change over the whole RH range. It was found that the organic content played an important role in the water uptake of mixed particles. When organic content was dominant in the mixture (75%), the measured hygroscopic growth was higher than predictions from the E-AIM or ZSR relation, especially under high RH conditions. For mass fractions of organics not larger than 50%, the hygroscopic growth of mixtures was in good agreement with model predictions. The influence of interactions between inorganic and organic components on the hygroscopicity of mixed particles was related to the salt type and organic content. These results could contribute to understanding of the hygroscopic behaviors of multicomponent aerosol particles. PMID:27372129

  13. Response predictions for organisms water-exposed to metal mixtures: a meta-analysis.

    PubMed

    Vijver, Martina G; Elliott, Elise G; Peijnenburg, Willie J G M; de Snoo, Geert R

    2011-06-01

    To develop a multimetal toxicity model requires insight into the relationships between the composition of metal mixtures and their toxicological effects on organisms. As a first step in developing such a model, quantitative data from binary and higher mixture studies of Cu, Cd, and Zn were compiled and used to assess trends in toxicological effects on various organisms. The findings of this meta-analysis show relatively little occurrence of additive effects compared with antagonistic and synergistic effects. This observation held true irrespective of test species, environmental compartment, or metal concentrations in the mixture. However, the type of effect was significantly correlated with the metal combination tested and the selected toxicological endpoint. It was also found that different methods were used for assessing deviation from additivity in the various individual studies. For robust comparison, standardization on this point is required. Toxicological responses of organisms to metal mixtures were shown to be hard to predict and were often slightly less than or slightly more than additive. The interactions observed could not be explained by metal-metal interactions alone. We therefore conclude that with current scientific knowledge it is not yet possible to predict responses to metal mixtures in individual cases; at best this is possible only in terms of general patterns. Nevertheless, in the context of environmental risk policy, the assumption of additivity produces a conservative prediction of toxicity, because toxicity of a metal mixture will be either predicted correctly or overpredicted by default in approximately 75% of all cases. The use of models based on noninteraction is satisfactory from this regulatory perspective.

  14. Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Zuend, A.; Marcolli, C.; Peter, T.

    2014-06-01

    This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic-water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~275 to ~400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures with the introduction of a new temperature dependence parameterisation. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multicomponent system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~190 to ~440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 25% in comparison to

  15. Toxicity of organic chemicals and their mixtures to activated sludge microorganisms

    SciTech Connect

    Hall, E.; Sun, B.; Prakash, J.; Nirmalakhandan, N.

    1996-05-01

    Toxicity of eight- and 10-component mixtures of several organic chemicals to activated sludge (A/S) microorganisms was analyzed. The joint toxic effects of the tested chemicals were found to be simply additive. The quantitative structure-activity relationship (QSAR) technique using molecular connectivity indices was used to develop single variable models to fit single chemical toxicity data. A QSAR-based approach is proposed to predict the concentrations of components in equitoxic mixtures that would jointly cause 50% inhibition of the A/S microorganisms. The validity of this predictive approach was demonstrated by comparing the predicted concentrations against those found experimentally.

  16. Azeotropic distillation assisted fabrication of silver nanocages and their catalytic property for reduction of 4-nitrophenol.

    PubMed

    Min, Jianzhong; Wang, Fei; Cai, Yunliang; Liang, Shuai; Zhang, Zhenwei; Jiang, Xingmao

    2015-01-14

    Monodisperse silver nanocages (AgNCs) with specific interiors were successfully synthesized by an azeotropic distillation (AD) assisted method and exhibited excellent catalytic activities for reduction of 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) due to the unique hollow morphology and small thickness of the silver shell.

  17. A quantitative structure-activity relationship approach for assessing toxicity of mixture of organic compounds.

    PubMed

    Chang, C M; Ou, Y H; Liu, T-C; Lu, S-Y; Wang, M-K

    2016-06-01

    Four types of reactivity indices were employed to construct quantitative structure-activity relationships for the assessment of toxicity of organic chemical mixtures. Results of analysis indicated that the maximum positive charge of the hydrogen atom and the inverse of the apolar surface area are the most important descriptors for the toxicity of mixture of benzene and its derivatives to Vibrio fischeri. The toxicity of mixture of aromatic compounds to green alga Scenedesmus obliquus is mainly affected by the electron flow and electrostatic interactions. The electron-acceptance chemical potential and the maximum positive charge of the hydrogen atom are found to be the most important descriptors for the joint toxicity of aromatic compounds.

  18. BYY harmony learning, structural RPCL, and topological self-organizing on mixture models.

    PubMed

    Xu, Lei

    2002-01-01

    The Bayesian Ying-Yang (BYY) harmony learning acts as a general statistical learning framework, featured by not only new regularization techniques for parameter learning but also a new mechanism that implements model selection either automatically during parameter learning or via a new class of model selection criteria used after parameter learning. In this paper, further advances on BYY harmony learning by considering modular inner representations are presented in three parts. One consists of results on unsupervisedmixture models, ranging from Gaussian mixture based Mean Square Error (MSE) clustering, elliptic clustering, subspace clustering to NonGaussian mixture based clustering not only with each cluster represented via either Bernoulli-Gaussian mixtures or independent real factor models, but also with independent component analysis implicitly made on each cluster. The second consists of results on supervised mixture-of-experts (ME) models, including Gaussian ME, Radial Basis Function nets, and Kernel regressions. The third consists of two strategies for extending the above structural mixtures into self-organized topological maps. All these advances are introduced with details on three issues, namely, (a) adaptive learning algorithms, especially elliptic, subspace, and structural rival penalized competitive learning algorithms, with model selection made automatically during learning; (b) model selection criteria for being used after parameter learning, and (c) how these learning algorithms and criteria are obtained from typical special cases of BYY harmony learning.

  19. Metabolism and DNA binding of BaP in the presence of complex organic mixtures

    SciTech Connect

    Springer, D.L.; Dankovic, D.A.; Thomas, B.L.; Hopkins, K.L.; Bean, R.E.; Mahlum, D.D.

    1986-04-01

    Previous studies have shown that the mutagenic, carcinogenic and DNA binding activities of benzo(a)pyrene (BaP) were decreased when BaP was coadministered with complex organic mixtures. We have continued these studies to identify the components of the mixture that were responsible for this effect. For this study a high-boiling coal liquid was separated into aliphatic, polycyclic aromatic hydrocarbon (PAH), nitrogen-containing polycyclic aromatic compounds (NPAC) and oxygen containing PAH fractions (HPAH); these were spiked with /sup 3/H-BaP, administered dermally to mice and DNA isolated twenty-four hours later. Binding of BaP, as estimated by radioactivity associated the DNA, decreased to 47, 55 and 66% of that for the same dose of BaP alone for the PAH, NPAC and HPAH fractions, respectively. In vitro studies with Aroclor-induced rat liver S9 demonstrated that the rate of metabolism of BaP decreased when it was coadministered with the mixtures but that the BaP metabolite profiles were similar for BaP alone and in the presence of the mixture. These data suggest that the differences in mutagenic, and presumable carcinogenic activities, for BaP, when administered with the complex mixture, were due to decreased rates of conversion of BaP to reactive metabolites. 15 refs., 2 figs., 3 tabs.

  20. Abatement of mixture of volatile organic compounds (VOCs) in a catalytic non-thermal plasma reactor.

    PubMed

    Karuppiah, J; Reddy, E Linga; Reddy, P Manoj Kumar; Ramaraju, B; Karvembu, R; Subrahmanyam, Ch

    2012-10-30

    Total oxidation of mixture of dilute volatile organic compounds was carried out in a dielectric barrier discharge reactor with various transition metal oxide catalysts integrated in-plasma. The experimental results indicated the best removal efficiencies in the presence of metal oxide catalysts, especially MnO(x), whose activity was further improved with AgO(x) deposition. It was confirmed water vapor improves the efficiency of the plasma reactor, probably due to the formation of hydroxyl species, whereas, in situ decomposition of ozone on the catalyst surface may lead to nascent oxygen. It may be concluded that non-thermal plasma approach is beneficial for the removal of mixture of volatile organic compounds than individual VOCs, probably due to the formation of reactive intermediates like aldehydes, peroxides, etc.

  1. Modeling the surface tension of complex, reactive organic-inorganic mixtures

    NASA Astrophysics Data System (ADS)

    Schwier, A. N.; Viglione, G. A.; Li, Z.; McNeill, V. Faye

    2013-11-01

    Atmospheric aerosols can contain thousands of organic compounds which impact aerosol surface tension, affecting aerosol properties such as heterogeneous reactivity, ice nucleation, and cloud droplet formation. We present new experimental data for the surface tension of complex, reactive organic-inorganic aqueous mixtures mimicking tropospheric aerosols. Each solution contained 2-6 organic compounds, including methylglyoxal, glyoxal, formaldehyde, acetaldehyde, oxalic acid, succinic acid, leucine, alanine, glycine, and serine, with and without ammonium sulfate. We test two semi-empirical surface tension models and find that most reactive, complex, aqueous organic mixtures which do not contain salt are well described by a weighted Szyszkowski-Langmuir (S-L) model which was first presented by Henning et al. (2005). Two approaches for modeling the effects of salt were tested: (1) the Tuckermann approach (an extension of the Henning model with an additional explicit salt term), and (2) a new implicit method proposed here which employs experimental surface tension data obtained for each organic species in the presence of salt used with the Henning model. We recommend the use of method (2) for surface tension modeling of aerosol systems because the Henning model (using data obtained from organic-inorganic systems) and Tuckermann approach provide similar modeling results and goodness-of-fit (χ2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

  2. Modeling the surface tension of complex, reactive organic-inorganic mixtures

    NASA Astrophysics Data System (ADS)

    Schwier, A. N.; Viglione, G. A.; Li, Z.; McNeill, V. F.

    2013-01-01

    Atmospheric aerosols can contain thousands of organic compounds which impact aerosol surface tension, affecting aerosol properties such as cloud condensation nuclei (CCN) ability. We present new experimental data for the surface tension of complex, reactive organic-inorganic aqueous mixtures mimicking tropospheric aerosols. Each solution contained 2-6 organic compounds, including methylglyoxal, glyoxal, formaldehyde, acetaldehyde, oxalic acid, succinic acid, leucine, alanine, glycine, and serine, with and without ammonium sulfate. We test two surface tension models and find that most reactive, complex, aqueous organic mixtures which do not contain salt are well-described by a weighted Szyszkowski-Langmuir (S-L) model which was first presented by Henning et al. (2005). Two approaches for modeling the effects of salt were tested: (1) the Tuckermann approach (an extension of the Henning model with an additional explicit salt term), and (2) a new implicit method proposed here which employs experimental surface tension data obtained for each organic species in the presence of salt used with the Henning model. We recommend the use of method (2) for surface tension modeling because the Henning model (using data obtained from organic-inorganic systems) and Tuckermann approach provide similar modeling fits and goodness of fit (χ2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

  3. Predicting the lifetime of organic vapor cartridges exposed to volatile organic compound mixtures using a partial differential equations model.

    PubMed

    Vuong, François; Chauveau, Romain; Grevillot, Georges; Marsteau, Stéphanie; Silvente, Eric; Vallieres, Cécile

    2016-09-01

    In this study, equilibria, breakthrough curves, and breakthrough times were predicted for three binary mixtures of four volatile organic compounds (VOCs) using a model based on partial differential equations of dynamic adsorption coupling a mass balance, a simple Linear Driving Force (LDF) hypothesis to describe the kinetics, and the well-known Extended-Langmuir (EL) equilibrium model. The model aims to predict with a limited complexity, the BTCs of respirator cartridges exposed to binary vapor mixtures from equilibria and kinetics data obtained from single component. In the model, multicomponent mass transfer was simplified to use only single dynamic adsorption data. The EL expression used in this study predicted equilibria with relatively good accuracy for acetone/ethanol and ethanol/cyclohexane mixtures, but the prediction of cyclohexane uptake when mixed with heptane is less satisfactory. The BTCs given by the model were compared to experimental BTCs to determine the accuracy of the model and the impact of the approximation on mass transfer coefficients. From BTCs, breakthrough times at 10% of the exposure concentration t10% were determined. All t10% were predicted within 20% of the experimental values, and 63% of the breakthrough times were predicted within a 10% error. This study demonstrated that a simple mass balance combined with kinetic approximations is sufficient to predict lifetime for respirator cartridges exposed to VOC mixtures. It also showed that a commonly adopted approach to describe multicomponent adsorption based on volatility of VOC rather than adsorption equilibrium greatly overestimated the breakthrough times.

  4. Dual-channel microcantilever heaters for volatile organic compound detection and mixture analysis.

    PubMed

    Jahangir, Ifat; Koley, Goutam

    2016-01-01

    We report on novel microcantilever heater sensors with separate AlGaN/GaN heterostructure based heater and sensor channels to perform advanced volatile organic compound (VOC) detection and mixture analysis. Operating without any surface functionalization or treatment, these microcantilevers utilize the strong surface polarization of AlGaN, as well as the unique heater and sensor channel geometries, to perform selective detection of analytes based on their latent heat of evaporation and molecular dipole moment over a wide concentration range with sub-ppm detection limit. The dual-channel microcantilevers have demonstrated much superior sensing behavior compared to the single-channel ones, with the capability to not only identify individual VOCs with much higher specificity, but also uniquely detect them in a generic multi-component mixture of VOCs. In addition, utilizing two different dual channel configurations and sensing modalities, we have been able to quantitatively determine individual analyte concentration in a VOC mixture. An algorithm for complete mixture analysis, with unique identification of components and accurate determination of their concentration, has been presented based on simultaneous operation of an array of these microcantilever heaters in multiple sensing modalities. PMID:27381318

  5. Dual-channel microcantilever heaters for volatile organic compound detection and mixture analysis

    PubMed Central

    Jahangir, Ifat; Koley, Goutam

    2016-01-01

    We report on novel microcantilever heater sensors with separate AlGaN/GaN heterostructure based heater and sensor channels to perform advanced volatile organic compound (VOC) detection and mixture analysis. Operating without any surface functionalization or treatment, these microcantilevers utilize the strong surface polarization of AlGaN, as well as the unique heater and sensor channel geometries, to perform selective detection of analytes based on their latent heat of evaporation and molecular dipole moment over a wide concentration range with sub-ppm detection limit. The dual-channel microcantilevers have demonstrated much superior sensing behavior compared to the single-channel ones, with the capability to not only identify individual VOCs with much higher specificity, but also uniquely detect them in a generic multi-component mixture of VOCs. In addition, utilizing two different dual channel configurations and sensing modalities, we have been able to quantitatively determine individual analyte concentration in a VOC mixture. An algorithm for complete mixture analysis, with unique identification of components and accurate determination of their concentration, has been presented based on simultaneous operation of an array of these microcantilever heaters in multiple sensing modalities. PMID:27381318

  6. Dual-channel microcantilever heaters for volatile organic compound detection and mixture analysis

    NASA Astrophysics Data System (ADS)

    Jahangir, Ifat; Koley, Goutam

    2016-07-01

    We report on novel microcantilever heater sensors with separate AlGaN/GaN heterostructure based heater and sensor channels to perform advanced volatile organic compound (VOC) detection and mixture analysis. Operating without any surface functionalization or treatment, these microcantilevers utilize the strong surface polarization of AlGaN, as well as the unique heater and sensor channel geometries, to perform selective detection of analytes based on their latent heat of evaporation and molecular dipole moment over a wide concentration range with sub-ppm detection limit. The dual-channel microcantilevers have demonstrated much superior sensing behavior compared to the single-channel ones, with the capability to not only identify individual VOCs with much higher specificity, but also uniquely detect them in a generic multi-component mixture of VOCs. In addition, utilizing two different dual channel configurations and sensing modalities, we have been able to quantitatively determine individual analyte concentration in a VOC mixture. An algorithm for complete mixture analysis, with unique identification of components and accurate determination of their concentration, has been presented based on simultaneous operation of an array of these microcantilever heaters in multiple sensing modalities.

  7. Toxicity of five antibiotics and their mixtures towards photosynthetic aquatic organisms: implications for environmental risk assessment.

    PubMed

    González-Pleiter, Miguel; Gonzalo, Soledad; Rodea-Palomares, Ismael; Leganés, Francisco; Rosal, Roberto; Boltes, Karina; Marco, Eduardo; Fernández-Piñas, Francisca

    2013-04-15

    The individual and combined toxicities of amoxicillin, erythromycin, levofloxacin, norfloxacin and tetracycline have been examined in two organisms representative of the aquatic environment, the cyanobacterium Anabaena CPB4337 as a target organism and the green alga Pseudokirchneriella subcapitata as a non-target organism. The cyanobacterium was more sensitive than the green alga to the toxic effect of antibiotics. Erythromycin was highly toxic for both organisms; tetracycline was more toxic to the green algae whereas the quinolones levofloxacin and norfloxacin were more toxic to the cyanobacterium than to the green alga. Amoxicillin also displayed toxicity to the cyanobacterium but showed no toxicity to the green alga. The toxicological interactions of antibiotics in the whole range of effect levels either in binary or multicomponent mixtures were analyzed using the Combination Index (CI) method. In most cases, synergism clearly predominated both for the green alga and the cyanobacterium. The CI method was compared with the classical models of additivity Concentration Addition (CA) and Independent Action (IA) finding that CI could accurately predict deviations from additivity. Risk assessment was performed by calculating the ratio between Measured Environmental Concentration (MEC) and the Predicted No Effect Concentration (PNEC). A MEC/PNEC ratio higher than 1 was found for the binary erythromycin and tetracycline mixture in wastewater effluents, a combination which showed a strong synergism at low effect levels in both organisms. From the tested antibiotic mixtures, it can be concluded that certain specific combinations may pose a potential ecological risk for aquatic ecosystems with the present environmentally measured concentrations. PMID:23399078

  8. Toxicity of Cúspide 480SL® spray mixture formulation of glyphosate to aquatic organisms.

    PubMed

    Currie, Zachary; Prosser, Ryan S; Rodriguez-Gil, Jose Luis; Mahon, Kim; Poirier, Dave; Solomon, Keith R

    2015-05-01

    In 2011, an alternative formulation of glyphosate (Cúspide 480SL®) was chosen to replace Roundup-SL®, Fuete-SL®, and Gly-41® for the control of Erythroxylum coca, the source of cocaine, in Colombia. Cúspide 480SL contains the active ingredient glyphosate isopropylamine (IPA) salt, which is the same active ingredient used in previous formulations. However, Cúspide 480SL contains an alkyl polyglycoside surfactant rather than the polyethoxylated tallow amine (POEA) surfactant used in other formulations and known to be more toxic to nonprimary producing aquatic organisms than glyphosate itself. An adjuvant, Cosmo-Flux F411, and water also are added to the spray mixture before application. Aquatic ecosystems adjacent to the target coca fields might be exposed to the spray mix, placing aquatic organisms at risk. Because no toxicity data were available for spray mixture on aquatic organisms, acute toxicity tests were conducted on aquatic plants, invertebrates, and fish, by using the Cúspide 480SL spray mix as described on the label. Based on the median effective concentration (EC50) values for similar organisms, the spray mixture was less toxic to aquatic organisms than formulations previously used for the control of coca (i.e., Roundup-SL, Fuete-SL, and Gly-41). A physical effect induced by Cosmo-Flux F411 was observed in Daphnia magna, Ceriodaphnia dubia, and Hyalella azteca, causing the invertebrates to be trapped in an oily film that was present at the surface of the water. However, a hazard assessment for the Cúspide 480SL spray mix, using estimated worst-case exposure scenario concentrations and EC50 values from the toxicity tests, indicated de minimis hazard for the tested aquatic animals, with hazard quotients all <1. PMID:25655706

  9. Pervaporative removal of organics from water using hydrophobic membranes. Binary mixtures

    SciTech Connect

    Kujawski, W.

    2000-01-01

    Results of pervaporation experiments are presented for the separation of several polar and nonpolar organic solvents from their aqueous solutions. Three membranes were evaluated: a polydimethylsiloxane (PERVAP-1060) membrane, a PDMS ZSM-5 zeolite filled (PERVAP-1070) membrane, and a poly(ether-block-amide) (PEBAX-4033) membrane. The effect of feed composition on flux and selectivity was also investigated. Performance parameters of a given membrane depended both on the kind of the organic solvent and the feed composition. The PERVAP-1070 membrane exhibited the highest selectivity with a separation factor over 900 in contact with a water-butyl acetate mixture. Polar solvents like methanol were also preferentially separated from aqueous solutions, but the separation factors were close to those obtained from liquid-vapor equilibria data. Permeate fluxes of organics increased with increasing feed concentration. Synergetic effects between water and organics fluxes were also observed.

  10. Laboratory appraisal of organic carbon changes in mixtures made with different inorganic wastes.

    PubMed

    Arbestain, M Camps; Ibargoitia, M L; Madinabeitia, Z; Gil, M V; Virgel, S; Morán, A; Pereira, R Calvelo; Macías, F

    2009-12-01

    Mixtures of organic and inorganic wastes were incubated to examine the changes in organic C (OC) contents. An anaerobic sludge and a CaO-treated aerobic sludge, with OC concentrations of 235 and 129 gkg(-1), were used. The inorganic wastes used - referred to as "conditioners" - were shot blasting scrap, fettling, Linz-Donawitz slag, foundry sand (FS), and fly ash from wood bark combustion (FA). The total OC (TOC) and KMnO(4)(-) oxidized OC were determined. DTA-TGA profiles and FTIR spectra were also obtained. Mixtures made with the FS contained significantly lower (P<0.05) amounts of TOC (45 gkg(-1)) than the rest of mixtures, which was attributed to the non-existence of reactive surfaces in the conditioner and the increased aeration induced by this material. Those made with FA contained significantly higher (P<0.05) amounts of TOC (170 gkg(-1)), which was attributed to: (i) the addition of an extra source of C - black carbon (BC) - in the FA, and (ii) the inhibition of mineralization from the compounds present in this conditioner (e.g., amorphous aluminosilicates, BC). The results highlight the importance of the characteristics of the conditioners on the fate of the OM originating from the sludges. PMID:19632821

  11. Enabling the identification, quantification, and characterization of organics in complex mixtures to understand atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Isaacman, Gabriel Avram

    Particles in the atmosphere are known to have negative health effects and important but highly uncertain impacts on global and regional climate. A majority of this particulate matter is formed through atmospheric oxidation of naturally and anthropogenically emitted gases to yield highly oxygenated secondary organic aerosol (SOA), an amalgamation of thousands of individual chemical compounds. However, comprehensive analysis of SOA composition has been stymied by its complexity and lack of available measurement techniques. In this work, novel instrumentation, analysis methods, and conceptual frameworks are introduced for chemically characterizing atmospherically relevant mixtures and ambient aerosols, providing a fundamentally new level of detailed knowledge on their structures, chemical properties, and identification of their components. This chemical information is used to gain insights into the formation, transformation and oxidation of organic aerosols. Biogenic and anthropogenic mixtures are observed in this work to yield incredible complexity upon oxidation, producing over 100 separable compounds from a single precursor. As a first step toward unraveling this complexity, a method was developed for measuring the polarity and volatility of individual compounds in a complex mixture using two-dimensional gas chromatography, which is demonstrated in Chapter 2 for describing the oxidation of SOA formed from a biogenic compound (longifolene: C15H24). Several major products and tens of substantial minor products were produced, but none could be identified by traditional methods or have ever been isolated and studied in the laboratory. A major realization of this work was that soft ionization mass spectrometry could be used to identify the molecular mass and formula of these unidentified compounds, a major step toward a comprehensive description of complex mixtures. This was achieved by coupling gas chromatography to high resolution time-of-flight mass spectrometry with

  12. Secondary organic aerosol formation from ozone reactions with single terpenoids and terpenoid mixtures

    NASA Astrophysics Data System (ADS)

    Waring, Michael S.; Wells, J. Raymond; Siegel, Jeffrey A.

    2011-08-01

    Ozone reacts with indoor-emitted terpenoids to form secondary organic aerosol (SOA). Most SOA research has focused on ozone reactions with single terpenoids or with consumer products, and this paper reports the results from an investigation of SOA formation from ozone reactions with both single terpenoids and mixtures of D-limonene, α-pinene, and α-terpineol. Transient experiments were conducted at low (25 ppb) and high (100 ppb) initial concentrations of ozone. The three terpenoids were tested singly and in combinations in a manner that controlled for their different reaction rates with ozone. The SOA formation was assessed by examining the evolution in time of the resulting number size-distributions and estimates of the mass concentrations. The results suggest that at higher ozone and terpenoid concentrations, SOA number formation follows a linear trend as a function of the initial rate of reaction. This finding was valid for both single terpenoids and mixtures. Generally speaking, higher ozone and terpenoid concentrations also led to larger geometric mean diameters and smaller geometric standard deviations of fitted lognormal distributions of the formed SOA. By assuming a density, mass concentrations were also assessed and did not follow as consistent of a trend. At low ozone concentration conditions, reactions with only D-limonene yielded the largest number concentrations of any experiment, even more than experiments with mixtures containing D-limonene and much higher overall terpenoid concentrations. This finding was not seen for high ozone concentrations. These experiments demonstrate quantifiable trends for SOA forming reactions of ozone and mixtures, and this work provides a framework for expanding these results to more complex mixtures and consumer products.

  13. Technical Note: Dissolved organic matter fluorescence - a finite mixture approach to deconvolve excitation-emission matrices

    NASA Astrophysics Data System (ADS)

    Butturini, A.; Ejarque, E.

    2013-09-01

    The analysis of the shape of excitation-emission matrices (EEMs) is a relevant tool for exploring the origin, transport and fate of dissolved organic matter (DOM) in aquatic ecosystems. Within this context, the decomposition of EEMs is acquiring a notable relevance. A simple mathematical algorithm that automatically deconvolves individual EEMs is described, creating new possibilities for the comparison of DOM fluorescence properties and EEMs that are very different from each other. A mixture model approach is adopted to decompose complex surfaces into sub-peaks. The laplacian operator and the Nelder-Mead optimisation algorithm are implemented to individuate and automatically locate potential peaks in the EEM landscape. The EEMs of a simple artificial mixture of fluorophores and DOM samples collected in a Mediterranean river are used to describe the model application and to illustrate a strategy that optimises the search for the optimal output.

  14. Feasibility of separations for distillation of nonideal ternary mixtures

    SciTech Connect

    Fidkowski, Z.T.; Doherty, M.F.; Malone, M.F. . Dept. of Chemical Engineering)

    1993-08-01

    The product compositions in single-feed distillation columns can be specified only in certain regions of the composition space, which depend only on the pressure, feed, and vapor-liquid equilibrium for the mixture. In nonideal mixtures, even without azeotropes, the regions may allow unusual product distributions. For example, the distillate in a direct split is composed primarily of the lightest component. Intuition and experience with relatively ideal mixtures suggest that the next most plentiful component is the intermediate boiler. In nonideal mixtures, however, with or without azeotropes, the next most plentiful component may be the highest-boiling species with only trace amounts of the intermediate boiler. For azeotropic mixtures, distillation boundaries may give rise to additional restrictions on the product compositions. The authors describe how simple distillation boundaries deform into continuous distillation boundaries and, in a limited number of cases, how the simple distillation boundaries can be crossed in continuous columns for certain ranges of the design variables. Unfortunately, such designs may be quite sensitive to model uncertainties or to disturbances in the parameters.

  15. Chemical Analysis of Complex Organic Mixtures Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Laskin, Julia; Eckert, Peter A.; Roach, Patrick J.; Heath, Brandi S.; Nizkorodov, Sergey A.; Laskin, Alexander

    2012-08-21

    Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies showed that LSOA constituents are multifunctional compounds containing aldehyde and ketone groups. In this study, we used the selectivity of the Girard T (GT) reagent towards carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures. In these experiments, 1-100 {micro}M GT solution was used as a working solvent for reactive nano-DESI analysis. Abundant products of a single addition of GT to LSOA constituents were observed at GT concentrations in excess of 10 {micro}M. We found that LSOA compounds with 18-20 carbon atoms (dimers) and 27-30 carbon atoms (trimers) react with GT through a simple addition reaction resulting in formation of the carbinolamine derivative. In contrast, reactions of GT with monomeric species result in formation of both the carbinolamine and the hydrazone derivatives. In addition, several monomers did not react with GT on the timescale of our experiment. These molecules were characterized by relatively high values of the double bond equivalent (DBE) and low oxygen content. Furthermore, because addition of a charged GT tag to a neutral molecule eliminates the discrimination against the low proton affinity compounds in the ionization process, reactive nano-DESI analysis enables quantification of individual compounds in the complex mixture. For example, we were able to estimate for the first time the amounts of dimers and trimers in the LSOA mixture. Specifically, we found that the most abundant LSOA dimer was detected at ca. 0.5 pg level and the total amount of dimers and trimers in the analyzed sample was just around 11 pg. Our results indicate that reactive nano-DESI is a valuable approach for examining the presence of specific functional groups and

  16. Chemical analysis of complex organic mixtures using reactive nanospray desorption electrospray ionization mass spectrometry.

    PubMed

    Laskin, Julia; Eckert, Peter A; Roach, Patrick J; Heath, Brandi S; Nizkorodov, Sergey A; Laskin, Alexander

    2012-08-21

    Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies have shown that LSOA constituents are multifunctional compounds containing at least one aldehyde or ketone groups. In this study, we used the selectivity of the Girard's reagent T (GT) toward carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures. In these experiments, 1-100 μM GT solutions were used as the working solvents for reactive nano-DESI analysis. Abundant products from the single addition of GT to LSOA constituents were observed at GT concentrations in excess of 10 μM. We found that LSOA dimeric and trimeric compounds react with GT through a simple addition reaction resulting in formation of the carbinolamine derivative. In contrast, reactions of GT with monomeric species result in the formation of both the carbinolamine and the hydrazone derivatives. In addition, several monomers did not react with GT on the time scale of our experiment. These molecules were characterized by relatively high values of the double bond equivalent and low oxygen content. Furthermore, because addition of a charged GT tag to a neutral molecule eliminates the discrimination against the low proton affinity compounds in the ionization process, reactive nano-DESI analysis enables quantification of individual compounds in the complex mixture. For example, we were able to estimate for the first time the amounts of dimers and trimers in the LSOA mixture. Specifically, we found that the most abundant LSOA dimer was detected at the ~0.5 pg level and the total amount of dimers and trimers in the analyzed sample was ~11 pg. Our results indicate that reactive nano-DESI is a valuable approach for examining the presence of specific functional groups and for the quantification of compounds possessing

  17. Effect of some organic solvent-water mixtures composition on precipitated calcium carbonate in carbonation process

    NASA Astrophysics Data System (ADS)

    Konopacka-Łyskawa, Donata; Kościelska, Barbara; Karczewski, Jakub

    2015-05-01

    Precipitated calcium carbonate particles were obtained during carbonation of calcium hydroxide slurry with carbon dioxide. Aqueous solutions of isopropyl alcohol, n-butanol and glycerol were used as solvents. Concentration of organic additives in the reactive mixture was from 0% to 20% (vol). Precipitation process were performed in a stirred tank reactor equipped with gas distributor. Multimodal courses of particles size distribution were determined for produced CaCO3 particles. Calcium carbonate as calcite was precipitated in all experiments. The mean Sauter diameter of CaCO3 particles decreased when the concentration of all used organic additives increased. The amount of small particle fraction in the product increased with the increasing concentration of organic solvents. Similar physical properties of used liquid phase resulted in the similar characteristics of obtained particles.

  18. Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Zuend, A.; Marcolli, C.; Peter, T.

    2015-01-01

    This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic-water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~ 275 to ~ 400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures. To this end we introduce a new parameterisation for the temperature dependence. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multi-component system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~ 190 to ~ 440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 28% in

  19. Hygroscopic behavior of multicomponent organic aerosols and their internal mixtures with ammonium sulfate

    NASA Astrophysics Data System (ADS)

    Jing, Bo; Tong, Shengrui; Liu, Qifan; Li, Kun; Wang, Weigang; Zhang, Yunhong; Ge, Maofa

    2016-03-01

    Water-soluble organic compounds (WSOCs) are important components of organics in the atmospheric fine particulate matter. Although WSOCs play an important role in the hygroscopicity of aerosols, knowledge on the water uptake behavior of internally mixed WSOC aerosols remains limited. Here, the hygroscopic properties of single components such as levoglucosan, oxalic acid, malonic acid, succinic acid, phthalic acid, and multicomponent WSOC aerosols mainly involving oxalic acid are investigated with the hygroscopicity tandem differential mobility analyzer (HTDMA). The coexisting hygroscopic species including levoglucosan, malonic acid, and phthalic acid have a strong influence on the hygroscopic growth and phase behavior of oxalic acid, even suppressing its crystallization completely during the drying process. The phase behaviors of oxalic acid/levoglucosan mixed particles are confirmed by infrared spectra. The discrepancies between measured growth factors and predictions from Extended Aerosol Inorganics Model (E-AIM) with the Universal Quasi-Chemical Functional Group Activity Coefficient (UNIFAC) method and Zdanovskii-Stokes-Robinson (ZSR) approach increase at medium and high relative humidity (RH) assuming oxalic acid in a crystalline solid state. For the internal mixture of oxalic acid with levoglucosan or succinic acid, there is enhanced water uptake at high RH compared to the model predictions based on reasonable oxalic acid phase assumption. Organic mixture has more complex effects on the hygroscopicity of ammonium sulfate than single species. Although hygroscopic species such as levoglucosan account for a small fraction in the multicomponent aerosols, they may still strongly influence the hygroscopic behavior of ammonium sulfate by changing the phase state of oxalic acid which plays the role of "intermediate" species. Considering the abundance of oxalic acid in the atmospheric aerosols, its mixtures with hygroscopic species may significantly promote water uptake

  20. Hygroscopic behavior of multicomponent organic aerosols and their internal mixtures with ammonium sulfate

    NASA Astrophysics Data System (ADS)

    Jing, B.; Tong, S. R.; Liu, Q. F.; Li, K.; Wang, W. G.; Zhang, Y. H.; Ge, M. F.

    2015-08-01

    Water soluble organic compounds (WSOCs) are important components of organics in the atmospheric fine particulate matter. Although WSOCs play an important role in the hygroscopicity of aerosols, water uptake behavior of internally mixed WSOC aerosols remains limited characterization. Here, the hygroscopic properties of single component such as levoglucosan, oxalic acid, malonic acid, succinic acid and phthalic acid and multicomponent WSOC aerosols mainly involving oxalic acid are investigated with the hygroscopicity tandem differential mobility analyzer (HTDMA). The coexisting hygroscopic species including levoglucosan, malonic acid and phthalic acid have strong influence on the hygroscopic growth and phase behavior of oxalic acid, even suppress its crystallization completely. The interactions between oxalic acid and levoglucosan are confirmed by infrared spectra. The discrepancies between measured growth factors and predictions from Extended Aerosol Inorganics Model (E-AIM) with UNIFAC method and Zdanovskii-Stokes-Robinson (ZSR) approach increase at medium and high relative humidity (RH) assuming oxalic acid in a solid state. For the internal mixture of oxalic acid with levoglucosan or succinic acid, there is enhanced water uptake at high RH due to positive chemical interactions between solutes. Organic mixture has more complex effect on the hygroscopicity of ammonium sulfate than single species. Although hygroscopic species such as levoglucosan accounts for a small fraction in the multicomponent aerosols, they may still strongly influence the hygroscopic behavior of ammonium sulfate by changing phase state of oxalic acid which plays the role of "intermediate" species. Considering the abundance of oxalic acid in the atmospheric aerosols, its mixtures with hygroscopic species may significantly promote water uptake under high RH conditions and thus affect the cloud condensation nuclei (CCN) activity, optical properties and chemical reactivity of atmospheric particles.

  1. Identifying operating units for the design and synthesis of azeotropic-distillation systems

    SciTech Connect

    Feng, G.; Fan, L.T.; Friedler, F.; Seib, P.A.

    2000-01-01

    A highly effective method has been established to identify processing or operating units necessary for the design or synthesis of azeotropic-distillation systems by resorting to the first principles and logical sequencing of such units. The materials represented in the space of the residue curve map are partitioned into lumped materials bounded by the thermodynamic boundaries and pinches. Subsequently, the operating units are identified on the basis of these lumped materials. The efficacy of the method has been amply illustrated by generating some feasible flowsheets with a set of relatively simple heuristics for the process of producing pure ethanol from its aqueous solution via azeotropic distillation, which is a typical complex process involving thermodynamic pinches, such as azeotropes, phase transition, and/or phase separation. The method is applicable to other complex processes, e.g., crystallization, extraction, reactive distillation, and their combinations. It is highly likely that the method can be an integral part of any conventional heuristic or algorithmic flowsheeting procedure because selecting plausible or candidate operating units is essential for synthesizing a flowsheet by any procedure.

  2. Enabling the identification, quantification, and characterization of organics in complex mixtures to understand atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Isaacman, Gabriel Avram

    Particles in the atmosphere are known to have negative health effects and important but highly uncertain impacts on global and regional climate. A majority of this particulate matter is formed through atmospheric oxidation of naturally and anthropogenically emitted gases to yield highly oxygenated secondary organic aerosol (SOA), an amalgamation of thousands of individual chemical compounds. However, comprehensive analysis of SOA composition has been stymied by its complexity and lack of available measurement techniques. In this work, novel instrumentation, analysis methods, and conceptual frameworks are introduced for chemically characterizing atmospherically relevant mixtures and ambient aerosols, providing a fundamentally new level of detailed knowledge on their structures, chemical properties, and identification of their components. This chemical information is used to gain insights into the formation, transformation and oxidation of organic aerosols. Biogenic and anthropogenic mixtures are observed in this work to yield incredible complexity upon oxidation, producing over 100 separable compounds from a single precursor. As a first step toward unraveling this complexity, a method was developed for measuring the polarity and volatility of individual compounds in a complex mixture using two-dimensional gas chromatography, which is demonstrated in Chapter 2 for describing the oxidation of SOA formed from a biogenic compound (longifolene: C15H24). Several major products and tens of substantial minor products were produced, but none could be identified by traditional methods or have ever been isolated and studied in the laboratory. A major realization of this work was that soft ionization mass spectrometry could be used to identify the molecular mass and formula of these unidentified compounds, a major step toward a comprehensive description of complex mixtures. This was achieved by coupling gas chromatography to high resolution time-of-flight mass spectrometry with

  3. Cacosmia and neurobehavioral dysfunction associated with occupational exposure to mixtures of organic solvents.

    PubMed

    Ryan, C M; Morrow, L A; Hodgson, M

    1988-11-01

    This study examined the interrelationships among occupational exposure to mixtures of organic solvents, neurobehavioral functioning, and complaints of cacosmia. The latter was defined as nausea, headaches, and subjective distress in individuals exposed to neutral environmental odors. The authors administered a battery of cognitive tests to men with and without a history of solvent exposure and found exposed workers to be impaired across a wide range of cognitive domains. Multiple regression analyses of exposed workers demonstrated a highly significant relationship between a history of cacosmia and performance decrements on measures of learning and memory. PMID:3189606

  4. Analysis of organic solvents and liquid mixtures using a fiber-tip evaporation sensor

    NASA Astrophysics Data System (ADS)

    Preter, Eyal; Donlagic, Denis; Artel, Vlada; Katims, Rachel A.; Sukenik, Chaim N.; Zadok, Avi

    2014-05-01

    The instantaneous size and rate of evaporation of pendant liquid droplets placed on the cleaved facet of a standard fiber are reconstructed based on reflected optical power. Using the evaporation dynamics, the relative contents of ethanol in ethanol-water binary mixtures are assessed with 1% precision and different blends of methanol in gasoline are properly recognized. The latter application, in particular, is significant for the use of alternative fuels in the automotive sector. Also, ten organic solvents are identified based on their evaporation from a fiber facet coated with a hydrophobic, selfassembled monolayer.

  5. Simultaneous Detection of Genetically Modified Organisms in a Mixture by Multiplex PCR-Chip Capillary Electrophoresis.

    PubMed

    Patwardhan, Supriya; Dasari, Srikanth; Bhagavatula, Krishna; Mueller, Steffen; Deepak, Saligrama Adavigowda; Ghosh, Sudip; Basak, Sanjay

    2015-01-01

    An efficient PCR-based method to trace genetically modified food and feed products is in demand due to regulatory requirements and contaminant issues in India. However, post-PCR detection with conventional methods has limited sensitivity in amplicon separation that is crucial in multiplexing. The study aimed to develop a sensitive post-PCR detection method by using PCR-chip capillary electrophoresis (PCR-CCE) to detect and identify specific genetically modified organisms in their genomic DNA mixture by targeting event-specific nucleotide sequences. Using the PCR-CCE approach, novel multiplex methods were developed to detect MON531 cotton, EH 92-527-1 potato, Bt176 maize, GT73 canola, or GA21 maize simultaneously when their genomic DNAs in mixtures were amplified using their primer mixture. The repeatability RSD (RSDr) of the peak migration time was 0.06 and 3.88% for the MON531 and Bt176, respectively. The RSD (RSDR) of the Cry1Ac peak ranged from 0.12 to 0.40% in multiplex methods. The method was sensitive in resolving amplicon of size difference up to 4 bp. The PCR-CCE method is suitable to detect multiple genetically modified events in a composite DNA sample by tagging their event specific sequences. PMID:26525256

  6. Simultaneous Detection of Genetically Modified Organisms in a Mixture by Multiplex PCR-Chip Capillary Electrophoresis.

    PubMed

    Patwardhan, Supriya; Dasari, Srikanth; Bhagavatula, Krishna; Mueller, Steffen; Deepak, Saligrama Adavigowda; Ghosh, Sudip; Basak, Sanjay

    2015-01-01

    An efficient PCR-based method to trace genetically modified food and feed products is in demand due to regulatory requirements and contaminant issues in India. However, post-PCR detection with conventional methods has limited sensitivity in amplicon separation that is crucial in multiplexing. The study aimed to develop a sensitive post-PCR detection method by using PCR-chip capillary electrophoresis (PCR-CCE) to detect and identify specific genetically modified organisms in their genomic DNA mixture by targeting event-specific nucleotide sequences. Using the PCR-CCE approach, novel multiplex methods were developed to detect MON531 cotton, EH 92-527-1 potato, Bt176 maize, GT73 canola, or GA21 maize simultaneously when their genomic DNAs in mixtures were amplified using their primer mixture. The repeatability RSD (RSDr) of the peak migration time was 0.06 and 3.88% for the MON531 and Bt176, respectively. The RSD (RSDR) of the Cry1Ac peak ranged from 0.12 to 0.40% in multiplex methods. The method was sensitive in resolving amplicon of size difference up to 4 bp. The PCR-CCE method is suitable to detect multiple genetically modified events in a composite DNA sample by tagging their event specific sequences.

  7. Personal Exposure to Mixtures of Volatile Organic Compounds: Modeling and Further Analysis of the RIOPA Data

    PubMed Central

    Batterman, Stuart; Su, Feng-Chiao; Li, Shi; Mukherjee, Bhramar; Jia, Chunrong

    2015-01-01

    INTRODUCTION Emission sources of volatile organic compounds (VOCs) are numerous and widespread in both indoor and outdoor environments. Concentrations of VOCs indoors typically exceed outdoor levels, and most people spend nearly 90% of their time indoors. Thus, indoor sources generally contribute the majority of VOC exposures for most people. VOC exposure has been associated with a wide range of acute and chronic health effects; for example, asthma, respiratory diseases, liver and kidney dysfunction, neurologic impairment, and cancer. Although exposures to most VOCs for most persons fall below health-based guidelines, and long-term trends show decreases in ambient emissions and concentrations, a subset of individuals experience much higher exposures that exceed guidelines. Thus, exposure to VOCs remains an important environmental health concern. The present understanding of VOC exposures is incomplete. With the exception of a few compounds, concentration and especially exposure data are limited; and like other environmental data, VOC exposure data can show multiple modes, low and high extreme values, and sometimes a large portion of data below method detection limits (MDLs). Field data also show considerable spatial or interpersonal variability, and although evidence is limited, temporal variability seems high. These characteristics can complicate modeling and other analyses aimed at risk assessment, policy actions, and exposure management. In addition to these analytic and statistical issues, exposure typically occurs as a mixture, and mixture components may interact or jointly contribute to adverse effects. However most pollutant regulations, guidelines, and studies remain focused on single compounds, and thus may underestimate cumulative exposures and risks arising from coexposures. In addition, the composition of VOC mixtures has not been thoroughly investigated, and mixture components show varying and complex dependencies. Finally, although many factors are

  8. Personal Exposure to Mixtures of Volatile Organic Compounds: Modeling and Further Analysis of the RIOPA Data

    PubMed Central

    Batterman, Stuart; Su, Feng-Chiao; Li, Shi; Mukherjee, Bhramar; Jia, Chunrong

    2015-01-01

    INTRODUCTION Emission sources of volatile organic compounds (VOCs) are numerous and widespread in both indoor and outdoor environments. Concentrations of VOCs indoors typically exceed outdoor levels, and most people spend nearly 90% of their time indoors. Thus, indoor sources generally contribute the majority of VOC exposures for most people. VOC exposure has been associated with a wide range of acute and chronic health effects; for example, asthma, respiratory diseases, liver and kidney dysfunction, neurologic impairment, and cancer. Although exposures to most VOCs for most persons fall below health-based guidelines, and long-term trends show decreases in ambient emissions and concentrations, a subset of individuals experience much higher exposures that exceed guidelines. Thus, exposure to VOCs remains an important environmental health concern. The present understanding of VOC exposures is incomplete. With the exception of a few compounds, concentration and especially exposure data are limited; and like other environmental data, VOC exposure data can show multiple modes, low and high extreme values, and sometimes a large portion of data below method detection limits (MDLs). Field data also show considerable spatial or interpersonal variability, and although evidence is limited, temporal variability seems high. These characteristics can complicate modeling and other analyses aimed at risk assessment, policy actions, and exposure management. In addition to these analytic and statistical issues, exposure typically occurs as a mixture, and mixture components may interact or jointly contribute to adverse effects. However most pollutant regulations, guidelines, and studies remain focused on single compounds, and thus may underestimate cumulative exposures and risks arising from coexposures. In addition, the composition of VOC mixtures has not been thoroughly investigated, and mixture components show varying and complex dependencies. Finally, although many factors are

  9. Effect of Exposure to a Mixture of Organic Solvents on Hearing Thresholds in Petrochemical Industry Workers

    PubMed Central

    Loukzadeh, Ziba; Shojaoddiny-Ardekani, Ahmad; Mehrparvar, Amir Houshang; Yazdi, Zohreh; Mollasadeghi, Abolfazl

    2014-01-01

    Introduction: Hearing loss is one of the most common occupational diseases. In most workplaces, workers are exposed to noise and solvents simultaneously, so the potential risk of hearing loss due to solvents may be attributed to noise. In this study we aimed to assess the effect of exposure to mixed aromatic solvents on hearing in the absence of exposure to hazardous noise. Materials and Methods: In a cross-sectional study, 99 workers from the petrochemical industry with exposure to a mixture of organic solvents whose noise exposure was lower than 85 dBA were compared with 100 un-exposed controls. After measuring sound pressure level and mean concentration of each solvent in the workplace, pure-tone-audiometry was performed and the two groups were compared in terms of high-frequency and low-frequency hearing loss. T-tests and Chi-square tests were used to compare the two groups. Results: The mean hearing threshold at all frequencies among petrochemical workers was normal (below 25 dB). We did not observe any significant association between solvent exposure and high-frequency or low-frequency hearing loss. Conclusion: This study showed that temporary exposure (less than 4 years) to a mixture of organic solvents, without exposure to noise, does not affect workers’ hearing threshold in audiometry tests. PMID:25320701

  10. Characterization of secondary organic aerosol generated from ozonolysis of α-pinene mixtures

    NASA Astrophysics Data System (ADS)

    Amin, Hardik S.; Hatfield, Meagan L.; Huff Hartz, Kara E.

    2013-03-01

    In the atmosphere, multiple volatile organic compounds (VOCs) co-exist, and they can be oxidized concurrently and generate secondary organic aerosol (SOA). In this work, SOA is formed by the oxidation (in presence of excess ozone) of mixtures containing α-pinene and other VOCs. The VOC mixtures were made so their composition approached a commercially-available α-pinene-based essential oil, Siberian fir needle oil. The SOA products were sampled using filters, solvent extracted and analyzed by gas chromatography/mass spectrometry with trimethylsilyl derivatization. The individual product yields for SOA generated from α-pinene changed upon the addition of other VOCs. An increase in concentration of non-reactive VOCs (bornyl acetate, camphene, and borneol) lead to a decrease in individual product yields of characteristic α-pinene SOA products. Although these experiments were carried out under higher VOC and ozone concentrations in comparison to the atmosphere, this work suggests that the role of non-reactive VOCs should be explored in SOA products formation.

  11. Organic tank safety project: Preliminary results of energetics and thermal behavior studies of model organic nitrate and/or nitrite mixtures and a simulated organic waste

    SciTech Connect

    Scheele, R.D.; Sell, R.L.; Sobolik, J.L.; Burger, L.L.

    1995-08-01

    As a result of years of production and recovery of nuclear defense materials and subsequent waste management at the Hanford Site, organic-bearing radioactive high-level wastes (HLW) are currently stored in large (up to 3. ML) single-shell storage tanks (SSTs). Because these wastes contain both fuels (organics) and the oxidants nitrate and nitrite, rapid energetic reactions at certain conditions could occur. In support of Westinghouse Hanford Company`s (WHC) efforts to ensure continued safe storage of these organic- and oxidant-bearing wastes and to define the conditions necessary for reactions to occur, we measured the thermal sensitivities and thermochemical and thermokinetic properties of mixtures of selected organics and sodium nitrate and/or nitrite and a simulated Hanford organic-bearing waste using thermoanalytical technologies. These thermoanalytical technologies are used by chemical reactivity hazards evaluation organizations within the chemical industry to assess chemical reaction hazards.

  12. Spectroscopic characterization of organic matter of a soil and vinasse mixture during aerobic or anaerobic incubation

    SciTech Connect

    Doelsch, Emmanuel Masion, Armand; Cazevieille, Patrick

    2009-06-15

    Mineralization potentials are often used to classify organic wastes. These methods involve measuring CO{sub 2} production during batch experiments, so variations in chemical compounds are not addressed. Moreover, the physicochemical conditions are not monitored during the reactions. The present study was designed to address these deficiencies. Incubations of a mixture of soil and waste (vinasse at 20% dry matter from a fermentation industry) were conducted in aerobic and anaerobic conditions, and liquid samples obtained by centrifugation were collected at 2 h, 1 d and 28 d. Dissolved organic carbon (DOC) patterns highlighted that: there was a 'soil effect' which increased organic matter (OM) degradation in all conditions compared to vinasse incubated alone; and OM degradation was faster under aerobic conditions since 500 mg kg{sup -1} of C remained after aerobic incubation, as compared to 4000 mg kg{sup -1} at the end of the anaerobic incubation period. No changes were detected by Fourier transform infrared spectroscopy (FTIR) between 2 h and 1 d incubation. At 28 days incubation, the FTIR signal of the aerobic samples was deeply modified, thus confirming the high OM degradation. Under anaerobic conditions, the main polysaccharide contributions ({nu}(C-O)) disappeared at 1000 and 1200 cm{sup -1}, as also confirmed by the {sup 13}C NMR findings. Under aerobic incubation, a 50% decrease in the polysaccharide proportion was observed. Under anaerobic conditions, significant chemical modifications of the organic fraction were detected, namely formation of low molecular weight organic acids.

  13. Multi-atlas segmentation for abdominal organs with Gaussian mixture models

    NASA Astrophysics Data System (ADS)

    Burke, Ryan P.; Xu, Zhoubing; Lee, Christopher P.; Baucom, Rebeccah B.; Poulose, Benjamin K.; Abramson, Richard G.; Landman, Bennett A.

    2015-03-01

    Abdominal organ segmentation with clinically acquired computed tomography (CT) is drawing increasing interest in the medical imaging community. Gaussian mixture models (GMM) have been extensively used through medical segmentation, most notably in the brain for cerebrospinal fluid / gray matter / white matter differentiation. Because abdominal CT exhibit strong localized intensity characteristics, GMM have recently been incorporated in multi-stage abdominal segmentation algorithms. In the context of variable abdominal anatomy and rich algorithms, it is difficult to assess the marginal contribution of GMM. Herein, we characterize the efficacy of an a posteriori framework that integrates GMM of organ-wise intensity likelihood with spatial priors from multiple target-specific registered labels. In our study, we first manually labeled 100 CT images. Then, we assigned 40 images to use as training data for constructing target-specific spatial priors and intensity likelihoods. The remaining 60 images were evaluated as test targets for segmenting 12 abdominal organs. The overlap between the true and the automatic segmentations was measured by Dice similarity coefficient (DSC). A median improvement of 145% was achieved by integrating the GMM intensity likelihood against the specific spatial prior. The proposed framework opens the opportunities for abdominal organ segmentation by efficiently using both the spatial and appearance information from the atlases, and creates a benchmark for large-scale automatic abdominal segmentation.

  14. A mixture of environmental organic contaminants in lake sediments affects hatching from Daphnia resting eggs.

    PubMed

    Möst, Markus; Chiaia-Hernandez, Aurea C; Frey, Martin P; Hollender, Juliane; Spaak, Piet

    2015-02-01

    Despite the relevance of resting eggs for ecology and evolution of many aquatic organisms and their exposure to contaminants accumulating in sediments, ecotoxicological studies using resting eggs are vastly underrepresented. The authors established a method to perform exposure assays with resting eggs produced by the Daphnia longispina species complex, key species in large lake ecosystems. A mixture of organic contaminants previously detected in sediments of Lake Greifensee was selected to test the potential effect of organic contaminants present in sediments on the hatching process. Resting eggs were exposed to a mix of 10 chemicals, which included corrosion inhibitors, biocides, pesticides, and personal care products, for a period of 15 d. Using an automated counting software, the authors found a significant increase in hatching success in the exposed resting eggs compared with controls. Such an effect has not yet been reported from ecotoxicological assays with resting eggs. Possible mechanistic explanations as well as the potential implications on the ecology and evolution of aquatic species that rely on a resting egg banks are discussed. Observed increased mortality and developmental abnormalities for hatchlings in the exposure treatments can be explained by toxic contaminant concentrations. The results of the present study highlight the need for additional studies assessing the effects of organic contaminants on resting egg banks and aquatic ecosystems.

  15. Residue organic mixtures from drinking water show in vitro mutagenic and transforming activity.

    PubMed

    Loper, J C; Lang, D R; Schoeny, R S; Richmond, B B; Gallagher, P M; Smith, C C

    1978-01-01

    Indications of possible health effects of residue organics in drinking water have been sought using short-term tests of mutagenic and transforming activity. Ten percent or less of the total organic material in drinking water has been identified; the remainder is believed to include thousands of unknown nonvolatile compounds. Residual organics were concentrated from drinking water from representative U.S. cities by reverse osmosis followed by liquid-liquid extraction [yielding the reverse osmosis concentrate-organic extract (ROC-OE) fraction] and sorption-desorption on XAD-2 resin. Samples of these residue organics were provided by the Environmental Protection Agency for bioassay. They were examined for mutagenic activity by using Salmonella tester strains (primarily TA98 and TA100) and for transforming activity by using mouse fibroblasts (BALB/3T3 clone 1-13). City-specific patterns of dose-dependent bacterial mutagenesis and of bacterial toxicity were observed for these samples and for subfractions generated by sequential extractions with hexane, ethyl ether, and acetone. Mutagenic effects were essentially independent of a microsome activation system prepared from liver of Aroclor 1254-induced rats. On the basis of strain-specific effects in mutagenesis and differential distributions of mutagenic activity during liquid-liquid extraction, at least some of the active compounds are thought to be acidic, frameshift mutagens. The ROC-OE fraction of a New Orleans sample transformed BALB/3T3 cells in replicate experiments. By comparison with the bacterial mutagenesis data, cell transformation is a relatively sensitive method for detecting possible mutagenic and carcinogenic activity in this sample. The appropriateness of these systems for the assay of complex mixtures and the degree to which reverse osmosis concentrates contain the unaltered organic compounds in the original samples are discussed.

  16. Use of partition models to evaluate guidelines for mixtures of volatile organic compounds.

    PubMed

    Hau, K M; Connell, D W; Richardson, B J

    2000-08-01

    Partition models based on the octanol-air parition coefficients and associated quantitative structure-activity relationships (QSARs) have been developed to describe the triggering of odor response and nasal irritation by common volatile organic compounds (VOCs). This study made use of the QSARs developed by Hau and Connell (1998, Indoor Air 8, 23-33) and Hau et al. (1999, Toxicol. Sci. 47, 93-98) to evaluate risk-based guidelines on the airborne concentrations of common VOCs in the nonindustrial environment. A new concept referred to as the "apparent internal threshold concentration" was developed for evaluating the odor and nasal pungency responses to a typical low-concentration VOC mixture described by Otto et al. (1990, Neurotoxicol. Teratol. 12, 649-652). The assessment indicated that odor can be detected at a total VOC concentration of about 3 mg/m(3), consistent with the findings of Molhave et al. (1991, Atmos. Environ. 25, 1283-1293). Nasal pungency, according to our assessment, should not ocur at a total concentration of 25 mg/m(3), which is apparently in conflict with the findings of Molhave (1986, ASHRAE Trans. 92(1A), 306-316). It can be inferred from this investigation that pure nasal pungency without the influence of odor is unlikely to result from exposure to low-concentration VOC mixtures typically found in the nonindustrial environment.

  17. Linking in Vitro Effects and Detected Organic Micropollutants in Surface Water Using Mixture-Toxicity Modeling.

    PubMed

    Neale, Peta A; Ait-Aissa, Selim; Brack, Werner; Creusot, Nicolas; Denison, Michael S; Deutschmann, Björn; Hilscherová, Klára; Hollert, Henner; Krauss, Martin; Novák, Jiří; Schulze, Tobias; Seiler, Thomas-Benjamin; Serra, Helene; Shao, Ying; Escher, Beate I

    2015-12-15

    Surface water can contain countless organic micropollutants, and targeted chemical analysis alone may only detect a small fraction of the chemicals present. Consequently, bioanalytical tools can be applied complementary to chemical analysis to detect the effects of complex chemical mixtures. In this study, bioassays indicative of activation of the aryl hydrocarbon receptor (AhR), activation of the pregnane X receptor (PXR), activation of the estrogen receptor (ER), adaptive stress responses to oxidative stress (Nrf2), genotoxicity (p53) and inflammation (NF-κB) and the fish embryo toxicity test were applied along with chemical analysis to water extracts from the Danube River. Mixture-toxicity modeling was applied to determine the contribution of detected chemicals to the biological effect. Effect concentrations for between 0 to 13 detected chemicals could be found in the literature for the different bioassays. Detected chemicals explained less than 0.2% of the biological effect in the PXR activation, adaptive stress response, and fish embryo toxicity assays, while five chemicals explained up to 80% of ER activation, and three chemicals explained up to 71% of AhR activation. This study highlights the importance of fingerprinting the effects of detected chemicals.

  18. Linking in Vitro Effects and Detected Organic Micropollutants in Surface Water Using Mixture-Toxicity Modeling.

    PubMed

    Neale, Peta A; Ait-Aissa, Selim; Brack, Werner; Creusot, Nicolas; Denison, Michael S; Deutschmann, Björn; Hilscherová, Klára; Hollert, Henner; Krauss, Martin; Novák, Jiří; Schulze, Tobias; Seiler, Thomas-Benjamin; Serra, Helene; Shao, Ying; Escher, Beate I

    2015-12-15

    Surface water can contain countless organic micropollutants, and targeted chemical analysis alone may only detect a small fraction of the chemicals present. Consequently, bioanalytical tools can be applied complementary to chemical analysis to detect the effects of complex chemical mixtures. In this study, bioassays indicative of activation of the aryl hydrocarbon receptor (AhR), activation of the pregnane X receptor (PXR), activation of the estrogen receptor (ER), adaptive stress responses to oxidative stress (Nrf2), genotoxicity (p53) and inflammation (NF-κB) and the fish embryo toxicity test were applied along with chemical analysis to water extracts from the Danube River. Mixture-toxicity modeling was applied to determine the contribution of detected chemicals to the biological effect. Effect concentrations for between 0 to 13 detected chemicals could be found in the literature for the different bioassays. Detected chemicals explained less than 0.2% of the biological effect in the PXR activation, adaptive stress response, and fish embryo toxicity assays, while five chemicals explained up to 80% of ER activation, and three chemicals explained up to 71% of AhR activation. This study highlights the importance of fingerprinting the effects of detected chemicals. PMID:26516785

  19. Neurotoxic effects of controlled exposure to a complex mixture of volatile organic compounds. Final report

    SciTech Connect

    Otto, D.A.; Molhave, L.; Hudnell, H.K.; Goldstein, G.; O'Neil, J.

    1990-03-01

    Subjective reactions of discomfort, impaired air quality, irritation of mucosal membranes, and impaired memory have been reported in chemically sensitive subjects during exposure to volatile organic compounds (VOCs) found in new buildings. 66 normal healthy male subjects aged 18-39 were exposed for 2.75 hrs to a complex VOC mixture at O and 25 mg/cu m. Each subject completed control and exposure sessions at one week intervals in counterbalanced order. Measurements included comfort ratings of eye, nose and throat irritation, symptom questionnaire and computerized behavioral tests. Subjects found the odor of VOCs unpleasant and strong and reported that VOC exposure degraded air quality, increased headache and produced general discomfort. VOC exposure did not affect performance on any behavioral tests. Results indicate that subjective reactions to VOCs are not limited to chemically sensitive individuals since the study population is a subgroup that is probably least likely to be affected by chemical exposure.

  20. Binary Solvent Organization at Silica/Liquid Interfaces: Preferential Ordering in Acetonitrile-Methanol Mixtures.

    PubMed

    Gobrogge, Eric A; Walker, Robert A

    2014-08-01

    Nonlinear vibrational spectroscopy experiments examined solvent organization at the silica/binary solvent interface where the binary solvent consisted of methanol and acetonitrile in varying mole fractions. Data were compared with surface vibrational spectra acquired from silica surfaces exposed to a vapor phase saturated with the same binary solvent mixtures. Changes in vibrational band intensities suggest that methanol ideally adsorbs to the silica/vapor interface but acetonitrile accumulates in excess relative to vapor-phase composition. At the silica/liquid interface, acetonitrile's signal increases until a solution phase mole fraction of ∼0.85. At higher acetonitrile concentrations, acetonitrile's signal decreases dramatically until only a weak signature persists with the neat solvent. This behavior is ascribed to dipole-paired acetonitrile forming a bilayer with the first sublayer associating with surface silanol groups and a second sublayer consisting of weakly associating, antiparallel partners. On the basis of recent simulations, we propose that the second sublayer accumulates in excess. PMID:26277964

  1. Neurobehavioral and sensory irritant effects of controlled exposure to a complex mixture of volatile organic compounds

    SciTech Connect

    Otto, D.; Molhave, L.; Rose, G.; Hudnell, H.K.; House, D. )

    1990-11-01

    Subjective reactions of discomfort, impaired air quality, irritation of mucosal membranes, and impaired memory have been reported in chemically sensitive subjects during exposure to volatile organic compounds (VOCs) found in new buildings. Sixty-six normal healthy male subjects aged 18-39 were exposed for 2.75 hr to a complex VOC mixture at 0 and 25 mg/m3. Each subject completed control and exposure sessions at one-week intervals in counterbalanced order. Measurements included comfort ratings of eye, nose and throat irritation, symptom questionnaire and computerized behavioral tests. Subjects found the odor of VOCs unpleasantly strong and reported that VOC exposure degraded air quality, increased headache and produced general discomfort. VOC exposure did not affect performance on any behavioral tests.

  2. Technical Note: Dissolved organic matter fluorescence - a finite mixture approach to deconvolve excitation-emission matrices

    NASA Astrophysics Data System (ADS)

    Butturini, A.; Ejarque, E.

    2013-03-01

    The analysis of the shape of excitation-emission matrices (EEMs) is a relevant tool for exploring the origin, transport and fate of dissolved organic matter (DOM) in aquatic ecosystems. Within this context, the decomposition of EEMs is acquiring a notable relevance. A simple mathematical algorithm that automatically deconvolves single EEM is described, creating new possibilities for the comparison of DOM fluorescence properties and EEMs that are very different from each other. A mixture model approach is adopted to decompose complex surfaces into sub-peaks. The laplacian operator and the Nelder-Mead optimization algorithm are implemented to individuate and automatically locate potential peaks in the EEM landscape. A small heterogeneous data set of 21 EEMs from a human-impacted Mediterranean river is used to describe the model application and to illustrate a strategy that optimises the search for the optimal output.

  3. A simple hydrophobicity-based approach to predict the toxicity of unknown organic micropollutant mixtures in marine water.

    PubMed

    Lin, Zhifen; Zhong, Ping; Niu, Xiaojun; Yin, Kedong; Yu, Hongxia; Du, Jianwei

    2005-06-01

    In this study, we propose a simple hydrophobicity-based approach to predict the toxicity of mixtures of marine organic micropollutants. Fifty mixtures were chosen, comprising individual chemicals randomly chosen from three halogenated benzenes, three phenols, two petroleum hydrocarbons, three polychlorinated biphenyls (PCBs), four organochlorine pesticides (OCPs) and two herbicides, with the intention of simulating the mixtures of organic micropollutants that may exist in some marine waters. The hydrophobicity of the mixtures was quantified by measuring the C(18)-Empore(TM) disk/water partition coefficients (K(MD)). A K(MD)-based approach was proposed to describe their toxicity to Photobacterium phosphoreum, and the application of this approach to another 10 related mixtures proved its predictive capability, as indicated by the consistency between the predicted and observed toxicities (r(2)=0.905, SE=0.101, and F=76.325 at P<0.001). This predictive capability convinces us that the K(MD)-based approach provides a general approach to predicting the toxicity of mixtures of organic micropollutants in marine water.

  4. The shock synthesis of complex organics from impacts into cometary analogue mixtures

    NASA Astrophysics Data System (ADS)

    Price, M.; Wozniakiewicz, P.; Cole, M.; Martins, Z.; Burchell, M.

    2014-07-01

    Introduction: If amino acids are required for the evolution of life, what was their source? Many different theories abound as to the source of amino acids on the early Earth including exogenous delivery from comets/asteroids (for example, glycine was found recently on comet Wild-2 [1]), formation in the protoplanetary nebula [2], or UV catalysed reactions of gases [3]. An alternative explanation is that amino acids can be shock-synthesised during the impact on an icy body onto a rocky body (or, equivalently, the impact of rocky body onto an icy surface). This theory is supported by computer simulations [4] and by very recent experimental data, which demonstrated the formation of simple (including abiotic) amino acids from shocks into ice mixtures mimicking the composition of comets and the surfaces of the icy Jovian and Saturnian satellites. Although the results from these experiments are fundamentally important, the yield of synthesised amino acids was low (nano-grams of material), complicating their detection and identification. In order to increase the collected yield of complex organics, and aid in their detection and identification, we have implemented a new collection technique within our hypervelocity impact facility. Experimental Methodology: Figure 1A) shows a low-resolution high-speed photograph of an impact plasma generated from an impact of a stainless-steel sphere into a mixture of water, CO_{2}, ammonia, and methanol ices. The plasma has an intense blue colour, and lasted for < 1 msec (the frame-rate of the camera). It is during and within this flash that complex organics are most likely synthesised, and thus to maximise the collection of these materials, we have implemented a new collection mechanism. Figure 1B) shows the prototype collection mechanism. Here an aluminium cold-plate (˜150 K) is placed in front of the target holder containing the ice mixtures. The plate has a central hole which allows the projectile to pass through to impact the ice

  5. Neither azeotropic drying, nor base nor other additives: a minimalist approach to (18)F-labeling.

    PubMed

    Richarz, R; Krapf, P; Zarrad, F; Urusova, E A; Neumaier, B; Zlatopolskiy, B D

    2014-10-28

    A novel, efficient, time-saving and reliable radiolabeling procedure via nucleophilic substitution with [(18)F]fluoride is described. Different radiolabeled aliphatic and aromatic compounds were prepared in high radiochemical yields simply by heating of quaternary anilinium, diaryliodonium and triarylsulfonium [(18)F]fluorides in suitable solvents. The latter were obtained via direct elution of (18)F(-) from an anion exchange resin with alcoholic solutions of onium precursors. Neither azeotropic evaporation of water, nor a base, nor any other additives like cryptands or crown ethers were necessary. Due to its simplicity this method should be highly suitable for automated radiosyntheses, especially in microfluidic devices. PMID:25190038

  6. Gas-particle partitioning of semivolatile organic compounds (SOCs) on mixtures of aerosols in a smog chamber.

    PubMed

    Chandramouli, Bharadwaj; Jang, Myoseon; Kamens, Richard M

    2003-09-15

    The partitioning behavior of a set of diverse SOCs on two and three component mixtures of aerosols from different sources was studied using smog chamber experimental data. A set of SOCs of different compound types was introduced into a system containing a mixture of aerosols from two or more sources. Gas and particle samples were taken using a filter-filter-denuder sampling system, and a partitioning coefficient Kp was estimated using Kp = Cp/(CgTSP). Particle size distributions were measured using a differential mobility analyzer and a light scattering detector. Gas and particle samples were analyzed using GCMS. The aerosol composition in the chamber was tracked chemically using a combination of signature compounds and the organic matter mass fraction (f(om)) of the individual aerosol sources. The physical nature of the aerosol mixture in the chamber was determined using particle size distributions, and an aggregate Kp was estimated from theoretically calculated Kp on the individual sources. Model fits for Kp showed that when the mixture involved primary sources of aerosol, the aggregate Kp of the mixture could be successfully modeled as an external mixture of the Kp on the individual aerosols. There were significant differences observed for some SOCs between modeling the system as an external and as an internal mixture. However, when one of the aerosol sources was secondary, the aggregate model Kp required incorporation of the secondary aerosol products on the preexisting aerosol for adequate model fits. Modeling such a system as an external mixture grossly overpredicted the Kp of alkanes in the mixture. Indirect evidence of heterogeneous, acid-catalyzed reactions in the particle phase was also seen, leading to a significant increase in the polarity of the resulting aerosol mix and a resulting decrease in the observed Kp of alkanes in the chamber. The model was partly consistent with this decrease but could not completely explain the reduction in Kp because of

  7. Determination of single photon ionization cross sections for quantitative analysis of complex organic mixtures.

    PubMed

    Adam, Thomas; Zimmermann, Ralf

    2007-11-01

    Soft single photon ionization (SPI)-time-of-flight mass spectrometry (TOFMS) is well suited for fast and comprehensive analysis of complex organic gas mixtures, which has been demonstrated in various applications. This work describes a calibration scheme for SPI, which enables quantification of a large number of compounds by only calibrating one compound of choice, in this case benzene. Photoionization cross sections of 22 substances were determined and related to the yield of benzene. These substances included six alkanes (pentane, hexane, heptane, octane, nonane, decane), three alkenes (propene, butane, pentene), two alkynes (propyne, butyne), two dienes (butadiene, isoprene), five monoaromatic species (benzene, toluene, xylene, styrene, monochlorobenzene) and NO. The cross sections of organic compounds differ by about one order of magnitude but the photoionization properties of compounds belonging to one compound class are rather similar. Therefore, the scheme can also be used for an approximate quantification of compound classes. This is demonstrated by a fast characterization and pattern recognition of two gasoline samples with different origins (Germany and South Africa) and a diesel sample (Germany). The on-line capability of the technique and the scheme is demonstrated by quantitatively monitoring and comparing the cold engine start of four vehicles: a gasoline passenger car, a diesel van, a motorbike and a two-stroke scooter.

  8. Improved electrolytes for Li-ion batteries: Mixtures of ionic liquid and organic electrolyte with enhanced safety and electrochemical performance

    NASA Astrophysics Data System (ADS)

    Guerfi, A.; Dontigny, M.; Charest, P.; Petitclerc, M.; Lagacé, M.; Vijh, A.; Zaghib, K.

    Physical and electrochemical characteristics of Li-ion battery systems based on LiFePO 4 cathodes and graphite anodes with mixture electrolytes were investigated. The mixed electrolytes are based on an ionic liquid (IL), and organic solvents used in commercial batteries. We investigated a range of compositions to determine an optimum conductivity and non-flammability of the mixed electrolyte. This led us to examine mixtures of ILs with the organic electrolyte usually employed in commercial Li-ion batteries, i.e., ethylene carbonate (EC) and diethylene carbonate (DEC). The IL electrolyte consisted of (trifluoromethyl sulfonylimide) (TFSI) as anion and 1-ethyl-3-methyleimidazolium (EMI) as the cation. The physical and electrochemical properties of some of these mixtures showed an improvement characteristics compared to the constituents alone. The safety was improved with electrolyte mixtures; when IL content in the mixture is ≥40%, no flammability is observed. A stable SEI layer was obtained on the MCMB graphite anode in these mixed electrolytes, which is not obtained with IL containing the TFSI-anion. The high-rate capability of LiFePO 4 is similar in the organic electrolyte and the mixture with a composition of 1:1. The interface resistance of the LiFePO 4 cathode is stabilized when the IL is added to the electrolyte. A reversible capacity of 155 mAh g -1 at C/12 is obtained with cells having at least some organic electrolyte compared to only 124 mAh g -1 with pure IL. With increasing discharge rate, the capacity is maintained close to that in the organic solvent up to 2 C rate. At higher rates, the results with mixture electrolytes start to deviate from the pure organic electrolyte cell. The evaluation of the Li-ion cells; LiFePO 4//Li 4Ti 5O 12 with organic and, 40% mixture electrolytes showed good 1st CE at 98.7 and 93.0%, respectively. The power performance of both cell configurations is comparable up to 2 C rate. This study indicates that safety and

  9. An assessment of air quality reflecting the chemosensory irritation impact of mixtures of volatile organic compounds.

    PubMed

    Abraham, Michael H; Gola, Joelle M R; Cometto-Muñiz, J Enrique

    2016-01-01

    We present a method to assess the air quality of an environment based on the chemosensory irritation impact of mixtures of volatile organic compounds (VOCs) present in such environment. We begin by approximating the sigmoid function that characterizes psychometric plots of probability of irritation detection (Q) versus VOC vapor concentration to a linear function. First, we apply an established equation that correlates and predicts human sensory irritation thresholds (SIT) (i.e., nasal and eye irritation) based on the transfer of the VOC from the gas phase to biophases, e.g., nasal mucus and tear film. Second, we expand the equation to include other biological data (e.g., odor detection thresholds) and to include further VOCs that act mainly by "specific" effects rather than by transfer (i.e., "physical") effects as defined in the article. Then we show that, for 72 VOCs in common, Q values based on our calculated SITs are consistent with the Threshold Limit Values (TLVs) listed for those same VOCs on the basis of sensory irritation by the American Conference of Governmental Industrial Hygienists (ACGIH). Third, we set two equations to calculate the probability (Qmix) that a given air sample containing a number of VOCs could elicit chemosensory irritation: one equation based on response addition (Qmix scale: 0.00 to 1.00) and the other based on dose addition (1000*Qmix scale: 0 to 2000). We further validate the applicability of our air quality assessment method by showing that both Qmix scales provide values consistent with the expected sensory irritation burden from VOC mixtures present in a wide variety of indoor and outdoor environments as reported on field studies in the literature. These scales take into account both the concentration of VOCs at a particular site and the propensity of the VOCs to evoke sensory irritation.

  10. An assessment of air quality reflecting the chemosensory irritation impact of mixtures of volatile organic compounds.

    PubMed

    Abraham, Michael H; Gola, Joelle M R; Cometto-Muñiz, J Enrique

    2016-01-01

    We present a method to assess the air quality of an environment based on the chemosensory irritation impact of mixtures of volatile organic compounds (VOCs) present in such environment. We begin by approximating the sigmoid function that characterizes psychometric plots of probability of irritation detection (Q) versus VOC vapor concentration to a linear function. First, we apply an established equation that correlates and predicts human sensory irritation thresholds (SIT) (i.e., nasal and eye irritation) based on the transfer of the VOC from the gas phase to biophases, e.g., nasal mucus and tear film. Second, we expand the equation to include other biological data (e.g., odor detection thresholds) and to include further VOCs that act mainly by "specific" effects rather than by transfer (i.e., "physical") effects as defined in the article. Then we show that, for 72 VOCs in common, Q values based on our calculated SITs are consistent with the Threshold Limit Values (TLVs) listed for those same VOCs on the basis of sensory irritation by the American Conference of Governmental Industrial Hygienists (ACGIH). Third, we set two equations to calculate the probability (Qmix) that a given air sample containing a number of VOCs could elicit chemosensory irritation: one equation based on response addition (Qmix scale: 0.00 to 1.00) and the other based on dose addition (1000*Qmix scale: 0 to 2000). We further validate the applicability of our air quality assessment method by showing that both Qmix scales provide values consistent with the expected sensory irritation burden from VOC mixtures present in a wide variety of indoor and outdoor environments as reported on field studies in the literature. These scales take into account both the concentration of VOCs at a particular site and the propensity of the VOCs to evoke sensory irritation. PMID:26550706

  11. Health Effects of a Mixture of Indoor Air Volatile Organics, Their Ozone Oxidation Products, and Stress

    PubMed Central

    Fiedler, Nancy; Laumbach, Robert; Kelly-McNeil, Kathie; Lioy, Paul; Fan, Zhi-Hua; Zhang, Junfeng; Ottenweller, John; Ohman-Strickland, Pamela; Kipen, Howard

    2005-01-01

    In our present study we tested the health effects among women of controlled exposures to volatile organic compounds (VOCs), with and without ozone (O3), and psychological stress. Each subject was exposed to the following three conditions at 1-week intervals (within-subject factor): VOCs (26 mg/m3), VOCs + O3 (26 mg/m3 + 40 ppb), and ambient air with a 1-min spike of VOCs (2.5 mg/m3). As a between-subjects factor, half the subjects were randomly assigned to perform a stressor. Subjects were 130 healthy women (mean age, 27.2 years; mean education, 15.2 years). Health effects measured before, during, and after each 140-min exposure included symptoms, neurobehavioral performance, salivary cortisol, and lung function. Mixing VOCs with O3 was shown to produce irritating compounds including aldehydes, hydrogen peroxide, organic acids, secondary organic aerosols, and ultrafine particles (particulate matter with aerodynamic diameter < 0.1 μm). Exposure to VOCs with and without O3 did not result in significant subjective or objective health effects. Psychological stress significantly increased salivary cortisol and symptoms of anxiety regardless of exposure condition. Neither lung function nor neurobehavioral performance was compromised by exposure to VOCs or VOCs + O3. Although numerous epidemiologic studies suggest that symptoms are significantly increased among workers in buildings with poor ventilation and mixtures of VOCs, our acute exposure study was not consistent with these epidemiologic findings. Stress appears to be a more significant factor than chemical exposures in affecting some of the health end points measured in our present study. PMID:16263509

  12. Persistence and potential effects of complex organic contaminant mixtures in wastewater-impacted streams.

    PubMed

    Barber, Larry B; Keefe, Steffanie H; Brown, Greg K; Furlong, Edward T; Gray, James L; Kolpin, Dana W; Meyer, Michael T; Sandstrom, Mark W; Zaugg, Steven D

    2013-03-01

    Natural and synthetic organic contaminants in municipal wastewater treatment plant (WWTP) effluents can cause ecosystem impacts, raising concerns about their persistence in receiving streams. In this study, Lagrangian sampling, in which the same approximate parcel of water is tracked as it moves downstream, was conducted at Boulder Creek, Colorado and Fourmile Creek, Iowa to determine in-stream transport and attenuation of organic contaminants discharged from two secondary WWTPs. Similar stream reaches were evaluated, and samples were collected at multiple sites during summer and spring hydrologic conditions. Travel times to the most downstream (7.4 km) site in Boulder Creek were 6.2 h during the summer and 9.3 h during the spring, and to the Fourmile Creek 8.4 km downstream site times were 18 and 8.8 h, respectively. Discharge was measured at each site, and integrated composite samples were collected and analyzed for >200 organic contaminants including metal complexing agents, nonionic surfactant degradates, personal care products, pharmaceuticals, steroidal hormones, and pesticides. The highest concentration (>100 μg L(-1)) compounds detected in both WWTP effluents were ethylenediaminetetraacetic acid and 4-nonylphenolethoxycarboxylate oligomers, both of which persisted for at least 7 km downstream from the WWTPs. Concentrations of pharmaceuticals were lower (<1 μg L(-1)), and several compounds, including carbamazepine and sulfamethoxazole, were detected throughout the study reaches. After accounting for in-stream dilution, a complex mixture of contaminants showed little attenuation and was persistent in the receiving streams at concentrations with potential ecosystem implications. PMID:23398602

  13. An Analytical Method to Measure Free-Water Tritium in Foods using Azeotropic Distillation.

    PubMed

    Soga, Keisuke; Kamei, Toshiyuki; Hachisuka, Akiko; Nishimaki-Mogami, Tomoko

    2016-01-01

    A series of accidents at the Fukushima Dai-ichi Nuclear Power Plant has raised concerns about the discharge of contaminated water containing tritium ((3)H) from the nuclear power plant into the environment and into foods. In this study, we explored convenient analytical methods to measure free-water (3)H in foods using a liquid scintillation counting and azeotropic distillation method. The detection limit was 10 Bq/L, corresponding to about 0.01% of 1 mSv/year. The (3)H recoveries were 85-90% in fruits, vegetables, meats and fishes, 75-85% in rice and cereal crops, and less than 50% in sweets containing little water. We found that, in the case of sweets, adding water to the sample before the azeotropic distillation increased the recovery and precision. Then, the recoveries reached more than 75% and RSD was less than 10% in all food categories (13 kinds). Considering its sensitivity, precision and simplicity, this method is practical and useful for (3)H analysis in various foods, and should be suitable for the safety assessment of foods. In addition, we examined the level of (3)H in foods on the Japanese market. No (3)H radioactivity was detected in any of 42 analyzed foods. PMID:27558225

  14. An Analytical Method to Measure Free-Water Tritium in Foods using Azeotropic Distillation.

    PubMed

    Soga, Keisuke; Kamei, Toshiyuki; Hachisuka, Akiko; Nishimaki-Mogami, Tomoko

    2016-01-01

    A series of accidents at the Fukushima Dai-ichi Nuclear Power Plant has raised concerns about the discharge of contaminated water containing tritium ((3)H) from the nuclear power plant into the environment and into foods. In this study, we explored convenient analytical methods to measure free-water (3)H in foods using a liquid scintillation counting and azeotropic distillation method. The detection limit was 10 Bq/L, corresponding to about 0.01% of 1 mSv/year. The (3)H recoveries were 85-90% in fruits, vegetables, meats and fishes, 75-85% in rice and cereal crops, and less than 50% in sweets containing little water. We found that, in the case of sweets, adding water to the sample before the azeotropic distillation increased the recovery and precision. Then, the recoveries reached more than 75% and RSD was less than 10% in all food categories (13 kinds). Considering its sensitivity, precision and simplicity, this method is practical and useful for (3)H analysis in various foods, and should be suitable for the safety assessment of foods. In addition, we examined the level of (3)H in foods on the Japanese market. No (3)H radioactivity was detected in any of 42 analyzed foods.

  15. COMPARISON OF SORPTION ENERGTICS FOR HYDROPHOBIC ORGANIC CHEMICALS BY SYNTHETIC AND NATURAL SORBENTS FROM METHANOL/WATER SOLVENT MIXTURES

    EPA Science Inventory

    Reversed-phase liquid chromatography (RPLC) was used to investigate the thermodynamics and mechanisms of hydrophobic organic chemical (HOC) retention from methanol/water solvent mixtures. The enthalpy-entropy compensation model was used to infer that the hydro- phobic sorptive me...

  16. A COMPARISON OF THE LETHAL AND SUBLETHAL TOXICITY OF ORGANIC CHEMICAL MIXTURES TO THE FATHEAD MINNOW (PIMEPHALES PROMELAS)

    EPA Science Inventory

    The joint toxic effects of known binary and multiple organic chemical mixtures to the fathead minnow (Pimephales promelas) were defined at both the 96-h 50% lethal effect concentration (LC50) and sublethal (32-d growth) response levels for toxicants with a narcosis I, narcosis II...

  17. Exposure of humans to a volatile organic mixture. 3. Inflammatory response

    SciTech Connect

    Koren, H.S.; Graham, D.E.; Devlin, R.B.

    1992-01-01

    A set of symptoms has been described during the past two decades that has been called the sick building syndrome. These symptoms include eye, nose, and throat irritation; headache; mental fatigue; and respiratory distress. It is likely that the volatile organic compounds (VOCs) present in synthetic materials used in homes and office buildings contribute to these symptoms. However, there have been very few studies in which humans have been exposed to known amounts of VOCs under carefully controlled conditions. In the study, 14 subjects were exposed to a mixture of VOCs (25 mg/sq meter total hydrocarbon) that is representative of what is found in new homes and office buildings. Because irritations of the nose and throat are symptoms often associated with the upper respiratory tract and may result from an inflammatory response in the upper airways, the authors used nasal lavage to monitor neutrophil (PMN) influx into the nasal passages following exposure to VOCs. There were statistically significant increases in PMNs, both immediately after a 4-h exposure to VOCs and 18 h later.

  18. Structure of Cholesterol/Ceramide Monolayer Mixtures: Implications to the Molecular Organization of Lipid Rafts

    PubMed Central

    Scheffer, Luana; Solomonov, Inna; Weygand, Markus Jan; Kjaer, Kristian; Leiserowitz, Leslie; Addadi, Lia

    2005-01-01

    The structure of monolayers of cholesterol/ceramide mixtures was investigated using grazing incidence x-ray diffraction, immunofluorescence, and atomic force microscopy techniques. Grazing incidence x-ray diffraction measurements showed the existence of a crystalline mixed phase of the two components within a range of compositions of cholesterol/ceramide between 100:0 and 67:33. The mixed phase coexists with the ceramide crystalline phase in the range of compositions between 50:50 and 30:70; between 30:70 and 0:100 only the highly crystalline phase of ceramide was detected. The latter was determined and modeled. Immunolabeling was performed with an antibody specific to the cholesterol monohydrate crystalline arrangement. The antibody recognizes crystalline cholesterol monolayers, but does not interact with crystalline ceramide. Immunofluorescence and atomic force microscopy data show that in uncompressed ceramide monolayers, the highly crystalline phase coexists with a disordered loosely packed phase. In contrast, no disordered phase coexists with the new crystalline mixed phase. We conclude that the new mixed phase represents a stable homogeneous arrangement of cholesterol with ceramide. As ceramide incorporates the lipid backbone common to all sphingolipids, this arrangement may be relevant to the understanding of the molecular organization of lipid rafts. PMID:15722431

  19. Micellization of alkyl-propoxy-ethoxylate surfactants in water-polar organic solvent mixtures.

    PubMed

    Sarkar, Biswajit; Lam, Stephanie; Alexandridis, Paschalis

    2010-07-01

    The effects of cosolvents (glycerol, ethanol, and isopropanol) on the self-assembly of novel alkyl-propoxy-ethoxylate surfactants in aqueous solutions have been investigated with a focus on the (i) quantification of solvent effects on the critical micelle concentration (cmc), (ii) free-energy contributions to micellization, (iii) local environment in the micellar solution, and (iv) structure of the micelles. The introduction of the polar organic solvents considered in this work into water decreases cohesive forces in the solvent mixture, resulting in an increase in the solubility of the surfactant molecules. As a result, micelle formation becomes less favorable and the cmc increases. The contribution of the cosolvent to the free energy of micellization is positive, and the data for different mixed solvents collapse onto a single straight line when plotted versus a function of the solubility parameters of the surfactant alkyl chains and the mixed solvents. The behavior of the poly(propylene oxide) part of the alkyl-propoxy-ethoxylate surfactants is hydrophilic, albeit less so in the ethanol-water mixed solvent than in plain water. Pyrene fluorescence emission I(1)/I(3) data suggest that the microenvironment in micellar solutions is affected mainly by the cosolvent concentration, not the surfactant degree of ethoxylation. Small-angle X-ray scattering data for both water and ethanol-water surfactant solutions are consistent with oblate ellipsoid micelles and reveal that the introduction of 20% ethanol decreases the micelle long axis by 10-15%.

  20. Human reactions to a mixture of indoor air volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kjærgaard, Søren K.; Mølhave, Lars; Pedersen, Ole F.

    A controlled experimental study of human reactions to a mixture of 22 volatile organic compounds often found in indoor air was performed in a climate chamber. Twenty-one healthy subjects were compared with a group of 14 subjects suffering from the 'sick building syndrome' (SBS subjects), i.e. having symptoms related to the indoor environment (irritated mucous membranes, headache, etc.) as defined by WHO in 1982. In groups of 4 these subjects were exposed during two successive periods to either 0 and 0 mg m -3, 25 and 0 mg m -3, or 0 and 25 mg m -3; 25 mg m -3 is equivalent to the highest concentrations expected in a new building. The study was double blinded, and a latin square design was used to balance out effects of day in the week and season. Both groups reacted subjectively to the air reporting worse odor, worse indoor air quality as defined by the subject, and more irritated mucous membranes in eye, throat and nose than in the clean environment. A tendency to a stronger response was seen among the SBS subjects. Objective measures indicated among others an exposure related reduction in lung function among SBS subjects. Both groups had an increased number of polymorphonuclear leucocytes in tear fluid as a result of exposure. This was not seen for nasal secretions. Psychological performance tests indicated an exposure related diminished ability to learn. In conclusion, the experiment indicates that exposure to volatile organic compounds in low concentrations as seen in new houses causes both subjective complaints and objective signs in normal healty subjects; but more so in subjects from the sick building syndrome.

  1. Transmission geometry laser desorption atmospheric pressure photochemical ionization mass spectrometry for analysis of complex organic mixtures.

    PubMed

    Nyadong, Leonard; Mapolelo, Mmilili M; Hendrickson, Christopher L; Rodgers, Ryan P; Marshall, Alan G

    2014-11-18

    We present laser desorption atmospheric pressure photochemical ionization mass spectrometry (LD/APPCI MS) for rapid throughput analysis of complex organic mixtures, without the need for matrix, electric discharge, secondary electrospray, or solvents/vaporizers. Analytes dried on a microscope slide are vaporized in transmission geometry by a laser beam aligned with the atmospheric pressure inlet of the mass spectrometer. The laser beam initiates a cascade of reactions in the region between the glass slide and MS inlet, leading to generation of reagent ions for chemical ionization of vaporized analyte. Positive analyte ions are generated predominantly by proton transfer, charge exchange, and hydride abstraction, whereas negative ions are generated by electron capture or proton transfer reactions, enabling simultaneous analysis of saturated, unsaturated, and heteroatom-containing hydrocarbons. The absence of matrix interference renders LD/APPCI MS particularly useful for analysis of small molecules (<2000 Da) such as those present in petroleum crude oil and petroleum deposits. [M + H](+) and M(+•) dominate the positive-ion mass spectra for olefins and polyaromatic hydrocarbons, whereas saturated hydrocarbons are observed mainly as [M - H](+) and/or M(+•). Heteroatom-containing hydrocarbons are observed predominantly as [M + H](+). [M - H](-) and M(-•) are the dominant negative ions observed for analytes of lower gas-phase basicity or higher electron affinity than O2. The source was coupled with a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer (FTICR MS) to resolve and identify thousands of peaks from Athabasca bitumen heavy vacuum gas oil distillates (400-425 and 500-538 °C), enabling simultaneous characterization of their polar and nonpolar composition. We also applied LD/APPCI FTICR MS for rapid analysis of sodium and calcium naphthenate deposits with little to no sample pretreatment to provide mass spectral fingerprints that enable

  2. Transmission geometry laser desorption atmospheric pressure photochemical ionization mass spectrometry for analysis of complex organic mixtures.

    PubMed

    Nyadong, Leonard; Mapolelo, Mmilili M; Hendrickson, Christopher L; Rodgers, Ryan P; Marshall, Alan G

    2014-11-18

    We present laser desorption atmospheric pressure photochemical ionization mass spectrometry (LD/APPCI MS) for rapid throughput analysis of complex organic mixtures, without the need for matrix, electric discharge, secondary electrospray, or solvents/vaporizers. Analytes dried on a microscope slide are vaporized in transmission geometry by a laser beam aligned with the atmospheric pressure inlet of the mass spectrometer. The laser beam initiates a cascade of reactions in the region between the glass slide and MS inlet, leading to generation of reagent ions for chemical ionization of vaporized analyte. Positive analyte ions are generated predominantly by proton transfer, charge exchange, and hydride abstraction, whereas negative ions are generated by electron capture or proton transfer reactions, enabling simultaneous analysis of saturated, unsaturated, and heteroatom-containing hydrocarbons. The absence of matrix interference renders LD/APPCI MS particularly useful for analysis of small molecules (<2000 Da) such as those present in petroleum crude oil and petroleum deposits. [M + H](+) and M(+•) dominate the positive-ion mass spectra for olefins and polyaromatic hydrocarbons, whereas saturated hydrocarbons are observed mainly as [M - H](+) and/or M(+•). Heteroatom-containing hydrocarbons are observed predominantly as [M + H](+). [M - H](-) and M(-•) are the dominant negative ions observed for analytes of lower gas-phase basicity or higher electron affinity than O2. The source was coupled with a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer (FTICR MS) to resolve and identify thousands of peaks from Athabasca bitumen heavy vacuum gas oil distillates (400-425 and 500-538 °C), enabling simultaneous characterization of their polar and nonpolar composition. We also applied LD/APPCI FTICR MS for rapid analysis of sodium and calcium naphthenate deposits with little to no sample pretreatment to provide mass spectral fingerprints that enable

  3. Numerical and experimental investigation of the impact of organic chemical mixtures on DNAPL migration and distribution in unsaturated porous media

    NASA Astrophysics Data System (ADS)

    Yoon, H.; Oostrom, M.; Wietsma, T. W.; Valocchi, A. J.; Werth, C. J.

    2009-12-01

    Two intermediate-scale flow cell experiments were conducted in order to account for the impact of organic chemical mixtures and wastewater properties on dense non-aqueous phase liquid (DNAPL) migration and distribution in a layered vadose zone. The flow cell was packed with two sandy soils including an embedded fine sand lens. For the two experiments, pure carbon tetrachloride (CT) and an organic mixture containing CT and three different surface-active chemicals were injected at the top of the flow cell, respectively. Numerous photos and video images were taken, and a dual-energy gamma radiation system was used to measure initial and final NAPL saturation profiles in the flow cell. For both cases, the NAPL front reached the top interface of coarse- and fine-grained sands very quickly. After the NAPL front reached the bottom of the fine lens, the pure CT quickly penetrated through the bottom of fine lens, resulting in multiple fingers at the interface of fine and coarse sands, while the mixture moved horizontally at the bottom of the fine lens without penetrating, resulting in higher NAPL saturations in the fine lens. Continuum-based multiphase flow simulation results predicted that the pure CT would penetrate through the bottom of the fine lens, while the mixture would not. Simulation results indicate that higher density, lower viscosity, and higher surface tension values for pure CT relative to the mixture can increase the total NAPL pressure of pure CT at the interface of the fine lens when the CT front reaches the bottom of the fine lens, resulting in overcoming the capillary barrier effect at the interface. However, simulations significantly under-predicted the amount of CT penetrating through the fine lens. The effect of water saturation and chemical properties on finger formation will be discussed. The effect of organic and aqueous phase properties on NAPL distribution at the field scale will be also explored through a case study.

  4. Structural features of polymer adsorbent LiChrolut EN and interfacial behavior of water and water/organic mixtures.

    PubMed

    Gun'ko, V M; Turov, V V; Zarko, V I; Nychiporuk, Y M; Goncharuk, E V; Pakhlov, E M; Yurchenko, G R; Kulik, T V; Palyanytsya, B B; Borodavka, T V; Krupskaya, T V; Leboda, R; Skubiszewska-Zieba, J; Osovskii, V D; Ptushinskii, Y G; Turov, A V

    2008-07-01

    The structural and adsorption characteristics of polymer adsorbent LiChrolut EN and the behavior of adsorbed water and water/organic mixtures were studied using adsorption, microcalorimetry, transmission and scanning electron microscopy, mass spectrometry, infrared spectroscopy, 1H NMR spectroscopy with layer-by-layer freezing-out of liquids (190-273 K), and thermally stimulated depolarization current method (90-265 K). This adsorbent is characterized by large specific surface area (approximately 1500 m2/g) and pore volume (0.83 cm3/g) with a major contribution of narrow pores (R<10 nm) of a complicated shape (long hysteresis loop is in nitrogen adsorption-desorption isotherm). The adsorbent includes aromatic and aliphatic structures and oxygen-containing functionalities and can effectively adsorb organics and water/organic mixtures. On co-adsorption of water and organics (dimethyl sulfoxide, chloroform, methane), there is a weak influence of one on another adsorbate due to their poor mixing in pores. Weakly polar chloroform displaces a fraction of water from narrow pores. These effects can explain high efficiency of the adsorbent in solid-phase extraction of organics from aqueous solutions. The influence of structural features of several carbon and polymer adsorbents on adsorbed nitrogen, water and water/organics is compared on the basis of the adsorption and 1H NMR data. PMID:18440015

  5. Adsorption of a polymeric siloxane surfactant on carbon black particles dispersed in mixtures of water with polar organic solvents.

    PubMed

    Lin, Yining; Smith, Thomas W; Alexandridis, Paschalis

    2002-11-01

    The adsorption of a rake-type polymeric siloxane surfactant (polydimethylsiloxane-graft-polyether copolymer) on carbon black (CB) particles dispersed in mixtures of water with polar organic solvents (ethanol, formamide, or glycerol) has been investigated. The adsorption obeys the Langmuir isotherm at low surfactant concentrations (below the critical micelle concentration, CMC). At these conditions, the average surface area occupied by one siloxane surfactant follows the sequence water+glycerol mixture >plain water >water+ethanol mixture. At higher surfactant concentrations in the solution in contact with the particles, a sharp increase in the adsorbed amount is observed. The adsorbed layer thickness has been determined by dynamic light scattering. Below the CMC the adsorbed layer thickness is less than 10 nm. Above the CMC, the adsorbed layer thickness increases to 20-30 nm, a length scale comparable to the diameter of the siloxane surfactant micelles in aqueous solution. This fact, together with SANS data that we have obtained in the absence of added polar organic solvent, indicates that the structure of the adsorbed layer is similar to that of micelles. The findings presented here are relevant to waterborne coatings and ink formulations, where polymeric surfactants are used in conjunction with polar organic solvents.

  6. Suppression of sourness: a comparative study involving mixtures of organic acids and sugars.

    PubMed

    Savant, Lotika; McDaniel, Mina R

    2004-05-01

    The degree of sourness suppression of perceptually equisour levels of citric, lactic, and malic acids by equal molar and weight amounts of sucrose, fructose, and glucose was determined in binary mixtures. Equisour acid levels were obtained by magnitude estimation. Mixture intensity ratings were collected on a categorical scale, using trained panelists. In general, equal sugar molarities and weights did not effect equivalent suppression. Instead, the perceived intensity of the sugars appeared to suppress sourness more systematically, implying that dominantly central neural mechanisms underlie suppression. This was confirmed when no significant differences were found between the suppressive abilities of sweetness-matched levels of sucrose, fructose, and an equiratio mixture of the two on citric acid sourness. The possibility of a separate receptor site/mechanism for glucose and a small peripheral component to suppression is also suggested.

  7. Pervaporation Separation of Water-Ethanol Mixtures Using Organic-Inorganic Nanocomposite Membranes

    EPA Science Inventory

    Preyssler type heteropolyacid viz., H14[NaP5W30O110] incorporated chitosan nanocomposite membranes (NCMs) were prepared by solution casting, characterized using a variety of techniques and employed in the pervaporation separation of water-ethanol mixtures as a function of feed wa...

  8. Sputtering Yields for Mixtures of Organic Materials Using Argon Gas Cluster Ions.

    PubMed

    Seah, M P; Havelund, R; Shard, A G; Gilmore, I S

    2015-10-22

    The sputtering yield volumes of binary mixtures of Irganox 1010 with either Irganox 1098 or Fmoc-pentafluoro-L-phenylalanine (FMOC) have been measured for 5 keV Ar2000(+) ions incident at 45° to the surface normal. The sputtering yields are determined from the doses to sputter through various compositions of 100 nm thick, intimately mixed, layers. Because of matrix effects, the profiles for secondary ions are distorted, and profile shifts in depth of 15 nm are observed leading to errors above 20% in the deduced sputtering yield. Secondary ions are selected to avoid this. The sputtering yield volumes for the mixtures are shown to be lower than those deduced from a linear interpolation from the pure materials. This is shown to be consistent with a simple model involving the changing energy absorbed for the sputtering of intimate mixtures. Evidence to support this comes from the secondary ion data for pairs of the different molecules. Both binary mixtures behave similarly, but matrix effects are stronger for the Irganox 1010/FMOC system.

  9. Binary Mixtures of Permanganate and Chlorinated Volatile Organic Compounds in Groundwater Samples: Sample Preservation and Analysis

    EPA Science Inventory

    Ground water samples collected at sites where in-situ chemical oxidation (ISCO) has been deployed may contain binary mixtures of ground water contaminants and permanganate (MnO4-), an oxidant injected into the subsurface to destroy the contaminant. Commingling of the oxidant and ...

  10. Influence of Wetting and Mass Transfer Properties of Organic Chemical Mixtures in Vadose Zone Materials on Groundwater Contamination by Nonaqueous Phase Liquids

    SciTech Connect

    Charles J Werth; Albert J Valocchi, Hongkyu Yoon

    2011-05-21

    Previous studies have found that organic acids, organic bases, and detergent-like chemicals change surface wettability. The wastewater and NAPL mixtures discharged at the Hanford site contain such chemicals, and their proportions likely change over time due to reaction-facilitated aging. The specific objectives of this work were to (1) determine the effect of organic chemical mixtures on surface wettability, (2) determine the effect of organic chemical mixtures on CCl4 volatilization rates from NAPL, and (3) accurately determine the migration, entrapment, and volatilization of organic chemical mixtures. Five tasks were proposed to achieve the project objectives. These are to (1) prepare representative batches of fresh and aged NAPL-wastewater mixtures, (2) to measure interfacial tension, contact angle, and capillary pressure-saturation profiles for the same mixtures, (3) to measure interphase mass transfer rates for the same mixtures using micromodels, (4) to measure multiphase flow and interphase mass transfer in large flow cell experiments, all using the same mixtures, and (5) to modify the multiphase flow simulator STOMP in order to account for updated P-S and interphase mass transfer relationships, and to simulate the impact of CCl4 in the vadose zone on groundwater contamination. Results and findings from these tasks and summarized in the attached final report.

  11. Rapid removal of selected volatile organic compounds from gaseous mixtures using a new dispersive vapor extraction technique: a feasibility study.

    PubMed

    Farrell, E S; Pacey, G E

    2010-07-15

    A new dispersive vapor extraction (DVE) technique for rapid removal of selected volatile organic compounds (VOCs) from gaseous mixtures was investigated. In this technique, less than 1.0 mL of a volatile solvent was vaporized for 8 min in a 250-mL flask containing a gaseous mixture. The flask was then cooled under running tap water for 2-3 min to induce condensation of the vapor and co-extraction of the VOCs from the headspace. The technique was tested over a concentration range of 4-23 ppb, and resulted in extraction efficiencies ranging from 80 to 97% for the VOCs tested. Because of its simplicity and the relatively short sampling time, DVE could potentially lead to high sample throughput and rapid air analysis.

  12. Microporous metal–organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures

    PubMed Central

    Hu, Tong-Liang; Wang, Hailong; Li, Bin; Krishna, Rajamani; Wu, Hui; Zhou, Wei; Zhao, Yunfeng; Han, Yu; Wang, Xue; Zhu, Weidong; Yao, Zizhu; Xiang, Shengchang; Chen, Banglin

    2015-01-01

    The removal of acetylene from ethylene/acetylene mixtures containing 1% acetylene is a technologically very important, but highly challenging task. Current removal approaches include the partial hydrogenation over a noble metal catalyst and the solvent extraction of cracked olefins, both of which are cost and energy consumptive. Here we report a microporous metal–organic framework in which the suitable pore/cage spaces preferentially take up much more acetylene than ethylene while the functional amine groups on the pore/cage surfaces further enforce their interactions with acetylene molecules, leading to its superior performance for this separation. The single X-ray diffraction studies, temperature dependent gas sorption isotherms, simulated and experimental column breakthrough curves and molecular simulation studies collaboratively support the claim, underlying the potential of this material for the industrial usage of the removal of acetylene from ethylene/acetylene mixtures containing 1% acetylene at room temperature through the cost- and energy-efficient adsorption separation process. PMID:26041691

  13. Complex mixture analysis of organic compounds in green coffee bean extract by two-dimensional NMR spectroscopy.

    PubMed

    Wei, Feifei; Furihata, Kazuo; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2010-11-01

    A complex mixture analysis by one- and two-dimensional nuclear magnetic resonance (NMR) spectroscopy was carried out for the first time for the identification and quantification of organic compounds in green coffee bean extract (GCBE). A combination of (1)H-(1)H DQF-COSY, (1)H-(13)C HSQC, and (1)H-(13)C CT-HMBC two-dimensional sequences was used, and 16 compounds were identified. In particular, three isomers of caffeoylquinic acid were identified in the complex mixture without any separation. In addition, GCBE components were quantified by the integration of carbon signals by use of a relaxation reagent and an inverse-gated decoupling method without a nuclear Overhauser effect. This NMR methodology provides detailed information about the kinds and amounts of GCBE components, and in our study, the chemical makeup of GCBE was clarified by the NMR results.

  14. Neurological and neurophysiological examinations of workers occupationally exposed to organic solvent mixtures used in the paint and varnish production.

    PubMed

    Indulski, J A; Sińczuk-Walczak, H; Szymczak, M; Wesołowski, W

    1996-01-01

    The aim of this work was to examine the nervous system of workers chronically exposed to mixtures of organic solvent at concentrations within or slightly exceeding the MAC values, used in the manufacture of paints and lacquers. The tests were performed on a group of 175 people, 107 men aged 22-59 (x = 41.25), and 68 women aged 20-55 (x = 38.62). The period of employment was x = 17.34 years and cumulative dose index 16.97 for males; for females, the corresponding values were x = 14.75 and x = 11.42, respectively. The control group included 175 people (107 men and 68 women) not exposed to chemicals matched according to sex, age, and work shift distribution. The neurological examinations included subjective and objective examinations of the nervous system, electroencephalographic (EEG) and visual evoked potential (VEP) evaluations. The assessment of organic solvent exposure was performed according to the method described in PN89/Z-04008/07, and the solvent mixtures were shown to contain xylenes, ethyltoluenes, trimethylbenzenes, propylbenzene, ethylbenzene, toluene, aliphatic hydrocarbons and the components of painter's naphtha. The most frequent complaints among the exposed males included headache, vertigo, concentration difficulties, sleep disorders, sleepiness during the day, increased emotional irritability, mood swings with a tendency to anxiety. The objective neurological examinations did not reveal organic lesions in the central or peripheral nervous systems. Generalised and paroxysmal changes were most common recordings in the abnormal EEG. VEP examinations revealed abnormalities, primarily in the latency of the response evoked. The results of this study suggest that exposures to concentrations within MAC values, or below 1.5 of the MAC values of organic solvents mixtures used in the manufacture of paints and lacquers produce subclinical health effect in the nervous system.

  15. Neurological and neurophysiological examinations of workers occupationally exposed to organic solvent mixtures used in the paint and varnish production.

    PubMed

    Indulski, J A; Sińczuk-Walczak, H; Szymczak, M; Wesołowski, W

    1996-01-01

    The aim of this work was to examine the nervous system of workers chronically exposed to mixtures of organic solvent at concentrations within or slightly exceeding the MAC values, used in the manufacture of paints and lacquers. The tests were performed on a group of 175 people, 107 men aged 22-59 (x = 41.25), and 68 women aged 20-55 (x = 38.62). The period of employment was x = 17.34 years and cumulative dose index 16.97 for males; for females, the corresponding values were x = 14.75 and x = 11.42, respectively. The control group included 175 people (107 men and 68 women) not exposed to chemicals matched according to sex, age, and work shift distribution. The neurological examinations included subjective and objective examinations of the nervous system, electroencephalographic (EEG) and visual evoked potential (VEP) evaluations. The assessment of organic solvent exposure was performed according to the method described in PN89/Z-04008/07, and the solvent mixtures were shown to contain xylenes, ethyltoluenes, trimethylbenzenes, propylbenzene, ethylbenzene, toluene, aliphatic hydrocarbons and the components of painter's naphtha. The most frequent complaints among the exposed males included headache, vertigo, concentration difficulties, sleep disorders, sleepiness during the day, increased emotional irritability, mood swings with a tendency to anxiety. The objective neurological examinations did not reveal organic lesions in the central or peripheral nervous systems. Generalised and paroxysmal changes were most common recordings in the abnormal EEG. VEP examinations revealed abnormalities, primarily in the latency of the response evoked. The results of this study suggest that exposures to concentrations within MAC values, or below 1.5 of the MAC values of organic solvents mixtures used in the manufacture of paints and lacquers produce subclinical health effect in the nervous system. PMID:8972166

  16. Stability of aspartame in water: organic solvent mixtures with different dielectric constants.

    PubMed

    Sanyude, S; Locock, R A; Pagliaro, L A

    1991-07-01

    In order to examine the influence of solvent composition on the stability of aspartame (N-alpha-L-aspartyl-L-phenylalanine-1-methyl ester) in solution (5 mg/mL), the degradation of aspartame was carried out in water:methanol, water:ethanol, and water:glycerine mixtures with dielectric constant values of 45, 55, and 65, respectively. The rate of disappearance of aspartame was measured by a sensitive HPLC assay. The degradation rate of aspartame increased as the dielectric constant of the solvent mixture decreased in all three solvents systems. For example, at 60 degrees C, the degradation rate constants were 4.1, 5.9, and 8.4 x 10(-3) h-1 at dielectric constant of 65, 55, and 45, respectively. From these results, it can be concluded that the stability of aspartame in aqueous solutions cannot be enhanced by the replacement of water by solvents of lower dielectric constant.

  17. Thermodynamic dissociation constant studies of caffeine at different temperatures and in organic water solvent mixture.

    PubMed

    Saeeduddin; Khanzada, A W K

    2004-01-01

    Thermodynamic dissociation studies have been carried out potentiometrically at various temperatures from 25 to 50 degrees C and in 10, 20, 30 and 40% v/v dioxane-water solvent mixture at 25 degrees C. The influence of temperature and nature of solvent on dissociation equilibria of caffeine is being investigated. A computer program in GW-BASIC has been used to calculate the pK values.

  18. Composition dependent structural organization in trihexyl(tetradecyl)phosphonium chloride ionic liquid-methanol mixtures

    SciTech Connect

    Gupta, Aditya; Sharma, Shobha; Kashyap, Hemant K.

    2015-04-07

    This article reports results from the molecular dynamics simulations on the structural arrangement of the ions and molecules in the mixtures of trihexyl(tetradecyl)phosphonium chloride ([P{sub 666,14}{sup +}][Cl{sup −}]) ionic liquid (IL) and methanol (MeOH) over the entire composition range. Effects of composition on the charge and polarity orderings have been investigated via computation of X-ray scattering structure function, S(q), and by using a partitioning scheme proposed for such multi-component mixtures. Except for the neat methanol liquid, the total S(q) shows two peaks in its intermolecular region for all the mole-fractions. The lowest q peak is dominated primarily by anion-anion, cation-anion, and methanol-anion correlations. Our results signify that the methanol bulk structure, which predominantly has short-distance characteristic correlations and is governed by polar group of methanol, is retained for x{sub IL} ≤ 0.1. Then, the mixture goes through gradual structural changes from methanol-like to the IL-like for 0.1 < x{sub IL} ≤ 0.7. The dipolar interaction between methanol molecules weakens in this range, and the structural landscape of the mixture is steered by strong ion-ion, anion-methanol, and nonpolar interactions. The IL-like structural arrangement is virtually recovered for x{sub IL} > 0.7. At all the compositions studied, while the cation head groups are predominantly solvated by anions and subsequently by methanol molecules, the polar hydroxyl group of methanol is preferentially solvated by the anions. The radial distribution functions of selected pair of atomic species have also confirmed these observations.

  19. Laboratory investigation of thermal degradation of a mixture of hazardous organic compounds. 1

    SciTech Connect

    Graham, J.L.; Hall, D.L.; Dellinger, B.

    1986-07-01

    In this report, the effect of oxygen concentration on the thermal stability of the components of a mixture of carbon tetrachloride, monochlorobenzene, 1,1,2-trichloro-,1,2,2-trifluoroethane (Freon 113 (Du Pont)), trichloroethylene, and toluene and the formation of thermal reaction products is examined. Thermal decomposition studies were conducted in atmospheres in which combustion oxygen was in excess, stoichiometric, and absent (pyrolysis). The components were also run individually in atmospheres with stoichiometric and excess oxygen. Results indicate that decreasing oxygen concentration increased the stability of the mixture components except Freon 113 and carbon tetrachloride. Furthermore, with the exception of Freon 113, each component was less stable in the mixture as compared to pure compound data. The stability of Freon 113 remained unchanged regardless of reaction atmosphere. It was found that the number and complexity of thermal reaction products increased with decreasing oxygen concentration. In all cases, products ranged from simple chlorinated aliphatics to complex polynuclear aromatics. 18 references, 7 figures, 2 tables.

  20. Band-selective excited ultrahigh resolution PSYCHE-TOCSY: fast screening of organic molecules and complex mixtures.

    PubMed

    Kakita, Veera Mohana Rao; Vemulapalli, Sahithya Phani Babu; Bharatam, Jagadeesh

    2016-04-01

    Precise assignments of (1) H atomic sites and establishment of their through-bond COSY or TOCSY connectivity are crucial for molecular structural characterization by using (1) H NMR spectroscopy. However, this exercise is often hampered by signal overlap, primarily because of (1) H-(1) H scalar coupling multiplets, even at typical high magnetic fields. The recent developments in homodecoupling strategies for effectively suppressing the coupling multiplets into nice singlets (pure-shift), particularly, Morris's advanced broadband pure-shift yielded by chirp excitation (PSYCHE) decoupling and ultrahigh resolution PSYCHE-TOCSY schemes, have shown new possibilities for unambiguous structural elucidation of complex organic molecules. The superior broadband PSYCHE-TOCSY exhibits enhanced performance over the earlier TOCSY methods, which however warrants prolonged experimental times due to the requirement of large number of dwell increments along the indirect dimension. Herein, we present fast and band-selective analog of the broadband PSYCHE-TOCSY, which is useful for analyzing complex organic molecules that exhibit characteristic yet crowded spectral regions. The simple pulse scheme relies on band-selective excitation (BSE) followed by PSYCHE homodecoupling in the indirect dimension. The BSE-PSYCHE-TOCSY has been exemplified for Estradiol and a complex carbohydrate mixture comprised of six constituents of closely comparable molecular weights. The experimental times are greatly reduced viz., ~20 fold for Estradiol and ~10 fold for carbohydrate mixture, with respect to the broadband PSYCHE-TOCSY. Furthermore, unlike the earlier homonuclear band-selective decoupling, the BSE-PSYCHE-decoupling provides fully decoupled pure-shift spectra for all the individual chemical sites within the excited band. The BSE-PSYCHE-TOCSY is expected to have significant potential for quick screening of complex organic molecules and mixtures at ultrahigh resolution. Copyright © 2015 John Wiley

  1. PROCEDURES FOR DERIVING EQUILIBRIUM PARTITIONING SEDIMENT BENCHMARKS (ESBS) FOR THE PROTECTION OF BENTHIC ORGANISMS: METALS MIXTURES (CADMIUM, COPPER, LEAD, NICKEL, SILVER, AND ZINC)

    EPA Science Inventory

    This equilibrium partitioning sediment benchmark (ESB) document describes procedures to derive concentrations of metal mixtures in sediment which are protective of the presence of benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it accounts for t...

  2. Effects of defined mixtures of persistent organic pollutants (POPs) on multiple cellular responses in the human hepatocarcinoma cell line, HepG2, using high content analysis screening.

    PubMed

    Wilson, Jodie; Berntsen, Hanne Friis; Zimmer, Karin Elisabeth; Frizzell, Caroline; Verhaegen, Steven; Ropstad, Erik; Connolly, Lisa

    2016-03-01

    Persistent organic pollutants (POPs) are toxic substances, highly resistant to environmental degradation, which can bio-accumulate and have long-range atmospheric transport potential. Most studies focus on single compound effects, however as humans are exposed to several POPs simultaneously, investigating exposure effects of real life POP mixtures on human health is necessary. A defined mixture of POPs was used, where the compound concentration reflected its contribution to the levels seen in Scandinavian human serum (total mix). Several sub mixtures representing different classes of POPs were also constructed. The perfluorinated (PFC) mixture contained six perfluorinated compounds, brominated (Br) mixture contained seven brominated compounds, chlorinated (Cl) mixture contained polychlorinated biphenyls and also p,p'-dichlorodiphenyldichloroethylene, hexachlorobenzene, three chlordanes, three hexachlorocyclohexanes and dieldrin. Human hepatocarcinoma (HepG2) cells were used for 2h and 48h exposures to the seven mixtures and analysis on a CellInsight™ NXT High Content Screening platform. Multiple cytotoxic endpoints were investigated: cell number, nuclear intensity and area, mitochondrial mass and membrane potential (MMP) and reactive oxygen species (ROS). Both the Br and Cl mixtures induced ROS production but did not lead to apoptosis. The PFC mixture induced ROS production and likely induced cell apoptosis accompanied by the dissipation of MMP. Synergistic effects were evident for ROS induction when cells were exposed to the PFC+Br mixture in comparison to the effects of the individual mixtures. No significant effects were detected in the Br+Cl, PFC+Cl or total mixtures, which contain the same concentrations of chlorinated compounds as the Cl mixture plus additional compounds; highlighting the need for further exploration of POP mixtures in risk assessment.

  3. Pesticide Toxicity Index: a tool for assessing potential toxicity of pesticide mixtures to freshwater aquatic organisms

    USGS Publications Warehouse

    Nowell, Lisa H.; Norman, Julia E.; Moran, Patrick W.; Martin, Jeffrey D.; Stone, Wesley W.

    2014-01-01

    Pesticide mixtures are common in streams with agricultural or urban influence in the watershed. The Pesticide Toxicity Index (PTI) is a screening tool to assess potential aquatic toxicity of complex pesticide mixtures by combining measures of pesticide exposure and acute toxicity in an additive toxic-unit model. The PTI is determined separately for fish, cladocerans, and benthic invertebrates. This study expands the number of pesticides and degradates included in previous editions of the PTI from 124 to 492 pesticides and degradates, and includes two types of PTI for use in different applications, depending on study objectives. The Median-PTI was calculated from median toxicity values for individual pesticides, so is robust to outliers and is appropriate for comparing relative potential toxicity among samples, sites, or pesticides. The Sensitive-PTI uses the 5th percentile of available toxicity values, so is a more sensitive screening-level indicator of potential toxicity. PTI predictions of toxicity in environmental samples were tested using data aggregated from published field studies that measured pesticide concentrations and toxicity to Ceriodaphnia dubia in ambient stream water. C. dubia survival was reduced to ≤ 50% of controls in 44% of samples with Median-PTI values of 0.1–1, and to 0% in 96% of samples with Median-PTI values > 1. The PTI is a relative, but quantitative, indicator of potential toxicity that can be used to evaluate relationships between pesticide exposure and biological condition.

  4. Renal and hepatotoxic alterations in adult mice on inhalation of specific mixture of organic solvents.

    PubMed

    Ketan, Vaghasia K; Bhavyata, Kalariya; Linzbuoy, George; Hyacinth, Highland N

    2015-12-01

    This study was aimed at investigating alterations in renal and hepatic toxicity induced by exposing to a combination of three solvents, namely, benzene, toluene and xylene in adult mice. The mice were divided into three groups (control, low-dose-treated (450 ppm) and high-dose (675 ppm) groups) using randomization methods. The treated groups were exposed to vapours of a mixture of benzene, toluene and xylene at doses of 450 and 675 ppm, for 6 h day(-1) for a short-term of 7-day exposure period. The study revealed that the solvent exposure resulted in an increase in the weight of liver and kidney as compared to the control. Biochemical analyses indicated a significant decline in the activities of superoxide dismutase and catalase in both the treated groups, with concomitant increase in lipid peroxidation. Liver aminotransferases (alanine aminotransferase and aspartate aminotransferase) were elevated with significant alterations in the levels of protein, creatinine and cholesterol in these tissues upon solvent exposure. Correlated with these changes, serum thyroid hormones T3 and T4 were also significantly altered. This study, therefore, demonstrates that inhalation of vapours from the solvent mixture resulted in significant dose-dependent biochemical and functional changes in the vital tissues (liver and kidney) studied. The study has specific relevance since humans are increasingly being exposed to such solvents due to increased industrial use in such combinations.

  5. Do persistent organic pollutants interact with the stress response? Individual compounds, and their mixtures, interaction with the glucocorticoid receptor.

    PubMed

    Wilson, Jodie; Berntsen, Hanne Friis; Zimmer, Karin Elisabeth; Verhaegen, Steven; Frizzell, Caroline; Ropstad, Erik; Connolly, Lisa

    2016-01-22

    Persistent organic pollutants (POPs) are toxic substances, highly resistant to environmental degradation, which can bio-accumulate and have long-range atmospheric transport potential (UNEP, 2001). The majority of studies on endocrine disruption have focused on interferences on the sexual steroid hormones and so have overlooked disruption to glucocorticoid hormones. Here the endocrine disrupting potential of individual POPs and their mixtures has been investigated in vitro to identify any disruption to glucocorticoid nuclear receptor transcriptional activity. POP mixtures were screened for glucocorticoid receptor (GR) translocation using a GR redistribution assay (RA) on a CellInsight™ NXT high content screening (HCS) platform. A mammalian reporter gene assay (RGA) was then used to assess the individual POPs, and their mixtures, for effects on glucocorticoid nuclear receptor transactivation. POP mixtures did not induce GR translocation in the GR RA or produce an agonist response in the GR RGA. However, in the antagonist test, in the presence of cortisol, an individual POP, p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE), was found to decrease glucocorticoid nuclear receptor transcriptional activity to 72.5% (in comparison to the positive cortisol control). Enhanced nuclear transcriptional activity, in the presence of cortisol, was evident for the two lowest concentrations of perfluorodecanoic acid (PFOS) potassium salt (0.0147mg/ml and 0.0294mg/ml), the two highest concentrations of perfluorodecanoic acid (PFDA) (0.0025mg/ml and 0.005mg/ml) and the highest concentration of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) (0.0000858mg/ml). It is important to gain a better understanding of how POPs can interact with GRs as the disruption of glucocorticoid action is thought to contribute to complex diseases. PMID:26599974

  6. Do persistent organic pollutants interact with the stress response? Individual compounds, and their mixtures, interaction with the glucocorticoid receptor.

    PubMed

    Wilson, Jodie; Berntsen, Hanne Friis; Zimmer, Karin Elisabeth; Verhaegen, Steven; Frizzell, Caroline; Ropstad, Erik; Connolly, Lisa

    2016-01-22

    Persistent organic pollutants (POPs) are toxic substances, highly resistant to environmental degradation, which can bio-accumulate and have long-range atmospheric transport potential (UNEP, 2001). The majority of studies on endocrine disruption have focused on interferences on the sexual steroid hormones and so have overlooked disruption to glucocorticoid hormones. Here the endocrine disrupting potential of individual POPs and their mixtures has been investigated in vitro to identify any disruption to glucocorticoid nuclear receptor transcriptional activity. POP mixtures were screened for glucocorticoid receptor (GR) translocation using a GR redistribution assay (RA) on a CellInsight™ NXT high content screening (HCS) platform. A mammalian reporter gene assay (RGA) was then used to assess the individual POPs, and their mixtures, for effects on glucocorticoid nuclear receptor transactivation. POP mixtures did not induce GR translocation in the GR RA or produce an agonist response in the GR RGA. However, in the antagonist test, in the presence of cortisol, an individual POP, p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE), was found to decrease glucocorticoid nuclear receptor transcriptional activity to 72.5% (in comparison to the positive cortisol control). Enhanced nuclear transcriptional activity, in the presence of cortisol, was evident for the two lowest concentrations of perfluorodecanoic acid (PFOS) potassium salt (0.0147mg/ml and 0.0294mg/ml), the two highest concentrations of perfluorodecanoic acid (PFDA) (0.0025mg/ml and 0.005mg/ml) and the highest concentration of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) (0.0000858mg/ml). It is important to gain a better understanding of how POPs can interact with GRs as the disruption of glucocorticoid action is thought to contribute to complex diseases.

  7. Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, Richard W.

    1998-04-28

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes .ltoreq.1000 .ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.

  8. Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, Richard W.

    1996-01-01

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes .ltoreq.1000.ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.

  9. Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, R.W.

    1995-12-19

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes{<=}1000{angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.

  10. Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, R.W.

    1996-09-17

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes {<=}1,000{angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1,050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.

  11. Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, Richard W.

    1995-01-01

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes.ltoreq.1000.ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.

  12. Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, R.W.

    1998-04-28

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes {<=}1000 {angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.

  13. Higher-order mass defect analysis for mass spectra of complex organic mixtures.

    PubMed

    Roach, Patrick J; Laskin, Julia; Laskin, Alexander

    2011-06-15

    Higher-order mass defect analysis is introduced as a unique formula assignment and visualization method for the analysis of complex mass spectra. This approach is an extension of the concepts of Kendrick mass transformation widely used for identification of homologous compounds differing only by a number of base units (e.g., CH(2), H(2), O, CH(2)O, etc.) in complex mixtures. We present an iterative renormalization routine for defining higher-order homologous series and multidimensional clustering of mass spectral features. This approach greatly simplifies visualization of complex mass spectra and increases the number of chemical formulas that can be confidently assigned for given mass accuracy. The potential for using higher-order mass defects for data reduction and visualization is shown. Higher-order mass defect analysis is described and demonstrated through third-order analysis of a deisotoped high-resolution mass spectrum of crude oil containing nearly 13,000 peaks. PMID:21526851

  14. Carcinogenesis, metabolism and DNA-binding studies of complex organic mixtures

    SciTech Connect

    Springer, D.L.; Mahlum, D.D.; Westerberg, R.B.; Hopkins, K.L.; Frazier, M.E.; Later, D.W.; Weimer, W.C.

    1984-10-01

    Studies were conducted to determine the skin-tumor-initiating activity of complex mixtures of synfuel derivation. Data from previous studies indicated that solvent refined coal (SRC)-II heavy distillate (HD; boiling range, 550 to > 850/sup 0/F) produced skin tumors in mice and that most of the carcinogenic activity occurred in materials boiling above 750/sup 0/F. Two of the highest-boiling fractions (i.e., 800 to 850/sup 0/F and >850/sup 0/F) contained approximately equal amounts of benzo(a)-pyrene (BaP; 1600 ppM), yet the >850/sup 0/F fraction produced 3.0 times as many skin tumors as the 800 to 850/sup 0/F fraction. Because of these findings, another study was conducted to determine the effects of a complex coal liquid (CL) matrix on the expression of BaP. For this study, BaP was mixed with a carcinogenic CL (50 ..mu..g BaP + 50 mg CL) and applied once to the shaved backs of mice to initiate tumor development. The number of tumors on animals receiving BaP + CL was substantially lower than for animals receiving the same amount of BaP only. These data demonstrate that the initiating activity of BaP was suppressed when it was presented to the animals in a complex chemical matrix. To extend these studies, in vitro and in vivo experiments were conducted to determine the extent of metabolism and DNA-binding of BaP alone or BaP in a complex mixture. 12 references, 5 tables.

  15. Molecular composition of aged secondary organic aerosol generated from a mixture of biogenic volatile compounds using ultrahigh resolution mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Doussin, J.-F.; Giorio, C.; Mahon, B.; Wilson, E. M.; Maurin, N.; Pangui, E.; Venables, D. S.; Wenger, J. C.; Kalberer, M.

    2015-02-01

    Field observations over the past decade indicate that a significant fraction of organic aerosol in remote areas may contain highly oxidised molecules. Aerosol processing or further oxidation (ageing) of organic aerosol has been suggested to be responsible for their formation through heterogeneous uptake of oxidants and multigenerational oxidation of vapours by OH radicals. In this study we investigated the influence of several ageing processes on the molecular composition of secondary organic aerosols (SOA) using direct infusion and liquid chromatography ultrahigh resolution mass spectrometry. SOA was formed in simulation chamber experiments from ozonolysis of a mixture of four biogenic volatile organic compounds (BVOC): α-pinene, β-pinene, Δ3-carene and isoprene. The SOA was subsequently aged under three different sets of conditions: in the dark in the presence of residual ozone, with UV irradiation and OH radicals, and using UV light only. Among all studied conditions, only OH radical-initiated ageing was found to influence the molecular composition of the aerosol and showed an increase in carbon oxidation state (OSC) and elemental O/C ratios of the SOA components. None of the ageing processes produced an observable effect on the oligomers formed from ozonolysis of the BVOC mixture, which were found to be equally abundant in both "fresh" and "aged" SOA. Additional experiments using α-pinene as the sole precursor demonstrated that oligomers are an important group of compounds in SOA produced from both ozonolysis and OH radical-initiated oxidation processes; however, a completely different set of oligomers is formed under these two oxidation regimes. SOA from the OH radical-initiated α-pinene oxidation had a significantly higher overall OSC and O/C compared to that from pure ozonolysis experiments confirming that the OH radical reaction is more likely to be responsible for the occurrence of highly oxidised species in ambient biogenic SOA.

  16. Greenhouse gas production in mixtures of soil with composted and noncomposted biochars is governed by char-associated organic compounds.

    PubMed

    Borchard, Nils; Spokas, Kurt; Prost, Katharina; Siemens, Jan

    2014-05-01

    Biochar application to soil has the potential to increase soil productivity while reducing anthropogenic greenhouse gas (GHG) emissions to the atmosphere. However, techniques for conditioning this material for maximizing its effects as a soil amendment require elucidation. We examined changes of organic matter associated with two biochars after 175 d of composting and the resulting effects on GHG emissions during a 150-d incubation period. Composting decreased the amount of organic compounds that could be thermally released from the biochars and affected their molecular nature. These thermally desorbable organic compounds from initial biochars likely stimulated the oxidation of CH and inhibited the production of NO in soil-biochar mixtures. However, these reductions of GHG emissions disappeared together with thermally desorbable organic compounds after the composting of chars. Instead, addition of composted gasification coke and charcoal stimulated the formation of CH and increased NO emissions by 45 to 56%. Nitrous oxide emissions equaled 20% of the total amount of N added with composted biochars, suggesting that organic compounds and N sorbed by the chars during composting fueled GHG production. The transient nature of the suppression of CH and NO production challenges the long-term GHG mitigation potential of biochar in soil.

  17. Thermodynamic functions, freezing transition, and phase diagram of dense carbon-oxygen mixtures in white dwarfs

    SciTech Connect

    Iyetomi, H.; Ogata, S.; Ichimaru, S.

    1989-07-01

    Equations of state for dense carbon-oxygen (C-O) binary-ionic mixtures (BIM's) appropriate to the interiors of white dwarfs are investigated through Monte Carlo simulations, by solution of relevant integral equations andvariational calculations in the density-functional formalism. It is thereby shown that the internal energies of the C-O BIM solids and fluids both obey precisely the linear mixing formulas. We then present an accurate calculation of the phase diagram associated with freezing transitions in such BIM materials, resulting in a novel prediction of an azeotropic diagram. Discontinuities of the mass density across the azeotropic phase boundaries areevaluated numerically for application to a study of white-dwarf evolution.

  18. Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy.

    PubMed

    Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2016-01-01

    NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (¹H, (13)C, and (31)P) and two-dimensional (¹H-(13)C and ¹H-(31)P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. ¹H, (13)C, and (31)P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the ¹H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative ¹H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the ¹H-(31)P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

  19. Biofilter treatment of volatile organic compound emissions from reformulated paint: complex mixtures, intermittent operation, and startup.

    PubMed

    Moe, William M; Qi, Bing

    2005-07-01

    Two biofilters were operated to treat a waste gas stream intended to simulate off-gases generated during the manufacture of reformulated paint. The model waste gas stream consisted of a five-component solvent mixture containing acetone (450 ppm(v)), methyl ethyl ketone (12 ppm(v)), toluene (29 ppm(v)), ethylbenzene (10 ppm(v)), and p-xylene (10 ppm(v)). The two biofilters, identical in construction and packed with a polyurethane foam support medium, were inoculated with an enrichment culture derived from compost and then subjected to different loading conditions during the startup phase of operation. One biofilter was subjected to intermittent loading conditions with contaminants supplied only 8 hr/day to simulate loading conditions expected at facilities where manufacturing operations are discontinuous. The other biofilter was subjected to continuous contaminant loading during the initial start period, and then was switched to intermittent loading conditions. Experimental results demonstrate that both startup strategies can ultimately achieve high contaminant removal efficiency (>99%) at a target contaminant mass loading rate of 80.3 g m(-3) hr(-1) and an empty bed residence time of 59 sec. The biofilter subjected to intermittent loading conditions at startup, however, took considerably longer to reach high performance. In both biofilters, ketone components (acetone and methyl ethyl ketone) were, more rapidly degraded than aromatic hydrocarbons (toluene, ethylbenzene, and p-xylene). Scanning electron microscopy and plate count data revealed that fungi, as well as bacteria, populated the biofilters. PMID:16111134

  20. Measuring the dielectric properties of soil-organic mixtures using coaxial impedance dielectric reflectometry

    NASA Astrophysics Data System (ADS)

    Francisca, Franco M.; Montoro, Marcos A.

    2012-05-01

    Contamination of soils with non-aqueous phase liquids (NAPLs) is frequently produced by accidental spills and storage tanks or pipes leakage. The main goals dealing with soil and groundwater contamination include determining the extension of the affected zone, monitoring the contaminant plume and quantifying the pollution degree. The objective of this work is to evaluate the potential of dielectric permittivity measurements to detect the presence of NAPLs in sands. Tested samples were fine, medium, coarse and silty sand with different volumetric contents of water and paraffin oil. The dielectric permittivity was measured by means of a Coaxial Impedance Dielectric Reflectometry method in specimens with either known fluid content or at different stages during immiscible displacement tests. A simplified method was developed to quantify the amount of oil from dielectric permittivity measurements and effective mixture media models. Obtained results showed that groundwater contamination with NAPL and the monitoring of immiscible fluid displacement in saturated porous media can be clearly identified from dielectric measurements. Finally, very accurate results can be obtained when computing the contamination degree with the proposed method in comparison with the real volumetric content of NAPL (r2 > 90%).

  1. Classification of Mixtures of Chinese Herbal Medicines Based on a Self-organizing Map (SOM).

    PubMed

    Wang, Maolin; Li, Li; Yu, Changyuan; Yan, Aixia; Zhao, Zhongzhen; Zhang, Ge; Jiang, Miao; Lu, Aiping; Gasteiger, Johann

    2016-04-01

    Chinese Herbal Medicines (CHMs) are typically mixtures of compounds and are often categorized into cold and hot according to the theory of Chinese Medicine. This classification is essential for guiding the clinical application of CHMs. In this study, three types of molecular descriptors were used to build models for classification of 59 CHMs with typical cold/hot properties in the training set taken from the original records on properties in China Pharmacopeia as reference. The accuracy and the Matthews correlation coefficient of the models were validated by a test set containing other 56 CHMs. The best model produced the accuracies of 94.92 % and 83.93 % on training set and test set, respectively. The MACCS fingerprint model is robust in predicting hot/cold properties of the CHMs from their major constituting compounds. This work shows how a classification model for data consisting of multi-components can be developed. The derived model can be used for the application of Chinese herbal medicines. PMID:27491920

  2. Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy

    PubMed Central

    Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2016-01-01

    NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (1H, 13C, and 31P) and two-dimensional (1H-13C and 1H-31P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. 1H, 13C, and 31P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the 1H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative 1H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the 1H-31P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

  3. SOLUBILITY OF ORGANIC BIOCIDES IN SUPERCRITICAL CO2 AND CO2+ COSOLVENT MIXTURES

    EPA Science Inventory

    Solubilities of four organic biocides in supercritical carbon dioxide (Sc-CO2) were measured using a dynamic flowr apparatus over a pressure range of 10 to 30 MPa and temperature of 35-80 degrees C. The biocides studied were: Amical-48 (diiodomethyl p-tolyl sulfone), chlorothalo...

  4. Nitric acid-organic mixtures surveyed for use in separation by anion exchange methods

    NASA Technical Reports Server (NTRS)

    Bloomquist, C. A. A.; Faris, J. P.; Stewart, D. C.

    1968-01-01

    Column elution-spectrographic analysis technique compares certain solvents directly to the methanol system, using inert rare earths instead of actinides. Distribution ratios for americium between 90 percent solvent, 10 percent 5 M nitric acid and Dowex 1 nitrate form resin for a large group of organics miscible in water was determined.

  5. A NEW MASS SPECTROMETRIC TECHNIQUE FOR IDENTIFYING TRACE-LEVEL ORGANIC COMPOUNDS IN COMPLEX MIXTURES

    EPA Science Inventory



    Most organic compounds are not found in mass spectral libraries and cannot be easily identified from low resolution mass spectra. Ion Composition Elucidation (ICE) utilizes selected ion recording with a double focusing mass spectrometer in a new way to determine exact mas...

  6. Uphill diffusion in multicomponent mixtures.

    PubMed

    Krishna, Rajamani

    2015-05-21

    Molecular diffusion is an omnipresent phenomena that is important in a wide variety of contexts in chemical, physical, and biological processes. In the majority of cases, the diffusion process can be adequately described by Fick's law that postulates a linear relationship between the flux of any species and its own concentration gradient. Most commonly, a component diffuses down the concentration gradient. The major objective of this review is to highlight a very wide variety of situations that cause the uphill transport of one constituent in the mixture. Uphill diffusion may occur in multicomponent mixtures in which the diffusion flux of any species is strongly coupled to that of its partner species. Such coupling effects often arise from strong thermodynamic non-idealities. For a quantitative description we need to use chemical potential gradients as driving forces. The transport of ionic species in aqueous solutions is coupled with its partner ions because of the electro-neutrality constraints; such constraints may accelerate or decelerate a specific ion. When uphill diffusion occurs, we observe transient overshoots during equilibration; the equilibration process follows serpentine trajectories in composition space. For mixtures of liquids, alloys, ceramics and glasses the serpentine trajectories could cause entry into meta-stable composition zones; such entry could result in phenomena such as spinodal decomposition, spontaneous emulsification, and the Ouzo effect. For distillation of multicomponent mixtures that form azeotropes, uphill diffusion may allow crossing of distillation boundaries that are normally forbidden. For mixture separations with microporous adsorbents, uphill diffusion can cause supra-equilibrium loadings to be achieved during transient uptake within crystals; this allows the possibility of over-riding adsorption equilibrium for achieving difficult separations.

  7. Uphill diffusion in multicomponent mixtures.

    PubMed

    Krishna, Rajamani

    2015-05-21

    Molecular diffusion is an omnipresent phenomena that is important in a wide variety of contexts in chemical, physical, and biological processes. In the majority of cases, the diffusion process can be adequately described by Fick's law that postulates a linear relationship between the flux of any species and its own concentration gradient. Most commonly, a component diffuses down the concentration gradient. The major objective of this review is to highlight a very wide variety of situations that cause the uphill transport of one constituent in the mixture. Uphill diffusion may occur in multicomponent mixtures in which the diffusion flux of any species is strongly coupled to that of its partner species. Such coupling effects often arise from strong thermodynamic non-idealities. For a quantitative description we need to use chemical potential gradients as driving forces. The transport of ionic species in aqueous solutions is coupled with its partner ions because of the electro-neutrality constraints; such constraints may accelerate or decelerate a specific ion. When uphill diffusion occurs, we observe transient overshoots during equilibration; the equilibration process follows serpentine trajectories in composition space. For mixtures of liquids, alloys, ceramics and glasses the serpentine trajectories could cause entry into meta-stable composition zones; such entry could result in phenomena such as spinodal decomposition, spontaneous emulsification, and the Ouzo effect. For distillation of multicomponent mixtures that form azeotropes, uphill diffusion may allow crossing of distillation boundaries that are normally forbidden. For mixture separations with microporous adsorbents, uphill diffusion can cause supra-equilibrium loadings to be achieved during transient uptake within crystals; this allows the possibility of over-riding adsorption equilibrium for achieving difficult separations. PMID:25761383

  8. Growth of columnar hydrogel colloidal crystals in water-organic solvent mixture.

    PubMed

    Zhou, Jun; Cai, Tong; Tang, Shijun; Marquez, Manuel; Hu, Zhibing

    2006-01-31

    A novel emulsion method has been demonstrated to grow columnar hydrogel colloidal crystals by mixing an aqueous suspension of poly-N-isopropylacrylamide-co-allylamine microgels with organic solvent, driven by the coalescence of micelles consisting of organic oil droplets coated by many microgels. This method leads to microgel colloidal crystals of several centimeters growing from the top to the bottom along the gravity direction. Both temperature and polymer concentration play critical roles for the formation of columnar crystals. A phase diagram has been determined, and it can be used as a guide to selectively grow different crystals, including columnar crystals and randomly oriented crystals, and enable the coexistence of columnar crystals and randomly oriented crystals.

  9. Evaluations of an Enhanced Total Hydrocarbon Analyzer With Complex Mixtures of Volatile Organic Compounds

    NASA Technical Reports Server (NTRS)

    Cross, John H.; Limero, Thomas F.; James, John T.; Breach, James; Hinton, Mark

    1995-01-01

    From the earliest manned missions, the volatile organic compound (VOC) content of spacecraft air has been a concern because of a much greater potential for contamination than air in most terrestrial settings. First, the volume of air is small compared to the mass of man- made materials comprising the interior furnishings of the spacecraft. These man-made materials offgas VOCs trapped during manufacture. Second, the nitrogen fraction of the air is recycled. Any VOCs not scrubbed out with charcoal filters or aqueous condensate (mainly water expired by the crew) will accumulate in the air. Third, the crew emits metabolic VOCs. Fourth, experimental payloads can also offgas or accidentally release a VOC; in fact a major organic constituent of the atmosphere is the disinfectant isopropanol released from swabs used in medical experiments.

  10. Enhancement of organ regeneration in animal models by a stem cell-stimulating plant mixture.

    PubMed

    Kiss, István; Tibold, Antal; Halmosi, Róbert; Bartha, Eva; Koltai, Katalin; Orsós, Zsuzsanna; Bujdosó, László; Ember, István

    2010-06-01

    Adult stem cells play an important role in the regeneration of damaged organs. Attempts have already been made to enhance stem cell production by cytokines, in order to increase the improvement of cardiac functions after myocardial infarction. In our present study we investigated the possibility whether instead of cytokine injection dietary stimulation of stem cell production accelerates the organ regeneration in animals. A dietary supplement, Olimpiq StemXCell (Crystal Institute Ltd., Eger, Hungary), containing plant extracts (previously proved to increase the number of circulating CD34(+) cells) was consumed in human equivalent doses by the experimental animals. In the first experiment carbon tetrachloride was applied to CBA/Ca mice, to induce liver damage, and liver weights between StemXCell-fed and control animals were compared 10 days after the treatment. In the second model experimental diabetes was induced in F344 rats by alloxan. Blood sugar levels were measured for 5 weeks in the control and StemXCell-fed groups. The third part of the study investigated the effect of StemXCell on cardiac functions. Eight weeks after causing a myocardial infarction in Wistar rats by isoproterenol, left ventricular ejection fraction was determined as a functional parameter of myocardial regeneration. In all three animal models StemXCell consumption statistically significantly improved the organ regeneration (relative liver weights, 4.78 +/-0.06 g/100 g vs. 4.97 +/- 0.07 g/100 g; blood sugar levels at week 5, 16 +/- 1.30 mmol/L vs. 10.2 +/- 0.92 mmol/L; ejection fraction, 57.5 +/- 2.23 vs. 68.2 +/- 4.94; controls vs. treated animals, respectively). Our study confirms the hypothesis that dietary enhancement of stem cell production may protect against organ injuries and helps in the regeneration.

  11. Evaluation of the COSHH Essentials model with a mixture of organic chemicals at a medium-sized paint producer.

    PubMed

    Lee, Eun Gyung; Slaven, James; Bowen, Russell B; Harper, Martin

    2011-01-01

    the threshold limit value of the mixture (P > 1 = 0.2375), the expected personal exposure after adjusting for the assigned protection factor for the respirators in use would be considerably lower (P > 1 = 0.0161). Thus, our findings suggested that the COSHH essentials model worked reasonably well for the volatile organic chemicals at the plant. However, it was difficult to override the reproductive hazard even though it was meant to be possible in principle. Further, it became apparent that an input of existing controls, which is not possible in the web-based model, may have allowed the model be more widely applicable. The experience of using the web-based COSHH Essentials model generated some suggestions to provide a more user-friendly tool to the model users who do not have expertise in occupational hygiene.

  12. Ionic liquids and deep eutectic mixtures: sustainable solvents for extraction processes.

    PubMed

    Pena-Pereira, Francisco; Namieśnik, Jacek

    2014-07-01

    In recent years, ionic liquids and deep eutectic mixtures have demonstrated great potential in extraction processes relevant to several scientific and technological activities. This review focuses on the applicability of these sustainable solvents in a variety of extraction techniques, including but not limited to liquid- and solid-phase (micro) extraction, microwave-assisted extraction, ultrasound-assisted extraction and pressurized liquid extraction. Selected applications of ionic liquids and deep eutectic mixtures on analytical method development, removal of environmental pollutants, selective isolation, and recovery of target compounds, purification of fuels, and azeotrope breaking are described and discussed.

  13. Self-organization in cytoskeletal mixtures: from synthetic cilia to flowing networks

    NASA Astrophysics Data System (ADS)

    Sanchez, Tim

    2013-03-01

    Inspired by biological functions such as ciliary beating and cytoplasmic streaming, we have developed a highly tunable and robust model system from biological components that self-organizes to produce a broad range of far-from-equilibrium materials with remarkable emergent properties. Using only simple components - microtubules, kinesin motor clusters, and a depletion agent that bundles MTs - we reproduced several essential biological functions, including cilia-like beating, the emergence of metachronal waves in bundle arrays, and internally generated flows in active cytoskeletal gels. The occurrence of these biomimetic functions as self-organized processes provides unique insight into the mechanisms that drive these processes in biology. Beyond these biomimetic behaviors, we have also used the same components to engineer novel active materials which have no biological analogues: active streaming 2D nematics, and finally self-propelled emulsion droplets. These observations exemplify how assemblages of animate microscopic objects exhibit highly sought-after collective and biomimetic properties, challenging us to develop a theoretical framework that would allow for a systematic engineering of their far-from-equilibrium material properties.

  14. Subsurface interactions of actinide species and microorganisms : implications for the bioremediation of actinide-organic mixtures.

    SciTech Connect

    Banaszak, J.E.; Reed, D.T.; Rittmann, B.E.

    1999-02-12

    By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs.

  15. Measurements of thermodynamic and optical properties of selected aqueous organic and organic-inorganic mixtures of atmospheric relevance.

    PubMed

    Lienhard, Daniel M; Bones, David L; Zuend, Andreas; Krieger, Ulrich K; Reid, Jonathan P; Peter, Thomas

    2012-10-11

    Atmospheric aerosol particles can exhibit liquid solution concentrations supersaturated with respect to the dissolved organic and inorganic species and supercooled with respect to ice. In this study, thermodynamic and optical properties of sub- and supersaturated aqueous solutions of atmospheric interest are presented. The density, refractive index, water activity, ice melting temperatures, and homogeneous ice freezing temperatures of binary aqueous solutions containing L(+)-tartaric acid, tannic acid, and levoglucosan and ternary aqueous solutions containing levoglucosan and one of the salts NH(4)HSO(4), (NH(4))(2)SO(4), and NH(4)NO(3) have been measured in the supersaturated concentration range for the first time. In addition, the density and refractive index of binary aqueous citric acid and raffinose solutions and the glass transition temperatures of binary aqueous L(+)-tartaric acid and levoglucosan solutions have been measured. The data presented here are derived from experiments on single levitated microdroplets and bulk solutions and should find application in thermodynamic and atmospheric aerosol models as well as in food science applications.

  16. Study on Exploration of Azeotropic Point of Pb-Sb Alloys by Vacuum Distillation and Ab Initio Molecular Dynamic Simulation

    NASA Astrophysics Data System (ADS)

    Song, Bingyi; Jiang, Wenlong; Yang, Bin; Chen, Xiumin; Xu, Baoqiang; Kong, Lingxin; Liu, Dachun; Dai, Yongnian

    2016-10-01

    The possibility of the separation of Pb-Sb alloys by vacuum distillation was investigated theoretically. The results show that Pb and Sb can be separated by vacuum distillation. However, the experimental results show that vacuum distillation technique does not provide clear separation. According to the literature, Pb-Sb alloys belong to azeotropic compounds under some certain temperature; the experiment and computer simulation were carried out based on the exceptional condition so as to analyze the reason from the experiment and microstructure of Pb-Sb alloys perspective. The separation of Pb-Sb alloys by vacuum distillation was experimentally carried out to probe the azeotropic point. Also, the functions, such as partial radial distributions functions, the structure factor, mean square displacement, and the density of state, were calculated by ab-initio molecular dynamics for the representation of the structure and properties of Pb-Sb alloys with different composition of Sb. The experimental results indicate that there exists common volatilization for Pb-Sb alloys when Sb content is 16.5 wt pct. On the other hand, the calculation results show that there is an intense interaction between Pb and Sb when Sb content is 22 wt pct, which supports the experimental results although Sb content is slightly deviation.

  17. Study on Exploration of Azeotropic Point of Pb-Sb Alloys by Vacuum Distillation and Ab Initio Molecular Dynamic Simulation

    NASA Astrophysics Data System (ADS)

    Song, Bingyi; Jiang, Wenlong; Yang, Bin; Chen, Xiumin; Xu, Baoqiang; Kong, Lingxin; Liu, Dachun; Dai, Yongnian

    2016-07-01

    The possibility of the separation of Pb-Sb alloys by vacuum distillation was investigated theoretically. The results show that Pb and Sb can be separated by vacuum distillation. However, the experimental results show that vacuum distillation technique does not provide clear separation. According to the literature, Pb-Sb alloys belong to azeotropic compounds under some certain temperature; the experiment and computer simulation were carried out based on the exceptional condition so as to analyze the reason from the experiment and microstructure of Pb-Sb alloys perspective. The separation of Pb-Sb alloys by vacuum distillation was experimentally carried out to probe the azeotropic point. Also, the functions, such as partial radial distributions functions, the structure factor, mean square displacement, and the density of state, were calculated by ab-initio molecular dynamics for the representation of the structure and properties of Pb-Sb alloys with different composition of Sb. The experimental results indicate that there exists common volatilization for Pb-Sb alloys when Sb content is 16.5 wt pct. On the other hand, the calculation results show that there is an intense interaction between Pb and Sb when Sb content is 22 wt pct, which supports the experimental results although Sb content is slightly deviation.

  18. Factors influencing inapplicability of cosolvency-induced model on organic acid sorption onto humic substance from methanol mixture.

    PubMed

    Kim, Minhee; Kim, Juhee; Kim, Jeong-Gyu; Hyun, Seunghun

    2015-10-01

    Applicability of cosolvency model for describing the sorption of organic acids to humic substance was investigated by analyzing dataset of sorption (K m) and solubility (S m) of selected solutes (benzoic acid, 1-naphthoic acid, 2,4-dichlorophenoxyacetic acid, and 2,4,6-trichlorophenol (2,4,6-TCP)) as a function of pH(appCME) (apparent pH of liquid phase) and f c (methanol volume fractions). For all solutes, the K m decreased with f c with the K m reduction being less than the S m-based prediction. The slope of log K m-f c plot in the three organic carboxylic acids was well correlated with their cosolvency power, whereas the data of organic phenolic acid (2,4,6-TCP) was placed above the trend, indicating the different actions of functional groups. The occurrence of Ca(2+) bridge between carboxylate and negatively charged humic surface may explain this phenomenon. Normalizing the K m to the corresponding S m (α' = K m/S m) was not in unity over the pH(app)-f c range but decreased with f c, indicating a possible structural modification of sorption domain favoring extra sorption. For a given solute, the α' of neutral species was always greater than that of anionic species, showing that extra interaction will be likely at pH(app) organic acids by humic substance in methanol/water mixtures. Modification of humic structure and hydrophilic interaction (such as Ca(2+) bridge and same-charge repulsion) is considered a relevant process that possibly restricts the applicability of the cosolvency model.

  19. Hygroscopicity of Amine Secondary Aerosol - Mixtures of Organic and Inorganic Components

    NASA Astrophysics Data System (ADS)

    Tang, X.; Cocker, D. R.; Purvis-Roberts, K.; Asa-Awuku, A. A.

    2012-12-01

    Aliphatic amines are emitted from both biogenic and anthropogenic sources and contribute to the formation of secondary aerosol in reactions with atmospheric radicals. However, the cloud condensation nuclei (CCN) ability of amine aerosol has not been explored yet. Here, we study the hygroscopicity of aerosol formed from three aliphatic amines (trimethylamine, diethylamine and butylamine) in the UCR environmental chamber. Amines can react with NO3, a dominant night time oxidant in acid-base and/or oxidation reactions. The mass fraction of organic and inorganic components of formed aerosol was measured by Particle-into-Liquid Sampler coupled to dual ion chromatographs (PILS-ICs) and Scanning Mobility Particle Sizer (SMPS). CCN counter was used to measure the water-uptake ability of these particles. Significantly high hygroscopicity (κ>0.3) was observed for aerosols formed from diethylamine and butylamine with NO3 radicals, which comprised >40% inorganic salt. Compared with amines oxidized by hydroxyl radicals, the presence of aminium salts formed in acid-base reactions greatly improved CCN activity of NO3-initiated aerosol. The effect of water vapor on the formation of aminium salts and aerosol hygroscopicity was also studied. Our results will significantly impact the estimation and role of amines in atmospheric chemistry and global climate models.

  20. Schiff base ligands and their transition metal complexes in the mixtures of ionic liquid + organic solvent: a thermodynamic study.

    PubMed

    Shekaari, Hemayat; Kazempour, Amir; Khoshalhan, Maryam

    2015-01-21

    Schiff bases and their metal complexes in the mixtures of ionic liquid (IL) + organic solvent have shown great potential in attractive oxidation catalytic processes. The efficiency of such a process is strongly dependent on the various molecular interactions occurring between components. Thermodynamic properties of these systems can provide valuable information about structural interactions. Therefore, in this work, the interactions of the IL 1-hexyl-3-methylimidazolium chloride ([HMIm]Cl) with Schiff bases in organic solvents were studied through the measurements of density, viscosity, and electrical conductivity. The effect of solvent on the interactions was examined by the solutions of IL + BPIC Schiff base + solvent (C2H6O-C3H8O-C4H10O). Moreover, the influence of Schiff base ligand and Schiff base complex structures was probed by the solutions of IL + DMA + ligand (salcn/salpr/salen) and IL + DMA + complex (VO(3-OMe-salen)/VO(salophen)/VO(salen)), respectively. Using the experimental data, some important thermodynamic properties, such as standard partial molar volume (V(0)(φ,IL)), experimental slope (Sv), viscosity B-coefficient, solvation number (B/V(0)(φ,IL) and limiting molar conductivity (Λ0) were calculated and discussed in terms of solute-solvent (IL-DMF/alcohol) and solute-cosolute (IL-Schiff base) interactions.

  1. Exergoeconomic analysis and optimization of an evaporator for a binary mixture of fluids in an organic Rankine cycle

    NASA Astrophysics Data System (ADS)

    Li, You-Rong; Du, Mei-Tang; Wang, Jian-Ning

    2012-12-01

    This paper focuses on the research of an evaporator with a binary mixture of organic working fluids in the organic Rankine cycle. Exergoeconomic analysis and performance optimization were performed based on the first and second laws of thermodynamics, and the exergoeconomic theory. The annual total cost per unit heat transfer rate was introduced as the objective function. In this model, the exergy loss cost caused by the heat transfer irreversibility and the capital cost were taken into account; however, the exergy loss due to the frictional pressure drops, heat dissipation to surroundings, and the flow imbalance were neglected. The variation laws of the annual total cost with respect to the number of transfer units and the temperature ratios were presented. Optimal design parameters that minimize the objective function had been obtained, and the effects of some important dimensionless parameters on the optimal performances had also been discussed for three types of evaporator flow arrangements. In addition, optimal design parameters of evaporators were compared with those of condensers.

  2. A Bayesian mixture model relating dose to critical organs and functional complication in 3D conformal radiation therapy.

    PubMed

    Johnson, Timothy D; Taylor, Jeremy M G; Ten Haken, Randall K; Eisbruch, Avraham

    2005-10-01

    A goal of cancer radiation therapy is to deliver maximum dose to the target tumor while minimizing complications due to irradiation of critical organs. Technological advances in 3D conformal radiation therapy has allowed great strides in realizing this goal; however, complications may still arise. Critical organs may be adjacent to tumors or in the path of the radiation beam. Several mathematical models have been proposed that describe the relationship between dose and observed functional complication; however, only a few published studies have successfully fit these models to data using modern statistical methods which make efficient use of the data. One complication following radiation therapy of head and neck cancers is the patient's inability to produce saliva. Xerostomia (dry mouth) leads to high susceptibility to oral infection and dental caries and is, in general, unpleasant and an annoyance. We present a dose-damage-injury model that subsumes any of the various mathematical models relating dose to damage. The model is a nonlinear, longitudinal mixed effects model where the outcome (saliva flow rate) is modeled as a mixture of a Dirac measure at zero and a gamma distribution whose mean is a function of time and dose. Bayesian methods are used to estimate the relationship between dose delivered to the parotid glands and the observational outcome-saliva flow rate. A summary measure of the dose-damage relationship is modeled and assessed by a Bayesian chi(2) test for goodness-of-fit. PMID:15917377

  3. Nonequimolar Mixture of Organic Acids and Bases: An Exception to the Rule of Thumb for Salt or Cocrystal.

    PubMed

    Pratik, Saied Md; Datta, Ayan

    2016-08-01

    Formation of salt and/or cocrystal from organic acid-base mixtures has significant consequences in the pharmaceutical industry and its related intellectual property rights (IPR). On the basis of calculations using periodic dispersion corrected DFT (DFT-D2) on formic acid-pyridine adduct, we have demonstrated that an equimolar stoichiometric ratio (1:1) exists as a neutral cocrystal. On the other hand, the nonequimolar stoichiometry (4:1) readily forms an ionic salt. While the former result is in agreement with the ΔpKa rule between the base and the acid, the latter is not. Calculations reveal that, within the equimolar manifold (n:n; n = 1-4), the mixture exists as a hydrogen bonded complex in a cocrystal-like environment. However, the nonequimolar mixture in a ratio of 5:1 and above readily forms salt-like structures. Because of the cooperative nature of hydrogen bonding, the strength of the O-H···N hydrogen bond increases and eventually transforms into O(-)···H-N(+) (complete proton transfer) as the ratio of formic acid increases and forms salt as experimentally observed. Clearly, an enhanced polarization of formic acid on aggregation increases its acidity and, hence, facilitates its transfer to pyridine. Motion of the proton from formic acid to pyridine is shown to follow a relay mechanism wherein the proton that is far away from pyridine is ionized and is subsequently transferred to pyridine via hopping across the neutral formic acid molecules (Grotthuss type pathway). The dynamic nature of protons in the condensed phase is also evident for cocrystals as the barrier of intramolecular proton migration in formic acid (leading to tautomerism), ΔH(⧧)tautomer = 17.1 kcal/mol in the presence of pyridine is half of that in free formic acid (cf. ΔH(⧧)tautomer = 34.2 kcal/mol). We show that an acid-base reaction can be altered in the solid state to selectively form a cocrystal or salt depending on the strength and nature of aggregation. PMID:27400140

  4. Nonequimolar Mixture of Organic Acids and Bases: An Exception to the Rule of Thumb for Salt or Cocrystal.

    PubMed

    Pratik, Saied Md; Datta, Ayan

    2016-08-01

    Formation of salt and/or cocrystal from organic acid-base mixtures has significant consequences in the pharmaceutical industry and its related intellectual property rights (IPR). On the basis of calculations using periodic dispersion corrected DFT (DFT-D2) on formic acid-pyridine adduct, we have demonstrated that an equimolar stoichiometric ratio (1:1) exists as a neutral cocrystal. On the other hand, the nonequimolar stoichiometry (4:1) readily forms an ionic salt. While the former result is in agreement with the ΔpKa rule between the base and the acid, the latter is not. Calculations reveal that, within the equimolar manifold (n:n; n = 1-4), the mixture exists as a hydrogen bonded complex in a cocrystal-like environment. However, the nonequimolar mixture in a ratio of 5:1 and above readily forms salt-like structures. Because of the cooperative nature of hydrogen bonding, the strength of the O-H···N hydrogen bond increases and eventually transforms into O(-)···H-N(+) (complete proton transfer) as the ratio of formic acid increases and forms salt as experimentally observed. Clearly, an enhanced polarization of formic acid on aggregation increases its acidity and, hence, facilitates its transfer to pyridine. Motion of the proton from formic acid to pyridine is shown to follow a relay mechanism wherein the proton that is far away from pyridine is ionized and is subsequently transferred to pyridine via hopping across the neutral formic acid molecules (Grotthuss type pathway). The dynamic nature of protons in the condensed phase is also evident for cocrystals as the barrier of intramolecular proton migration in formic acid (leading to tautomerism), ΔH(⧧)tautomer = 17.1 kcal/mol in the presence of pyridine is half of that in free formic acid (cf. ΔH(⧧)tautomer = 34.2 kcal/mol). We show that an acid-base reaction can be altered in the solid state to selectively form a cocrystal or salt depending on the strength and nature of aggregation.

  5. The Challenge of Peat Substitution in Organic Seedling Production: Optimization of Growing Media Formulation through Mixture Design and Response Surface Analysis

    PubMed Central

    Ceglie, Francesco Giovanni; Bustamante, Maria Angeles; Ben Amara, Mouna; Tittarelli, Fabio

    2015-01-01

    Peat replacement is an increasing demand in containerized and transplant production, due to the environmental constraints associated to peat use. However, despite the wide information concerning the use of alternative materials as substrates, it is very complex to establish the best materials and mixtures. This work evaluates the use of mixture design and surface response methodology in a peat substitution experiment using two alternative materials (green compost and palm fibre trunk waste) for transplant production of tomato (Lycopersicon esculentum Mill.); melon, (Cucumis melo L.); and lettuce (Lactuca sativa L.) in organic farming conditions. In general, the substrates showed suitable properties for their use in seedling production, showing the best plant response the mixture of 20% green compost, 39% palm fibre and 31% peat. The mixture design and applied response surface methodology has shown to be an useful approach to optimize substrate formulations in peat substitution experiments to standardize plant responses. PMID:26070163

  6. The Challenge of Peat Substitution in Organic Seedling Production: Optimization of Growing Media Formulation through Mixture Design and Response Surface Analysis.

    PubMed

    Ceglie, Francesco Giovanni; Bustamante, Maria Angeles; Ben Amara, Mouna; Tittarelli, Fabio

    2015-01-01

    Peat replacement is an increasing demand in containerized and transplant production, due to the environmental constraints associated to peat use. However, despite the wide information concerning the use of alternative materials as substrates, it is very complex to establish the best materials and mixtures. This work evaluates the use of mixture design and surface response methodology in a peat substitution experiment using two alternative materials (green compost and palm fibre trunk waste) for transplant production of tomato (Lycopersicon esculentum Mill.); melon, (Cucumis melo L.); and lettuce (Lactuca sativa L.) in organic farming conditions. In general, the substrates showed suitable properties for their use in seedling production, showing the best plant response the mixture of 20% green compost, 39% palm fibre and 31% peat. The mixture design and applied response surface methodology has shown to be an useful approach to optimize substrate formulations in peat substitution experiments to standardize plant responses.

  7. A chromatographic method to analyze products from photo-oxidation of anthropogenic and biogenic mixtures of volatile organic compounds in smog chambers.

    PubMed

    Pindado Jiménez, Oscar; Pérez Pastor, Rosa M; Vivanco, Marta G; Santiago Aladro, Manuel

    2013-03-15

    A method for quantifying secondary organic aerosol compounds (SOA) and water soluble secondary organic aerosol compounds (WSOA) produced from photo-oxidation of complex mixtures of volatile organic compounds (VOCs) in smog chambers by gas chromatography/mass spectrometry (GC/MS) has been developed. This method employs a double extraction with water and methanol jointly to a double derivatization with N,O-bis (trimethylsilil) trifluoroacetamide (BSTFA) and O-(2,3,4,5,6)-pentafluorobenzyl-hydroxylamine hydrochloride (PFBHA) followed by an analysis performed by GC/MS. The analytical procedure complements other methodologies because it can analyze SOA and WSOA compounds simultaneously at trace levels. As application, the methodology was employed to quantify the organic composition of aerosols formed in a smog chamber as a result of photo-oxidation of two different mixtures of volatile organic compounds: an anthropogenic mixture and a biogenic mixture. The analytical method allowed us to quantify up to 17 SOA compounds at levels higher than 20 ng m(-3) with reasonable recovery and a precision below 11%. Values found for applicability, selectivity, linearity, precision, recovery, detection limit, quantification limit and sensitivity demonstrated that the methodology can be satisfactorily applied to quantify SOA and WSOA.

  8. Evaluation of the COSHH Essentials Model with a Mixture of Organic Chemicals at a Medium-Sized Paint Producer

    PubMed Central

    Lee, Eun Gyung; Slaven, James; Bowen, Russell B.; Harper, Martin

    2011-01-01

    exceed the threshold limit value of the mixture (P > 1 = 0.2375), the expected personal exposure after adjusting for the assigned protection factor for the respirators in use would be considerably lower (P > 1 = 0.0161). Thus, our findings suggested that the COSHH essentials model worked reasonably well for the volatile organic chemicals at the plant. However, it was difficult to override the reproductive hazard even though it was meant to be possible in principle. Further, it became apparent that an input of existing controls, which is not possible in the web-based model, may have allowed the model be more widely applicable. The experience of using the web-based COSHH Essentials model generated some suggestions to provide a more user-friendly tool to the model users who do not have expertise in occupational hygiene. PMID:21047985

  9. Evaluation of the COSHH Essentials model with a mixture of organic chemicals at a medium-sized paint producer.

    PubMed

    Lee, Eun Gyung; Slaven, James; Bowen, Russell B; Harper, Martin

    2011-01-01

    the threshold limit value of the mixture (P > 1 = 0.2375), the expected personal exposure after adjusting for the assigned protection factor for the respirators in use would be considerably lower (P > 1 = 0.0161). Thus, our findings suggested that the COSHH essentials model worked reasonably well for the volatile organic chemicals at the plant. However, it was difficult to override the reproductive hazard even though it was meant to be possible in principle. Further, it became apparent that an input of existing controls, which is not possible in the web-based model, may have allowed the model be more widely applicable. The experience of using the web-based COSHH Essentials model generated some suggestions to provide a more user-friendly tool to the model users who do not have expertise in occupational hygiene. PMID:21047985

  10. Detailed chemical characterization of unresolved complex mixtures in atmospheric organics: Insights into emission sources, atmospheric processing, and secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Chan, Arthur W. H.; Isaacman, Gabriel; Wilson, Kevin R.; Worton, David R.; Ruehl, Christopher R.; Nah, Theodora; Gentner, Drew R.; Dallmann, Timothy R.; Kirchstetter, Thomas W.; Harley, Robert A.; Gilman, Jessica B.; Kuster, William C.; Gouw, Joost A.; Offenberg, John H.; Kleindienst, Tadeusz E.; Lin, Ying H.; Rubitschun, Caitlin L.; Surratt, Jason D.; Hayes, Patrick L.; Jimenez, Jose L.; Goldstein, Allen H.

    2013-06-01

    Recent studies suggest that semivolatile organic compounds (SVOCs) are important precursors to secondary organic aerosol (SOA) in urban atmospheres. However, knowledge of the chemical composition of SVOCs is limited by current analytical techniques, which are typically unable to resolve a large number of constitutional isomers. Using a combination of gas chromatography and soft photoionization mass spectrometry, we characterize the unresolved complex mixture (UCM) of semivolatile aliphatic hydrocarbons observed in Pasadena, California (~16 km NE of downtown Los Angeles), and Bakersfield, California, during the California Research at the Nexus of Air Quality and Climate Change 2010. To the authors' knowledge, this work represents the most detailed characterization of the UCM in atmospheric samples to date. Knowledge of molecular structures, including carbon number, alkyl branching, and number of rings, provides important constraints on the rate of atmospheric processing, as the relative amounts of branched and linear alkanes are shown to be a function of integrated exposure to hydroxyl radicals. Emissions of semivolatile branched alkanes from fossil fuel-related sources are up to an order of magnitude higher than those of linear alkanes, and the gas-phase OH rate constants of branched alkanes are ~30% higher than their linear isomers. Based on a box model considering gas/particle partitioning, emissions, and reaction rates, semivolatile branched alkanes are expected to play a more important role than linear alkanes in the photooxidation of the UCM and subsequent transformations into SOA. Detailed speciation of semivolatile compounds therefore provides essential understanding of SOA sources and formation processes in urban areas.

  11. A Comparison of delO18 Composition of Water Extracted from Suction Lysimeters, Centrifugation, and Azeotropic Distillation

    NASA Astrophysics Data System (ADS)

    Figueroa, A.; Tindall, J. A.; Friedel, M. J.

    2005-12-01

    Concentration of delO18 in water samples extracted by suction lysimeters is compared to samples obtained by methods of centrifugation and azeotropic distillation. Intact soil cores (30 cm diameter by 40 cm height) were extracted from two different sites. Site 1 was rapid infiltration basin number 50, near Altamonte Springs in Seminole County, Florida on properties belonging to the Walt Disney World Resort Complex. Site 2 was the Missouri Management System Evaluation Area (MSEA) near Centralia in Boone County, Missouri. The delO18 water was analyzed on a mass spectrophotometer. Potassium Bromide (KBr) was also used as a tracer and analyzed by ion chromatography. A portion of the data obtained was modeled using CXTFIT. Water collected by centrifugation and azeotropic distillation data were about 2-5% more negative than that collected by suction lysimeter values from the Florida (sandy) soil and about 5-7 % more negative from the Missouri (well structured clay) soil. Results indicate that the majority of soil water in well structured soil is strongly bound to soil grain surfaces and is not easily sampled by suction lysimeters. Also, it is plausible that evaporation caused some delO18 enrichment in the suction lysimeters. Suction lysimeters preferentially sampled water held at lower matric potentials, which may not represent total soil water. In cases where a sufficient volume of water has passed through the soil profile and displaced all previous pore water, suction lysimeters will however collect a representative sample of all the water at that depth interval. It is suggested that for stable isotope studies monitoring precipitation and soil water, suction lysimeters be installed at shallow depths (10 cm). Samples should also be coordinated with precipitation events. The CXTFIT program worked well for Florida soils (a more homogeneous sand), but gave poor performance for Missouri soils (well structured clays) except for deeper depths where clay structure was less

  12. Entropic separations of mixtures of aromatics by selective face-to-face molecular stacking in one-dimensional channels of metal-organic frameworks and zeolites.

    PubMed

    Torres-Knoop, Ariana; Balestra, Salvador R G; Krishna, Rajamani; Calero, Sofía; Dubbeldam, David

    2015-02-23

    Separation of challenging mixtures using metal-organic frameworks can be achieved by an entropy-driven mechanism, where one of the components can arrange into a "face-to-face" stacking, thus reducing its "footprint" and reaching a higher saturation loading.

  13. Formation of Secondary Organic Aerosol from Irradiated a-Pinene/Tolueme/NOx Mixtures and the Effect of Isoprene and Sulfur Dioxide

    EPA Science Inventory

    Secondary organic aerosol (SOA) was generated by irradiating a series of a-pinene/toluene/NOx mixtures in the absence and presence of isoprene or sulfur dioxide. The purpose of the experiment was to evaluate the extent to which chemical perturbations to this base-case (a-pinene/...

  14. Influence of the organic component on the geometry and stability of Dy(III) complexes with benzoic and aminobenzoic acids in water-80 vol % DMSO (DMFA) mixtures

    SciTech Connect

    Kondrashina, Y.G.; Mustafina, A.R.; Devyatov, F.V.

    1995-07-01

    The stability and structure of dysprosium (III) benzoate and aminobenzoate complexes are estimated pH-metrically and magnetooptically in water and water-80 vol% DMSO (DMFA) mixtures. The factors responsible for the structural and stability changes that take place upon transition from water to water-organic solvents are discussed.

  15. Self-Organization in Active Cytoskeletal Mixtures: Cilia-like Beating of Microtubule Bundles and Spontaneous Bulk Mixing

    NASA Astrophysics Data System (ADS)

    Sanchez, Tim

    This thesis discusses circularization and supercoiling of actin biofilaments, as well as the various examples of self-organization observed in a simple non-equilibrium system of microtubules, motor clusters, and a depletion agent (PEG). When the ends of an actin filament approach each other, annealing can occur, resulting in the assumption of a circular conformation. In order to facilitate this experimentally, we dramatically reduce the space available for the ends to explore by confining the filaments to a quasi-2D region. This is accomplished through the use of a depletion attraction. In addition to the pronounced effects of this topological ring constraint on the statistical fluctuations of the filaments, we also observe a spontaneous supercoiling transition in fluorescently labeled actin rings that is directly driven by illumination. To better understand this transition in natural twist, we investigate real-time twist of a filament trapped between two beads, held by optical traps. The main focus of this graduate work was on the behavior of non-equilibrium in vitro mixtures of microtubules, kinesin motor clusters, and a depletion agent. We observed several striking and distinct examples of self-organization on near-macroscopic length scales, due to the interactions of very simple components. First we investigate the driving mechanism behind the beating of biological cilia and flagella, and find that this beating functionality can be reproduced in our vastly simpler system. This occurs only when minimalist components are reconstituted: motors, biofilaments, elastic links to hold the filaments together, and a basal attachment. Beyond the cooperativity of the motors to produce oscillatory beating in individual bundles, we also observe that active bundles in close proximity can synchronize their beating to produce stable, periodic metachronal waves that propagate along the bundle array. By changing only the length distribution of the microtubules in our system, we

  16. Quantitative structure-activity relationships and mixture toxicity of organic chemicals in Photobacterium phosphoreum: the Microtox test

    SciTech Connect

    Hermens, J.; Busser, F.; Leeuwangh, P.; Musch, A.

    1985-02-01

    Quantitative structure-activity relationships were calculated for the inhibition of bioluminescence of Photobacterium phosphoreum by 22 nonreactive organic chemicals. The inhibition was measured using the Microtox test and correlated with the partition coefficient between n-octanol and water (Poct), molar refractivity (MR), and molar volume (MW/d). At log Poct less than 1 and greater than 3, deviations from linearity were observed. Introduction of MR and MW/d improved the quality of the relationships. The influences of MR or MW/d may be related with an interaction of the tested chemicals to the enzyme system which produces the light emission. The sensitivity of the Microtox test to the 22 tested compounds is comparable to a 14-day acute mortality test with guppies for chemicals with log Poct less than 4. The inhibition of bioluminescence by a mixture of the tested compounds was slightly less than was expected in case of concentration addition. The Microtox test can give a good estimate of the total aspecific minimum toxicity of polluted waters. When rather lipophilic compounds or pollutants with more specific modes of action are present, this test will underestimate the toxicity to other aquatic life.

  17. Thermodynamic study of (anthracene + phenanthrene) solid state mixtures

    PubMed Central

    Rice, James W.; Fu, Jinxia; Sandström, Emma; Ditto, Jenna C.; Suuberg, Eric M.

    2015-01-01

    Polycyclic aromatic hydrocarbons (PAH) are common components of many materials, such as petroleum and various types of tars. They are generally present in mixtures, occurring both naturally and as byproducts of fuel processing operations. It is important to understand the thermodynamic properties of such mixtures in order to understand better and predict their behavior (i.e., fate and transport) in the environment and in industrial operations. To characterize better the thermodynamic behavior of PAH mixtures, the phase behavior of a binary (anthracene + phenanthrene) system was studied by differential scanning calorimetry, X-ray diffraction, and the Knudsen effusion technique. Mixtures of (anthracene + phenanthrene) exhibit non-ideal mixture behavior. They form a lower-melting, phenanthrene-rich phase with an initial melting temperature of 372 K (identical to the melting temperature of pure phenanthrene) and a vapor pressure of roughly lnP/Pa = −2.38. The phenanthrene-rich phase coexists with an anthracene-rich phase when the mole fraction of phenanthrene (xP) in the mixture is less than or equal to 0.80. Mixtures initially at xP = 0.90 consist entirely of the phenanthrene-rich phase and sublime at nearly constant vapor pressure and composition, consistent with azeotrope-like behavior. Quasi-azeotropy was also observed for very high-content anthracene mixtures (2.5 < xP < 5) indicating that anthracene may accommodate very low levels of phenanthrene in its crystal structure. PMID:26973354

  18. Validating the Equilibrium Stage Model for an Azeotropic System in a Laboratorial Distillation Column

    ERIC Educational Resources Information Center

    Duarte, B. P. M.; Coelho Pinheiro, M. N.; Silva, D. C. M.; Moura, M. J.

    2006-01-01

    The experiment described is an excellent opportunity to apply theoretical concepts of distillation, thermodynamics of mixtures and process simulation at laboratory scale, and simultaneously enhance the ability of students to operate, control and monitor complex units.

  19. The structural organization of N-methyl-2-pyrrolidone + water mixtures: A densitometry, x-ray diffraction, and molecular dynamics study

    SciTech Connect

    Usula, M.; Marincola, F. Cesare; Porcedda, S.; Mocci, F.; Gontrani, L.; Caminiti, R.

    2014-03-28

    A combined approach of molecular dynamics simulations, wide angle X-ray scattering experiments, and density measurements was employed to study the structural properties of N-methyl-2-pyrrolidone (NMP) + water mixtures over the whole concentration range. Remarkably, a very good agreement between computed and experimental densities and diffraction patterns was achieved, especially if the effect of the mixture composition on NMP charges is taken into account. Analysis of the intermolecular organization, as revealed by the radial and spatial distribution functions of relevant solvent atoms, nicely explained the density maximum observed experimentally.

  20. Densities and vapor-liquid equilibria in binary mixtures formed by propyl methanoate + ethanol, + propan-1-ol, and + butan-1-ol at 160.0 kPa

    SciTech Connect

    Falcon, J.; Ortega, J.; Gonzalez, E.

    1996-07-01

    Densities and excess volumes were determined at 298.15 K for propyl methanoate + ethanol, + propan-1-ol, and + butan-1-ol. The results of those quantities were then correlated to get the concentrations of vapor-liquid equilibrium obtained isobarically at 160 kPa for the same mixtures. Two mixtures show azeotropes: for propyl methanoate (1) + ethanol (2), x{sub 1} = 0.443 at T = 358.7 K; and for propyl methanoate (1) + propan-1-ol (2), x{sub 1} = 0.762 at T = 368.2 K. The mixtures are thermodynamically consistent, and the predictions made using several group-contribution models are satisfactory.

  1. Endocrine effects of real-life mixtures of persistent organic pollutants (POP) in experimental models and wild fish.

    PubMed

    Berg, Vidar; Kraugerud, Marianne; Nourizadeh-Lillabadi, Rasoul; Olsvik, Pål A; Skåre, Janneche U; Alestrøm, Peter; Ropstad, Erik; Zimmer, Karin Elisabeth; Lyche, Jan L

    2016-01-01

    A series of studies have assessed the occurrence, levels, and potential adverse effects of persistent organic pollutants (POP) in fish from Lake Mjøsa. In this lake, high levels of various POP were detected in biota. Fish from the nearby Lake Losna contain background levels of POP and served as reference (controls) in these studies. Significantly higher prevalence of mycobacteriosis and pathological changes were documented in burbot (Lota lota) from Mjøsa compared to burbot from Losna. Further, transcriptional profiling identified changes in gene expression in burbot from Mjøsa compared to burbot from Losna associated with drug metabolism enzymes and oxidative stress. POP extracted from burbot liver oil from the two lakes was used to expose zebrafish (Danio rerio) during two consecutive generations. During both generations, POP mixtures from both lakes increased the rate of mortality, induced earlier onset of puberty, and skewed sex ratio toward males. However, opposite effects on weight gain were found in exposure groups compared to controls during the two generations. Exposure to POP from both lakes was associated with suppression of ovarian follicle development. Analyses of genome-wide transcription profiling identified functional networks of genes associated with weight homeostasis, steroid hormone functions, and insulin signaling. In human cell studies using adrenocortical H295R and primary porcine theca and granulosa cells, exposure to lake extracts from both populations modulated steroid hormone production with significant difference from controls. The results suggest that POP from both lakes may possess the potential to induce endocrine disruption and may adversely affect health in wild fish. PMID:27484136

  2. Factors associated with sources, transport, and fate of volatile organic compounds and their mixtures in aquifers of the United States

    USGS Publications Warehouse

    Squillace, P.J.; Moran, M.J.

    2007-01-01

    Factors associated with sources, transport, and fate of volatile organic compounds (VOCs) in groundwater from aquifers throughout the United States were evaluated using statistical methods. Samples were collected from 1631 wells throughout the conterminous United States between 1996 and 2002 as part of the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey. Water samples from wells completed in aquifers used to supply drinking water were analyzed for more than 50 VOCs. Wells were primarily rural domestic water supplies (1184), followed by public water supplies (216); the remaining wells (231) supplied a variety of uses. The median well depth was 50 meters. Age-date information shows that about 60% of the samples had a fraction of water recharged after 1953. Chloroform, toluene, 1,2,4-trimethylbenzene, and perchloroethene were some of the frequently detected VOCs. Concentrations generally were less than 1 ??g/L. Source factors include, in order of importance, general land-use activity, septic/sewer density, and sites where large concentrations of VOCs are potentially released, such as leaking underground storage tanks. About 10% of all samples had VOC mixtures that were associated with concentrated sources; 20% were associated with dispersed sources. Important transport factors included well/screen depth, precipitation/groundwater recharge, air temperature, and various soil characteristics. Dissolved oxygen was strongly associated with VOCs and represents the fate of many VOCs in groundwater. Well type (domestic or public water supply) was also an important explanatory factor. Results of multiple analyses show the importance of (1) accounting for both dispersed and concentrated sources of VOCs, (2) measuring dissolved oxygen when sampling wells to help explain the fate of VOCs, and (3) limiting the type of wells sampled in monitoring networks to avoid unnecessary variance in the data, or controlling for this variance during data analysis.

  3. Influence of Seeding Ratio, Planting Date, and Termination Date on Rye-Hairy Vetch Cover Crop Mixture Performance under Organic Management.

    PubMed

    Lawson, Andrew; Cogger, Craig; Bary, Andy; Fortuna, Ann-Marie

    2015-01-01

    Cover crop benefits include nitrogen accumulation and retention, weed suppression, organic matter maintenance, and reduced erosion. Organic farmers need region-specific information on winter cover crop performance to effectively integrate cover crops into their crop rotations. Our research objective was to compare cover crop seeding mixtures, planting dates, and termination dates on performance of rye (Secale cereale L.) and hairy vetch (Vicia villosa Roth) monocultures and mixtures in the maritime Pacific Northwest USA. The study included four seed mixtures (100% hairy vetch, 25% rye-75% hairy vetch, 50% rye-50% hairy vetch, and 100% rye by seed weight), two planting dates, and two termination dates, using a split-split plot design with four replications over six years. Measurements included winter ground cover; stand composition; cover crop biomass, N concentration, and N uptake; and June soil NO3(-)-N. Rye planted in mid-September and terminated in late April averaged 5.1 Mg ha(-1) biomass, whereas mixtures averaged 4.1 Mg ha(-1) and hairy vetch 2.3 Mg ha(-1). Delaying planting by 2.5 weeks reduced average winter ground cover by 65%, biomass by 50%, and cover crop N accumulation by 40%. Similar reductions in biomass and N accumulation occurred for late March termination, compared with late April termination. Mixtures had less annual biomass variability than rye. Mixtures accumulated 103 kg ha(-1) N and had mean C:N ratio <17:1 when planted in mid-September and terminated in late April. June soil NO3(-)-N (0 to 30 cm depth) averaged 62 kg ha(-1) for rye, 97 kg ha(-1) for the mixtures, and 119 kg ha(-1) for hairy vetch. Weeds comprised less of the mixtures biomass (20% weeds by weight at termination) compared with the monocultures (29%). Cover crop mixtures provided a balance between biomass accumulation and N concentration, more consistent biomass over the six-year study, and were more effective at reducing winter weeds compared with monocultures.

  4. Influence of Seeding Ratio, Planting Date, and Termination Date on Rye-Hairy Vetch Cover Crop Mixture Performance under Organic Management

    PubMed Central

    Lawson, Andrew; Cogger, Craig; Bary, Andy; Fortuna, Ann-Marie

    2015-01-01

    Cover crop benefits include nitrogen accumulation and retention, weed suppression, organic matter maintenance, and reduced erosion. Organic farmers need region-specific information on winter cover crop performance to effectively integrate cover crops into their crop rotations. Our research objective was to compare cover crop seeding mixtures, planting dates, and termination dates on performance of rye (Secale cereale L.) and hairy vetch (Vicia villosa Roth) monocultures and mixtures in the maritime Pacific Northwest USA. The study included four seed mixtures (100% hairy vetch, 25% rye-75% hairy vetch, 50% rye-50% hairy vetch, and 100% rye by seed weight), two planting dates, and two termination dates, using a split-split plot design with four replications over six years. Measurements included winter ground cover; stand composition; cover crop biomass, N concentration, and N uptake; and June soil NO3--N. Rye planted in mid-September and terminated in late April averaged 5.1 Mg ha-1 biomass, whereas mixtures averaged 4.1 Mg ha-1 and hairy vetch 2.3 Mg ha-1. Delaying planting by 2.5 weeks reduced average winter ground cover by 65%, biomass by 50%, and cover crop N accumulation by 40%. Similar reductions in biomass and N accumulation occurred for late March termination, compared with late April termination. Mixtures had less annual biomass variability than rye. Mixtures accumulated 103 kg ha-1 N and had mean C:N ratio <17:1 when planted in mid-September and terminated in late April. June soil NO3--N (0 to 30 cm depth) averaged 62 kg ha-1 for rye, 97 kg ha-1 for the mixtures, and 119 kg ha-1 for hairy vetch. Weeds comprised less of the mixtures biomass (20% weeds by weight at termination) compared with the monocultures (29%). Cover crop mixtures provided a balance between biomass accumulation and N concentration, more consistent biomass over the six-year study, and were more effective at reducing winter weeds compared with monocultures. PMID:26080008

  5. CONTRIBUTIONS OF TOLUENE AND Α -PINENE TO SOA FORMED IN AN IRRADIATED TOLUENE/Α-PINENE/NOX/AIR MIXTURE: COMPARISON OF RESULTS USING 14C CONTENT AND SOA ORGANIC TRACER METHODS

    EPA Science Inventory

    An organic tracer method, recently proposed for estimating individual contributions of toluene and α-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydro...

  6. Parental exposure to natural mixtures of persistent organic pollutants (POP) induced changes in transcription of apoptosis-related genes in offspring zebrafish embryos.

    PubMed

    Lyche, Jan L; Grześ, Irena M; Karlsson, Camilla; Nourizadeh-Lillabadi, Rasoul; Aleström, Peter; Ropstad, Erik

    2016-01-01

    Apoptosis is an integral element of development that may also be initiated by environmental contaminants. The aim of the present study was to assess potential changes in the regulation of apoptotic genes in zebrafish embryos following parental exposure to two natural mixtures of persistent organic pollutants (POP). The mixture from Lake Mjøsa contained exceptionally high concentrations of polybrominated diphenyl ethers (PBDE), as well as relatively high levels of polychlorinated biphenyls (PCB) and dichlorodiphenyltrichloroethane (DDT). The mixture from Lake Losna contained background concentrations of POP. Genes involved in the apoptotic machinery were screened for their expression profile at four time points during embryonic development. Thirteen and 15 genes involved in apoptosis were found to be significantly upregulated in the high-exposure and background exposure groups, respectively, compared with controls. Modulation of apoptotic genes was restricted only to the first time point, which corresponds with the blastula stage. Although there were substantial differences in POP concentrations between mixtures, genes underlying the apoptosis process showed almost similar responses to the two mixtures. In both exposure groups the main executors of apoptosis p53, casp 2, casp 6, cassp 8, and BAX displayed upregulation compared to controls, suggesting that these POP induce apoptosis via a p53-dependent mechanism. Upregulation of genes that play a critical role in apoptosis suggests that disturbance of normal apoptotic signaling during gametogenesis and embryogenesis may be one of the central mechanisms involved in adverse reproductive effects produced by POP in zebrafish. PMID:27484141

  7. Adsorption of a binary gas mixture which laterally interacts on a random heterogeneous surface

    SciTech Connect

    Ritter, J.A.

    1992-10-01

    Analytical expressions for the adsorption of a binary gas mixture which laterally interacts on a heterogeneous surface are developed. The lateral interactions are of the Bragg-Williams type and the surface heterogeneity is modeled via a random distribution of sites described by a uniform distribution of Henry`s Law constants. The parametric study shows that complex phase behavior can be predicted, including azeotropes and sigmoidal shaped X-Y diagrams. Also, this model may be useful for modeling and designing adsorption processes as it requires few iterations to simultaneously solve the implicit and coupled algebraic expressions.

  8. Adsorption of a binary gas mixture which laterally interacts on a random heterogeneous surface

    SciTech Connect

    Ritter, J.A.

    1992-01-01

    Analytical expressions for the adsorption of a binary gas mixture which laterally interacts on a heterogeneous surface are developed. The lateral interactions are of the Bragg-Williams type and the surface heterogeneity is modeled via a random distribution of sites described by a uniform distribution of Henry's Law constants. The parametric study shows that complex phase behavior can be predicted, including azeotropes and sigmoidal shaped X-Y diagrams. Also, this model may be useful for modeling and designing adsorption processes as it requires few iterations to simultaneously solve the implicit and coupled algebraic expressions.

  9. Thermodynamic and kinetic control of charged, amphiphilic triblock copolymer assembly via interaction with organic counterions in solvent mixtures

    NASA Astrophysics Data System (ADS)

    Cui, Honggang

    2007-12-01

    Amphiphilic block copolymers, consisting of at least two types of monomers with different affinity to the dissolving solvent(s), have been recognized as a molecular building unit for their chemical tunability and design flexibility. Amphiphilic block copolymers with a chargeable block have structural features of polyelectrolytes, block copolymers and surfactants. The combination of these different features offers great flexibility for developing novel assembled morphologies at the nanoscale and outstanding ability to control and manipulate those morphologies. The nanostructures, formed from the spontaneous association of amphiphilic block copolymer in selective solvents, show promise for applications in nanotechnology and pharmaceuticals, including drug delivery, tissue engineering and bio-imaging. A basic knowledge of their modes of self-assembly and their correspondence to application-related properties is just now being developed and poses a considerable scientific challenge. The goal of this dissertation is to investigate the associative behavior of charged, amphiphilic block copolymers in solvent mixtures while in the presence of organic counterions. Self-assembly of poly (acrylic acid)- block-poly (methyl acrylate)-block-polystyrene (PAA- b-PMA-b-PS) triblock copolymers produces nanodomains in THF/water solution specifically through the interaction with organic counterions (polyamines). These assembled structures can include classic micelles (spheres, cylinders and vesicles), but, more importantly, include non-classic micelles (disks, toroids, branched micelles and segmented micelles). Each micelle structure is stable and reproducible at different assembly conditions. The assembled micellar structures depend on not only solution components (thermodynamics) but also mixing procedure and consequent self-assembly pathway (kinetics). The key factors that determine the thermodynamic interactions that partially define the assembled structures and the kinetic

  10. Neurobehavioral deficits and brain oxidative stress induced by chronic low dose exposure of persistent organic pollutants mixture in adult female rat.

    PubMed

    Lahouel, Asma; Kebieche, Mohamed; Lakroun, Zohra; Rouabhi, Rachid; Fetoui, Hamadi; Chtourou, Yassine; Djamila, Zama; Soulimani, Rachid

    2016-10-01

    Persistent organic pollutants (POPs) are long-lived organic compounds that are considered one of the major risks to ecosystem and human health. Recently, great concerns are raised about POPs mixtures and its potential toxicity even in low doses of daily human exposure. The brain is mostly targeted by these lipophilic compounds because of its important contain in lipids. So, it would be quite interesting to study the effects of exposure to these mixtures and evaluate their combined toxicity on brain cells. The present study was designed to characterize the cognitive and locomotors deficits and brain areas redox status in rat model. An orally chronic exposure to a representative mixture of POPs composed of endosulfan (2.6 μg/kg), chlorpyrifos (5.2 μg/kg), naphthalene (0.023 μg/kg) and benzopyrane (0.002 μg/kg); the same mixture with concentration multiplied by 10 and 100 was also tested. Exposed rats have shown a disturbance of memory and a decrease in learning ability concluded by Morris water maze and the open field tests results and anxiolytic behaviour in the test of light/dark box compared to control. Concerning brain redox homeostasis, exposed rats have shown an increased malondialdehyde (MDA) amount and an alteration in glutathione (GSH) levels in both the brain mitochondria and cytosolic fractions of the cerebellum, striatum and hippocampus. These effects were accompanied by a decrease in levels of cytosolic glutathione S-transferase (GST) and a highly significant increase in superoxide dismutase (SOD) and catalase (CAT) activities in both cytosolic and mitochondrial fractions. The current study suggests that environmental exposure to daily even low doses of POPs mixtures through diet induces oxidative stress status in the brain and especially in the mitochondria with important cognitive and locomotor behaviour variations in the rats.

  11. Neurobehavioral deficits and brain oxidative stress induced by chronic low dose exposure of persistent organic pollutants mixture in adult female rat.

    PubMed

    Lahouel, Asma; Kebieche, Mohamed; Lakroun, Zohra; Rouabhi, Rachid; Fetoui, Hamadi; Chtourou, Yassine; Djamila, Zama; Soulimani, Rachid

    2016-10-01

    Persistent organic pollutants (POPs) are long-lived organic compounds that are considered one of the major risks to ecosystem and human health. Recently, great concerns are raised about POPs mixtures and its potential toxicity even in low doses of daily human exposure. The brain is mostly targeted by these lipophilic compounds because of its important contain in lipids. So, it would be quite interesting to study the effects of exposure to these mixtures and evaluate their combined toxicity on brain cells. The present study was designed to characterize the cognitive and locomotors deficits and brain areas redox status in rat model. An orally chronic exposure to a representative mixture of POPs composed of endosulfan (2.6 μg/kg), chlorpyrifos (5.2 μg/kg), naphthalene (0.023 μg/kg) and benzopyrane (0.002 μg/kg); the same mixture with concentration multiplied by 10 and 100 was also tested. Exposed rats have shown a disturbance of memory and a decrease in learning ability concluded by Morris water maze and the open field tests results and anxiolytic behaviour in the test of light/dark box compared to control. Concerning brain redox homeostasis, exposed rats have shown an increased malondialdehyde (MDA) amount and an alteration in glutathione (GSH) levels in both the brain mitochondria and cytosolic fractions of the cerebellum, striatum and hippocampus. These effects were accompanied by a decrease in levels of cytosolic glutathione S-transferase (GST) and a highly significant increase in superoxide dismutase (SOD) and catalase (CAT) activities in both cytosolic and mitochondrial fractions. The current study suggests that environmental exposure to daily even low doses of POPs mixtures through diet induces oxidative stress status in the brain and especially in the mitochondria with important cognitive and locomotor behaviour variations in the rats. PMID:27240828

  12. Using molecular docking between organic chemicals and lipid membrane to revise the well known octanol-water partition coefficient of the mixture.

    PubMed

    Wang, Ting; Zhou, Xianghong; Wang, Dali; Yin, Daqiang; Lin, Zhifen

    2012-07-01

    The octanol-water partition coefficient of a mixture has been widely used to predict the baseline toxicity of non-polar narcotic chemical mixtures, since toxic effects are usually generated by multiple mixtures. However, it remains unclear whether the validity of log Kowmix can be demonstrated, because experimental methods cannot be used to determine this parameter. The invalidity and the further revision of log Kowmix were therefore studied by using molecular docking between non-polar narcotic chemicals and lipid membrane (E(binding)). The results show E(binding) is a feasible substitute parameter for log Kow because their relationship is linear. Based on a molecular docking and QSAR model, a new calculated method of log Kowmix was proposed as follows: log(Kowmix)=∑x(i)log Kowi. Comparison of this new method with the established methods demonstrates the invalidity of the latter, and therefore the former is suggested to be used to calculate the log Kowmix of organic chemical mixtures.

  13. Mixture Experiments

    SciTech Connect

    Piepel, Gregory F.

    2007-12-01

    A mixture experiment involves combining two or more components in various proportions or amounts and then measuring one or more responses for the resulting end products. Other factors that affect the response(s), such as process variables and/or the total amount of the mixture, may also be studied in the experiment. A mixture experiment design specifies the combinations of mixture components and other experimental factors (if any) to be studied and the response variable(s) to be measured. Mixture experiment data analyses are then used to achieve the desired goals, which may include (i) understanding the effects of components and other factors on the response(s), (ii) identifying components and other factors with significant and nonsignificant effects on the response(s), (iii) developing models for predicting the response(s) as functions of the mixture components and any other factors, and (iv) developing end-products with desired values and uncertainties of the response(s). Given a mixture experiment problem, a practitioner must consider the possible approaches for designing the experiment and analyzing the data, and then select the approach best suited to the problem. Eight possible approaches include 1) component proportions, 2) mathematically independent variables, 3) slack variable, 4) mixture amount, 5) component amounts, 6) mixture process variable, 7) mixture of mixtures, and 8) multi-factor mixture. The article provides an overview of the mixture experiment designs, models, and data analyses for these approaches.

  14. Effect of incorporation of walnut cake (Juglans regia) in concentrate mixture on degradation of dry matter, organic matter and production of microbial biomass in vitro in goat

    PubMed Central

    Mir, Mohsin Ahmad; Sharma, R. K.; Rastogi, Ankur; Barman, Keshab

    2015-01-01

    Aim: This study was carried out to investigate the effect of incorporation of different level of walnut cake in concentrate mixture on in vitro dry matter degradation in order to determine its level of supplementation in ruminant ration. Materials and Methods: Walnut cake was used @ 0, 10, 15, 20, 25 and 30% level to formulate an iso-nitrogenous concentrate mixtures and designated as T1, T2, T3, T4, T5 and T6 respectively. The different formulae of concentrate mixtures were used for in vitro gas production studies using goat rumen liquor with wheat straw in 40:60 ratio. Proximate composition, fiber fractionation and calcium and phosphrous content of walnut cake were estimated. Result: The per cent IVDMD value of T1 and T2 diets was 68.42 ± 1.20 and 67.25 ± 1.37 respectively which was found highest (P<0.05) T3, T4, T5 and T6. Similar trend was also found for TDOM and MBP. Inclusion of walnut cake at 10% level in the concentrate mixture does not affect in vitro dry matter digestibility (IVDMD), truly degradable organic matter (TDOM, mg/200 mg DM), total gas production, microbial biomass production (MBP) and efficiency of microbial biomass production (EMP). Conclusion: It is concluded that walnut cake incorporation up to 10% level in the iso -nitrogenous concentrate mixture has no any negative effect on in vitro digestibility of dry matter (DM), TDOM, MBP, EMP and total gas production in goat. PMID:27047013

  15. Efficiency of methods for Karl Fischer determination of water in oils based on oven evaporation and azeotropic distillation.

    PubMed

    Larsson, William; Jalbert, Jocelyn; Gilbert, Roland; Cedergren, Anders

    2003-03-15

    The efficiency of azeotropic distillation and oven evaporation techniques for trace determination of water in oils has recently been questioned by the National Institute of Standards and Technology (NIST), on the basis of measurements of the residual water found after the extraction step. The results were obtained by volumetric Karl Fischer (KF) titration in a medium containing a large excess of chloroform (> or = 65%), a proposed prerequisite to ensure complete release of water from the oil matrix. In this work, the extent of this residual water was studied by means of a direct zero-current potentiometric technique using a KF medium containing more than 80% chloroform, which is well above the concentration recommended by NIST. A procedure is described that makes it possible to correct the results for dilution errors as well as for chemical interference effects caused by the oil matrix. The corrected values were found to be in the range of 0.6-1.5 ppm, which should be compared with the 12-34 ppm (uncorrected values) reported by NIST for the same oils. From this, it is concluded that the volumetric KF method used by NIST gives results that are much too high. PMID:12659179

  16. Efficiency of methods for Karl Fischer determination of water in oils based on oven evaporation and azeotropic distillation.

    PubMed

    Larsson, William; Jalbert, Jocelyn; Gilbert, Roland; Cedergren, Anders

    2003-03-15

    The efficiency of azeotropic distillation and oven evaporation techniques for trace determination of water in oils has recently been questioned by the National Institute of Standards and Technology (NIST), on the basis of measurements of the residual water found after the extraction step. The results were obtained by volumetric Karl Fischer (KF) titration in a medium containing a large excess of chloroform (> or = 65%), a proposed prerequisite to ensure complete release of water from the oil matrix. In this work, the extent of this residual water was studied by means of a direct zero-current potentiometric technique using a KF medium containing more than 80% chloroform, which is well above the concentration recommended by NIST. A procedure is described that makes it possible to correct the results for dilution errors as well as for chemical interference effects caused by the oil matrix. The corrected values were found to be in the range of 0.6-1.5 ppm, which should be compared with the 12-34 ppm (uncorrected values) reported by NIST for the same oils. From this, it is concluded that the volumetric KF method used by NIST gives results that are much too high.

  17. Organic matter characteristics in boreal forest soils under stands of silver birch, Norway spruce, and Norway spruce with a mixture of silver birch

    NASA Astrophysics Data System (ADS)

    Smolander, A.; Kitunen, V.

    2012-04-01

    The aim was to study how tree species and a tree species mixture affect microbial C and N transformations and two major plant secondary compound groups, terpenes and phenolic compounds in soil. The study site was a tree-species experiment in middle-eastern part of Finland containing plots of 43-year-old silver birch, Norway spruce and Norway spruce with a mixture of silver birch (22 and 37 % birch of the total stem number). Soil was podzol and humus type mor. Samples were taken from the organic layer. C and N in the microbial biomass, rates of C mineralization (CO2 evolution), net N mineralization and nitrification, and concentrations of total water-soluble phenolic compounds, condensed tannins and different kind of terpenes were measured. Amounts of C and N in the microbial biomass and the rates of C mineralization and net N mineralization were all lower under spruce than birch, and particularly net N mineralization was stimulated by birch mixture. Concentrations of total water-soluble phenolic compounds were on a similar level, irrespective of tree species. However, there were less low-molecular-weight phenolics and more high-molecular-weight phenolics under spruce than birch. Concentrations of condensed tannins and both sesqui- and diterpenes were all higher under spruce than birch but the concentrations of triterpenes were similar in all soils. The difference between tree species was greatest with monoterpenes which were measured from both organic layer and soil atmosphere: high concentrations under spruce and negligible under birch. Birch mixture tended to decrease the concentrations of condensed tannins and mono-, sesqui- and diterpenes.

  18. Mixture effects of organic micropollutants present in water: towards the development of effect-based water quality trigger values for baseline toxicity.

    PubMed

    Tang, Janet Y M; McCarty, Shane; Glenn, Eva; Neale, Peta A; Warne, Michel St J; Escher, Beate I

    2013-06-15

    In this study we propose for the first time an approach for the tentative derivation of effect-based water quality trigger values for an apical endpoint, the cytotoxicity measured by the bioluminescence inhibition in Vibrio fischeri. The trigger values were derived for the Australian Drinking Water Guideline and the Australian Guideline for Water Recycling as examples, but the algorithm can be adapted to any other set of guideline values. In the first step, a Quantitative Structure-Activity Relationship (QSAR) describing the 50% effect concentrations, EC50, was established using chemicals known to act according to the nonspecific mode of action of baseline toxicity. This QSAR described the effect of most of the chemicals in these guidelines satisfactorily, with the exception of antibiotics, which were more potent than predicted by the baseline toxicity QSAR. The mixture effect of 10-56 guideline chemicals mixed at various fixed concentration ratios (equipotent mixture ratios and ratios of the guideline values) was adequately described by concentration addition model of mixture toxicity. Ten water samples were then analysed and 5-64 regulated chemicals were detected (from a target list of over 200 chemicals). These detected chemicals were mixed in the ratios of concentrations detected and their mixture effect was predicted by concentration addition. Comparing the effect of these designed mixtures with the effect of the water samples, it became evident that less than 1% of effect could be explained by known chemicals, making it imperative to derive effect-based trigger values. The effect-based water quality trigger value, EBT-EC50, was calculated from the mixture effect concentration predicted for concentration-additive mixture effects of all chemicals in a given guideline divided by the sum of the guideline concentrations for individual components, and dividing by an extrapolation factor that accounts for the number of chemicals contained in the guidelines and for

  19. Analytical Phase Equilibrium Function for Mixtures Obeying Raoult's and Henry's Laws

    NASA Astrophysics Data System (ADS)

    Hayes, Robert

    When a mixture of two substances exists in both the liquid and gas phase at equilibrium, Raoults and Henry's laws (ideal solution and ideal dilute solution approximations) can be used to estimate the gas and liquid mole fractions at the extremes of either very little solute or solvent. By assuming that a cubic polynomial can reasonably approximate the intermediate values to these extremes as a function of mole fraction, the cubic polynomial is solved and presented. A closed form equation approximating the pressure dependence on mole fraction of the constituents is thereby obtained. As a first approximation, this is a very simple and potentially useful means to estimate gas and liquid mole fractions of equilibrium mixtures. Mixtures with an azeotrope require additional attention if this type of approach is to be utilized. This work supported in part by federal Grant NRC-HQ-84-14-G-0059.

  20. Analytical Phase Equilibrium Function for Mixtures Obeying Raoult's and Henry's Laws

    NASA Astrophysics Data System (ADS)

    Hayes, Robert

    When a mixture of two substances exists in both the liquid and gas phase at equilibrium, Raoults and Henry's laws (ideal solution and ideal dilute solution approximations) can be used to estimate the gas and liquid mole fractions at the extremes of either very little solute or solvent. By assuming that a cubic polynomial can reasonably approximate the intermediate values to these extremes as a function of mole fraction, the cubic polynomial is solved and presented. A closed form equation approximating the pressure dependence on mole fraction of the constituents is thereby obtained. As a first approximation, this is a very simple and potentially useful means to estimate gas and liquid mole fractions of equilibrium mixtures. Mixtures with an azeotrope require additional attention if this type of approach is to be utilized. This work paid for under NRC-HQ-84-14-G-0059.

  1. Vapor-liquid equilibria for the binary difluoromethane (R-32) + propane (R-290) mixture

    SciTech Connect

    Higashi, Y. . Dept. of Mechanical Engineering)

    1999-03-01

    The vapor-liquid equilibrium of the mixture composed of difluoromethane (R-32) and propane (R-290) was studied in the temperature range between 273.15 and 313.15 K. The experimental uncertainties of temperature, pressure, and composition measurements were estimated to be within [+-]10 mK, [+-]3 kPa, and [+-]0.4 mol%, respectively. Comparisons between the present data and available experimental data were made using the Helmholz free energy mixture model (HMM) adopted in the thermophysical properties program package, REFPOP 6.0, as a baseline. In addition, the existence of an azeotrope and the determination of new adjustable parameters for HMM for the R-32 + R-290 mixture are discussed.

  2. Vapor-liquid equilibria for the binary difluoromethane (R-32) + propane (R-290) mixture

    SciTech Connect

    Higashi, Y.

    1999-03-01

    The vapor-liquid equilibrium of the mixture composed of difluoromethane (R-32) and propane (R-290) was studied in the temperature range between 273.15 and 313.15 K. The experimental uncertainties of temperature, pressure, and composition measurements were estimated to be within {+-}10 mK, {+-}3 kPa, and {+-}0.4 mol%, respectively. Comparisons between the present data and available experimental data were made using the Helmholz free energy mixture model (HMM) adopted in the thermophysical properties program package, REFPOP 6.0, as a baseline. In addition, the existence of an azeotrope and the determination of new adjustable parameters for HMM for the R-32 + R-290 mixture are discussed.

  3. Improved anaerobic digestion of a thermally pretreated mixture of physicochemical sludge; broiler excreta and sugar cane wastes (SCW): Effect on organic matter solubilization, biodegradability and bioenergy production.

    PubMed

    Nava-Valente, Noemí; Alvarado-Lassman, Alejandro; Nativitas-Sandoval, Liliana S; Mendez-Contreras, Juan M

    2016-01-01

    Thermal pretreatment effect of a mixture of organic wastes (physicochemical sludge, excreta of broiler chickens and sugarcane wastes (SCW)) in the solubilization and biodegradability organic matter as well as bioenergy production by anaerobic digestion was evaluated. Two different mixtures of physicochemical sludge, excreta of broiler chickens and SCW (70%, 15%, 15% and 60%, 20%, 20% of VS, respectively) were treated at different temperatures (80 °C, 85 °C and 90 °C) and contact time (30, 60 and 90 min). Results indicate that, organic matter solubilization degree increased from 1.14 to 6.56%; subsequently, in the anaerobic digestion process, an increase of 50% in the volatile solids removal and 10% in biogas production was observed, while, retention time decreased from 23 up to 9 days. The results obtained were similar to pilot-scale. In both experimental scales it showed that the synergy produced by the simultaneous anaerobic digestion of different substrates could increase bioenergy production up to 1.3 L bio g(-1) VS removed and 0.82 L CH4 g(-1) VS removed. The treatment conditions presented in this study allow for large residue quantities to be treated and large bioenergy quantities to be produced (10% higher than during conventional treatment) without increasing the anaerobic digester volume.

  4. Improved anaerobic digestion of a thermally pretreated mixture of physicochemical sludge; broiler excreta and sugar cane wastes (SCW): Effect on organic matter solubilization, biodegradability and bioenergy production.

    PubMed

    Nava-Valente, Noemí; Alvarado-Lassman, Alejandro; Nativitas-Sandoval, Liliana S; Mendez-Contreras, Juan M

    2016-01-01

    Thermal pretreatment effect of a mixture of organic wastes (physicochemical sludge, excreta of broiler chickens and sugarcane wastes (SCW)) in the solubilization and biodegradability organic matter as well as bioenergy production by anaerobic digestion was evaluated. Two different mixtures of physicochemical sludge, excreta of broiler chickens and SCW (70%, 15%, 15% and 60%, 20%, 20% of VS, respectively) were treated at different temperatures (80 °C, 85 °C and 90 °C) and contact time (30, 60 and 90 min). Results indicate that, organic matter solubilization degree increased from 1.14 to 6.56%; subsequently, in the anaerobic digestion process, an increase of 50% in the volatile solids removal and 10% in biogas production was observed, while, retention time decreased from 23 up to 9 days. The results obtained were similar to pilot-scale. In both experimental scales it showed that the synergy produced by the simultaneous anaerobic digestion of different substrates could increase bioenergy production up to 1.3 L bio g(-1) VS removed and 0.82 L CH4 g(-1) VS removed. The treatment conditions presented in this study allow for large residue quantities to be treated and large bioenergy quantities to be produced (10% higher than during conventional treatment) without increasing the anaerobic digester volume. PMID:26819145

  5. The dynamic behavior of a liquid ethanol-water mixture: a perspective from quantum chemical topology.

    PubMed

    Mejía, Sol M; Mills, Matthew J L; Shaik, Majeed S; Mondragon, Fanor; Popelier, Paul L A

    2011-05-01

    Quantum Chemical Topology (QCT) is used to reveal the dynamics of atom-atom interactions in a liquid. A molecular dynamics simulation was carried out on an ethanol-water liquid mixture at its azeotropic concentration (X(ethanol)=0.899), using high-rank multipolar electrostatics. A thousand (ethanol)(9)-water heterodecamers, respecting the water-ethanol ratio of the azeotropic mixture, were extracted from the simulation. Ab initio electron densities were computed at the B3LYP/6-31+G(d) level for these molecular clusters. A video shows the dynamical behavior of a pattern of bond critical points and atomic interaction lines, fluctuating over 1 ns. A bond critical point distribution revealed the fluctuating behavior of water and ethanol molecules in terms of O-H···O, C-H···O and H···H interactions. Interestingly, the water molecule formed one to six C-H···O and one to four O-H···O interactions as a proton acceptor. We found that the more localized a dynamical bond critical point distribution, the higher the average electron density at its bond critical points. The formation of multiple C-H···O interactions affected the shape of the oxygen basin of the water molecule, which is shown in three dimensions. The hydrogen atoms of water strongly preferred to form H···H interactions with ethanol's alkyl hydrogen atoms over its hydroxyl hydrogen.

  6. Deposition and characterization of organic polymer thin films using a dielectric barrier discharge with different C2Hm/N2 (m = 2, 4, 6) gas mixtures

    NASA Astrophysics Data System (ADS)

    Chandrashekaraiah, Thejaswini Halethimmanahally; Bogdanowicz, Robert; Danilov, Vladimir; Schäfer, Jan; Meichsner, Jürgen; Hippler, Rainer

    2015-06-01

    Organic polymer thin films have been deposited on Si(100) and aluminum coated glass substrates by a dielectric barrier discharge (DBD) operated at medium pressure using different C2H m /N2 ( m = 2, 4, 6) gas mixtures. The deposited films were characterized by various spectroscopic techniques. Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) revealed the chemical functional groups present in the films. The surface chemical compositions have been derived from X-ray photo electron spectroscopy (XPS). FT-IRRAS and XPS show the presence of sp, s p 2 and s p 3 bonds of carbon and nitrogen. Various functional groups such as NH containing, saturated and unsaturated alkyl groups have been identified. Thin films obtained from C2H2/N2 and C2H4/N2 gas mixtures revealed a higher N/C ratio when compared to thin films obtained from C2H6/N2. Thickness, refractive index and extinction coefficient were evaluated by spectroscopic ellipsometry (SE). Significant differences between the films obtained with different gas mixtures are observed.

  7. Deposition and characterization of organic polymer thin films using a dielectric barrier discharge with different C2Hm/N2 (m = 2, 4, 6) gas mixtures

    NASA Astrophysics Data System (ADS)

    Halethimmanahally Chandrashekaraiah, Thejaswini; Bogdanowicz, Robert; Danilov, Vladimir; Schäfer, Jan; Meichsner, Jürgen; Hippler, Rainer

    2015-06-01

    Organic polymer thin films have been deposited on Si(100) and aluminum coated glass substrates by a dielectric barrier discharge (DBD) operated at medium pressure using different C2Hm/N2 (m = 2, 4, 6) gas mixtures. The deposited films were characterized by various spectroscopic techniques. Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) revealed the chemical functional groups present in the films. The surface chemical compositions have been derived from X-ray photo electron spectroscopy (XPS). FT-IRRAS and XPS show the presence of sp, sp2 and sp3 bonds of carbon and nitrogen. Various functional groups such as NH containing, saturated and unsaturated alkyl groups have been identified. Thin films obtained from C2H2/N2 and C2H4/N2 gas mixtures revealed a higher N/C ratio when compared to thin films obtained from C2H6/N2. Thickness, refractive index and extinction coefficient were evaluated by spectroscopic ellipsometry (SE). Significant differences between the films obtained with different gas mixtures are observed.

  8. Orientational order, molecular organization, and dynamics in mixtures of bent-core and rod-shaped mesogens: a 2H NMR study.

    PubMed

    Calucci, Lucia; Fodor-Csorba, Katalin; Forte, Claudia; Geppi, Marco

    2011-01-27

    Mixtures of a bent-core mesogen (ClPbis10BB) and a calamitic mesogen (6OO8), showing a nematic phase over the entire compositional range and one or two smectic phases (namely, SmA, SmC, or SmC(A)) below the nematic one over a wide concentration range, were investigated by means of (2)H NMR spectroscopy, exploiting selectively deuterated isotopomers of both mesogens. The analysis of (2)H NMR spectra recorded in the liquid crystalline phases on several representative mixtures gave information on the orientational order properties and the molecular organization within the phases as well as on the alignment properties upon application of a magnetic field. On the other hand, the analysis of (2)H longitudinal relaxation times (T(1Z) and T(1Q)) in 6OO8-d(2)/ClPbis10BB mixtures and pure 6OO8-d(2) allowed the influence of the bent-core mesogen on the dynamics of the calamitic one to be highlighted.

  9. Pesticide Toxicity Index--a tool for assessing potential toxicity of pesticide mixtures to freshwater aquatic organisms.

    PubMed

    Nowell, Lisa H; Norman, Julia E; Moran, Patrick W; Martin, Jeffrey D; Stone, Wesley W

    2014-04-01

    Pesticide mixtures are common in streams with agricultural or urban influence in the watershed. The Pesticide Toxicity Index (PTI) is a screening tool to assess potential aquatic toxicity of complex pesticide mixtures by combining measures of pesticide exposure and acute toxicity in an additive toxic-unit model. The PTI is determined separately for fish, cladocerans, and benthic invertebrates. This study expands the number of pesticides and degradates included in previous editions of the PTI from 124 to 492 pesticides and degradates, and includes two types of PTI for use in different applications, depending on study objectives. The Median-PTI was calculated from median toxicity values for individual pesticides, so is robust to outliers and is appropriate for comparing relative potential toxicity among samples, sites, or pesticides. The Sensitive-PTI uses the 5th percentile of available toxicity values, so is a more sensitive screening-level indicator of potential toxicity. PTI predictions of toxicity in environmental samples were tested using data aggregated from published field studies that measured pesticide concentrations and toxicity to Ceriodaphnia dubia in ambient stream water. C. dubia survival was reduced to ≤50% of controls in 44% of samples with Median-PTI values of 0.1-1, and to 0% in 96% of samples with Median-PTI values >1. The PTI is a relative, but quantitative, indicator of potential toxicity that can be used to evaluate relationships between pesticide exposure and biological condition.

  10. Detailed Chemical Characterization of Unresolved Complex Mixtures (UCM) inAtmospheric Organics: Insights into Emission Sources, Atmospheric Processing andSecondary Organic Aerosol Formation

    EPA Science Inventory

    Recent studies suggest that semivolatile organic compounds (SVOCs) are important precursors to secondary organic aerosol (SOA) in urban atmospheres. However, knowledge of the chemical composition of SVOCs is limited by current analytical techniques, which are typically unable to...

  11. Secondary Organic Aerosol Formation from the Photooxidation of Complex Hydrocarbon Mixtures: Composition, effect of SO2, and Relevance to Ambient Aerosol

    NASA Astrophysics Data System (ADS)

    Surratt, J. D.; Gao, S.; Knipping, E.; Edgerton, E.; Shahgoli, M.; Seinfeld, J. H.; Edney, E.; Kleindiesnt, T.; Lewandowski, M.; Offenberg, J.; Jaoui, M.

    2005-12-01

    Secondary organic aerosol (SOA) formation from single hydrocarbon precursors is commonly studied in smog chamber experiments to obtain SOA yield and organic composition data. However, very few complex air mixture experiments have been conducted to simulate possible conditions in ambient atmospheres. A six-phase experiment involving various combinations of alpha-pinene, toluene, isoprene, and SO2 were irradiated in the EPA's dynamic smog chamber at the National Exposure Research Laboratory in Raleigh, NC. Glass fiber filters and impactor plates were collected for each phase of the experiment to identify and quantify the nature of the SOA composition. The following suite of analytical techniques analyzed the resultant polar organic compounds and the high molecular weight species: liquid chromatography-electrospray ionization (ESI)-mass spectrometry, gas chromatography-mass spectrometry, ESI-ion trap mass spectrometry, matrix assisted laser desorption (MALDI)-time of flight mass spectrometry, and high-resolution mass spectrometry. When SO2 is present in the chamber, increases in the gravimetric aerosol mass concentration and in the abundance of polar organic compounds are observed, likely suggesting an acid catalysis effect stemming from the conversion of SO2 to H2SO4 that condenses onto aerosol formed. The addition of isoprene to a alpha-pinene/toluene mixture is found to lower the amount of aerosol produced and is also found to lower the abundance of organic compounds identified by the various analytical techniques. Lastly, many of the polar organic compounds identified and quantified here are also seen in the Southeastern Aerosol Research and Characterization (SEARCH) network during the summer of 2004. In particular, a sulfur and nitrogen containing organic species (MW = 295 gmol) is found to be the most abundant polar organic species identified in this field study (~28 % on average of the total identified organic mass). This species is also detected in the chamber

  12. Improving the (18)F-fluoromethylcholine ((18)F-FCH) radiochemical yield via optimising the azeotropic drying of non-carrier-added (18)F-fluorine.

    PubMed

    Hassan, Hishar; Abu Bakar, Suharzelim; Halim, Khairul Najah Che A; Idris, Jaleezah; Ahmad Saad, Fathinul Fikri; Nordin, Abdul Jalil

    2015-01-01

    (18)F-Fluoromethylcholine ((18)F-FCH) has been suggested as one of the reputable imaging tracers for diagnosis of prostate tumour in PET/CT examination. Nevertheless, it has never been synthesised in Malaysia. We acknowledged the major problem with (18)F-FCH is due to its relatively low radiochemical yield at the end of synthesis (EOS). Therefore, this technical note presents improved (18)F-FCH radiochemical yields after carrying out optimisation on azeotropic drying of non-carrier-added (18)F-Fluorine.

  13. Molecular composition of fresh and aged secondary organic aerosol from a mixture of biogenic volatile compounds: a high-resolution mass spectrometry study

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Doussin, J.-F.; Giorio, C.; Mahon, B.; Wilson, E. M.; Maurin, N.; Pangui, E.; Venables, D. S.; Wenger, J. C.; Kalberer, M.

    2015-05-01

    Field observations over the past decade indicate that a significant fraction of organic aerosol in remote areas may contain highly oxidized molecules. Aerosol processing or further oxidation (aging) of organic aerosol has been suggested to be responsible for their formation through heterogeneous reaction with oxidants and multigenerational oxidation of vapours by OH radicals. In this study we investigated the influence of several aging processes on the molecular composition of secondary organic aerosols (SOA) using direct infusion and liquid chromatography high-resolution mass spectrometry. SOA was formed in simulation chamber experiments from ozonolysis of a mixture of four biogenic volatile organic compounds (BVOC): α-pinene, β-pinene, Δ3-carene and isoprene. The SOA was subsequently aged under three different sets of conditions: in the dark in the presence of residual ozone, with UV irradiation and OH radicals, and using UV light only. Among all studied conditions, only OH radical-initiated aging was found to influence the molecular composition of the aerosol and showed an increase in carbon oxidation state (OSC) and elemental O / C ratios of the SOA components. None of the aging processes produced an observable effect on the oligomers formed from ozonolysis of the BVOC mixture, which were found to be equally abundant in both "fresh" and "aged" SOA. Additional experiments using α-pinene as the sole precursor demonstrated that oligomers are an important group of compounds in SOA produced from both ozonolysis and OH radical-initiated oxidation processes; however, a completely different set of oligomers is formed under these two oxidation regimes. SOA from the OH-initiated oxidation of α-pinene had a significantly higher overall OSC and O / C compared to that from pure ozonolysis experiments confirming that the OH radical reaction is more likely to be responsible for the occurrence of highly oxidized species in ambient biogenic SOA.

  14. The Effect of Circuiting Arrangement on the Thermal Performance of Refrigeration Mixtures in Tube-and-Fin Condensing Heat Exchangers

    SciTech Connect

    Chen, D.T.; Conklin, J.C.

    1999-03-15

    For the pure or azeotropic refrigerants typically used in present air conditioning and refrigeration applications, the refrigerant changes phase at a constant temperature. Thus, the refrigerant circuiting arrangement such as crossfiow, counterfiow, or cross-counterflow, has no effect on the thermal performance. For zeotropic refrigerant mixtures, however, the phase-change occurs over a temperature range, or "glide", and the refrigerant circuiting arrangement, or flow path through the heat exchanger, can affect the thermal performance of both the heat exchangers as well as the overall efficiency of the vapor compression cooling cycle. The effects of tsvo diflerent circuiting arrangements on the thermal performance of a zeotropic retligerant mixture and an almost azeotropic refrigerant mixture in a four-row cross-countertlow heat exchanger arrangement are reported here. The two condensers differ only in the manner of circuiting the refrigerant tubes, where one has refrigerant always flowing downward in the active heat transfer region ("identical order") and the other has refrigerant alternating flow direction in the active heat transfer region ("inverted order"). All other geometric parameters, such as bce are% fin louver geometry, refrigerant tube size and enhancement etc., are the same for both heat exchangers. One refrigerant mixture (R-41OA) un&rgoes a small temperature change ("low glide") during phase change, and the other retligerant mixture (a multi- component proprietary mixture) has a substantial temperature change ("high glide") of approximately 10"C during the phase change process. The overall thermal conductance, two-phase conductance, and pressure drop are presented. For the flow conditions of these tests, which are representative of resi&ntial cooling conditions, inverted order circuiting is more desirable than identical order. The potential thermal advantages of the i&ntical order arrangement for high-glide zeotropic refrigerant mixtures are negated

  15. A predictive method for crude oil volatile organic compounds emission from soil: evaporation and diffusion behavior investigation of binary gas mixtures.

    PubMed

    Wang, Haijing; Fischer, Thomas; Wieprecht, Wolfgang; Möller, Detlev

    2015-05-01

    Due to their mobility and toxicity, crude oil volatile organic compounds (VOCs) are representative components for oil pipeline contaminated sites detection. Therefore, contaminated location risk assessment, with airborne light detection and ranging (LIDAR) survey, in particular, requires ground-based determinative methods for oil VOCs, the interaction between oil VOCs and soil, and information on how they diffuse from underground into atmosphere. First, we developed a method for determination of crude oil VOC binary mixtures (take n-pentane and n-hexane as examples), taking synergistic effects of VOC mixtures on polydimethylsiloxane (PDMS) solid-phase microextraction (SPME) fibers into consideration. Using this method, we further aim to extract VOCs from small volumes, for example, from soil pores, using a custom-made sampling device for nondestructive SPME fiber intrusion, and to study VOC transport through heterogeneous porous media. Second, specific surface Brunauer-Emmett-Teller (BET) analysis was conducted and used for estimation of VOC isotherm parameters in soil. Finally, two models were fitted for VOC emission prediction, and the results were compared to the experimental emission results. It was found that free diffusion mode worked well, and an empirical correction factor seems to be needed for the other model to adapt to our condition for single and binary systems.

  16. Performance of innovative PU-foam and natural fiber-based composites for the biofiltration of a mixture of volatile organic compounds by a fungal biofilm.

    PubMed

    Gutiérrez-Acosta, O B; Arriaga, S; Escobar-Barrios, V A; Casas-Flores, S; Almendarez-Camarillo, A

    2012-01-30

    The performance of perlite and two innovative carriers that consist of polyurethane (PU) chemically modified with starch; and polypropylene reinforced with agave fibers was evaluated in the biofiltration of a mixture of VOCs composed of hexane, toluene and methyl-ethyl-ketone. At a total organic loading rate of 145 gCm(-3)h(-1) the elimination capacities (ECs) obtained were 145, 24 and 96 gCm(-3)h(-1) for the biofilters packed with the PU, the reinforced polypropylene, and perlite, respectively. Specific maximum biodegradation rates of the mixture, in the biofilters, were 416 mgCg(protein)(-1)  h(-1) for the PU and 63 mgCg(protein)(-1) h(-1) for perlite, which confirms the highest performance of the PU-composite. 18S rDNA analysis from the PU-biofilter revealed the presence of Fusarium solani in its sexual and asexual states, respectively. The modified PU carrier significantly reduced the start-up period of the biofilter and enhanced the EC of the VOCs. Thus, this study gives new alternatives in the field of packing materials synthesis, promoting the addition of easily biodegradable sources to enhance the performance of biofilters.

  17. Letter: Fast detection of polycyclic aromatic hydrocarbons in complex mixtures of organic compounds based on gas chromatography-mass spectrometry with atmospheric pressure photoionization.

    PubMed

    Revelsky, Igor A; Tikhonova, I N; Yashin, Yu S

    2015-01-01

    The research is devoted to the investigation of the selectivity detection of 16 polycyclic aromatic hydrocarbons (PAHs) using gas chromatography-mass spectrometry (GC-MS), electron ionization (EI) GC-MS with atmospheric pressure photoionization (APPhI) and GC-MS atmospheric pressure photochemical ionization (APPhCI) when vapors of different substances (benzene, toluene, and naphthalene) were used as gas reagents. Capillary columns of different lengths were used for the separation of the components of the mixture of 44 semivolatile organic compounds. It was shown that the most-selective detection of 16 PAHs in a 44- component mixture was possible when GC-MS APPhCI was used. Only 16 PAHs were registered on the respective mass chromatograms and a fast detection of them was possible. The respective APPhI and APPhCI mass spectra consisted of only peak of the respective molecular ion, M⁺⁺ - the radical cation. Detection limits were 3 pg μL⁻¹ to 15 pg μL. PMID:26579932

  18. Induced Mesophase in Mixtures of Photopolymerizable Hyperbranched Polyester and Liquid Crystal Mesogen

    NASA Astrophysics Data System (ADS)

    Kim, Namil; Kyu, Thein; Nosaka, Mami; Kudo, Hiroto; Nishikubo, Tadatomi

    2008-03-01

    Phase behavior of a mixture of eutectic liquid crystals (E7) and hyperbranched polyester (HBPEAc-COOH) has been investigated using polarized optical microscopy and differential scanning calorimetry. The observed phase diagram is an upper azeotrope, exhibiting the coexistence of nematic + isotropic phase in the vicinity of 90˜110^oC above the clearing temperature of neat E7 (60^oC). With decreasing temperature a focal-conic fan shaped texture develops in the composition range of 70˜90 wt% of E7, suggestive of induced smectic Sm-A phase in the mixture containing no known smectic phase in their neat forms. Wide angle x-ray diffraction (WAXD) technique revealed the existence of higher order mesophase(s). The phenomenon of induced mesophase in the hyperbranched polyester/E7 system will be discussed.

  19. New theoretical model and experiments on the leakage of refrigerant mixtures in a tank

    SciTech Connect

    Gao, Z.; Schreiber, W.; Ma, Y.

    1999-07-01

    A theoretical model of the isothermal leakage of refrigerant mixtures from a tank is presented. The model analyzes the isothermal leakage process of non-azeotropic mixture and the influence of leakage ratio on composition shift, vapor quality, and pressure. A simulation based on the model shows: (1) the composition shift caused by vapor leakage is more pronounced than by liquid leakage; (2) with the leakage ratio increasing, the composition shift trend varies with initial mass capacity, particularly when the leakage ratio is greater than 0.8; (3) the pressure drop is pronounced during the vapor leakage, but does not change during liquid leakage unless the leakage ratio is high. A series of leakage experiments are performed in a newly developed experimental system. The theoretical and experimental results match closely.

  20. A numerical procedure for simulation of Fanno flows of refrigerants or refrigerant mixtures in capillary tubes

    SciTech Connect

    Chung, M.

    1998-12-31

    An ordinary differential equation (ODE), particularly suitable for numerical simulations of Fanno flows in capillary tubes, is derived by combining the conservation equations. Taking pressure as the independent variable, better control over design variables is achieved and the singularities involved in the choked flows can be avoided. For refrigerants without temperature glide, such as pure refrigerants or azeotropic refrigerant mixtures, the single ODE can be easily integrated if the saturation thermodynamic properties are given. For nonazeotropic refrigerant mixtures (NARMs), iteration in the temperature glide zone is required. As an alternative procedure for the iteration, a system of two ODEs is derived by taking thermodynamic relations into account. The system of ODE is not only in a numerically efficient form but also reveals important physics regarding choking. Sample numerical results for ternary NARM R-407C are presented to show the performance of the proposed procedures.

  1. Induced smectic phase in mixtures of hyperbranched polyester and liquid crystal mesogens.

    PubMed

    Kim, Namil; Huang, Tsang-Min; Kyu, Thein; Nosaka, Mami; Kudo, Hiroto; Nishikubo, Tadatomi

    2008-10-23

    The phase diagram of a mixture consisting of hyperbranched polyester (HBPEAc-COOH) and eutectic nematic liquid crystals (E7) has been established experimentally by means of differential scanning calorimetry and polarized optical microscopy subjected to prolonged annealing. The observed phase diagram is an upper azeotrope, exhibiting the coexistence of nematic + isotropic phase in the vicinity of 90 approximately 110 degrees C above the clearing temperature of neat E7 (60 degrees C). With decreasing temperature, a focal-conic fan shaped texture develops in the composition range of 63 approximately 93 wt % of the annealed E7/HBPEAc-COOH blends, suggestive of induced smectic phase in the mixture. Wide angle X-ray diffraction (WAXD) technique revealed the existence of higher order mesophase(s).

  2. Carcinogenic mixtures.

    PubMed

    Krewski, D; Thomas, R D

    1992-03-01

    Human populations are generally exposed simultaneously to a number of toxicants present in the environment, including complex mixtures of unknown and variable origin. While scientific methods for evaluating the potential carcinogenic risks of pure compounds are relatively well established, methods for assessing the risks of complex mixtures are somewhat less developed. This article provides a report of a recent workshop on carcinogenic mixtures sponsored by the Committee on Toxicology of the U.S. National Research Council, in which toxicological, epidemiological, and statistical approaches to carcinogenic risk assessment for mixtures were discussed. Complex mixtures, such as diesel emissions and tobacco smoke, have been shown to have carcinogenic potential. Bioassay-directed fractionation based on short-term screening test for genotoxicity has also been used in identifying carcinogenic components of mixtures. Both toxicological and epidemiological studies have identified clear interactions between chemical carcinogens, including synergistic effects at moderate to high doses. To date, laboratory studies have demonstrated over 900 interactions involving nearly 200 chemical carcinogens. At lower doses, theoretical arguments suggest that risks may be near additive. Thus, additivity at low doses has been invoked as as a working hypothesis by regulatory authorities in the absence of evidence to the contrary. Future studies of the joint effects of carcinogenic agents may serve to elucidate the mechanisms by which interactions occur at higher doses.

  3. Hierarchical max-flow segmentation framework for multi-atlas segmentation with Kohonen self-organizing map based Gaussian mixture modeling.

    PubMed

    Rajchl, Martin; Baxter, John S H; McLeod, A Jonathan; Yuan, Jing; Qiu, Wu; Peters, Terry M; Khan, Ali R

    2016-01-01

    The incorporation of intensity, spatial, and topological information into large-scale multi-region segmentation has been a topic of ongoing research in medical image analysis. Multi-region segmentation problems, such as segmentation of brain structures, pose unique challenges in image segmentation in which regions may not have a defined intensity, spatial, or topological distinction, but rely on a combination of the three. We propose a novel framework within the Advanced segmentation tools (ASETS)(2), which combines large-scale Gaussian mixture models trained via Kohonen self-organizing maps, with deformable registration, and a convex max-flow optimization algorithm incorporating region topology as a hierarchy or tree. Our framework is validated on two publicly available neuroimaging datasets, the OASIS and MRBrainS13 databases, against the more conventional Potts model, achieving more accurate segmentations. Each component is accelerated using general-purpose programming on graphics processing Units to ensure computational feasibility. PMID:26072170

  4. Hydrophobic treatment of organics against glass employing nonequilibrium atmospheric pressure pulsed plasmas with a mixture of CF{sub 4} and N{sub 2} gases

    SciTech Connect

    Inui, Hirotoshi; Takeda, Keigo; Ishikawa, Kenji; Sekine, Makoto; Hori, Masaru; Yara, Takuya; Uehara, Tsuyoshi

    2011-01-01

    A hydrophobic organics surface selectively against glass was realized by employing nonequilibrium atmospheric-pressure pulsed plasmas with a mixture of CF{sub 4} and N{sub 2} gases. The organic surface was drastically altered to have a high hydrophobicity, while the glass surface itself remained hydrophilic after the plasma treatment with the addition of a small amount of CF{sub 4} to the N{sub 2} gas. After 100 CF{sub 4}/N{sub 2} plasma treatments, no thin film deposition was observed on the organic material. To investigate the characteristics of the CF{sub 4}/N{sub 2} plasma, the exhaust gas from the plasma was measured by using ion attachment mass spectroscopy (IAMS). The IAMS spectrum indicated that the amounts of CF{sub 3} and F radicals were increased drastically with increasing addition of CF{sub 4}. A mechanism of the selective surface modification was clarified on a result of surface chemical bonding with the gas phase.

  5. Molecular modeling of phase behavior and microstructure of acetone-chloroform-methanol binary mixtures.

    PubMed

    Kamath, Ganesh; Georgiev, Grigor; Potoff, Jeffrey J

    2005-10-20

    Force fields based on a Lennard-Jones (LJ) 12-6 plus point charge functional form are developed for acetone and chloroform specifically to reproduce the minimum pressure azeotropy found experimentally in this system. Point charges are determined from a CHELPG population analysis performed on an acetone-chloroform dimer. The required electrostatic surface for this dimer is determined from ab initio calculations performed with MP2 theory and the 6-31g++(3df,3pd) basis set. LJ parameters are then optimized such that the liquid-vapor coexistence curve, critical parameters, and vapor pressures are well reproduced by simulation. Histogram-reweighting Monte Carlo simulations in the grand canonical ensemble are used to determine the phase diagrams for the binary mixtures acetone-chloroform, acetone-methanol, and chloroform-methanol. The force fields developed in this work reproduce the minimum pressure azeotrope in the acetone-chloroform mixture found in experiment. The predicted azeotropic composition of x(CHCl3) = 0.77 is in fair agreement with the experimental value of x(CHCl3)expt = 0.64. The new force fields were also found to provide improved predictions of the pressure-composition behavior of acetone-methanol and chloroform-methanol when compared to other force fields commonly used for vapor-liquid equilibria calculations. NPT simulations were conducted at 300 K and 1 bar for equimolar mixtures of acetone-chloroform, acetone-methanol, and methanol-chloroform. Analysis of the microstructure reveals significant hydrogen bonding occurring between acetone and chloroform. Limited interspecies hydrogen bonding was found in the acetone-methanol or chloroform-methanol mixtures.

  6. A case study on co-exposure to a mixture of organic solvents in a Tunisian adhesive-producing company

    PubMed Central

    2011-01-01

    Objectives to assess environmental and biological monitoring of exposure to organic solvents in a glue-manufacturing company in Sfax, Tunisia. Methods Exposure of volunteer workers, in the solvented glue-work-stations, in the control laboratory and in the storage rooms of the finished products, was assessed through indoor-air and urine measurements. Informed consent of the workers was obtained. Results and discussion The exposure indexes were found with high values in the solvented workshop as well as in the control laboratory and were respectively, 8.40 and 3.12. These indexes were also correlated with hexane and toluene indoor air concentrations. As to urine, the obtained results for the 2,5-hexandione and hippuric acid, metabolites of hexane and toluene, respectively, were in accord with the indoor-air measurements, with an average of 0.46 mg/l and 1240 mg/g of creatinine. Conclusion This study assessed for the first time biological exposure to organic solvents used in Tunisian adhesive industries. Although values are likely to underestimate true exposure levels, some figures exceed European and American occupational exposure guidelines. PMID:22082240

  7. Assessing the bioremediation potential of algal species indigenous to oil sands process-affected waters on mixtures of oil sands acid extractable organics.

    PubMed

    Ruffell, Sarah E; Frank, Richard A; Woodworth, Adam P; Bragg, Leslie M; Bauer, Anthony E; Deeth, Lorna E; Müller, Kirsten M; Farwell, Andrea J; Dixon, D George; Servos, Mark R; McConkey, Brendan J

    2016-11-01

    Surface mining extraction of bitumen from oil sand in Alberta, Canada results in the accumulation of oil sands process-affected water (OSPW). In attempts to maximize water recycling, and because its constituents are recognized as being toxic, OSPW is retained in settling basins. Consequently, research efforts are currently focused on developing remediation strategies capable of detoxifying OSPW to allow for eventual release. One potential bioremediation strategy proposes to utilize phytoplankton native to the Alberta oil sand region to sequester, break down, or modify the complex oil sands acid extractable organic (AEO) mixtures in OSPW. Preliminary attempts to quantify changes in total oil sands AEO concentration in test solutions by ESI-MS following a 14-day algal remediation period revealed the presence of unknown organic acids in control samples, likely released by the phytoplankton strains and often of the same atomic mass range as the oil sands AEO under investigation. To address the presence of these "biogenic" organic acids in test samples, ESI-MS in MRM mode was utilized to identify oil sands AEO "marker ions" that were a) present within the tested oil sands AEO extract and b) unique to the oil sands AEO extract only (e.g. atomic masses different from biogenic organic acids). Using this approach, one of the 21 tested algal strains, Stichococcus sp. 1, proved capable of significantly reducing the AEO marker ion concentration at test concentrations of 10, 30, and 100mgL(-1). This result, along with the accelerated growth rate and recalcitrance of this algal strain with exposure to oil sands AEO, suggests the strong potential for the use of the isolated Stichococcus sp. 1 as a candidate for bioremediation strategies.

  8. Assessing the bioremediation potential of algal species indigenous to oil sands process-affected waters on mixtures of oil sands acid extractable organics.

    PubMed

    Ruffell, Sarah E; Frank, Richard A; Woodworth, Adam P; Bragg, Leslie M; Bauer, Anthony E; Deeth, Lorna E; Müller, Kirsten M; Farwell, Andrea J; Dixon, D George; Servos, Mark R; McConkey, Brendan J

    2016-11-01

    Surface mining extraction of bitumen from oil sand in Alberta, Canada results in the accumulation of oil sands process-affected water (OSPW). In attempts to maximize water recycling, and because its constituents are recognized as being toxic, OSPW is retained in settling basins. Consequently, research efforts are currently focused on developing remediation strategies capable of detoxifying OSPW to allow for eventual release. One potential bioremediation strategy proposes to utilize phytoplankton native to the Alberta oil sand region to sequester, break down, or modify the complex oil sands acid extractable organic (AEO) mixtures in OSPW. Preliminary attempts to quantify changes in total oil sands AEO concentration in test solutions by ESI-MS following a 14-day algal remediation period revealed the presence of unknown organic acids in control samples, likely released by the phytoplankton strains and often of the same atomic mass range as the oil sands AEO under investigation. To address the presence of these "biogenic" organic acids in test samples, ESI-MS in MRM mode was utilized to identify oil sands AEO "marker ions" that were a) present within the tested oil sands AEO extract and b) unique to the oil sands AEO extract only (e.g. atomic masses different from biogenic organic acids). Using this approach, one of the 21 tested algal strains, Stichococcus sp. 1, proved capable of significantly reducing the AEO marker ion concentration at test concentrations of 10, 30, and 100mgL(-1). This result, along with the accelerated growth rate and recalcitrance of this algal strain with exposure to oil sands AEO, suggests the strong potential for the use of the isolated Stichococcus sp. 1 as a candidate for bioremediation strategies. PMID:27497784

  9. Reflectance spectroscopy of natural organic solids, iron sulfides and their mixtures as refractory analogues for Rosetta/VIRTIS' surface composition analysis of 67P/CG

    NASA Astrophysics Data System (ADS)

    Moroz, Lyuba V.; Markus, Kathrin; Arnold, Gabriele; Henckel, Daniela; Kappel, David; Schade, Ulrich; Rousseau, Batiste; Quirico, Eric; Schmitt, Bernard; Capaccioni, Fabrizio; Bockelee-Morvan, Dominique; Filacchione, Gianrico; Érard, Stéphane; Leyrat, Cedric; VIRTIS Team

    2016-10-01

    Analysis of 0.25-5 µm reflectance spectra provided by the Visible and InfraRed Thermal Imaging Spectrometer (VIRTIS) onboard Rosetta orbiter revealed that the surface of 67P/CG is dark from the near-UV to the IR and is enriched in refractory phases such as organic and opaque components. The broadness and complexity of the ubiquitous absorption feature around 3.2 µm suggest a variety of cometary organic constituents. For example, complex hydrocarbons (aliphatic and polycyclic aromatic) can contribute to the feature between 3.3 and 3.5 µm and to the low reflectance of the surface in the visible. Here we present the 0.25-5 µm reflectance spectra of well-characterized terrestrial hydrocarbon materials (solid oil bitumens, coals) and discuss their relevance as spectral analogues for a hydrocarbon part of 67P/CG's complex organics. However, the expected low degree of thermal processing of cometary hydrocarbons (high (H+O+N+S)/C ratios and low carbon aromaticities) suggests high IR reflectance, intense 3.3-3.5 µm absorption bands and steep red IR slopes that are not observed in the VIRTIS spectra. Fine-grained opaque refractory phases (e.g., iron sulfides, Fe-Ni alloys) intimately mixed with other surface components are likely responsible for the low IR reflectance and low intensities of absorption bands in the VIRTIS spectra of the 67P/CG surface. In particular, iron sulfides are common constituents of cometary dust, "cometary" chondritic IDPs, and efficient darkening agents in primitive carbonaceous chondrites. Their effect on reflectance spectra of an intimate mixture is strongly affected by grain size. We report and discuss the 0.25-5 µm reflectance spectra of iron sulfides (meteoritic troilite and several terrestrial pyrrhotites) ground and sieved to various particle sizes. In addition, we present reflectance spectra of several intimate mixtures of powdered iron sulfides and solid oil bitumens. Based on the reported laboratory data, we discuss the ability of

  10. Greening pharmaceutical applications of liquid chromatography through using propylene carbonate-ethanol mixtures instead of acetonitrile as organic modifier in the mobile phases.

    PubMed

    Tache, Florentin; Udrescu, Stefan; Albu, Florin; Micăle, Florina; Medvedovici, Andrei

    2013-03-01

    Substitution of acetonitrile (ACN) as organic modifier in mobile phases for liquid chromatography by mixtures of propylene carbonate (PC) and ethanol (EtOH) may be considered a greener approach for pharmaceutical applications. Such a replacement is achievable without any major compromise in terms of elution order, chromatographic retention, efficiency and peak symmetry. This has been equally demonstrated for reverse phase (RP), ion pair formation (IP) and hydrophilic interaction liquid chromatography (HILIC) separation modes. The impact on the sensitivity induced by the replacement between these organic solvents is discussed for UV-vis and mass spectrometric detection. A comparison between Van Deemter plots obtained under elution conditions based on ACN and PC/EtOH is presented. The alternative elution modes were also compared in terms of thermodynamic parameters, such as standard enthalpy (ΔH⁰) and entropic contributions to the partition between the mobile and the stationary phases, for some model compounds. Van't Hoff plots demonstrated that differences between the thermodynamic parameters are minor when shifting from ACN/water to PC/EtOH/water elution on an octadecyl chemically modified silicagel stationary phase. As long as large volume injection (LVI) of diluents non-miscible with the mobile phase is a recently developed topic having a high potential of greening the sample preparation procedures through elimination of the solvent evaporation stage, this feature was also assessed in the case of ACN replacement by PC/EtOH. PMID:23277155

  11. Surface Partitioning in Organic-Inorganic Mixtures Contributes to the Size-Dependence of the Phase-State of Atmospheric Nanoparticles.

    PubMed

    Werner, Josephina; Dalirian, Maryam; Walz, Marie-Madeleine; Ekholm, Victor; Wideqvist, Ulla; Lowe, Samuel J; Öhrwall, Gunnar; Persson, Ingmar; Riipinen, Ilona; Björneholm, Olle

    2016-07-19

    Atmospheric particulate matter is one of the main factors governing the Earth's radiative budget, but its exact effects on the global climate are still uncertain. Knowledge on the molecular-scale surface phenomena as well as interactions between atmospheric organic and inorganic compounds is necessary for understanding the role of airborne nanoparticles in the Earth system. In this work, surface composition of aqueous model systems containing succinic acid and sodium chloride or ammonium sulfate is determined using a novel approach combining X-ray photoelectron spectroscopy, surface tension measurements and thermodynamic modeling. It is shown that succinic acid molecules are accumulated in the surface, yielding a 10-fold surface concentration as compared with the bulk for saturated succinic acid solutions. Inorganic salts further enhance this enrichment due to competition for hydration in the bulk. The surface compositions for various mixtures are parametrized to yield generalizable results and used to explain changes in surface tension. The enhanced surface partitioning implies an increased maximum solubility of organic compounds in atmospheric nanoparticles. The results can explain observations of size-dependent phase-state of atmospheric nanoparticles, suggesting that these particles can display drastically different behavior than predicted by bulk properties only. PMID:27326704

  12. The use of cyprinodont fish, Aphanius fasciatus, as a sentinel organism to detect complex genotoxic mixtures in the coastal lagoon ecosystem.

    PubMed

    Mosesso, Pasquale; Angeletti, Dario; Pepe, Gaetano; Pretti, Carlo; Nascetti, Giuseppe; Bellacima, Raffaela; Cimmaruta, Roberta; Jha, Awadhesh N

    2012-02-18

    In the present work we aimed to standardise the alkaline comet assay with erythrocytes of the cyprinodont, Mediterranean Killifish, Aphanius fasciatus. The aims of the study were to explore the suitability of this fish to assess biomarkers of genotoxic effects and as a sentinel organism to detect complex genotoxic mixtures in coastal lagoon ecosystems. Following proper optimisation, the application and effectiveness of the comet assay in erythrocytes of A. fasciatus were tested by measuring the tail DNA (%) induced by (a) in vivo exposure of individual fish to X-rays (dose, 3Gy) and (b) following in vitro challenge of erythrocytes with restriction endonucleases Fok-I and Eco-RI, which selectively induce double-strand breaks with cohesive and blunt termini, respectively. Furthermore, in order to evaluate whether circulating fish blood contained actively proliferating cells that could influence the extent of DNA damage in control (untreated) fish, we measured the number of "comets" positive for 5-bromo-2'-deoxyuridine (BrdU) by the use of anti-BrdU antibody and immuno-histochemical methods. Both treatments (i.e. with X-rays and restriction endonucleases) induced statistically significant increases in tail DNA (%) values compared with the relevant untreated controls, indicating the effectiveness of the comet assay in the erythrocytes of A. fasciatus to detect different types of DNA lesions. Results from anti-BrdU antibody labelling of erythrocytes indicated a very low percentage (5%) of "comets" positive for BrdU. Following optimisation and validation of the assay under laboratory conditions, fish were collected in the Orbetello lagoon (Tuscany, Italy), considered to be a significantly polluted site. The results showed statistically significant increases for tail DNA (%) compared with corresponding values observed in erythrocytes of fish caught in the unpolluted reference site "Saline di Tarquinia". The effects of physico-chemical parameters of the water (i

  13. Dissipation of a commercial mixture of polyoxyethylene amine surfactants in aquatic outdoor microcosms: Effect of water depth and sediment organic carbon.

    PubMed

    Rodriguez-Gil, Jose Luis; Lissemore, Linda; Solomon, Keith; Hanson, Mark

    2016-04-15

    This study optimized existing analytical approaches and characterized the effect of sediment total organic carbon (0.05-2.05% TOC), and water depth (15, 30, and 90cm) on the fate of MON 0818, a commercial mixture of polyoxyethylene amine surfactants (POEAs), in outdoor microcosms. Mixtures of POEAs are commonly used as adjuvants in commercial herbicide formulations containing glyphosate. Until recently, analytical methods sensitive enough to monitor environmental concentrations of POEAs in aquatic systems were not available. After optimizing recently developed analytical methods, we found that the combined use of accelerated solvent extraction (ASE) and liquid chromatography-tandem mass spectrometry provided a reliable approach for determining the concentration of sediment-adsorbed POEAs. The surfactant showed strong affinity for sediment materials, with low maximum recoveries by ASE of 52%. Under microcosm conditions, water depth or sediment characteristics did not significantly affect the water-column half-life of POEA, which ranged from 3.2 to 5.3h. Binding of POEAs to suspended solids was observed, which dissipated via one- or two-phase exponential decay; when two-phase decay occurred, fast phase half-life values ranged from 0.71 to 1.3h and slow-phase values ranged from 18 to 44h. Concentrations of POEA increased in sediment shortly after application and decreased over the study period with a half-life of 5.8 to 71d. The concentrations of POEAs in the sediment of the shallow (15cm) ponds dissipated following a two-phase exponential decay model with an initial fast-phase half-life of 1.1 to 8.9d and a slower second-phase half-life of 21d. Our results suggest that aquatic organisms are unlikely to be exposed to POEAs in aqueous phase for periods of more than a few hours following an over-water application, and that sediment is a significant sink for POEAs in aquatic systems.

  14. Potential of Effective micro-organisms and Eisenia fetida in enhancing vermi-degradation and nutrient release of fly ash incorporated into cow dung-paper waste mixture.

    PubMed

    Mupambwa, Hupenyu Allan; Ravindran, Balasubramani; Mnkeni, Pearson Nyari Stephano

    2016-02-01

    The interactions between earthworms and microorganisms activity has prompted several researchers to evaluate the potential of artificially inoculating vermicomposts with additional specific microbes, with the intention of enhancing the vermicomposting process. This study evaluated the potential of inoculating fly ash (F)-cow dung-paper waste (CP) mixture (F-CP) with a specialized microbial cocktail called Effective micro-organisms (EM) during vermicomposting using Eisenia fetida earthworms. Inoculation with EM alone did not result in significantly (P>0.05) different changes in C/N ratio and dissolved organic matter (DOC) compared to the control with no EM and E. fetida. A significant interaction between EM and E. fetida presence resulted in greater changes in C/N ratio and DOC, which were not statistically different from the E. fetida alone treatment. It was also noteworthy that the activity of ß-Glucosidase was not influenced by the presence of EM, but was significantly influenced (P=0.0014) by the presence of E. fetida. However, the EM+E. fetida treatment resulted in a rate of weekly Olsen P release of 54.32mgkg(-1) which was 12.3%, 89.2% and 228.0% more that the E. fetida alone, EM alone and control treatments, respectively. Similarly, though higher in the E. fetida plus EM treatment, the phosphate solubilizing bacteria counts were not significantly different (P>0.05) from the E. fetida alone treatment. It is concluded that inoculation of F-CP composts with EM alone may not be beneficial, while combining EM with E. fetida results in faster compost maturity and significantly greater Olsen P release. It would be interesting to evaluate higher optimized rates of EM inoculation and fortifying EM cocktails with phosphate solubilizing bacteria (PSB) on F-CP vermicompost degradation and phosphorus mineralization. PMID:26459189

  15. Potential of Effective micro-organisms and Eisenia fetida in enhancing vermi-degradation and nutrient release of fly ash incorporated into cow dung-paper waste mixture.

    PubMed

    Mupambwa, Hupenyu Allan; Ravindran, Balasubramani; Mnkeni, Pearson Nyari Stephano

    2016-02-01

    The interactions between earthworms and microorganisms activity has prompted several researchers to evaluate the potential of artificially inoculating vermicomposts with additional specific microbes, with the intention of enhancing the vermicomposting process. This study evaluated the potential of inoculating fly ash (F)-cow dung-paper waste (CP) mixture (F-CP) with a specialized microbial cocktail called Effective micro-organisms (EM) during vermicomposting using Eisenia fetida earthworms. Inoculation with EM alone did not result in significantly (P>0.05) different changes in C/N ratio and dissolved organic matter (DOC) compared to the control with no EM and E. fetida. A significant interaction between EM and E. fetida presence resulted in greater changes in C/N ratio and DOC, which were not statistically different from the E. fetida alone treatment. It was also noteworthy that the activity of ß-Glucosidase was not influenced by the presence of EM, but was significantly influenced (P=0.0014) by the presence of E. fetida. However, the EM+E. fetida treatment resulted in a rate of weekly Olsen P release of 54.32mgkg(-1) which was 12.3%, 89.2% and 228.0% more that the E. fetida alone, EM alone and control treatments, respectively. Similarly, though higher in the E. fetida plus EM treatment, the phosphate solubilizing bacteria counts were not significantly different (P>0.05) from the E. fetida alone treatment. It is concluded that inoculation of F-CP composts with EM alone may not be beneficial, while combining EM with E. fetida results in faster compost maturity and significantly greater Olsen P release. It would be interesting to evaluate higher optimized rates of EM inoculation and fortifying EM cocktails with phosphate solubilizing bacteria (PSB) on F-CP vermicompost degradation and phosphorus mineralization.

  16. Density functional theory of freezing for binary mixtures of 2D superparamagnetic colloids.

    PubMed

    Mukherjee, Manjori; Mishra, Pankaj; Löwen, Hartmut

    2014-11-19

    Density functional theory of freezing is used to study the phase diagram of a binary mixture of superparamagnetic colloidal particles in two dimensions. The particles interact via a purely repulsive potential that scales as the inverse cube of the inter-particle separation. This corresponds to a magnetic dipole interaction where the dipoles are induced by an external magnetic field applied normal to the plane. The pair correlation functions needed as input information in the density functional theory are calculated by the hypernetted chain integral equation closure. Considering the freezing into a disordered triangular solid phase, a spindle phase diagram is found for the susceptibility ratio 0.9 of the species, which changes to an azeotrope at a ratio 0.8. A eutectic-like phase diagram with an intervening solid phase emerges for the susceptibility ratio 0.7. The results are verifiable in real-space experiments on superparamagnetic colloids in external magnetic fields.

  17. Large outdoor chamber experiments and computer simulations: (I) Secondary organic aerosol formation from the oxidation of a mixture of d-limonene and α-pinene

    NASA Astrophysics Data System (ADS)

    Li, Qianfeng; Hu, Di; Leungsakul, Sirakarn; Kamens, Richard M.

    This work merges kinetic models for α-pinene and d-limonene which were individually developed to predict secondary organic aerosol (SOA) formation from these compounds. Three major changes in the d-limonene and α-pinene combined mechanism were made. First, radical-radical reactions were integrated so that radicals formed from both individual mechanisms all reacted with each other. Second, all SOA model species from both compounds were used to calculate semi-volatile partitioning for new semi-volatiles formed in the gas phase. Third particle phase reactions for particle phase α-pinene and d-limonene aldehydes, carboxylic acids, etc. were integrated. Experiments with mixtures of α-pinene and d-limonene, nitric oxide (NO), nitrogen dioxide (NO 2), and diurnal natural sunlight were carried out in a dual 270 m 3 outdoor Teflon film chamber located in Pittsboro, NC. The model closely simulated the behavior and timing for α-pinene, d-limonene, NO, NO 2, O 3 and SOA. Model sensitivities were tested with respect to effects of d-limonene/α-pinene ratios, initial hydrocarbon to NO x (HC 0/NO x) ratios, temperature, and light intensity. The results showed that SOA yield ( YSOA) was very sensitive to initial d-limonene/α-pinene ratio and temperature. The model was also used to simulate remote atmospheric SOA conditions that hypothetically could result from diurnal emissions of α-pinene, d-limonene and NO x. We observed that the volatility of the simulated SOA material on the aging aerosol decreased with time, and this was consistent with chamber observations. Of additional importance was that our simulation did not show a loss of SOA during the daytime and this was consistent with observed measurements.

  18. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-05-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  19. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-09-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  20. Two persistent organic pollutants which act through different xenosensors (alpha-endosulfan and 2,3,7,8 tetrachlorodibenzo-p-dioxin) interact in a mixture and downregulate multiple genes involved in human hepatocyte lipid and glucose metabolism.

    PubMed

    Ambolet-Camoit, Ariane; Ottolenghi, Chris; Leblanc, Alix; Kim, Min Ji; Letourneur, Franck; Jacques, Sébastien; Cagnard, Nicolas; Guguen-Guillouzo, Christiane; Barouki, Robert; Aggerbeck, Martine

    2015-09-01

    Individuals, typically, are exposed to mixtures of environmental xenobiotics affecting multiple organs and acting through different xenosensors and pathways in species and cell-type specific manners. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and α-endosulfan are Persistent Organic Pollutants (POPs) and endocrine disruptors which act through different xenosensors and accumulate in the liver. Our objective in this HEALS study was to investigate the effects of the mixture of these POPs on gene expression in a human-derived hepatocyte cell line, HepaRG. We found that, in spite of having largely uncorrelated effects, TCDD and α-endosulfan, when mixed, alter the expression of genes. The combined effects of the mixture of the POPs significantly altered the expression of 100 genes (42 up- and 58 down-regulated) whereas the same concentration of either POP alone did not alter significantly the expression of these genes. For 32 other genes, selective inhibitory crosstalk between TCDD and α-endosulfan was observed. One of the POPs inhibited the effect, on gene expression, of the other in the mixture although, when used alone, that POP did not affect expression. The expression of another 82 genes was significantly altered (up- or down-regulated) by a single POP. The addition of the second POP either increased, in the same direction, the effect on gene expression or had no further effect. At low concentrations (0.2 nM TCDD and 1 μM α-endosulfan), the POPs still had significant effects and the levels of expression of the corresponding proteins were found to be affected for some genes. Particularly striking was the 80-90% inhibition, by the mixture, of the expression of a number of genes of several hepatic intermediary metabolic pathways (glycerolipid metabolism, FXR/RXR activation, glycolysis/gluconeogenesis, retinoid and bile acid biosynthesis), whereas each pollutant alone had only a moderate effect.

  1. Application of solubility parameters in 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol organogel in binary organic mixtures.

    PubMed

    Shen, Huahua; Niu, Libo; Fan, Kaiqi; Li, Jingjing; Guan, Xidong; Song, Jian

    2014-08-01

    The gelation behavior of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) in binary solvents has been systematically investigated. DMDBS is soluble in DMSO and insoluble in toluene (apolar) or 1-propanol (polar). When DMSO is added to a poor solvent at a certain volume fraction, DMDBS forms an organogel in the mixed solvent. With increasing DMSO content, the minimum gelation concentration increases and the gel-to-sol transition temperature decreases in both systems. However, compared with those in toluene-DMSO mixtures, the gelation ability and thermal stability are better in 1-propanol-DMSO mixtures. Scanning electron microscopy images reveal that the gelators aggregate to form three-dimensional networks. X-ray diffraction shows that the gel has a lamellar structure, which is different from the structure of the precipitate. Fourier transform infrared results reveal H-bonding is the main driving force for self-aggregation and indicate that stronger H-bonding interactions exist between gelators in 1-propanol-DMSO mixtures in contrast with toluene-DMSO mixtures. Attempts have been taken to correlate solvent parameters to gelation behavior in binary solvents. A Teas plot exhibits distinctly different solvent zones in the studied mixed solvents. The polar parameter (δp) indicates a narrow favorable domain for gel formation in the range of 1.64-7.99 MPa(1/2) for some apolar solvent-DMSO mixtures. The hydrogen-bonding parameter (δh) predicts that gelation occurs for values of 14.00-16.50 MPa(1/2) for some polar solvent-DMSO mixtures. The result may have potential applications in predicting the gelation behavior of 1,3:2,4-di-O-benzylidene-d-sorbitol derivatives in mixed solvents. PMID:25019199

  2. Isothermal liquid-vapor equilibria of mixtures containing organic compounds. 2. excess Gibbs free energies of a hydrocarbon or tetrachloromethane + a cyclic ketone at 298. 15 K

    SciTech Connect

    Matteoli, E.; Lepori, L. )

    1988-07-01

    Vapor-liquid equilibrium data for mixtures of heptane, cyclohexane, tetrachloromethane, or benzene with cyclopentanone or with cyclohexanone were determined at 298.15 K by headspace gas chromatographic analysis of the equilibrated vapor phase. Excess molar Gibbs free energies G/sup E/ for the examined mixtures were obtained by a least-squares treatment of the equilibrium results. G/sup E/ are positive for all systems except for benzene + cyclohexanone and, for each given cosolvent, are in the order cytclopentanone > cyclohexanone and heptane > cyclohexane > tetrachloromethane > benzene. Activity coefficients at infinite dilution as well as free energies of solvation were evaluated for all the solutes in all the solvents investigated here.

  3. Mixture design and multivariate analysis in mixture research.

    PubMed Central

    Eide, I; Johnsen, H G

    1998-01-01

    Mixture design has been used to identify possible interactions between mutagens in a mixture. In this paper the use of mixture design in multidimensional isobolographic studies is introduced. Mutagenicity of individual nitro-polycyclic aromatic hydrocarbons (PAH) was evaluated is an organic extract of diesel exhaust particles (DEPs). The particles were extracted with dichloromethane (DCM). After replacing DCM with dimethyl sulfoxide, the extract was spiked with three individual nitro-PAH: 1-nitropyrene, 2-nitrofluorene, and 1,8-dinitropyrene. The nitro-PAH were added separately and in various combinations to the extract to determine the effects of each variable and to identify possible interactions between the individual nitro-PAH and between the nitro-PAH and the extract. The composition of the mixtures was determined by mixture design (linear axial normal) with four variables (the DEP extract and the three nitro-PAH, giving 8 different mixtures plus a triplicate centerpoint, i.e., a total of 11. The design supports a model with linear and interaction (product) terms. Two different approaches were used: traditional mixture design within a well-defined range on the linear part of the dose-response curves and an isobolographic mixture design with equipotent doses of each variable. The mixtures were tested for mutagenicity in the Ames assay using the TA98 strain of Salmonella typhimurium. The data were analyzed with projections to latent structures (PLS). The three individual nitro-PAH and the DEP extract acted additively in the Ames test. The use of mixture design either within a well-defined range of the linear part on the dose-response curve or with equipotent doses saves experiments and reduces the possibility of false interaction terms in situations with dose additivity or response additivity. Images Figure 1 Figure 2 PMID:9860895

  4. Mixture design and multivariate analysis in mixture research.

    PubMed

    Eide, I; Johnsen, H G

    1998-12-01

    Mixture design has been used to identify possible interactions between mutagens in a mixture. In this paper the use of mixture design in multidimensional isobolographic studies is introduced. Mutagenicity of individual nitro-polycyclic aromatic hydrocarbons (PAH) was evaluated is an organic extract of diesel exhaust particles (DEPs). The particles were extracted with dichloromethane (DCM). After replacing DCM with dimethyl sulfoxide, the extract was spiked with three individual nitro-PAH: 1-nitropyrene, 2-nitrofluorene, and 1,8-dinitropyrene. The nitro-PAH were added separately and in various combinations to the extract to determine the effects of each variable and to identify possible interactions between the individual nitro-PAH and between the nitro-PAH and the extract. The composition of the mixtures was determined by mixture design (linear axial normal) with four variables (the DEP extract and the three nitro-PAH, giving 8 different mixtures plus a triplicate centerpoint, i.e., a total of 11. The design supports a model with linear and interaction (product) terms. Two different approaches were used: traditional mixture design within a well-defined range on the linear part of the dose-response curves and an isobolographic mixture design with equipotent doses of each variable. The mixtures were tested for mutagenicity in the Ames assay using the TA98 strain of Salmonella typhimurium. The data were analyzed with projections to latent structures (PLS). The three individual nitro-PAH and the DEP extract acted additively in the Ames test. The use of mixture design either within a well-defined range of the linear part on the dose-response curve or with equipotent doses saves experiments and reduces the possibility of false interaction terms in situations with dose additivity or response additivity. PMID:9860895

  5. The product composition regions of azeotropic distillation columns. 2. Separability in two-feed columns and entrainer selection

    SciTech Connect

    Wahnschafft, O.M.; Westerberg, A.W. . Engineering Design Research Center and Department of Chemical Engineering)

    1993-06-01

    A method to assess the product composition regions for distillation of ternary mixtures in single-feed distillation columns, introduced in the first paper of this series, is generalized to account for the effect of introducing multiple feeds of different trays. The method relies on so-called fixed point curves which are trajectories in the compositions space. These trajectories describe the possible compositions of pinch points in each column section as functions of the energy supplied to a column, i.e., for all conceivable values of the reflux ratio. Pinch point trajectories may be determined analytically or, for ternary mixtures, can be located graphically using residue curve maps. The authors carry out a mostly graphical analysis, using pinch point trajectories to establish separation feasibility ahead of design calculations. This analysis also provides information on the minimum entrainer supply for a specified separation and visualizes the phenomenon of the occurrence of a maximum reflux ratio for separation in a column with a separate, extractive agent feed. The analysis is analogous to that for single-feed columns, only the critical pinch trajectories may be those for the extractive column section between the feeds. This analogy suggests the notion of a generalized extractive distillation process, for which new entrainer selection criteria are proposed.

  6. Interactions in Ternary Mixtures of MnO2, Al2O3, and Natural Organic Matter (NOM) and the Impact on MnO2 Oxidative Reactivity.

    PubMed

    Taujale, Saru; Baratta, Laura R; Huang, Jianzhi; Zhang, Huichun

    2016-03-01

    Our previous work reported that Al2O3 inhibited the oxidative reactivity of MnO2 through heteroaggregation between oxide particles and surface complexation of the dissolved Al ions with MnO2 (S. Taujale and H. Zhang, "Impact of interactions between metal oxides to oxidative reactivity of manganese dioxide" Environ. Sci. Technol. 2012, 46, 2764-2771). The aim of the current work was to investigate interactions in ternary mixtures of MnO2, Al2O3, and NOM and how the interactions affect MnO2 oxidative reactivity. For the effect of Al ions, we examined ternary mixtures of MnO2, Al ions, and NOM. Our results indicated that an increase in the amount of humic acids (HAs) increasingly inhibited Al adsorption by forming soluble Al-HA complexes. As a consequence, there was less inhibition on MnO2 reactivity than by the sum of two binary mixtures (MnO2+Al ions and MnO2+HA). Alginate or pyromellitic acid (PA)-two model NOM compounds-did not affect Al adsorption, but Al ions increased alginate/PA adsorption by MnO2. The latter effect led to more inhibition on MnO2 reactivity than the sum of the two binary mixtures. In ternary mixtures of MnO2, Al2O3, and NOM, NOM inhibited dissolution of Al2O3. Zeta potential measurements, sedimentation experiments, TEM images, and modified DLVO calculations all indicated that HAs of up to 4 mg-C/L increased heteroaggregation between Al2O3 and MnO2, whereas higher amounts of HAs completely inhibited heteroaggregation. The effect of alginate is similar to that of HAs, although not as significant, while PA had negligible effects on heteroaggregation. Different from the effects of Al ions and NOMs on MnO2 reactivity, the MnO2 reactivity in ternary mixtures of Al2O3, MnO2, and NOM was mostly enhanced. This suggests MnO2 reactivity was mainly affected through heteroaggregation in the ternary mixtures because of the limited availability of Al ions.

  7. Viscosity of Gaseous Mixtures of HCFC-22 + HCFC-142b at Pressures to 6.3 MPa

    NASA Astrophysics Data System (ADS)

    Takahashi, M.; Tomida, D.; Yokoyama, C.

    2009-06-01

    The gaseous viscosity of non-azeotropic mixtures of HCFC-22 and HCFC-142b was measured by an oscillating disk viscometer of the Maxwell type from 298.15 K to 423.15 K and at pressures up to 6.3 MPa. The viscosity at approximately atmospheric pressure was predicted with a maximum deviation of 1.84 % and an average deviation of 0.61 % by the Sutherland-Thiesen equation, coefficients of which were determined by the Brokaw method. An empirical equation was developed for the viscosity as a function of composition, temperature, and density. This equation reproduced the observed viscosity with a maximum deviation of 5.61 % and an average deviation of 1.14 %.

  8. Cationic Porphyrin-Anionic Surfactant Mixtures for the Promotion of Self-Organized 1:4 Ion Pairs in Water with Strong Aggregation Properties.

    PubMed

    Pradines, Vincent; Bijani, Christian; Stigliani, Jean-Luc; Blanzat, Muriel; Rico-Lattes, Isabelle; Pratviel, Geneviève

    2015-12-21

    We performed a systematic study on the spectroscopic and aggregation properties of stoichiometric mixtures (1:4) of the tetracationic meso-tetrakis(4-N-methylpyridinium)porphyrin (H2 TMPyP) and three sodium alkylsulfate surfactants (tetradecyl, hexadecyl, and octadecylsulfate) in an aqueous solution. The objective was to build a supramolecular aggregate, which would favor the internalization of tetracationic porphyrins in cells without chemical modification of the structure of the porphyrin. We show that stoichiometric H2 TMPyP/alkylsulfate (1:4) mixtures lead to the formation of large hollow spherical aggregates (60-160 nm). The TEM images show that the membrane of these aggregates are composed of smaller aggregates, which are probably rod-like micelles. These rod-like micelles have a hydrophobic core composed of the alkyl chains of the alkylsulfate surfactant, whereas the charged surface corresponds to the tetracationic porphyrins.

  9. Structural effects of pH and deacylation on surfactant protein C in an organic solvent mixture: a constant-pH MD study.

    PubMed

    Carvalheda, Catarina A; Campos, Sara R R; Machuqueiro, Miguel; Baptista, António M

    2013-11-25

    The pulmonary surfactant protein C (SP-C) is a small highly hydrophobic protein that adopts a mainly helical structure while associated with the membrane but misfolds into a β-rich metastable structure upon deacylation, membrane dissociation, and exposure to the neutral pH of the aqueous alveolar subphase, eventually leading to the formation of amyloid aggregates associated with pulmonary alveolar proteinosis. The present constant-pH MD study of the acylated and deacylated isoforms of SP-C in a chloroform/methanol/water mixture, often used to mimic the membrane environment, shows that the loss of the acyl groups has a structural destabilizing effect and that the increase of pH promotes intraprotein contacts which contribute to the loss of helical structure in solution. These contacts result from the poor solvation of charged groups by the solvent mixture, which exhibits a limited membrane-mimetic character. Although a single SP-C molecule was used in the simulations, we propose that analogous intermolecular interactions may play a role in the early stages of the protein misfolding and aggregation in this mixture.

  10. IDENTIFICATION AND EXPERIMENTAL DATABASE FOR BINARY AND MULTICOMPONENT MIXTURES WITH POTENTIAL FOR INCREASING OVERALL CYCLE EFFICIENCY

    SciTech Connect

    Stephen M Bajorek; J. Schnelle

    2002-05-01

    This report describes an experimental investigation designed to identify binary and multicomponent mixture systems that may be for increasing the overall efficiency of a coal fired unit by extracting heat from flue gases. While ammonia-water mixtures have shown promise for increasing cycle efficiencies in a Kalina cycle, the costs and associated range of thermal conditions involved in a heat recovery system may prohibit its use in a relatively low temperature heat recovery system. This investigation considered commercially available non-azeotropic binary mixtures with a boiling range applicable to a flue gas initially at 477.6 K (400 F) and developed an experimental database of boiling heat transfer coefficients for those mixtures. In addition to their potential as working fluids for increasing cycle efficiency, cost, ease of handling, toxicity, and environmental concerns were considered in selection of the mixture systems to be examined experimentally. Based on this review, water-glycol systems were identified as good candidates. However, previous investigations of mixture boiling have focused on aqueous hydrocarbon mixtures, where water is the heaviest component. There have been few studies of water-glycol systems, and those that do exist have investigated boiling on plain surfaces only. In water-glycol systems, water is the light component, which makes these systems unique compared to those that have been previously examined. This report examines several water-glycol systems, and documents a database of experimental heat transfer coefficients for these systems. In addition, this investigation also examines the effect of an enhanced surface on pool boiling in water-glycol mixtures, by comparing boiling on a smooth surface to boiling on a Turbo IIIB. The experimental apparatus, test sections, and the experimental procedures are described. The mixture systems tested included water-propylene glycol, water-ethylene glycol, and water-diethylene glycol. All

  11. Emergence of Photoautotrophic Minimal Protocell-Like Supramolecular Assemblies, "Jeewanu" Synthesied Photo Chemically in an Irradiated Sterilised Aqueous Mixture of Some Inorganic and Organic Substances

    NASA Astrophysics Data System (ADS)

    Gupta, Vinod Kumar

    2014-12-01

    Sunlight exposed sterilised aqueous mixture of ammonium molybdate, diammonium hydrogen phosphate, biological minerals and formaldehyde showed photochemical formation of self-sustaining biomimetic protocell-like supramolecular assemblies "Jeewanu" (Bahadur and Ranganayaki J Brit Interplanet Soc 23:813-829 1970). The structural and functional characteristics of Jeewanu suggests that in possible prebiotic atmosphere photosy nergistic collaboration of non-linear processes at mesoscopic level established autocatalytic pathways on mineral surfaces by selforganisation and self recognition and led to emergence of similar earliest energy transducing supramolecular assemblies which might have given rise to common universal ancestor on the earth or elsewhere.

  12. Emergence of photoautotrophic minimal protocell-like supramolecular assemblies, "Jeewanu" synthesied photo chemically in an irradiated sterilised aqueous mixture of some inorganic and organic substances.

    PubMed

    Gupta, Vinod Kumar

    2014-12-01

    Sunlight exposed sterilised aqueous mixture of ammonium molybdate, diammonium hydrogen phosphate, biological minerals and formaldehyde showed photochemical formation of self-sustaining biomimetic protocell-like supramolecular assemblies "Jeewanu" (Bahadur and Ranganayaki J Brit Interplanet Soc 23:813-829 1970). The structural and functional characteristics of Jeewanu suggests that in possible prebiotic atmosphere photosy nergistic collaboration of non-linear processes at mesoscopic level established autocatalytic pathways on mineral surfaces by selforganisation and self recognition and led to emergence of similar earliest energy transducing supramolecular assemblies which might have given rise to common universal ancestor on the earth or elsewhere. PMID:25567741

  13. Generation of sub-ppb level vapor phase mixtures of biogenic volatile organic compounds from liquid phase standards and stepwise characterization of their volatilization properties by thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Iqbal, Mohammad Asif; Kim, Ki-Hyun

    2014-12-19

    In the analysis of biogenic volatile organic compounds (BVOCs) in ambient air, preparation of a sub-ppb level standard is an important factor. This task is very challenging as most BVOCs (e.g., monoterpenes) are highly volatile and reactive in nature. As a means to produce sub-ppb gaseous standards for BVOCs, we investigated the dynamic headspace (HS) extraction technique through which their vapors are generated from a liquid standard (mixture of 10 BVOCs: (1) α-pinene, (2) β-pinene, (3) 3-carene, (4) myrcene, (5) α-phellandrene, (6) α-terpinene, (7) R-limonene, (8) γ-terpinene, (9) p-cymene, and (10) Camphene) spiked into a chamber-style impinger. The quantification of BVOCs was made by collection on multiple-bed sorbent tubes (STs) and subsequent analysis by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Using this approach, sub-ppb level mixtures of gaseous BVOCs were generated at different sweep cycles. The mean concentrations of 10 BVOCs generated from the most stable conditions (i.e., in the third sweep cycle) varied in the range of 0.37±0.05 to 7.27±0.86ppb depending on the initial concentration of liquid standard spiked into the system. The reproducibility of the gaseous BVOCs generated as mixture standards, if expressed in terms of relative standard error using the concentration datasets acquired under stable conditions, ranged from 1.64 (α-phellandrene) to 9.67% (R-limonene).

  14. Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units.

    PubMed

    Yao, Zizhu; Zhang, Zhangjing; Liu, Lizhen; Li, Ziyin; Zhou, Wei; Zhao, Yunfeng; Han, Yu; Chen, Banglin; Krishna, Rajamani; Xiang, Shengchang

    2016-04-11

    Acetylene separation is a very important but challenging industrial separation task. Here, through the solvothermal reaction of CuI and 5-triazole isophthalic acid in different solvents, two metal-organic frameworks (MOFs, FJU-21 and FJU-22) with open O donor sites and controllable robustness have been obtained for acetylene separation. They contain the same paddle-wheel {Cu2(COO2)4} nodes and metal-ligand connection modes, but with different helical chains as secondary building units (SBUs), leading to different structural robustness for the MOFs. FJU-21 and FJU-22 are the first examples in which the MOFs' robustness is controlled by adjusting the helical chain SBUs. Good robustness gives the activated FJU-22 a, which has higher surface area and gas uptakes than the flexible FJU-21 a. Importantly, FJU-22 a shows extraordinary separation of acetylene mixtures under ambient conditions. The separation capacity of FJU-22 a for 50:50 C2H2/CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2H2/C2H4 mixtures containing 1% acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2H2 molecules with the open O donors on the wall, which provide better recognition ability for C2H2 than other functional sites, including open metal sites and amino groups.

  15. Mixtures research at NIEHS: an evolving program.

    PubMed

    Rider, Cynthia V; Carlin, Danielle J; Devito, Micheal J; Thompson, Claudia L; Walker, Nigel J

    2013-11-16

    The National Institute of Environmental Health Sciences (NIEHS) has a rich history in evaluating the toxicity of mixtures. The types of mixtures assessed by the Division of the National Toxicology Program (DNTP) and the extramural community (through the Division of Extramural Research and Training, DERT) have included a broad range of chemicals and toxicants, with each study having a unique set of questions and design considerations. Some examples of the types of mixtures studied include: groundwater contaminants, pesticides/fertilizers, dioxin-like chemicals (assessing the toxic equivalency approach), drug combinations, air pollution, metals, polycyclic aromatic hydrocarbons, technical mixtures (e.g., pentachlorophenol, flame retardants), and mixed entities (e.g., herbals, asbestos). These endeavors have provided excellent data on the toxicity of specific mixtures and have been informative to the human health risk assessment process in general (e.g., providing data on low dose exposures to environmental chemicals). However, the mixtures research effort at NIEHS, to date, has been driven by test article nominations to the DNTP or by investigator-initiated research through DERT. Recently, the NIEHS has embarked upon an effort to coordinate mixtures research across both intramural and extramural divisions in order to maximize mixtures research results. A path forward for NIEHS mixtures research will be based on feedback from a Request for Information (RFI) designed to gather up-to-date views on the knowledge gaps and roadblocks to evaluating mixtures and performing cumulative risk assessment, and a workshop organized to bring together mixtures experts from risk assessment, exposure science, biology, epidemiology, and statistics. The future of mixtures research at NIEHS will include projects from nominations to DNTP, studies by extramural investigators, and collaborations across government agencies that address high-priority questions in the field of mixtures research

  16. Mixtures research at NIEHS: an evolving program.

    PubMed

    Rider, Cynthia V; Carlin, Danielle J; Devito, Micheal J; Thompson, Claudia L; Walker, Nigel J

    2013-11-16

    The National Institute of Environmental Health Sciences (NIEHS) has a rich history in evaluating the toxicity of mixtures. The types of mixtures assessed by the Division of the National Toxicology Program (DNTP) and the extramural community (through the Division of Extramural Research and Training, DERT) have included a broad range of chemicals and toxicants, with each study having a unique set of questions and design considerations. Some examples of the types of mixtures studied include: groundwater contaminants, pesticides/fertilizers, dioxin-like chemicals (assessing the toxic equivalency approach), drug combinations, air pollution, metals, polycyclic aromatic hydrocarbons, technical mixtures (e.g., pentachlorophenol, flame retardants), and mixed entities (e.g., herbals, asbestos). These endeavors have provided excellent data on the toxicity of specific mixtures and have been informative to the human health risk assessment process in general (e.g., providing data on low dose exposures to environmental chemicals). However, the mixtures research effort at NIEHS, to date, has been driven by test article nominations to the DNTP or by investigator-initiated research through DERT. Recently, the NIEHS has embarked upon an effort to coordinate mixtures research across both intramural and extramural divisions in order to maximize mixtures research results. A path forward for NIEHS mixtures research will be based on feedback from a Request for Information (RFI) designed to gather up-to-date views on the knowledge gaps and roadblocks to evaluating mixtures and performing cumulative risk assessment, and a workshop organized to bring together mixtures experts from risk assessment, exposure science, biology, epidemiology, and statistics. The future of mixtures research at NIEHS will include projects from nominations to DNTP, studies by extramural investigators, and collaborations across government agencies that address high-priority questions in the field of mixtures research.

  17. Biological degradation of a mixture of municipal wastewater and organic garbage leachate in expanded bed anaerobic reactors and a zeolite filter.

    PubMed

    Castilla, P; Aguilar, L; Escamilla, M; Silva, B; Milán, Z; Monroy, O; Meraz, M

    2009-01-01

    Municipal wastewater was amended with organic garbage leachates at a concentration around 700 mgCOD(soluble)/L and fed to three different anaerobic systems to compare their performance: a down flow fluidized bed (DFFB), an expanded granular sludge bed (EGSB) and a zeolite-packed anaerobic filter reactor (ZPF). The DFFB and EGSB reactors were operated at HRT of 6 and 4 h and the ZPF reactor at 12 and 36 h. Organic loads rate for the DFFB reactor were 2.3+/-0.9 and 4.8+/-1.8 gCOD/L.d, with removal efficiencies around 40% and a methane productivity of 0.2+/-0.03 L/L(reactor).d. For the EGSB reactor, organic loads tested were 2.1+/-0.9 and 4.3+/-1.3 gCOD/L.d, removal efficiencies attained were of 77.6+/-12.7% and 84.4+/-4.9%, respectively at both conditions and total suspended solids were removed in 54.6+/-19.3%, while methane productivity at 4 h HRT was of 1.29+/-0.4 L/L(reactor).d. The ZPF reactor was operated at lower organic loading rates, 1.4+/-0.27 and 0.42+/-0.13 gCOD/L.d and attained removal efficiencies of 48+/-18% and 83+/-8%, respectively, reaching a methane productivity of 0.21+/-0.09 and 0.12+/-0.04 L/L(reactor).d, 83+/-8.0% of total suspended solids were retained in the reactor and as HRT was increased ammonium concentrations increased in 39%. Specific methanogenic activity in all systems was around 0.2 gCOD-CH(4)/gVSS d. PMID:19237766

  18. Comparison of neurobehavioral function in workers exposed to a mixture of organic and inorganic lead and in workers exposed to solvents.

    PubMed

    Bolla, K I; Schwartz, B S; Stewart, W; Rignani, J; Agnew, J; Ford, D P

    1995-02-01

    The neurobehavioral effects of lead (organic and inorganic) and organic solvents were compared in 386 U.S. workers (52 reference, 190 lead, and 144 solvent workers). The association between neurobehavioral test performance and duration of exposure to lead or solvents was also examined and compared. The neurobehavioral test battery consisted of examiner and computer-administered neurobehavioral tests, a test of olfactory function, and questionnaires that assessed neuropsychiatric symptoms. Adjusted mean differences on the neurobehavioral test scores were estimated by comparing the exposed group to the referent group using linear regression and adjusting for premorbid intellectual ability, age, and race. Both lead and solvents were associated with diminished neurobehavioral performance in all neurobehavioral areas tested. Specifically, while lead and solvent exposure had the same magnitude of adverse effects on tests of manual dexterity, lead exposure was associated with greater adverse effects on memory and learning tests but with less adverse effects on executive/motor tests and on a test of olfaction than solvent exposure. An elevated number of neuropsychiatric symptoms was reported by 7% of the referent group, 43% of the lead group, and 15% of the solvent group. For exposure duration of < or = 10 years, more neurobehavioral decrements were found in the solvent group relative to the lead group. However, for exposure duration of > or = 18 years, the lead group showed more decrements than the solvent group. Overall, these data suggest differences in neurobehavioral functioning between the lead (organic and inorganic) and solvent exposed workers examined in this study. PMID:7755013

  19. Organizations.

    ERIC Educational Resources Information Center

    Aviation/Space, 1980

    1980-01-01

    This is a list of aerospace organizations and other groups that provides educators with assistance and information in specific areas. Both government and nongovernment organizations are included. (Author/SA)

  20. Mixtures of quaternary ammonium compounds and anionic organic compounds in the aquatic environment: Elimination and biodegradability in the closed bottle test monitored by LC-MS/MS.

    PubMed

    Sütterlin, H; Alexy, R; Coker, A; Kümmerer, K

    2008-06-01

    Quaternary ammonium compounds (QACs) are widely used as disinfectants, detergents and fabric softeners. Anionic detergents are one of the most widely used chemical substances. QACs and anionic surfactants can form ionic pairs. In the present study we investigated the biodegradability of QACs in the presence of different anionic surfactants. The biodegradability of three QACs, namely benzalkonium chloride (BAC), didecyldimethylammonium chloride (DDMAC) and ethacridine lactate (EL), when applied as single substances and in combination with anionic surfactants such as benzene sulfonic acid (BSA), LAS, naphthalene sulfonic acid (NSA) and sodium dodecylsulfonate (SDS) was studied applying the closed bottle test (CBT) [OECD 301D, 1992. Guidelines for Testing of Chemicals. Closed bottle test. Organisation of Economic Cooperation and Development, Paris] at a ratio of 1:1 (mol:mol). Biodegradation was monitored by measuring oxygen concentration in the test vessels with an oxygen electrode in accordance with international standard methods [ISO 5414, 1990. Water quality - determination of dissolved oxygen. In: German Standard Methods for the Examination of Water, Wastewater and Sludge. VCH Verlagsgesellschaft, Weinheim, New York, Basel Cambridge]. Primary elimination of the QACs and of LAS was monitored by LC-MS/MS. There was little biodegradability of the QACs as either single compounds or in the presence of organic counter ions. The biodegradability of the organic counter ions was lower in the presence of QACs as compared to the single substances. Primary elimination of the QACs by sorption took place. PMID:18439651

  1. Toxicology of chemical mixtures: international perspective.

    PubMed Central

    Feron, V J; Cassee, F R; Groten, J P

    1998-01-01

    This paper reviews major activities outside the United States on human health issues related to chemical mixtures. In Europe an international study group on combination effects has been formed and has started by defining synergism and antagonism. Successful research programs in Europe include the development and application of statistically designed experiments combined with multivariate data analysis and modeling in vitro and in vivo studies on a wide variety of chemicals such as petroleum hydrocarbons, aldehydes, food contaminants, industrial solvents, and mycotoxins. Other major activities focus on the development of safety evaluation strategies for mixtures such as the use of toxic equivalence factors or alternatives such as the question-and-answer approach, fractionation followed by recombination of the mixture in combination with a mixture design, and quantitative structure-activity relationship analysis combined with lumping analysis and physiologically based pharmacokinetic/pharmacodynamic modeling for studying complex mixtures. A scheme for hazard identification and risk assessment of complex mixtures and a consistent way to generate total volatile organic compound values for indoor air have also been developed. Examples of other activities are carcinogenicity studies on complex mixtures (petroleum middle distillates, foundry fumes, pesticides, heterocyclic amines, diesel exhaust, solid particles), neurotoxicity studies of mixtures of solvents alone or in combination with exposure to physical factors, and toxicity studies of outdoor air pollutants, focusing on particulates. Outside the United States, toxicologists and regulators clearly have a growing interest in the toxicology and risk assessment of chemical mixtures. PMID:9860882

  2. Carburetor mixture control apparatus

    SciTech Connect

    Dalke, A.E.

    1983-11-29

    A mixture control device is disclosed for automatically controlling the air to fuel mixture of a conventional carburetor involving a plurality of sloped radial vanes circumferentially located within the annulus formed by the booster venturi and the venturi tube. By inducing significant centrifugal motion in the air passing outside the booster venturi the problems associated with fuel to air mixture changes associated with changes in elevation and changes in seasonal temperatures are alleviated.

  3. Organics.

    ERIC Educational Resources Information Center

    Chian, Edward S. K.; DeWalle, Foppe B.

    1978-01-01

    Presents water analysis literature for 1978. This review is concerned with organics, and it covers: (1) detergents and surfactants; (2) aliphatic and aromatic hydrocarbons; (3) pesticides and chlorinated hydrocarbons; and (4) naturally occurring organics. A list of 208 references is also presented. (HM)

  4. Organizers.

    ERIC Educational Resources Information Center

    Callison, Daniel

    2000-01-01

    Focuses on "organizers," tools or techniques that provide identification and classification along with possible relationships or connections among ideas, concepts, and issues. Discusses David Ausubel's research and ideas concerning advance organizers; the implications of Ausubel's theory to curriculum and teaching; "webbing," a specific…

  5. Remediation of the effect of adding cyanides on an algal/bacterial treatment of a mixture of organic pollutants in a continuous photobioreactor.

    PubMed

    Essam, Tamer; ElRakaiby, Marwa; Agha, Azza

    2014-09-01

    The effect of inorganic pollutants on the treatment of organic pollutants using algal/bacterial microcosm was investigated in a continuous photobioreactor. The microcosm was composed of Chlorella vulgaris MM1 and Pseudomonas MT1 and was able to efficiently treat artificial waste-water contaminated with 6.4 salicylate and 2.2 mM phenol at a hydraulic retention time of 4 days. No negative effect was recorded when the waste-water was supplemented with 1.6 mM thiocyanate; however, the treatment efficiency severely deteriorated when the system was challenged with 0.74 mM cyanide. Addition of 2 g NaHCO3 l(-1) did not improve the efficiency of the treatment. Toxicity of the pollutants to the alga was cyanide > thiocyanate > phenol > salicylate. The high toxicity of the waste-water was eliminated either by a 25-fold dilution or by photocatalytic pre-treatment which allowed the subsequent efficient biological treatment.

  6. Inhibition of Listeria monocytogenes in full- and low-sodium frankfurters at 4, 7, or 10°C using spray-dried mixtures of organic acid salts.

    PubMed

    Sansawat, Thanikarn; Zhang, Lei; Jeong, Jong Y; Xu, Yanyang; Hessell, Gerald W; Ryser, Elliot T; Harte, Janice B; Tempelman, Robert; Kang, Iksoon

    2013-09-01

    In meat processing, powdered ingredients are preferred to liquids because of ease of handling, mixing, and storing. This study was conducted to assess Listeria monocytogenes inhibition and the physicochemical and organoleptic characteristics of frankfurters that were prepared with organic acid salts as spray-dried powders (sodium lactate-sodium acetate, sodium lactate-sodium acetate-sodium diacetate, and potassium acetate-potassium diacetate) or liquids (sodium lactate, sodium lactate-sodium diacetate, potassium lactate, and potassium lactate-sodium diacetate). Full-sodium (1.8% salt) and low-sodium (1.0% salt) frankfurters were prepared according to 10 and 5 different formulations (n = 3), respectively, and were dip inoculated with a six-strain cocktail of L. monocytogenes (∼4 log CFU/g). Populations of Listeria and mesophilic aerobic bacteria were quantified during storage at 4, 7, and 10°C for up to 90 days. Four powder and two liquid full-sodium formulations and one powder low-sodium formulation, all of which contained diacetate except for 1% sodium lactate-sodium acetate powder, completely inhibited Listeria growth at 4°C. However, Listeria grew in full-sodium formulations at 10°C and in low-sodium formulations at 7 and 10°C except for the formulation containing 0.8% potassium acetate-0.2% potassium diacetate powder. All formulations were similar in terms of water activity, cooking yield, moisture, and protein content. Sodium content and pH were affected by the concentrations of sodium and diacetate, respectively. Frankfurter appearance, texture, flavor, and overall acceptability were similar (P > 0.05) regardless of the formulation, except for flavor and overall acceptability of the low-sodium formulation containing potassium acetate-potassium diacetate. Based on these findings, cosprayed powders appear to be a viable alternative to current liquid inhibitors for control of Listeria in processed meats.

  7. Symmetric normal mixtures

    NASA Technical Reports Server (NTRS)

    Turmon, Michael

    2004-01-01

    We consider mixture density estimation under the symmetry constraint x = Az for an orthogonal matrix A. This distributional constraint implies a corresponding constraint on the mixture parameters. Focusing on the gaussian case, we derive an expectation-maximization (EM) algorithm to enforce the constraint and show results for modeling of image feature vectors.

  8. Method of extracting iodine from liquid mixtures of iodine, water and hydrogen iodide

    DOEpatents

    Mysels, Karol J.

    1979-01-01

    The components of a liquid mixture consisting essentially of HI, water and at least about 50 w/o iodine are separated in a countercurrent extraction zone by treating with phosphoric acid containing at least about 90 w/o H.sub.3 PO.sub.4. The bottom stream from the extraction zone is substantially completely molten iodine, and the overhead stream contains water, HI, H.sub.3 PO.sub.4 and a small fraction of the amount of original iodine. When the water and HI are present in near-azeotropic proportions, there is particular advantage in feeding the overhead stream to an extractive distillation zone wherein it is treated with additional concentrated phosphoric acid to create an anhydrous HI vapor stream and bottoms which contain at least about 85 w/o H.sub.3 PO.sub.4. Concentration of these bottoms provides phosphoric acid infeed for both the countercurrent extraction zone and for the extractive distillation zone.

  9. Perception of trigeminal mixtures.

    PubMed

    Filiou, Renée-Pier; Lepore, Franco; Bryant, Bruce; Lundström, Johan N; Frasnelli, Johannes

    2015-01-01

    The trigeminal system is a chemical sense allowing for the perception of chemosensory information in our environment. However, contrary to smell and taste, we lack a thorough understanding of the trigeminal processing of mixtures. We, therefore, investigated trigeminal perception using mixtures of 3 relatively receptor-specific agonists together with one control odor in different proportions to determine basic perceptual dimensions of trigeminal perception. We found that 4 main dimensions were linked to trigeminal perception: sensations of intensity, warmth, coldness, and pain. We subsequently investigated perception of binary mixtures of trigeminal stimuli by means of these 4 perceptual dimensions using different concentrations of a cooling stimulus (eucalyptol) mixed with a stimulus that evokes warmth perception (cinnamaldehyde). To determine if sensory interactions are mainly of central or peripheral origin, we presented stimuli in a physical "mixture" or as a "combination" presented separately to individual nostrils. Results showed that mixtures generally yielded higher ratings than combinations on the trigeminal dimensions "intensity," "warm," and "painful," whereas combinations yielded higher ratings than mixtures on the trigeminal dimension "cold." These results suggest dimension-specific interactions in the perception of trigeminal mixtures, which may be explained by particular interactions that may take place on peripheral or central levels. PMID:25500807

  10. Perception of trigeminal mixtures.

    PubMed

    Filiou, Renée-Pier; Lepore, Franco; Bryant, Bruce; Lundström, Johan N; Frasnelli, Johannes

    2015-01-01

    The trigeminal system is a chemical sense allowing for the perception of chemosensory information in our environment. However, contrary to smell and taste, we lack a thorough understanding of the trigeminal processing of mixtures. We, therefore, investigated trigeminal perception using mixtures of 3 relatively receptor-specific agonists together with one control odor in different proportions to determine basic perceptual dimensions of trigeminal perception. We found that 4 main dimensions were linked to trigeminal perception: sensations of intensity, warmth, coldness, and pain. We subsequently investigated perception of binary mixtures of trigeminal stimuli by means of these 4 perceptual dimensions using different concentrations of a cooling stimulus (eucalyptol) mixed with a stimulus that evokes warmth perception (cinnamaldehyde). To determine if sensory interactions are mainly of central or peripheral origin, we presented stimuli in a physical "mixture" or as a "combination" presented separately to individual nostrils. Results showed that mixtures generally yielded higher ratings than combinations on the trigeminal dimensions "intensity," "warm," and "painful," whereas combinations yielded higher ratings than mixtures on the trigeminal dimension "cold." These results suggest dimension-specific interactions in the perception of trigeminal mixtures, which may be explained by particular interactions that may take place on peripheral or central levels.

  11. SEPARATION OF FLUID MIXTURES

    DOEpatents

    Lipscomb, R.; Craig, A.; Labrow, S.; Dunn, J.F.

    1958-10-28

    An apparatus is presented for separating gaseous mixtures by selectively freezing a constituent of the mixture and subsequently separating the frozen gas. The gas mixture is passed through a cylinder fltted with a cooling jacket, causing one gas to freeze on the walls of the cylinder. A set of scraper blades are provided in the interior of the cyllnder, and as the blades oscillate, the frozen gas is scraped to the bottom of the cylinder. Means are provided for the frozen material to pass into a heating chamber where it is vaporized and the product gas collected.

  12. Some aspects in the design of multicomponent reactive distillation columns with a reacting core: Mixtures containing inerts

    SciTech Connect

    Espinosa, J.; Aguirre, P.; Perez, G.

    1996-12-01

    Some aspects related to the design of reactive distillation columns with a reacting core are addressed in this paper. A set of transformed composition variables proposed in a previous paper is used to develop both the design equations and the reactive residue curve maps for quaternary reacting mixtures. Also, conventional residue curve maps are employed to achieve a better physical and conceptual insight into the relationships between the different constitutive parts of a column with a reacting core. Limitations in product specifications of entirely reactive distillation columns are explained by means of reactive residue curve maps, and a new feasibility criterion of a given separation for reactive columns with a reacting core is also developed on the basis of the two extreme operation conditions of a column. Finally, the behavior of column profiles for both high-conversion and low-conversion cases is analyzed and optimal product specifications are suggested to obtain high purity products. As the authors concluded in previous works, the inerts have a central role in both the design and synthesis of a reactive distillation column. All the concepts are applied to azeotrope-forming mixtures.

  13. Evaluation of the stability of a mixture of volatile organic compounds on sorbents for the determination of emissions from indoor materials and products using thermal desorption/gas chromatography/mass spectrometry.

    PubMed

    Brown, Veronica M; Crump, Derrick R; Plant, Neil T; Pengelly, Ian

    2014-07-11

    The standard method for the determination of volatile organic compounds (VOCs) in indoor and test chamber air (ISO 16000-6:2011) specifies sampling onto the sorbent Tenax TA followed by analysis using thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS). The informative Annex D to the standard suggests the use of multi-sorbent samplers to extend the volatility range of compounds which can be determined. The aim of this study was to investigate the storage performance of Tenax TA and two multi-sorbent tubes loaded with a mixture of nine VOCs of relevance for material emissions testing. The sorbent combinations tested were quartz wool/Tenax TA/Carbograph™ 5TD and quartz wool/Tenax TA/Carbopack™ X. A range of loading levels, loading conditions (humidities and air volume), storage times (1-4 weeks) and storage conditions (refrigerated and ambient) were investigated. Longer term storage trials (up to 1 year) were conducted with Tenax TA tubes to evaluate the stability of tubes used for proficiency testing (PT) of material emissions analyses. The storage performance of the multi-sorbent tubes tested was found to be equal to that for Tenax TA, with recoveries after 4 weeks storage of within about 10% of the amounts loaded. No consistent differences in recoveries were found for the different loading or storage conditions. The longer term storage trials also showed good recovery for these compounds, although two other compounds, hexanal and BHT, were found to be unstable when stored on Tenax TA. The results of this study provide confidence in the stability of nine analytes for up to 4 weeks on two multi-sorbent tubes for material emissions testing and the same compounds loaded on Tenax TA sorbent for a recently introduced PT scheme for material emissions testing.

  14. An interpretation of the CONSERT and SESAME-PP results based on new permittivity measurements of porous water ice and ice-basaltic/organic dust mixtures suggests an increase of porosity with depth in 67P.

    NASA Astrophysics Data System (ADS)

    Brouet, Yann; Levasseur-Regourd, Anny-Chantal; Sabouroux, Pierre; Neves, Luisa; Encrenaz, Pierre; Poch, Olivier; Pommerol, Antoine; Thomas, Nicolas; Kofman, Wlodek; Le Gall, Alice; Ciarletti, Valérie; Hérique, Alain; Lethuillier, Anthony

    2016-10-01

    The CONSERT bistatic radar on Rosetta and Philae sounded the interior of the small lobe of 67P/C-G at 90 MHz and determined the average of the real part of the complex permittivity (hereafter ɛ') to be equal to 1.27±0.05 [1,2]. The permittivity probe (PP) of the SESAME package sounded the near-surface in the 400–800 Hz range and derived a lower limit of ɛ' equal to 2.45±0.20 [3,4]. At the time of the measurements, the temperature was found to be below 150 K at Philae's location and expected to be close or below 100 K inside the nucleus [4-6].The complex permittivity depends of the frequency, the composition, the porosity and the temperature of the material [7,8,9]. These parameters have to be taken into account to interpret the permittivity values. The non-dispersive behavior of ɛ' below 150 K [9], allows us to compare the CONSERT and SESAME-PP results and to interpret their difference in terms of porosity and/or composition. For this purpose we use a semi-empirical formula obtained from reproducible permittivity measurements performed in the laboratory at 243 K on water ice particles and ice-basaltic dust mixtures [10], with a controlled porosity in the 26–91% range and dust-to-ice volumetric ratios in the 0.1–2.8 range. The influence of the presence of organic materials on ɛ' is also discussed based on new measurements of analogues of complex extraterrestrial organic matter [11]. Our results suggest an increase of the porosity of the small lobe of 67P with depth [11], in agreement Lethuillier et al. [4]'s conclusion using a different method.[1]Kofman et al., 1998. Adv. Space Res., 21, 1589.[2]Ciarletti et al., 2015. A&A, 583, A40.[3]Seidensticker et al., 2007. Space Sci. Rev., 128, 301.[4]Lethuillier et al., 2016. A&A, 591, A32.[5]Spohn et al., 2015. Science, 349, aab0464.[6]Festou et al. (Eds.), Comets II. Univ. of Arizona Press.[7]Campbell and Ulrichs, 1969. J. Geophys. Res., 74, 5867.[8]Brouet et al., 2015. A&A, 583, A39.[9]Mattei et al., 2014

  15. Photoisomerization- and photopolymerization-induced phase transitions in mixtures of photoresponsive chromophores and reactive mesogens

    NASA Astrophysics Data System (ADS)

    Kim, Namil

    mixtures underwent phase separation. As the crystalline and nematic ordering of monomeric unit was frozen, LMWLC was dispersed in the continuum of isotropic or anisotropic networks. Phase diagram exhibited the broad immiscible regions. The phase diagram of annealed hyperbranched polymer/LMWLC mixtures was an upper azeotrope, exhibiting the coexistence of nematic + isotropic phase above the clearing temperature of neat LMWLC. With decreasing temperature a focal-conic fan shaped texture developed in the composition range of 63~93 wt %, suggestive of induced smectic phase in the mixture.

  16. Methods of increasing net work output of organic Rankine cycles for low-grade waste heat recovery with a detailed analysis using a zeotropic working fluid mixture and scroll expander

    NASA Astrophysics Data System (ADS)

    Woodland, Brandon Jay

    An organic Rankine cycle (ORC) is a thermodynamic cycle that is well-suited for waste heat recovery. It is generally employed for waste heat with temperatures in the range of 80 °C -- 300 °C. When the application is strictly to convert waste heat into work, thermal efficiency is not recommended as a key performance metric. In such an application, maximization of the net power output should be the objective rather than maximization of the thermal efficiency. Two alternative cycle configurations that can increase the net power produced from a heat source with a given temperature and flow rate are proposed and analyzed. These cycle configurations are 1) an ORC with two-phase flash expansion and 2) an ORC with a zeotropic working fluid mixture (ZRC). A design-stage ORC model is presented for consistent comparison of multiple ORC configurations. The finite capacity of the heat source and heat sink fluids is a key consideration in this model. Of all working fluids studied for the baseline ORC, R134a and R245fa yield the highest net power output from a given heat source. Results of the design-stage model indicate that the ORC with two-phase flash expansion offers the most improvement over the baseline ORC. However, the level of improvement that could be achieved in practice is highly uncertain due to the requirement of highly efficient two-phase expansion. The ZRC shows improvement over the baseline as long as the condenser fan power requirement is not negligible. At the highest estimated condenser fan power, the ZRC shows the most improvement, while the ORC with flash expansion is no longer beneficial. The ZRC was selected for detailed study because it does not require two-phase expansion. An experimental test rig was used to evaluate baseline ORC performance with R134a and with R245fa. The ZRC was tested on the same rig with a mixture of 62.5% R134a and 37.5% R245fa. The tested expander is a minimally-modified, of-the-shelf automotive scroll compressor. The high

  17. Evaluating Whole Chemical Mixtures and Sufficient Similarity

    EPA Science Inventory

    This powerpoint presentation supports apresentation describing dose-response assessment for complex chemical mixtures including deriving reference doses for mixtures evaluating sufficient similarity among chemical mixtures.

  18. Transcriptional responses to complex mixtures: a review.

    PubMed

    Sen, Banalata; Mahadevan, Brinda; DeMarini, David M

    2007-01-01

    Exposure of people to hazardous compounds is primarily through complex environmental mixtures, those that occur through media such as air, soil, water, food, cigarette smoke, and combustion emissions. Microarray technology offers the ability to query the entire genome after exposure to such an array of compounds, permitting a characterization of the biological effects of such exposures. This review summarizes the published literature on the transcriptional profiles resulting from exposure of cells or organisms to complex environmental mixtures such as cigarette smoke, diesel emissions, urban air, motorcycle exhaust, carbon black, jet fuel, and metal ore and fumes. The majority of the mixtures generally up-regulate gene expression, with heme oxygenase 1 and CYP1A1 being up-regulated by all of the mixtures. Most of the mixtures altered the expression of genes involved in oxidative stress response (OH-1, metallothioneins), immune/inflammation response (IL-1b, protein kinase), xenobiotic metabolism (CYP1A1, CYP1B1), coagulation and fibrinolysis (plasminogen activator/inhibitor), proto-oncogenes (FUS1, JUN), heat-shock response (HSP60, HSP70), DNA repair (PCNA, GADD45), structural unit of condensed DNA (Crf15Orf16, DUSP 15), and extracellular matrix degradation (MMP1, 8, 9, 11, 12). Genes involved in aldehyde metabolism, such as ALDH3, appeared to be uniquely modulated by cigarette smoke. Cigarette smoke-exposed populations have been successfully distinguished from control nonexposed populations based on the expression pattern of a subset of genes, thereby demonstrating the utility of this approach in identifying biomarkers of exposure and susceptibility. The analysis of gene-expression data at the pathway and functional level, along with a systems biology approach, will provide a more comprehensive insight into the biological effects of complex mixtures and will improve risk assessment of the same. We suggest critical components of study design and reporting that will

  19. Transcriptional responses to complex mixtures: a review.

    PubMed

    Sen, Banalata; Mahadevan, Brinda; DeMarini, David M

    2007-01-01

    Exposure of people to hazardous compounds is primarily through complex environmental mixtures, those that occur through media such as air, soil, water, food, cigarette smoke, and combustion emissions. Microarray technology offers the ability to query the entire genome after exposure to such an array of compounds, permitting a characterization of the biological effects of such exposures. This review summarizes the published literature on the transcriptional profiles resulting from exposure of cells or organisms to complex environmental mixtures such as cigarette smoke, diesel emissions, urban air, motorcycle exhaust, carbon black, jet fuel, and metal ore and fumes. The majority of the mixtures generally up-regulate gene expression, with heme oxygenase 1 and CYP1A1 being up-regulated by all of the mixtures. Most of the mixtures altered the expression of genes involved in oxidative stress response (OH-1, metallothioneins), immune/inflammation response (IL-1b, protein kinase), xenobiotic metabolism (CYP1A1, CYP1B1), coagulation and fibrinolysis (plasminogen activator/inhibitor), proto-oncogenes (FUS1, JUN), heat-shock response (HSP60, HSP70), DNA repair (PCNA, GADD45), structural unit of condensed DNA (Crf15Orf16, DUSP 15), and extracellular matrix degradation (MMP1, 8, 9, 11, 12). Genes involved in aldehyde metabolism, such as ALDH3, appeared to be uniquely modulated by cigarette smoke. Cigarette smoke-exposed populations have been successfully distinguished from control nonexposed populations based on the expression pattern of a subset of genes, thereby demonstrating the utility of this approach in identifying biomarkers of exposure and susceptibility. The analysis of gene-expression data at the pathway and functional level, along with a systems biology approach, will provide a more comprehensive insight into the biological effects of complex mixtures and will improve risk assessment of the same. We suggest critical components of study design and reporting that will

  20. Toxicological approaches to complex mixtures.

    PubMed Central

    Mauderly, J L

    1993-01-01

    This paper reviews the role of toxicological studies in understanding the health effects of environmental exposures to mixtures. The approach taken is to review mixtures that have received the greatest emphasis from toxicology; major mixtures research programs; the toxicologist's view of mixtures and approaches to their study; and the complementary roles of toxicological, clinical, and epidemiological studies. Studies of tobacco smoke, engine exhaust, combustion products, and air pollutants comprise most of the past research on mixtures. Because of their great experimental control over subjects, exposures, and endpoints, toxicologists tend to consider a wider range of toxic interactions among mixture components and sequential exposures than is practical for human studies. The three fundamental experimental approaches used by toxicologists are integrative (studying the mixture as a whole), dissective (dissecting a mixture to determine causative constituents), and synthetic (studying interactions between agents in simple combinations). Toxicology provides information on potential hazards, mechanisms by which mixture constituents interact to cause effects, and exposure dose-effect relationships; but extrapolation from laboratory data to quantitative human health risks is problematic. Toxicological, clinical, and epidemiological approaches are complementary but are seldom coordinated. Fostering synergistic interactions among the disciplines in studying the risks from mixtures could be advantageous. PMID:7515806

  1. Toxicological approaches to complex mixtures.

    PubMed

    Mauderly, J L

    1993-12-01

    This paper reviews the role of toxicological studies in understanding the health effects of environmental exposures to mixtures. The approach taken is to review mixtures that have received the greatest emphasis from toxicology; major mixtures research programs; the toxicologist's view of mixtures and approaches to their study; and the complementary roles of toxicological, clinical, and epidemiological studies. Studies of tobacco smoke, engine exhaust, combustion products, and air pollutants comprise most of the past research on mixtures. Because of their great experimental control over subjects, exposures, and endpoints, toxicologists tend to consider a wider range of toxic interactions among mixture components and sequential exposures than is practical for human studies. The three fundamental experimental approaches used by toxicologists are integrative (studying the mixture as a whole), dissective (dissecting a mixture to determine causative constituents), and synthetic (studying interactions between agents in simple combinations). Toxicology provides information on potential hazards, mechanisms by which mixture constituents interact to cause effects, and exposure dose-effect relationships; but extrapolation from laboratory data to quantitative human health risks is problematic. Toxicological, clinical, and epidemiological approaches are complementary but are seldom coordinated. Fostering synergistic interactions among the disciplines in studying the risks from mixtures could be advantageous.

  2. Stabilizer for fuel mixtures

    SciTech Connect

    Abe, M.; Moriyama, N.; Yamamura, M.

    1981-02-24

    A stabilizer for fuel mixtures of finely divided coal and fuel oil is composed of an active ingredient, a non-ionic surface active agent consisting of a block copolymer represented by the following general formula (I): R/sub 1/O-(C/sub 2/H/sup 4/O)l-(C/sub 3/H/sup 6/O)m-(C/sub 2/H/sup 4/O)n-R/sub 2/ (I) wherein r/sub 1/ and r/sub 2/ stand for a hydrogen atom or an alklyl group having 1 to 6 carbon atoms, the mole number (L+n) of added ethylene oxide is in the range of from 30 to 300, the mole number (M) of added propylene oxide is in the range of from 15 to 80, and the content of ethylene oxide in the whole molecule is 40 to 85% by weight.

  3. Oxidative particle mixtures for groundwater treatment

    DOEpatents

    Siegrist, Robert L.; Murdoch, Lawrence C.

    2000-01-01

    The invention is a method and a composition of a mixture for degradation and immobilization of contaminants in soil and groundwater. The oxidative particle mixture and method includes providing a material having a minimal volume of free water, mixing at least one inorganic oxidative chemical in a granular form with a carrier fluid containing a fine grained inorganic hydrophilic compound and injecting the resulting mixture into the subsurface. The granular form of the inorganic oxidative chemical dissolves within the areas of injection, and the oxidative ions move by diffusion and/or advection, therefore extending the treatment zone over a wider area than the injection area. The organic contaminants in the soil and groundwater are degraded by the oxidative ions, which form solid byproducts that can sorb significant amounts of inorganic contaminants, metals, and radionuclides for in situ treatment and immobilization of contaminants. The method and composition of the oxidative particle mixture for long-term treatment and immobilization of contaminants in soil and groundwater provides for a reduction in toxicity of contaminants in a subsurface area of contamination without the need for continued injection of treatment material, or for movement of the contaminants, or without the need for continuous pumping of groundwater through the treatment zone, or removal of groundwater from the subsurface area of contamination.

  4. Thermodynamic study of (anthracene + benzo[a]pyrene) solid mixtures.

    PubMed

    Rice, James W; Suuberg, Eric M

    2010-11-01

    To characterize better the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the {anthracene (1) + benzo[a]pyrene (2)} system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at x(1) = 0.26. The eutectic mixture is an amorphous solid that lacks organized crystal structure and melts between T = (414 and 420) K. For mixtures that contain 0.10 < x(1) < 0.90, the enthalpy of fusion is dominated by that of the eutectic. Solid-vapor equilibrium studies show that mixtures of anthracene and benzo[a]pyrene at x(1) < 0.10 sublime at the vapor pressure of pure benzo[a]pyrene. These results suggest that the solid-vapor equilibrium of benzo[a]pyrene is not significantly influenced by moderate levels of anthracene in the crystal structure.

  5. Thermodynamic study of (anthracene + benzo[a]pyrene) solid mixtures

    PubMed Central

    Rice, James W.; Suuberg, Eric M.

    2010-01-01

    To characterize better the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the {anthracene (1) + benzo[a]pyrene (2)} system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at x1 = 0.26. The eutectic mixture is an amorphous solid that lacks organized crystal structure and melts between T = (414 and 420) K. For mixtures that contain 0.10 < x1 < 0.90, the enthalpy of fusion is dominated by that of the eutectic. Solid-vapor equilibrium studies show that mixtures of anthracene and benzo[a]pyrene at x1 < 0.10 sublime at the vapor pressure of pure benzo[a]pyrene. These results suggest that the solid-vapor equilibrium of benzo[a]pyrene is not significantly influenced by moderate levels of anthracene in the crystal structure. PMID:20814451

  6. Complex mixtures, complex responses: Assessing pharmaceutical mixtures using field and laboratory approaches

    USGS Publications Warehouse

    Schoenfuss, Heiko L.; Furlong, Edward T.; Phillips, Patrick J.; Scott, Tia-Marie; Kolpin, Dana W.; Cetkovic-Cvrlje, Marina; Lesteberg, Kelsey E.; Rearick, Daniel C.

    2016-01-01

    Pharmaceuticals are present in low concentrations (<100 ng/L) in most municipal wastewater effluents but may be elevated locally because of factors such as input from pharmaceutical formulation facilities. Using existing concentration data, the authors assessed pharmaceuticals in laboratory exposures of fathead minnows (Pimephales promelas) and added environmental complexity through effluent exposures. In the laboratory, larval and mature minnows were exposed to a simple opioid mixture (hydrocodone, methadone, and oxycodone), an opioid agonist (tramadol), a muscle relaxant (methocarbamol), a simple antidepressant mixture (fluoxetine, paroxetine, venlafaxine), a sleep aid (temazepam), or a complex mixture of all compounds. Larval minnow response to effluent exposure was not consistent. The 2010 exposures resulted in shorter exposed minnow larvae, whereas the larvae exposed in 2012 exhibited altered escape behavior. Mature minnows exhibited altered hepatosomatic indices, with the strongest effects in females and in mixture exposures. In addition, laboratory-exposed, mature male minnows exposed to all pharmaceuticals (except the selective serotonin reuptake inhibitor mixture) defended nest sites less rigorously than fish in the control group. Tramadol or antidepressant mixture exposure resulted in increased splenic T lymphocytes. Only male minnows exposed to whole effluent responded with increased plasma vitellogenin concentrations. Female minnows exposed to pharmaceuticals (except the opioid mixture) had larger livers, likely as a compensatory result of greater prominence of vacuoles in liver hepatocytes. The observed alteration of apical endpoints central to sustaining fish populations confirms that effluents containing waste streams from pharmaceutical formulation facilities can adversely impact fish populations but that the effects may not be temporally consistent. The present study highlights the importance of including diverse biological endpoints spanning

  7. Complex mixtures, complex responses: Assessing pharmaceutical mixtures using field and laboratory approaches.

    PubMed

    Schoenfuss, Heiko L; Furlong, Edward T; Phillips, Pat J; Scott, Tia-Marie; Kolpin, Dana W; Cetkovic-Cvrlje, Marina; Lesteberg, Kelsey E; Rearick, Daniel C

    2016-04-01

    Pharmaceuticals are present in low concentrations (<100 ng/L) in most municipal wastewater effluents but may be elevated locally because of factors such as input from pharmaceutical formulation facilities. Using existing concentration data, the authors assessed pharmaceuticals in laboratory exposures of fathead minnows (Pimephales promelas) and added environmental complexity through effluent exposures. In the laboratory, larval and mature minnows were exposed to a simple opioid mixture (hydrocodone, methadone, and oxycodone), an opioid agonist (tramadol), a muscle relaxant (methocarbamol), a simple antidepressant mixture (fluoxetine, paroxetine, venlafaxine), a sleep aid (temazepam), or a complex mixture of all compounds. Larval minnow response to effluent exposure was not consistent. The 2010 exposures resulted in shorter exposed minnow larvae, whereas the larvae exposed in 2012 exhibited altered escape behavior. Mature minnows exhibited altered hepatosomatic indices, with the strongest effects in females and in mixture exposures. In addition, laboratory-exposed, mature male minnows exposed to all pharmaceuticals (except the selective serotonin reuptake inhibitor mixture) defended nest sites less rigorously than fish in the control group. Tramadol or antidepressant mixture exposure resulted in increased splenic T lymphocytes. Only male minnows exposed to whole effluent responded with increased plasma vitellogenin concentrations. Female minnows exposed to pharmaceuticals (except the opioid mixture) had larger livers, likely as a compensatory result of greater prominence of vacuoles in liver hepatocytes. The observed alteration of apical endpoints central to sustaining fish populations confirms that effluents containing waste streams from pharmaceutical formulation facilities can adversely impact fish populations but that the effects may not be temporally consistent. The present study highlights the importance of including diverse biological endpoints spanning

  8. Complex mixtures, complex responses: Assessing pharmaceutical mixtures using field and laboratory approaches.

    PubMed

    Schoenfuss, Heiko L; Furlong, Edward T; Phillips, Pat J; Scott, Tia-Marie; Kolpin, Dana W; Cetkovic-Cvrlje, Marina; Lesteberg, Kelsey E; Rearick, Daniel C

    2016-04-01

    Pharmaceuticals are present in low concentrations (<100 ng/L) in most municipal wastewater effluents but may be elevated locally because of factors such as input from pharmaceutical formulation facilities. Using existing concentration data, the authors assessed pharmaceuticals in laboratory exposures of fathead minnows (Pimephales promelas) and added environmental complexity through effluent exposures. In the laboratory, larval and mature minnows were exposed to a simple opioid mixture (hydrocodone, methadone, and oxycodone), an opioid agonist (tramadol), a muscle relaxant (methocarbamol), a simple antidepressant mixture (fluoxetine, paroxetine, venlafaxine), a sleep aid (temazepam), or a complex mixture of all compounds. Larval minnow response to effluent exposure was not consistent. The 2010 exposures resulted in shorter exposed minnow larvae, whereas the larvae exposed in 2012 exhibited altered escape behavior. Mature minnows exhibited altered hepatosomatic indices, with the strongest effects in females and in mixture exposures. In addition, laboratory-exposed, mature male minnows exposed to all pharmaceuticals (except the selective serotonin reuptake inhibitor mixture) defended nest sites less rigorously than fish in the control group. Tramadol or antidepressant mixture exposure resulted in increased splenic T lymphocytes. Only male minnows exposed to whole effluent responded with increased plasma vitellogenin concentrations. Female minnows exposed to pharmaceuticals (except the opioid mixture) had larger livers, likely as a compensatory result of greater prominence of vacuoles in liver hepatocytes. The observed alteration of apical endpoints central to sustaining fish populations confirms that effluents containing waste streams from pharmaceutical formulation facilities can adversely impact fish populations but that the effects may not be temporally consistent. The present study highlights the importance of including diverse biological endpoints spanning

  9. EVALUATION OF THE JOINT TOXIC ACTION OF MIXTURES OF HALOACETIC ACIDS CONSTRUCTED USING ENVIRONMENTAL CONCENTRATION/EXPOSURE DATA

    EPA Science Inventory

    Disinfection byproducts (DBPs) are formed by reactions between chemicals used to disinfect water and organic compounds present in source water. The composition of DBP mixtures varies based on a number of factors, including treatment scenario, with different DBP mixtures contain...

  10. Thermophysical Properties of Hydrocarbon Mixtures

    National Institute of Standards and Technology Data Gateway

    SRD 4 NIST Thermophysical Properties of Hydrocarbon Mixtures (PC database for purchase)   Interactive computer program for predicting thermodynamic and transport properties of pure fluids and fluid mixtures containing up to 20 components. The components are selected from a database of 196 components, mostly hydrocarbons.

  11. COMPLEX MIXTURES AND GROUNDWATER QUALITY

    EPA Science Inventory

    Experience has shown that many soil and ground-water contamination problems involve complex mixtures of chemicals. his manuscript identifies and discusses, in a generic sense, some of the important processes which must be considered when dealing with complex mixtures in the subsu...

  12. Latent classiness and other mixtures.

    PubMed

    Neale, Michael C

    2014-05-01

    The aim of this article is to laud Lindon Eaves' role in the development of mixture modeling in genetic studies. The specification of models for mixture distributions was very much in its infancy when Professor Eaves implemented it in his own FORTRAN programs, and extended it to data collected from relatives such as twins. It was his collaboration with the author of this article which led to the first implementation of mixture distribution modeling in a general-purpose structural equation modeling program, Mx, resulting in a 1996 article on linkage analysis in Behavior Genetics. Today, the popularity of these methods continues to grow, encompassing methods for genetic association, latent class analysis, growth curve mixture modeling, factor mixture modeling, regime switching, marginal maximum likelihood, genotype by environment interaction, variance component twin modeling in the absence of zygosity information, and many others. This primarily historical article concludes with some consideration of some possible future developments. PMID:24477932

  13. TEST REPORT #33: Compressor Calorimeter Test of R-410A Alternative: R-32/R-134a Mixture Using a Scroll Compressor

    SciTech Connect

    Shrestha, Som; Sharma, Vishaldeep; Abdelaziz, Omar

    2014-02-18

    This report investigates the tested performance of lower - GWP candidate refrigerant, 94.07 wt% R - 32 + 5.93 wt % R - 134 a mixture (hereafter referred to as R - 32/134a), as an alternative to baseline refrigerant R - 410 A using a 36,000 Btu/hr compressor calorimeter located at the Heat Exchanger Advanced Testing Facility at Oak Ridge National Laboratory . These tests were conducted during May and August 2013. R - 410A is a near - azeotropic blend of R - 32 and R - 125 with 0.5/0.5 mass fraction and has a GWP 100 of 2100. R - 32 and R - 134a are pure refrigerants and have GWP 100 of 716 and 1370 1, respectively. Based on the GWP 100 values of pure refrigerants and their mass fraction in the blend, GWP 100 of R - 32/134a, which is under development by National Refrigerant, is 755. This report compares various performance parameters, such as cooling capacity, compressor power, refrigerant mass flow rate, EER, isentropic efficiency and discharge temperature of the alternative refrigerant to that of R - 410 A.

  14. Electrokinetic remediation of PAH mixtures from kaolin.

    PubMed

    Alcántara, M T; Gómez, J; Pazos, M; Sanromán, M A

    2010-07-15

    Because of increased industrialisation and new manufacturing processes, elevated amounts of organic pollutants are released into the environment. Hydrophobic organic contaminants, including polycyclic aromatic hydrocarbons (PAHs), are toxic and persistent contaminants that are not treatable by natural attenuation. In this work, electroremediation is proposed for cleaning soil contaminated by organic compounds. Model samples of kaolin clay polluted with a mixture of PAHs (fluoranthene, pyrene, and benzanthracene) were treated. Electroremediation of kaolin contaminated with a mixture of these three PAHs was carried out using a solution of 1% Tween 80 and 0.1 M Na(2)SO(4) as the processing fluid. Under these conditions, low removal was obtained. However, by using the same processing fluid and controlling the pH at 7 in the anode chamber, high electro-osmotic flow was detected. After the treatment, removal of around 40% of the PAHs was achieved. The created environment inside the soil during the electrokinetic treatment greatly influenced the process. The results of this work reveal the high potential for the application of the electroremediation process on soil polluted with different PAHs.

  15. Patch testing with perfume mixture.

    PubMed

    Veien, N K; Hattel, T; Justesen, O; Nørholm, A

    1982-01-01

    145 of 1116 patients patch tested with the standard series of the International Contact Dermatitis Research Group, including the recently introduced perfume mixture, had positive patch test reactions to at least one of the traditional screening agents for fragrance allergy or to the perfume mixture. In 96 of 145 patients the positive patch tests could be explained as being related to fragrance allergy. The perfume mixture was considered a useful screening agent for fragrance allergy. However, the results indicate that it is still necessary to employ several screening agents to detect this type of hypersensitivity.

  16. TEA laser gas mixture optimization

    NASA Astrophysics Data System (ADS)

    Lipchak, W. Michael; Luck, Clarence F.

    1982-11-01

    The topographical plot of an optimized parameter, such as pulse energy or peak power, on the gas mixture plane is presented as a useful aid in realizing optimum mixtures of helium, carbon dioxide, and nitrogen, for operation of CO2 TEA lasers. A method for generating such a plot is discussed and an example is shown. The potential benefits of this graphical technique are also discussed.

  17. TEA laser gas mixture optimization

    SciTech Connect

    Lipchak, W.M.; Luck, C.F.

    1982-11-01

    The topographical plot of an optimized parameter, such as pulse energy or peak power, on the gas mixture plane is presented as a useful aid in realizing optimum mixtures of helium, carbon dioxide, and nitrogen, for operation of CO/sub 2/ TEA lasers. A method for generating such a plot is discussed and an example is shown. The potential benefits of this graphical technique are also discussed.

  18. Investigating Mixture Interactions of Astringent Stimuli Using the Isobole Approach.

    PubMed

    Fleming, Erin E; Ziegler, Gregory R; Hayes, John E

    2016-09-01

    Astringents (alum, malic acid, tannic acid) representing 3 broad classes (multivalent salts, organic acids, and polyphenols) were characterized alone, and as 2- and 3-component mixtures using isoboles. In experiment 1, participants rated 7 attributes ("astringency," the sub-qualities "drying," "roughing," and "puckering," and the side tastes "bitterness," "sourness," and "sweetness") using direct scaling. Quality specific power functions were calculated for each stimulus. In experiment 2, the same participants characterized 2- and 3-component mixtures. Multiple factor analysis (MFA) and hierarchical clustering on attribute ratings across stimuli indicate "astringency" is highly related to "bitterness" as well as "puckering," and the subqualities "drying" and "roughing" are somewhat redundant. Moreover, power functions were used to calculate indices of interaction (I) for each attribute/mixture combination. For "astringency," there was evidence of antagonism, regardless of the type of mixture. Conversely, for subqualities, the pattern of interaction depended on the mixture type. Alum/tannic acid and tannic acid/malic acid mixtures showed evidence of synergy for "drying" and "roughing"; alum/malic acid mixtures showed evidence of antagonism for "drying," "roughing," and "puckering." Collectively, these data clarify some semantic ambiguity regarding astringency and its subqualities, as well as the nature of interactions of among different types of astringents. Present data are not inconsistent with the idea that astringency arises from multiple mechanisms, although it remains to be determined whether the synergy observed here might reflect simultaneous activation of these multiple mechanisms. PMID:27252355

  19. Ionization coefficients in gas mixtures

    NASA Astrophysics Data System (ADS)

    Marić, D.; Šašić, O.; Jovanović, J.; Radmilović-Rađenović, M.; Petrović, Z. Lj.

    2007-03-01

    We have tested the application of the common E/N ( E—electric field, N—gas number density) or Wieland approximation [Van Brunt, R.J., 1987. Common parametrizations of electron transport, collision cross section, and dielectric strength data for binary gas mixtures. J. Appl. Phys. 61 (5), 1773-1787.] and the common mean energy (CME) combination of the data for pure gases to obtain ionization coefficients for mixtures. Test calculations were made for Ar-CH4, Ar-N2, He-Xe and CH4-N2 mixtures. Standard combination procedure gives poor results in general, due to the fact that the electron energy distribution is considerably different in mixtures and in individual gases at the same values of E/N. The CME method may be used for mixtures of gases with ionization coefficients that do not differ by more than two orders of magnitude which is better than any other technique that was proposed [Marić, D., Radmilović-Rađenović, M., Petrović, Z.Lj., 2005. On parametrization and mixture laws for electron ionization coefficients. Eur. Phys. J. D 35, 313-321.].

  20. RELIABLE COMPUTATION OF REACTIVE AZEOTROPES. (R826734)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  1. Modeling and interpreting biological effects of mixtures in the environment: introduction to the metal mixture modeling evaluation project.

    PubMed

    Van Genderen, Eric; Adams, William; Dwyer, Robert; Garman, Emily; Gorsuch, Joseph

    2015-04-01

    The fate and biological effects of chemical mixtures in the environment are receiving increased attention from the scientific and regulatory communities. Understanding the behavior and toxicity of metal mixtures poses unique challenges for incorporating metal-specific concepts and approaches, such as bioavailability and metal speciation, in multiple-metal exposures. To avoid the use of oversimplified approaches to assess the toxicity of metal mixtures, a collaborative 2-yr research project and multistakeholder group workshop were conducted to examine and evaluate available higher-tiered chemical speciation-based metal mixtures modeling approaches. The Metal Mixture Modeling Evaluation project and workshop achieved 3 important objectives related to modeling and interpretation of biological effects of metal mixtures: 1) bioavailability models calibrated for single-metal exposures can be integrated to assess mixture scenarios; 2) the available modeling approaches perform consistently well for various metal combinations, organisms, and endpoints; and 3) several technical advancements have been identified that should be incorporated into speciation models and environmental risk assessments for metals.

  2. Predicting the toxicity of metal mixtures

    USGS Publications Warehouse

    Balistrieri, Laurie S.; Mebane, Christopher A.

    2013-01-01

    The toxicity of single and multiple metal (Cd, Cu, Pb, and Zn) solutions to trout is predicted using an approach that combines calculations of: (1) solution speciation; (2) competition and accumulation of cations (H, Ca, Mg, Na, Cd, Cu, Pb, and Zn) on low abundance, high affinity and high abundance, low affinity biotic ligand sites; (3) a toxicity function that accounts for accumulation and potency of individual toxicants; and (4) biological response. The approach is evaluated by examining water composition from single metal toxicity tests of trout at 50% mortality, results of theoretical calculations of metal accumulation on fish gills and associated mortality for single, binary, ternary, and quaternary metal solutions, and predictions for a field site impacted by acid rock drainage. These evaluations indicate that toxicity of metal mixtures depends on the relative affinity and potency of toxicants for a given aquatic organism, suites of metals in the mixture, dissolved metal concentrations and ratios, and background solution composition (temperature, pH, and concentrations of major ions and dissolved organic carbon). A composite function that incorporates solution composition, affinity and competition of cations for two types of biotic ligand sites, and potencies of hydrogen and individual metals is proposed as a tool to evaluate potential toxicity of environmental solutions to trout.

  3. Mixtures of amino-acid based ionic liquids and water.

    PubMed

    Chaban, Vitaly V; Fileti, Eudes Eterno

    2015-09-01

    New ionic liquids (ILs) involving increasing numbers of organic and inorganic ions are continuously being reported. We recently developed a new force field; in the present work, we applied that force field to investigate the structural properties of a few novel imidazolium-based ILs in aqueous mixtures via molecular dynamics (MD) simulations. Using cluster analysis, radial distribution functions, and spatial distribution functions, we argue that organic ions (imidazolium, deprotonated alanine, deprotonated methionine, deprotonated tryptophan) are well dispersed in aqueous media, irrespective of the IL content. Aqueous dispersions exhibit desirable properties for chemical engineering. The ILs exist as ion pairs in relatively dilute aqueous mixtures (10 mol%), while more concentrated mixtures feature a certain amount of larger ionic aggregates.

  4. Separation of a Five-Component Mixture in the Microscale Laboratory.

    ERIC Educational Resources Information Center

    O'Hara-Mays, Ellen P.; Yuen, George U.

    1989-01-01

    Described is a microscale organic chemistry laboratory which involves the separation and purification of a mixture consisting of a strong organic acid, a weak organic acid, an organic base, and two neutral compounds. Reinforced are the basic principles of acid/base chemistry and the physical properties of the associated functional groups. (CW)

  5. Bayesian Kernel Mixtures for Counts

    PubMed Central

    Canale, Antonio; Dunson, David B.

    2011-01-01

    Although Bayesian nonparametric mixture models for continuous data are well developed, there is a limited literature on related approaches for count data. A common strategy is to use a mixture of Poissons, which unfortunately is quite restrictive in not accounting for distributions having variance less than the mean. Other approaches include mixing multinomials, which requires finite support, and using a Dirichlet process prior with a Poisson base measure, which does not allow smooth deviations from the Poisson. As a broad class of alternative models, we propose to use nonparametric mixtures of rounded continuous kernels. An efficient Gibbs sampler is developed for posterior computation, and a simulation study is performed to assess performance. Focusing on the rounded Gaussian case, we generalize the modeling framework to account for multivariate count data, joint modeling with continuous and categorical variables, and other complications. The methods are illustrated through applications to a developmental toxicity study and marketing data. This article has supplementary material online. PMID:22523437

  6. Bayesian Kernel Mixtures for Counts.

    PubMed

    Canale, Antonio; Dunson, David B

    2011-12-01

    Although Bayesian nonparametric mixture models for continuous data are well developed, there is a limited literature on related approaches for count data. A common strategy is to use a mixture of Poissons, which unfortunately is quite restrictive in not accounting for distributions having variance less than the mean. Other approaches include mixing multinomials, which requires finite support, and using a Dirichlet process prior with a Poisson base measure, which does not allow smooth deviations from the Poisson. As a broad class of alternative models, we propose to use nonparametric mixtures of rounded continuous kernels. An efficient Gibbs sampler is developed for posterior computation, and a simulation study is performed to assess performance. Focusing on the rounded Gaussian case, we generalize the modeling framework to account for multivariate count data, joint modeling with continuous and categorical variables, and other complications. The methods are illustrated through applications to a developmental toxicity study and marketing data. This article has supplementary material online. PMID:22523437

  7. Quantification of joint effect for hydrogen bond and development of QSARs for predicting mixture toxicity.

    PubMed

    Lin, Zhifen; Zhong, Ping; Yin, Kedong; Wang, Liansheng; Yu, Hongxia

    2003-08-01

    A QSAR model is successfully proposed to predict the toxicity effect on Photobacterium phosphoreum by nonpolar-narcotic-chemical mixtures and/or polar-narcotic-chemical mixtures. For nonpolar-narcotic-chemical mixtures and polar-narcotic-chemical mixtures, their corresponding hydrophobicity-based QSAR models are derived from regression analysis. Comparison of these two QSAR models make us believe that it is the joint effect of hydrogen bond in polar-narcotic-chemical mixture that leads to the difference between these two models. Such joint effect of hydrogen bond can be quantified as AMH and BMH by using the different partition coefficients of mixtures in various organic phase/water systems. And the regression analysis results convinced us that the introduction of AMH does improve the quality of the QSAR model with r2=0.948, S.E.=0.166 and F=745.201 at P=0.000 for total 84 mixtures.

  8. Unrestricted Mixture Models for Class Identification in Growth Mixture Modeling

    ERIC Educational Resources Information Center

    Liu, Min; Hancock, Gregory R.

    2014-01-01

    Growth mixture modeling has gained much attention in applied and methodological social science research recently, but the selection of the number of latent classes for such models remains a challenging issue, especially when the assumption of proper model specification is violated. The current simulation study compared the performance of a linear…

  9. Landfilling ash/sludge mixtures

    SciTech Connect

    Benoit, J.; Eighmy, T.T.; Crannell, B.S.

    1999-10-01

    The geotechnical properties of a mixture of municipal solid waste incinerator bottom ash and municipal wastewater treatment plant sludge was investigated for a proposed ash/sludge secure landfill. The components as well as mixtures ranging from 10:1 to 5:1 (ash:sludge, by volume) were evaluated, where appropriate, for a number of geotechnical index and mechanical properties including particle size, water content, specific gravity, density-moisture relationships, shear strength, and compressibility. The results from a compactibility study and stability analysis of the proposed landfill were used to help approve a landfill codisposal concept; a full-scale facility was constructed and is currently operating successfully.

  10. Phylogenetic mixture models for proteins.

    PubMed

    Le, Si Quang; Lartillot, Nicolas; Gascuel, Olivier

    2008-12-27

    Standard protein substitution models use a single amino acid replacement rate matrix that summarizes the biological, chemical and physical properties of amino acids. However, site evolution is highly heterogeneous and depends on many factors: genetic code; solvent exposure; secondary and tertiary structure; protein function; etc. These impact the substitution pattern and, in most cases, a single replacement matrix is not enough to represent all the complexity of the evolutionary processes. This paper explores in maximum-likelihood framework phylogenetic mixture models that combine several amino acid replacement matrices to better fit protein evolution.We learn these mixture models from a large alignment database extracted from HSSP, and test the performance using independent alignments from TREEBASE.We compare unsupervised learning approaches, where the site categories are unknown, to supervised ones, where in estimations we use the known category of each site, based on its exposure or its secondary structure. All our models are combined with gamma-distributed rates across sites. Results show that highly significant likelihood gains are obtained when using mixture models compared with the best available single replacement matrices. Mixtures of matrices also improve over mixtures of profiles in the manner of the CAT model. The unsupervised approach tends to be better than the supervised one, but it appears difficult to implement and highly sensitive to the starting values of the parameters, meaning that the supervised approach is still of interest for initialization and model comparison. Using an unsupervised model involving three matrices, the average AIC gain per site with TREEBASE test alignments is 0.31, 0.49 and 0.61 compared with LG (named after Le & Gascuel 2008 Mol. Biol. Evol. 25, 1307-1320), WAG and JTT, respectively. This three-matrix model is significantly better than LG for 34 alignments (among 57), and significantly worse for 1 alignment only. Moreover

  11. 16 CFR 1500.5 - Hazardous mixtures.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 16 Commercial Practices 2 2014-01-01 2014-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...

  12. 14 CFR 23.1147 - Mixture controls.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...

  13. 16 CFR 1500.5 - Hazardous mixtures.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 16 Commercial Practices 2 2010-01-01 2010-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...

  14. 14 CFR 23.1147 - Mixture controls.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...

  15. 16 CFR 1500.5 - Hazardous mixtures.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 16 Commercial Practices 2 2011-01-01 2011-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...

  16. 14 CFR 23.1147 - Mixture controls.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...

  17. 14 CFR 23.1147 - Mixture controls.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...

  18. 16 CFR 1500.5 - Hazardous mixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 16 Commercial Practices 2 2013-01-01 2013-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...

  19. 14 CFR 23.1147 - Mixture controls.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...

  20. 16 CFR 1500.5 - Hazardous mixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 16 Commercial Practices 2 2012-01-01 2012-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...

  1. [Study on transdermal absorption of borneol-salicylic acid eutectic mixture].

    PubMed

    Cui, D X; Sugibayashi, K; Morimoto, Y; Li, F L

    1989-01-01

    Borneol is an organic drug having property to form eutectic mixture with salicylic acid. We compared the transdermal absorption rate of borneol alone with that of borneol-salicylic acid eutectic mixture in hairless rats. The results showed that the borneol-salicylic acid eutectic mixture can evidently increase the absorption rate of borneol and provided a method for manufacturing borneol preparation which can easily be absorbed transdermally.

  2. Molecular Complexation and Phase Diagrams of Urea/PEG Mixtures

    NASA Astrophysics Data System (ADS)

    Fu, Guoepeng; Kyu, Thein

    2014-03-01

    Polyethylene glycol (PEG) and urea complexation has been known to form a stable crystal due to molecular complexation. The effect of molecular weight of PEG on the phase diagrams of its blends with urea has been explored. In the case of high molecular weight PEG8k/urea, the observed phase diagram is azeotrope, accompanied by eutectoid reactions in the submerged phases such as induced stable ``alpha'' phase crystals and metastable ``beta'' phase crystals. The metastable crystal can transform to stable crystal under a certain thermal annealing condition. However, the phase diagram of PEG1k/urea is of coexistence loop, whereas PEG400/urea exhibits eutectic character. Subsequently, the change of azeotrope to eutectic behavior with PEG molecular weight is analyzed in the context of the combined Flory-Huggins theory of liquid-liquid demixing and phase field theory of crystal solidification. Of particular interest is that only a very small urea amount (2 wt%) is needed to form a stable inclusion crystal via complexation with PEG. Potential application in lithium battery is discussed based on AC impedance spectroscopy and cyclic voltammetry. Supported by NSF-DMR 1161070.

  3. A regression model for calculating the boiling point isobars of tetrachloromethane-based binary solutions

    NASA Astrophysics Data System (ADS)

    Preobrazhenskii, M. P.; Rudakov, O. B.

    2016-01-01

    A regression model for calculating the boiling point isobars of tetrachloromethane-organic solvent binary homogeneous systems is proposed. The parameters of the model proposed were calculated for a series of solutions. The correlation between the nonadditivity parameter of the regression model and the hydrophobicity criterion of the organic solvent is established. The parameter value of the proposed model is shown to allow prediction of the potential formation of azeotropic mixtures of solvents with tetrachloromethane.

  4. Method and compositions for the degradation of tributyl phosphate in chemical waste mixtures

    DOEpatents

    Stoner, Daphne L.; Tien, Albert J.

    1995-01-01

    A method and process for the degradation of tributyl phosphate in an organic waste mixture and a biologically pure, novel bacteria culture for accomplishing the same. A newly-discovered bacteria (a strain of Acinetobacter sp. ATCC 55587) is provided which is combined in a reactor vessel with a liquid waste mixture containing tributyl phosphate and one or more organic waste compounds capable of functioning as growth substrates for the bacteria. The bacteria is thereafter allowed to incubate within the waste mixture. As a result, the tributyl phosphate and organic compounds within the waste mixture are metabolized (degraded) by the bacteria, thereby eliminating such materials which are environmentally hazardous. In addition, the bacteria is capable of degrading waste mixtures containing high quantities of tributyl phosphate (e.g. up to about 1.0% by weight tributyl phosphate).

  5. Method and compositions for the degradation of tributyl phosphate in chemical waste mixtures

    DOEpatents

    Stoner, D.L.; Tien, A.J.

    1995-09-26

    A method and process are disclosed for the degradation of tributyl phosphate in an organic waste mixture and a biologically pure, novel bacteria culture for accomplishing the same. A newly-discovered bacteria (a strain of Acinetobacter sp. ATCC 55587) is provided which is combined in a reactor vessel with a liquid waste mixture containing tributyl phosphate and one or more organic waste compounds capable of functioning as growth substrates for the bacteria. The bacteria is thereafter allowed to incubate within the waste mixture. As a result, the tributyl phosphate and organic compounds within the waste mixture are metabolized (degraded) by the bacteria, thereby eliminating such materials which are environmentally hazardous. In addition, the bacteria is capable of degrading waste mixtures containing high quantities of tributyl phosphate (e.g. up to about 1.0% by weight tributyl phosphate). 6 figs.

  6. Odour suppression in binary mixtures.

    PubMed

    Cashion, Larry; Livermore, Andrew; Hummel, Thomas

    2006-10-01

    It has been suggested that odours causing stronger trigeminal activation suppress weaker trigeminal stimuli and that mixed olfactory-trigeminal stimuli suppress odorants that only activate one of these systems. Volunteer normosmic participants (n=20) were exposed to six odorants with varying trigeminal impact to test the hypothesis that more intense "trigeminal" odorants would suppress weaker trigeminal stimuli in binary odour mixtures. It was also hypothesised that stronger trigeminal odorants would dominate six-odour mixtures. The predicted linear pattern of suppression was not seen, with a quadratic model emerging from the data. Stronger trigeminal stimuli failed to dominate six-odour mixtures. Despite the fact that the major hypothesis was not supported, it can be hypothesised from this experiment that the effect of suppression in binary mixtures is reliant upon two major effects: (1) the association formed between odours and the multiple memory systems that they interact with during the encoding and recognition processes, and (2) the balance between activation of the olfactory and trigeminal systems.

  7. Bioavailability of genotoxic mixtures in soil

    SciTech Connect

    Bordelon, N.; Washburn, K.; He, L.Y.; Donnelly, K.C.

    1996-12-31

    Contaminated media at Superfund sites typically consist of complex mixtures of organic and inorganic chemicals which are difficult to characterize, both analytically and toxicologically. The current EPA approach to risk assessment uses solvent extraction to remove chemicals from the soil as a basis for estimating risk to the human population. However, contaminants that can be recovered with a solvent extract may not represent the mixture of chemicals that are available for human exposure. A procedure using an aqueous extraction was investigated to provide a more realistic estimate of what chemicals are bioavailable. A study was conducted with two soil types: creosote-contaminated sandy soil and coal tar-contaminated clay soil spiked with benzo(a)pyrene [B(a)P], and trinitrotoluene (TNT). Samples were extracted with hexane:acetone and water titrated to pH2 and pH7. HPLC analysis demonstrated up to 35% and 29% recovery of contaminants using the aqueous extracts. The estimated cancer risk for the aqueous extract was one order of magnitude less than that for solvent extracts. Analysis using the Salmonella/microsome assay demonstrated that solvent extracts were genotoxic (133 revertants/mg) with metabolic activation while aqueous extracts of clay soil were not genotoxic. Sandy soil showed genotoxicity both with and without metabolic activation. These results suggest that solvent extraction techniques may overestimate the concentration of contaminants that are available for human exposure and, hence, the risk associated with the presence of the contaminants in soil.

  8. MULTIVARIATE KERNEL PARTITION PROCESS MIXTURES

    PubMed Central

    Dunson, David B.

    2013-01-01

    Mixtures provide a useful approach for relaxing parametric assumptions. Discrete mixture models induce clusters, typically with the same cluster allocation for each parameter in multivariate cases. As a more flexible approach that facilitates sparse nonparametric modeling of multivariate random effects distributions, this article proposes a kernel partition process (KPP) in which the cluster allocation varies for different parameters. The KPP is shown to be the driving measure for a multivariate ordered Chinese restaurant process that induces a highly-flexible dependence structure in local clustering. This structure allows the relative locations of the random effects to inform the clustering process, with spatially-proximal random effects likely to be assigned the same cluster index. An exact block Gibbs sampler is developed for posterior computation, avoiding truncation of the infinite measure. The methods are applied to hormone curve data, and a dependent KPP is proposed for classification from functional predictors. PMID:24478563

  9. Gas adsorption and gas mixture separations using mixed-ligand MOF material

    DOEpatents

    Hupp, Joseph T.; Mulfort, Karen L.; Snurr, Randall Q.; Bae, Youn-Sang

    2011-01-04

    A method of separating a mixture of carbon dioxiode and hydrocarbon gas using a mixed-ligand, metal-organic framework (MOF) material having metal ions coordinated to carboxylate ligands and pyridyl ligands.

  10. Gene Expression Responses in Male Fathead Minnows Exposed to Binary Mixtures of an Estrogen and Antiestrogen

    EPA Science Inventory

    Aquatic organisms are continuously exposed to complex mixtures of chemicals, many of which can interfere with their endocrine system, resulting in impaired reproduction, development or survival, among others. In order to analyze the effects and mechanisms of action of estrogen...

  11. International issues on human health effects of exposure to chemical mixtures.

    PubMed Central

    Feron, Victor J; Cassee, Flemming R; Groten, John P; van Vliet, Petronella W; van Zorge, Job A

    2002-01-01

    In this article, we highlight new developments and recent studies concerning adverse human health effects related to chemical mixtures. One group of activities comprises the development of a new computer program for analyzing mixture studies and a mathematical model as a basis for combination rules that predict the toxicity of mixtures. Other new activities in the area of experimental studies are the application of gene expression technologies in mixture research, and pattern recognition as a tool in safety evaluation of complex mixtures. A "bottom-up" approach for chemosensory detection of mixtures has recently been presented. Other topics include a method for the safety evaluation of natural flavoring complexes, and an evaluation of the possible health effects of the simultaneous intake of food additives. Examples of issues related to mixtures of airborne chemicals are potential interaction of fine particles and gaseous pollutants in ambient air, nasal cancer associated with inhaled chemical mixtures, and the recommendation of a limit value for volatile organic compounds. Topics of a more strategic nature include studies concerning the public health effects of large airports, and the development of criteria for a harmonized classification of chemical mixtures. This overview illustrates that strategies to tackle the safety evaluation of combined exposures and complex mixtures as well as models facilitating the interpretation of findings in the context of risk assessment of mixtures have become increasingly important. It is true that exposure of humans to chemical mixtures is the rule rather than the exception, and therefore health risk assessments should focus on mixtures and not on single chemicals. It is also true, however, that humans have learned to cope with exposure to huge numbers of chemicals simultaneously (food, water, air, soil, and consumer products). Therefore, in view of limited resources for toxicological research, the focus in toxicology should be

  12. Assessment of solid reactive mixtures for the development of biological permeable reactive barriers.

    PubMed

    Pagnanelli, Francesca; Viggi, Carolina Cruz; Mainelli, Sara; Toro, Luigi

    2009-10-30

    Solid reactive mixtures were tested as filling material for the development of biological permeable reactive barriers for the treatment of heavy metals contaminated waters. Mixture selection was performed by taking into account the different mechanisms operating in sulphate and cadmium removal with particular attention to bioprecipitation and sorption onto the organic matrices in the mixtures. Suspensions of eight reactive mixtures were tested for sulphate removal (initial concentration 3 g L(-1)). Each mixture was made up of four main functional components: a mix of organic sources for bacterial growth, a neutralizing agent, a porous medium and zero-valent iron. The best mixture among the tested ones (M8: 6% leaves, 9% compost, 3% zero-valent iron, 30% silica sand, 30% perlite, 22% limestone) presented optimal conditions for SRB growth (pH 7.8 +/- 0.1; E(h)= -410 +/- 5 mV) and 83% sulphate removal in 22 days (25% due to bioreduction, 32% due to sorption onto compost and 20% onto leaves). M8 mixture allowed the complete abatement of cadmium with a significant contribution of sorption over bioprecipitation (6% Cd removal due to SRB activity). Sorption properties, characterised by potentiometric titrations and related modelling, were mainly due to carboxylic sites of organic components used in reactive mixtures.

  13. Variable mixture ratio performance through nitrogen augmentation

    NASA Technical Reports Server (NTRS)

    Beichel, R.; Obrien, C. J.; Bair, E. K.

    1988-01-01

    High/variable mixture ratio O2/H2 candidate engine cycles are examined for earth-to-orbit vehicle application. Engine performance and power balance information are presented for the candidate cycles relative to chamber pressure, bulk density, and mixture ratio. Included in the cycle screening are concepts where a third fluid (liquid nitrogen) is used to achieve a variable mixture ratio over the trajectory from liftoff to earth orbit. The third fluid cycles offer a very low risk, fully reusable, low operation cost alternative to high/variable mixture ratio bipropellant cycles. Variable mixture ratio engines with extendible nozzle are slightly lower performing than a single mixture ratio engine (MR = 7:1) with extendible nozzle. Dual expander engines (MR = 7:1) have slightly better performance than the single mixture ratio engine. Dual fuel dual expander engines offer a 16 percent improvement over the single mixture ratio engine.

  14. Uncertainty in Mixtures and Cumulative Risk Assessment

    EPA Science Inventory

    Humans and environmental species are rarely exposed to single chemicals. These chemicals typically affect multiple tissues through multiple modes of action, which may depend on the dose. Mixtures risk assessment may employ dose response information from the mixture of interest,...

  15. Medicines, shaken and stirred: a critical review on the ecotoxicology of pharmaceutical mixtures.

    PubMed

    Backhaus, Thomas

    2014-11-19

    Analytical monitoring surveys routinely confirm that organisms in the environment are exposed to complex multi-component pharmaceutical mixtures. We are hence tasked with the challenge to take this into consideration when investigating the ecotoxicology of pharmaceuticals. This review first provides a brief overview of the fundamental approaches for mixture toxicity assessment, which is then followed by a critical review on the empirical evidence that is currently at hand on the ecotoxicology of pharmaceutical mixtures. It is concluded that, while the classical concepts of concentration addition and independent action (response addition) provide a robust scientific footing, several knowledge gaps remain. This includes, in particular, the need for more and better empirical data on the effects of pharmaceutical mixtures on soil organisms as well as marine flora and fauna, and exploring the quantitative consequences of toxicokinetic, toxicodynamic and ecological interactions. Increased focus should be put on investigating the ecotoxicology of pharmaceutical mixtures in environmentally realistic settings.

  16. Experimental evaluation of drying characteristics of sewage sludge and hazelnut shell mixtures

    NASA Astrophysics Data System (ADS)

    Pehlivan, Hüseyin; Ateş, Asude; Özdemir, Mustafa

    2016-11-01

    In this study the drying behavior of organic and agricultural waste mixtures has been experimentally investigated. The usability of sewage sludge as an organic waste and hazelnut shell as an agricultural waste was assessed in different mixture range. The paper discusses the applicability of these mixtures as a recovery energy source. Moisture content of mixtures has been calculated in laboratory and plant conditions. Indoor and outdoor solar sludge drying plants were constructed in pilot scale for experimental purposes. Dry solids and climatic conditions were constantly measured. A total more than 140 samples including for drying has been carried out to build up results. Indoor and outdoor weather conditions are taken into consideration in winter and summer. The most effective drying capacity is obtained in mixture of 20 % hazelnut shell and 80 % sewage sludge.

  17. Medicines, shaken and stirred: a critical review on the ecotoxicology of pharmaceutical mixtures

    PubMed Central

    Backhaus, Thomas

    2014-01-01

    Analytical monitoring surveys routinely confirm that organisms in the environment are exposed to complex multi-component pharmaceutical mixtures. We are hence tasked with the challenge to take this into consideration when investigating the ecotoxicology of pharmaceuticals. This review first provides a brief overview of the fundamental approaches for mixture toxicity assessment, which is then followed by a critical review on the empirical evidence that is currently at hand on the ecotoxicology of pharmaceutical mixtures. It is concluded that, while the classical concepts of concentration addition and independent action (response addition) provide a robust scientific footing, several knowledge gaps remain. This includes, in particular, the need for more and better empirical data on the effects of pharmaceutical mixtures on soil organisms as well as marine flora and fauna, and exploring the quantitative consequences of toxicokinetic, toxicodynamic and ecological interactions. Increased focus should be put on investigating the ecotoxicology of pharmaceutical mixtures in environmentally realistic settings. PMID:25405972

  18. Experimental evaluation of drying characteristics of sewage sludge and hazelnut shell mixtures

    NASA Astrophysics Data System (ADS)

    Pehlivan, Hüseyin; Ateş, Asude; Özdemir, Mustafa

    2016-01-01

    In this study the drying behavior of organic and agricultural waste mixtures has been experimentally investigated. The usability of sewage sludge as an organic waste and hazelnut shell as an agricultural waste was assessed in different mixture range. The paper discusses the applicability of these mixtures as a recovery energy source. Moisture content of mixtures has been calculated in laboratory and plant conditions. Indoor and outdoor solar sludge drying plants were constructed in pilot scale for experimental purposes. Dry solids and climatic conditions were constantly measured. A total more than 140 samples including for drying has been carried out to build up results. Indoor and outdoor weather conditions are taken into consideration in winter and summer. The most effective drying capacity is obtained in mixture of 20 % hazelnut shell and 80 % sewage sludge.

  19. Combined toxicity of pesticide mixtures on green algae and photobacteria.

    PubMed

    Liu, Shu-Shen; Wang, Cheng-Lin; Zhang, Jin; Zhu, Xiang-Wei; Li, Wei-Ying

    2013-09-01

    Different organisms have diverse responses to the same chemicals or mixtures. In this paper, we selected the green algae Chlorella pyrenoidosa (C. pyrenoidosa) and photobacteria Vibrio qinghaiensis sp.-Q67 (V. qinghaiensis) as target organisms and determined the toxicities of six pesticides, including three herbicides (simetryn, bromacil and hexazinone), two fungicides (dodine and metalaxyl) and one insecticide (propoxur), and their mixtures by using the microplate toxicity analysis. The toxicities of three herbicides to C. pyrenoidosa are much higher than those to V. qinghaiensis, and the toxicities of metalaxyl and propoxur to V. qinghaiensis are higher than those to C. pyrenoidosa, while the toxicity of dodine to C. pyrenoidosa is similar to those to V. qinghaiensis. Using the concentration addition as an additive reference model, the binary pesticide mixtures exhibited different toxicity interactions, i.e., displayed antagonism to C. pyrenoidosa but synergism to V. qinghaiensis. However, the toxicities of the multi-component mixtures of more than two components are additive and can be predicted by the concentration addition model.

  20. 21 CFR 82.6 - Certifiable mixtures.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Certifiable mixtures. 82.6 Section 82.6 Food and... PROVISIONALLY LISTED COLORS AND SPECIFICATIONS General Provisions § 82.6 Certifiable mixtures. (a) A batch of a mixture which contains no straight color listed in subpart C or D may be certified for use in food,...

  1. 14 CFR 27.1147 - Mixture controls.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Mixture controls. 27.1147 Section 27.1147... STANDARDS: NORMAL CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 27.1147 Mixture controls. If there are mixture controls, each engine must have a separate control and the controls must...

  2. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  3. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  4. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  5. 21 CFR 82.6 - Certifiable mixtures.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Certifiable mixtures. 82.6 Section 82.6 Food and... PROVISIONALLY LISTED COLORS AND SPECIFICATIONS General Provisions § 82.6 Certifiable mixtures. (a) A batch of a mixture which contains no straight color listed in subpart C or D may be certified for use in food,...

  6. 14 CFR 27.1147 - Mixture controls.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Mixture controls. 27.1147 Section 27.1147... STANDARDS: NORMAL CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 27.1147 Mixture controls. If there are mixture controls, each engine must have a separate control and the controls must...

  7. 14 CFR 27.1147 - Mixture controls.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Mixture controls. 27.1147 Section 27.1147... STANDARDS: NORMAL CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 27.1147 Mixture controls. If there are mixture controls, each engine must have a separate control and the controls must...

  8. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  9. 14 CFR 27.1147 - Mixture controls.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Mixture controls. 27.1147 Section 27.1147... STANDARDS: NORMAL CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 27.1147 Mixture controls. If there are mixture controls, each engine must have a separate control and the controls must...

  10. 14 CFR 25.1147 - Mixture controls.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Mixture controls. 25.1147 Section 25.1147... STANDARDS: TRANSPORT CATEGORY AIRPLANES Powerplant Powerplant Controls and Accessories § 25.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control. The controls must...

  11. 14 CFR 29.1147 - Mixture controls.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Mixture controls. 29.1147 Section 29.1147... STANDARDS: TRANSPORT CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 29.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and the...

  12. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  13. 14 CFR 29.1147 - Mixture controls.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Mixture controls. 29.1147 Section 29.1147... STANDARDS: TRANSPORT CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 29.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and the...

  14. 14 CFR 29.1147 - Mixture controls.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Mixture controls. 29.1147 Section 29.1147... STANDARDS: TRANSPORT CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 29.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and the...

  15. 21 CFR 82.6 - Certifiable mixtures.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Certifiable mixtures. 82.6 Section 82.6 Food and... PROVISIONALLY LISTED COLORS AND SPECIFICATIONS General Provisions § 82.6 Certifiable mixtures. (a) A batch of a mixture which contains no straight color listed in subpart C or D may be certified for use in food,...

  16. 14 CFR 25.1147 - Mixture controls.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Mixture controls. 25.1147 Section 25.1147... STANDARDS: TRANSPORT CATEGORY AIRPLANES Powerplant Powerplant Controls and Accessories § 25.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control. The controls must...

  17. 14 CFR 25.1147 - Mixture controls.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Mixture controls. 25.1147 Section 25.1147... STANDARDS: TRANSPORT CATEGORY AIRPLANES Powerplant Powerplant Controls and Accessories § 25.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control. The controls must...

  18. 14 CFR 25.1147 - Mixture controls.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Mixture controls. 25.1147 Section 25.1147... STANDARDS: TRANSPORT CATEGORY AIRPLANES Powerplant Powerplant Controls and Accessories § 25.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control. The controls must...

  19. 14 CFR 29.1147 - Mixture controls.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Mixture controls. 29.1147 Section 29.1147... STANDARDS: TRANSPORT CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 29.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and the...

  20. 14 CFR 25.1147 - Mixture controls.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Mixture controls. 25.1147 Section 25.1147... STANDARDS: TRANSPORT CATEGORY AIRPLANES Powerplant Powerplant Controls and Accessories § 25.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control. The controls must...

  1. 14 CFR 27.1147 - Mixture controls.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Mixture controls. 27.1147 Section 27.1147... STANDARDS: NORMAL CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 27.1147 Mixture controls. If there are mixture controls, each engine must have a separate control and the controls must...

  2. 14 CFR 29.1147 - Mixture controls.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Mixture controls. 29.1147 Section 29.1147... STANDARDS: TRANSPORT CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 29.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and the...

  3. Superionic water-ammonia mixtures

    NASA Astrophysics Data System (ADS)

    Bethkenhagen, M.; Cebulla, D.; Redmer, R.; Hamel, S.

    2014-12-01

    The interior of the Giant Planets Uranus and Neptune contains large amounts of water, ammonia and methane (referred to as planetary ices). Many observable properties of these planets, such as luminosity, gravitational moments and magnetic fields, are thought to be determined by the physical and chemical properties of matter within this ice layer. Hence, the phase diagrams, equations of state and structural properties of these materials and their respective mixtures are of great interest.Especially the phase diagrams of water and ammonia gained much attention since Cavazzoni et al. [1] proposed superionic phases for these materials, which are characterized by highly mobile hydrogen ions in a lattice of oxygen and nitrogen ions, respectively. For water, the influence of such a phase on the properties of the Giant Planets as well as on exoplanets has been discussed widely. [2,3] Nevertheless, it is an open question how the properties of such a water layer change when another compound, e.g., ammonia is introduced. Considering a 1:1 mixture, we have performed ab initio simulations based on density functional theory using the VASP code [4] heating up structures which we had found from evolutionary random structure search calculations with XtalOpt [5]. We propose possible superionic water-ammonia structures present up to several Mbar. Moreover, we investigate the equation of state and transport properties of this mixture such as diffusion coefficients in order to compare with the pure compounds. These results are essential to construct new interior models for Neptune-like planets.[1] C. Cavazzoni et al., Science 283, 44 (1999).[2] R. Redmer et al., Icarus 211, 798 (2011).[3] L. Zeng and D. Sasselov, ApJ 784, 96 (2014).[4] G. Kresse and J. Hafner, Phys. Rev. B 47, 558 (1993).[5] D. C. Lonie and E. Zurek, Comput. Phys. Commun. 182, 372 (2011).

  4. Plasma polymerization of an ethylene-nitrogen gas mixture

    NASA Technical Reports Server (NTRS)

    Hudis, M.; Wydeven, T.

    1975-01-01

    A procedure has been developed whereby nitrogen can be incorporated into an organic film from an ethylene-nitrogen gas mixture using an internal electrode capacitively coupled radio frequency reactor. The presence of nitrogen has been shown directly by infrared transmittance spectra and electron spectroscopic chemical analysis data, and further indirect evidence was provided by dielectric measurements and by the reverse osmosis properties of the film. Preparation of a nitrogen containing film did not require vapor from an organic nitrogen containing liquid monomer. Some control over the bonding and stoichiometry of the polymer film was provided by the added degree of freedom of the nitrogen partial pressure in the gas mixture. This new parameter strongly affected the dielectric properties of the plasma polymerized film and could affect the reverse osmosis behavior.

  5. Separation and IR Analysis of a Mixture of Organic Compounds.

    ERIC Educational Resources Information Center

    Thompson, Evan M.; Almy, John

    1982-01-01

    Presents an experiment which includes fractional distillation with gas-liquid chromatography (GLC) and infrared analysis. Objectives are to introduce students to fractional distillation and analysis of each fraction by GLC, to induce them to decide if each fraction is sufficient for infrared analysis, and to identify unknowns. (Author/JN)

  6. Analysis of Analgesic Mixtures: An Organic Chemistry Experiment.

    ERIC Educational Resources Information Center

    Martin, Ned H.

    1981-01-01

    Describes an experiment to analyze commercial analgesic preparations (pain relievers) by silica gel thin layer chromatography, followed by preparative (thick) layer chromatographic separation and spectroscopic analysis. Key difference from similar experiments is that students are responsible for devising suitable solvent systems for the thin layer…

  7. Thermal conductivity of nanoparticle-fluid mixture.

    SciTech Connect

    Wang, X.; Xu, X.; Choi, S. U.-S.; Energy Technology; Purdue Univ.

    1999-10-01

    Effective thermal conductivity of mixtures of fluids and nanometer-size particles is measured by a steady-state parallel-plate method. The tested fluids contain two types of nanoparticles, Al{sub 2}O{sub 3} and CuO, dispersed in water, vacuum pump fluid, engine oil, and ethylene glycol. Experimental results show that the thermal conductivities of nanoparticle-fluid mixtures are higher than those of the base fluids. Using theoretical models of effective thermal conductivity of a mixture, we have demonstrated that the predicted thermal conductivities of nanoparticle-fluid mixtures are much lower than our measured data, indicating the deficiency in the existing models when used for nanoparticle-fluid mixtures. Possible mechanisms contributing to enhancement of the thermal conductivity of the mixtures are discussed. A more comprehensive theory is needed to fully explain the behavior of nanoparticle-fluid mixtures.

  8. Supercritical Water Mixture (SCWM) Experiment

    NASA Technical Reports Server (NTRS)

    Hicks, Michael C.; Hegde, Uday G.

    2012-01-01

    The subject presentation, entitled, Supercritical Water Mixture (SCWM) Experiment, was presented at the International Space Station (ISS) Increment 33/34 Science Symposium. This presentation provides an overview of an international collaboration between NASA and CNES to study the behavior of a dilute aqueous solution of Na2SO4 (5% w) at near-critical conditions. The Supercritical Water Mixture (SCWM) investigation, serves as important precursor work for subsequent Supercritical Water Oxidation (SCWO) experiments. The SCWM investigation will be performed in DECLICs High Temperature Insert (HTI) for the purpose of studying critical fluid phenomena at high temperatures and pressures. The HTI includes a completely sealed and integrated test cell (i.e., Sample Cell Unit SCU) that will contain approximately 0.3 ml of the aqueous test solution. During the sequence of tests, scheduled to be performed in FY13, temperatures and pressures will be elevated to critical conditions (i.e., Tc = 374C and Pc = 22 MPa) in order to observe salt precipitation, precipitate agglomeration and precipitate transport in the presence of a temperature gradient without the influences of gravitational forces. This presentation provides an overview of the motivation for this work, a description of the DECLIC HTI hardware, the proposed test sequences, and a brief discussion of the scientific research objectives.

  9. Accelerated Hazards Mixture Cure Model

    PubMed Central

    Zhang, Jiajia; Peng, Yingwei

    2010-01-01

    We propose a new cure model for survival data with a surviving or cure fraction. The new model is a mixture cure model where the covariate effects on the proportion of cure and the distribution of the failure time of uncured patients are separately modeled. Unlike the existing mixture cure models, the new model allows covariate effects on the failure time distribution of uncured patients to be negligible at time zero and to increase as time goes by. Such a model is particularly useful in some cancer treatments when the treat effect increases gradually from zero, and the existing models usually cannot handle this situation properly. We develop a rank based semiparametric estimation method to obtain the maximum likelihood estimates of the parameters in the model. We compare it with existing models and methods via a simulation study, and apply the model to a breast cancer data set. The numerical studies show that the new model provides a useful addition to the cure model literature. PMID:19697127

  10. Interpreting Y chromosome STR haplotype mixture.

    PubMed

    Ge, Jianye; Budowle, Bruce; Chakraborty, Ranajit

    2010-05-01

    Mixture interpretation is a challenging problem in forensic DNA analyses. The interpretation of Y short tandem repeat (STR) haplotype mixtures, due to a lack of recombination, differs somewhat from that of the autosomal DNA markers and is more complex. We describe approaches for calculating the probability of exclusion (PE) and likelihood ratio (LR) methods to interpret Y-STR mixture evidence with population substructure incorporated. For a mixture sample, first, all possible contributor haplotypes in a reference database are listed as a candidate list. The PE is the complement of the summation of the frequencies of haplotypes in the candidate list. The LR method compares the probabilities of the evidence given alternative hypotheses. The hypotheses are possible explanations for the mixture. Population substructure may be further incorporated in likelihood calculation. The maximum number of contributors is based on the candidate list and the computing complexity is polynomial. Additionally, mixtures were simulated by combining two or three 16 Y-STR marker haplotypes derived from the US forensic Y-STR database. The average PE was related to the size of database. With a database comprised of 500 haplotypes an average PE value of at least 0.995 can be obtained for two-person mixtures. The PE decreases with an increasing number of contributors to the mixture. Using the total sample population, the average number of candidate haplotypes of two-person mixtures is 3.73 and 95% mixtures have less than or equal to 10 candidate haplotypes. More than 98.7% of two-person mixtures can only be explained by the haplotype combinations that mixtures are composed. These values are generally higher for three-person mixtures. A small proportion of three-person mixture can also be explained by only two haplotypes.

  11. Effects of active pharmaceutical ingredients mixtures in mussel Mytilus galloprovincialis.

    PubMed

    Gonzalez-Rey, M; Mattos, J J; Piazza, C E; Bainy, A C D; Bebianno, M J

    2014-08-01

    Active pharmaceutical ingredients (APIs) are emergent environmental contaminants widely detected in surface waters as result of incomplete waste water treatment plant (WWTP) removal processes and improper disposal. The assessment of potential effects of APIs on non-target organisms is still scarce since besides presenting multiple chemical structures, properties and modes of action, these compounds occur as complex mixtures. This study comprises a 15-day exposure of mussels Mytilus galloprovincialis to mixtures (at environmentally relevant nominal concentrations) of non-steroidal inflammatory drugs ibuprofen (IBU) and diclofenac (DCF) (250 ng L(-1) each) and selective serotonin reuptake inhibitor (SSRI) fluoxetine (FLX) (75 ng L(-1)) (MIX 1) along with the addition of classical pro-oxidant copper (Cu) (5 μg L(-1)) (MIX 2). The goals included the assessment of oxidative stress, neurotoxic and endocrine effects on this sentinel species applying both a multibiomarker and gene expression (here and later gene expression is taken as synonym to gene transcription, although it is acknowledged that it is also affected by, e.g. translation, and mRNA and protein stability) analysis approaches. The results revealed a swifter antioxidant response in digestive glands than in gills induced by MIX 1, nevertheless the presence of Cu in MIX 2 promoted a higher lipid peroxidation (LPO) induction. Neither mixture altered acetylcholinesterase (AChE) activity, while both triggered the formation of vitellogenin-like proteins in females confirming the xenoestrogenic effect of mixtures. All these results varied with respect to those obtained in previous single exposure essays. Moreover, RT-PCR analysis revealed a catalase (CAT) and CYP4Y1 gene expression down- and upregulation, respectively, with no significant changes in mRNA levels of genes encoding superoxide dismutase (SOD) and glutathione-S-transferase (GST). Finally, this study highlights variable tissue and time-specific biomarker

  12. Mixture theory-based poroelasticity as a model of interstitial tissue growth

    PubMed Central

    Cowin, Stephen C.; Cardoso, Luis

    2011-01-01

    This contribution presents an alternative approach to mixture theory-based poroelasticity by transferring some poroelastic concepts developed by Maurice Biot to mixture theory. These concepts are a larger RVE and the subRVE-RVE velocity average tensor, which Biot called the micro-macro velocity average tensor. This velocity average tensor is assumed here to depend upon the pore structure fabric. The formulation of mixture theory presented is directed toward the modeling of interstitial growth, that is to say changing mass and changing density of an organism. Traditional mixture theory considers constituents to be open systems, but the entire mixture is a closed system. In this development the mixture is also considered to be an open system as an alternative method of modeling growth. Growth is slow and accelerations are neglected in the applications. The velocity of a solid constituent is employed as the main reference velocity in preference to the mean velocity concept from the original formulation of mixture theory. The standard development of statements of the conservation principles and entropy inequality employed in mixture theory are modified to account for these kinematic changes and to allow for supplies of mass, momentum and energy to each constituent and to the mixture as a whole. The objective is to establish a basis for the development of constitutive equations for growth of tissues. PMID:22184481

  13. Mixture theory-based poroelasticity as a model of interstitial tissue growth.

    PubMed

    Cowin, Stephen C; Cardoso, Luis

    2012-01-01

    This contribution presents an alternative approach to mixture theory-based poroelasticity by transferring some poroelastic concepts developed by Maurice Biot to mixture theory. These concepts are a larger RVE and the subRVE-RVE velocity average tensor, which Biot called the micro-macro velocity average tensor. This velocity average tensor is assumed here to depend upon the pore structure fabric. The formulation of mixture theory presented is directed toward the modeling of interstitial growth, that is to say changing mass and changing density of an organism. Traditional mixture theory considers constituents to be open systems, but the entire mixture is a closed system. In this development the mixture is also considered to be an open system as an alternative method of modeling growth. Growth is slow and accelerations are neglected in the applications. The velocity of a solid constituent is employed as the main reference velocity in preference to the mean velocity concept from the original formulation of mixture theory. The standard development of statements of the conservation principles and entropy inequality employed in mixture theory are modified to account for these kinematic changes and to allow for supplies of mass, momentum and energy to each constituent and to the mixture as a whole. The objective is to establish a basis for the development of constitutive equations for growth of tissues.

  14. Mixture distributions in human genetics research.

    PubMed

    Schork, N J; Allison, D B; Thiel, B

    1996-06-01

    The use of mixture distributions in genetics research dates back to at least the late 1800s when Karl Pearson applied them in an analysis of crab morphometry. Pearson's use of normal mixture distributions to model the mixing of different species of crab (or 'families' of crab as he referred to them) within a defined geographic area motivated further use of mixture distributions in genetics research settings, and ultimately led to their development and recognition as intuitive modelling devices for the effects of underlying genes on quantitative phenotypic (i.e. trait) expression. In addition, mixture distributions are now used routinely to model or accommodate the genetic heterogeneity thought to underlie many human diseases. Specific applications of mixture distribution models in contemporary human genetics research are, in fact, too numerous to count. Despite this long, consistent and arguably illustrious history of use, little mention of mixture distributions in genetics research is made in many recent reviews on mixture models. This review attempts to rectify this by providing insight into the role that mixture distributions play in contemporary human genetics research. Tables providing examples from the literature that describe applications of mixture models in human genetics research are offered as a way of acquainting the interested reader with relevant studies. In addition, some of the more problematic aspects of the use of mixture models in genetics research are outlined and addressed. PMID:8817796

  15. Chronic toxicity of a mixture of chlorinated alkanes and alkenes in ICR mice.

    PubMed

    Wang, Fun-In; Kuo, Min-Liang; Shun, Chia-Tung; Ma, Yee-Chung; Wang, Jung-Der; Ueng, Tzuu-Huei

    2002-02-01

    The aim of this study was to determine the chronic toxicity of a mixture of chlorinated alkanes and alkenes (CA) consisting of chloroform, 1,1-dichloroethane, 1,1-dichloroethylene, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene. These chlorinated organic solvents were present in the underground water near an electronic appliances manufactory in Taoyuan, Taiwan. Male and female weanling ICR mice were treated with low-, medium-, and high-dose CA mixtures in drinking water for 16 and 18 mo, respectively. A significant number of male mice treated with the high-dose CA mixture developed tail alopecia and deformation, which was not prominent in CA-treated female mice. Medium- and high-dose CA mixtures induced marginal increases of liver and lung weights, blood urea nitrogen, and serum creatinine levels in male mice. In female mice, the high-dose CA mixture increased liver, kidney, and uterus and ovary total weights, without affecting serum biochemistry parameters. CA mixtures had no effects on the total glutathione content or the level of glutathione S-transferase activity in the livers and kid- neys of male and female mice. Treatments with CA mixtures produced a trend of increasing frequency of hepatocelluar neoplasms in male mice, compared to male and female controls and CA-treated female mice. The high-dose CA mixture induced a significantly higher incidence of mammary adenocarcinoma in female mice. The calculated odds ratios of mammary adenocarcinoma in female mice induced by low-, medium-, and high-dose CA mixtures were 1.14, 1.37, and 3.53 times that of the controls, respectively. The low-dose CA mixture induced a higher incidence of cysts and inflammation in and around the ovaries. This study has demonstrated that the CA mixture is a potential carcinogen to male and female mice. These animal toxicology data may be important in assessing the health effects of individuals exposed to the CA mixture.

  16. Modeling biofiltration of VOC mixtures under steady-state conditions

    SciTech Connect

    Baltzis, B.C.; Wojdyla, S.M.; Zarook, S.M.

    1997-06-01

    Treatment of air streams contaminated with binary volatile organic compound (VOC) mixtures in classical biofilters under steady-state conditions of operation was described with a general mathematical model. The model accounts for potential kinetic interactions among the pollutants, effects of oxygen availability on biodegradation, and biomass diversification in the filter bed. While the effects of oxygen were always taken into account, two distinct cases were considered for the experimental model validation. The first involves kinetic interactions, but no biomass differentiation, used for describing data from biofiltration of benzene/toluene mixtures. The second case assumes that each pollutant is treated by a different type of biomass. Each biomass type is assumed to form separate patches of biofilm on the solid packing material, thus kinetic interference does not occur. This model was used for describing biofiltration of ethanol/butanol mixtures. Experiments were performed with classical biofilters packed with mixtures of peat moss and perlite (2:3, volume:volume). The model equations were solved through the use of computer codes based on the fourth-order Runge-Kutta technique for the gas-phase mass balances and the method of orthogonal collocation for the concentration profiles in the biofilms. Good agreement between model predictions and experimental data was found in almost all cases. Oxygen was found to be extremely important in the case of polar VOCs (ethanol/butanol).

  17. Perceptual and imaginary mixtures in chemosensation.

    PubMed

    Schifferstein, H N

    1997-02-01

    D. Algom and W.S. Cain (1991) reported similar interaction patterns for perceived and imaginary mixtures of odorants. However, their experimental design did not allow sensitive statistical testing to demonstrate differences between conditions. Three experiments on 16 mixtures of sucrose-citric acid mixtures yielded significantly different interaction pattern for perceived and imaginary mixtures. Inconsistencies in the degrees of suppression in the imaginary condition suggested that participants did not base their responses on the inspection of a mental image but on incomplete implicit or explicit knowledge of sensory interactions. Participants knew the phenomenon of mixture suppression and knew that its effects were level dependent, but they were unable to predict the exact intensity of a mixture on the basis of the intensities of its unmixed components. PMID:9157186

  18. Performance-based asphalt mixture design methodology

    NASA Astrophysics Data System (ADS)

    Ali, Al-Hosain Mansour

    Today, several State D.O.T.s are being investigating the use of tire rubber with local conventional materials. Several of the ongoing investigations identified potential benefits from the use of these materials, including improvements in material properties and performance. One of the major problems is being associated with the transferability of asphalt rubber technology without appropriately considering the effects of the variety of conventional materials on mixture behavior and performance. Typically, the design of these mixtures is being adapted to the physical properties of the conventional materials by using the empirical Marshall mixture design and without considering fundamental mixture behavior and performance. Use of design criteria related to the most common modes of failure for asphalt mixtures, such as rutting, fatigue cracking, and low temperature thermal cracking have to be developed and used for identifying the "best mixture," in term of performance, for the specific local materials and loading conditions. The main objective of this study was the development of a mixture design methodology that considers mixture behavior and performance. In order to achieve this objective a laboratory investigation able to evaluate mixture properties that can be related to mixture performance, (in terms of rutting, low temperature cracking, moisture damage and fatigue), and simulating the actual field loading conditions that the material is being exposed to, was conducted. The results proved that the inclusion of rubber into asphalt mixtures improved physical characteristics such as elasticity, flexibility, rebound, aging properties, increased fatigue resistance, and reduced rutting potential. The possibility of coupling the traditional Marshall mix design method with parameters related to mixture behavior and performance was investigated. Also, the SHRP SUPERPAVE mix design methodology was reviewed and considered in this study for the development of an integrated

  19. Deduction of paternity index from DNA mixture.

    PubMed

    Liao, Xiang Hai; Lau, Tai Shang; Ngan, Karenda Fai Ngor; Wang, Jun

    2002-08-28

    Determination of individual genotypes in DNA mixture remains a challenge in forensic science. Using an approach of mixture of distributions, this article provides formula for calculation of paternity index (PI) in cases where only tissue mixture of the mother and alleged father, the genotypes of the mother and child, but not that of the alleged father are available. The formula has been used to solve a real case using mother's vaginal tissue contaminated with semen from alleged father.

  20. Mixture toxicity and tissue interactions of Cd, Cu, Pb and Zn in earthworms (Oligochaeta) in laboratory and field soils: a critical evaluation of data.

    PubMed

    Weltje, L

    1998-05-01

    Soil organisms inhabiting contaminated field sites are usually exposed to mixtures of toxicants. In such mixtures, toxicants can interact to express enhanced or weakened toxicity. Therefore, mixture effects should be considered in risk assessment methods for polluted soils. Data on mixture toxicity to soil organisms are scarce, however. In this paper, data on sublethal toxicity and tissue concentrations of Cd. Cu, Pb and Zn mixtures in earthworms are evaluated and compared with data on other organisms. Toxic effects were mainly antagonistic for total soil concentrations and nearly concentration-additive for 0.01 M CaCl2-extractable soil concentrations. Evidence to support concentration-additive behaviour of metals was found in interaction patterns within earthworm tissues. A method is proposed to assess the sublethal toxicity of metal mixtures in field soils to earthworms, based on single metal experiments from the laboratory. Finally, suggestions are made on how to incorporate mixture toxicity in risk assessment for polluted soils. PMID:9570111

  1. Performance Test for Open Grade Bitumen and Cement Mixture OGBC-20

    NASA Astrophysics Data System (ADS)

    Li, Y. Y.; Wu, Z. L.; Li, C. M.; Gan, X. Z.; Xiong, X. J.

    For effective prevention of urban road intersection special sections for nit diseases and improving the pavement durability, an open grade bitumen and cement (OGBC-20) mixture is proposed. In organic hydraulic cement mixture design, mix proportion designs of cement mortar and matrix open-graded bitumen were done. The matrix mixture gradation was adjusted .It has greater void of air volume than that of ATPB-25. A variety of tests in laboratory for OGBC-20 were performed. The experimental results show that: The void of air volume of adjusted gradation matrix asphalt mixture is up to 23%. and binder drainage loss is ≤ 0.3%. Cement mortar filling is fuller and better water stability and low temperature crack resistance compared to ordinary bitumen mixture. It has the absolute advantage on high temperature stability and shows the superiority of the new pavement materials.

  2. Flame stabilization in chlorine-hydrocarbon mixtures

    SciTech Connect

    Steblev, A.V.

    1986-11-01

    The authors determine the limits of stable steady-state combustion of binary mixtures of methane, propane, ethylene, and chlorine using cylindrical stabilizers of various diameters. The studies were performed on Bunsen burners. Two series of experiments were performed. The first studied the effect of stabilizer size on the limits of flame stabilization in mixtures of fixed composition having the highest flame velocity; the second studied the effect on combustion limits of mixture composition for the fixed stabilizer diameter at which the combustion limits were widest. The principles established by these experiments are used as contributing factors in the design of high-output combustion chambers for hydrocarbon-chlorine mixtures.

  3. Dielectric gas mixtures containing sulfur hexafluoride

    DOEpatents

    Cooke, Chathan M.

    1979-01-01

    Electrically insulating gaseous media of unexpectedly high dielectric strength comprised of mixtures of two or more dielectric gases are disclosed wherein the dielectric strength of at least one gas in each mixture increases at less than a linear rate with increasing pressure and the mixture gases are present in such proportions that the sum of their electrical discharge voltages at their respective partial pressures exceeds the electrical discharge voltage of each individual gas at the same temperature and pressure as that of the mixture.

  4. Metal mixtures modeling evaluation project: 1. Background.

    PubMed

    Meyer, Joseph S; Farley, Kevin J; Garman, Emily R

    2015-04-01

    Despite more than 5 decades of aquatic toxicity tests conducted with metal mixtures, there is still a need to understand how metals interact in mixtures and to predict their toxicity more accurately than what is currently done. The present study provides a background for understanding the terminology, regulatory framework, qualitative and quantitative concepts, experimental approaches, and visualization and data-analysis methods for chemical mixtures, with an emphasis on bioavailability and metal-metal interactions in mixtures of waterborne metals. In addition, a Monte Carlo-type randomization statistical approach to test for nonadditive toxicity is presented, and an example with a binary-metal toxicity data set demonstrates the challenge involved in inferring statistically significant nonadditive toxicity. This background sets the stage for the toxicity results, data analyses, and bioavailability models related to metal mixtures that are described in the remaining articles in this special section from the Metal Mixture Modeling Evaluation project and workshop. It is concluded that although qualitative terminology such as additive and nonadditive toxicity can be useful to convey general concepts, failure to expand beyond that limited perspective could impede progress in understanding and predicting metal mixture toxicity. Instead of focusing on whether a given metal mixture causes additive or nonadditive toxicity, effort should be directed to develop models that can accurately predict the toxicity of metal mixtures.

  5. Cluster kinetics model for mixtures of glassformers

    NASA Astrophysics Data System (ADS)

    Brenskelle, Lisa A.; McCoy, Benjamin J.

    2007-10-01

    For glassformers we propose a binary mixture relation for parameters in a cluster kinetics model previously shown to represent pure compound data for viscosity and dielectric relaxation as functions of either temperature or pressure. The model parameters are based on activation energies and activation volumes for cluster association-dissociation processes. With the mixture parameters, we calculated dielectric relaxation times and compared the results to experimental values for binary mixtures. Mixtures of sorbitol and glycerol (seven compositions), sorbitol and xylitol (three compositions), and polychloroepihydrin and polyvinylmethylether (three compositions) were studied.

  6. Separation of gas mixtures by supported complexes

    SciTech Connect

    Lilga, M.A.

    1987-05-29

    The current project centers on the preparation and characterization of complexes that can be used to separate H/sub 2/ from gas mixtures. Of interest are complexes which are inexpensive and which reversibly bind H/sub 2/. In particular, dimeric complexes of chromium, ((C/sub 5/H/sub 4/R)Cr(CO)/sub 3/)/sub 2/ (R = H, CO/sub 2/CH/sub 3/, alkyl), are being studied in this project. The basic methodology used is to prepare various derivatives containing substitution on the cyclopentadienyl ligand and to screen these derivatives for reversible reaction with H/sub 2/. Once reversibility is achieved, kinetic and equilibrium data will be collected to fully characterize the system and possibly elucidate the effects of substituents on H/sub 2/ binding. Also of interest are complexes which reversibly and catalytically incorporate H/sub 2/ into an organic ketone substrate. An Rh/Sn complex which reversibly hydrogenates/dehydrogenates cyclohexanone will be discussed. Although Rh is not inexpensive, it is present in very low concentration and represents a potentially inexpensive yet selective H/sub 2/ separation method. 5 refs.

  7. Preparative-scale isoelectric trapping separations in methanol-water mixtures.

    PubMed

    Shave, Evan; Vigh, Gyula

    2004-05-14

    The typically low aqueous solubilities of small, hydrophobic organic ampholytic molecules limit the production rates that can be achieved in their isoelectric trapping (IET) separations and call for the use of hydro-organic mixtures as solvents. The compatibility of methanol-water mixtures and poly(ethylene terephthalate) substrate-supported isoelectric polyacrylamide hydrogels, developed for binary IET separations in a Gradiflow BF200IET unit, was investigated. The isoelectric polyacrylamide-based hydrogels retained their functional and mechanical integrities when the methanol concentration in the hydro-organic solvent mixture was kept at or below 25% (v/v). The utility of the hydro-organic media was demonstrated in the purification of a hydrophobic ampholytic compound, technical grade 4-hydroxy-3-(morpholinomethyl) benzoic acid. Production rates as high as 7 mg/h were achieved using small, 15 cm2 active surface area isoelectric membranes.

  8. Preparative-scale isoelectric trapping separations in methanol-water mixtures.

    PubMed

    Shave, Evan; Vigh, Gyula

    2004-05-14

    The typically low aqueous solubilities of small, hydrophobic organic ampholytic molecules limit the production rates that can be achieved in their isoelectric trapping (IET) separations and call for the use of hydro-organic mixtures as solvents. The compatibility of methanol-water mixtures and poly(ethylene terephthalate) substrate-supported isoelectric polyacrylamide hydrogels, developed for binary IET separations in a Gradiflow BF200IET unit, was investigated. The isoelectric polyacrylamide-based hydrogels retained their functional and mechanical integrities when the methanol concentration in the hydro-organic solvent mixture was kept at or below 25% (v/v). The utility of the hydro-organic media was demonstrated in the purification of a hydrophobic ampholytic compound, technical grade 4-hydroxy-3-(morpholinomethyl) benzoic acid. Production rates as high as 7 mg/h were achieved using small, 15 cm2 active surface area isoelectric membranes. PMID:15139407

  9. Deciding which chemical mixtures risk assessment methods work best for what mixtures

    SciTech Connect

    Teuschler, Linda K.

    2007-09-01

    The most commonly used chemical mixtures risk assessment methods involve simple notions of additivity and toxicological similarity. Newer methods are emerging in response to the complexities of chemical mixture exposures and effects. Factors based on both science and policy drive decisions regarding whether to conduct a chemical mixtures risk assessment and, if so, which methods to employ. Scientific considerations are based on positive evidence of joint toxic action, elevated human exposure conditions or the potential for significant impacts on human health. Policy issues include legislative drivers that may mandate action even though adequate toxicity data on a specific mixture may not be available and risk assessment goals that impact the choice of risk assessment method to obtain the amount of health protection desired. This paper discusses three important concepts used to choose among available approaches for conducting a chemical mixtures risk assessment: (1) additive joint toxic action of mixture components; (2) toxicological interactions of mixture components; and (3) chemical composition of complex mixtures. It is proposed that scientific support for basic assumptions used in chemical mixtures risk assessment should be developed by expert panels, risk assessment methods experts, and laboratory toxicologists. This is imperative to further develop and refine quantitative methods and provide guidance on their appropriate applications. Risk assessors need scientific support for chemical mixtures risk assessment methods in the form of toxicological data on joint toxic action for high priority mixtures, statistical methods for analyzing dose-response for mixtures, and toxicological and statistical criteria for determining sufficient similarity of complex mixtures.

  10. Simulation of mixture microstructures via particle packing models and their direct comparison with real mixtures

    NASA Astrophysics Data System (ADS)

    Gulliver, Eric A.

    The objective of this thesis to identify and develop techniques providing direct comparison between simulated and real packed particle mixture microstructures containing submicron-sized particles. This entailed devising techniques for simulating powder mixtures, producing real mixtures with known powder characteristics, sectioning real mixtures, interrogating mixture cross-sections, evaluating and quantifying the mixture interrogation process and for comparing interrogation results between mixtures. A drop and roll-type particle-packing model was used to generate simulations of random mixtures. The simulated mixtures were then evaluated to establish that they were not segregated and free from gross defects. A powder processing protocol was established to provide real mixtures for direct comparison and for use in evaluating the simulation. The powder processing protocol was designed to minimize differences between measured particle size distributions and the particle size distributions in the mixture. A sectioning technique was developed that was capable of producing distortion free cross-sections of fine scale particulate mixtures. Tessellation analysis was used to interrogate mixture cross sections and statistical quality control charts were used to evaluate different types of tessellation analysis and to establish the importance of differences between simulated and real mixtures. The particle-packing program generated crescent shaped pores below large particles but realistic looking mixture microstructures otherwise. Focused ion beam milling was the only technique capable of sectioning particle compacts in a manner suitable for stereological analysis. Johnson-Mehl and Voronoi tessellation of the same cross-sections produced tessellation tiles with different the-area populations. Control charts analysis showed Johnson-Mehl tessellation measurements are superior to Voronoi tessellation measurements for detecting variations in mixture microstructure, such as altered

  11. Alcohol production from sugar mixtures by Pachysolen tannophilus

    SciTech Connect

    Neirinck, L.; Maleszka, R.; Schneider, H.

    1982-01-01

    The ability of P. tannophilus to produce ethanol from sugar mixtures was investigated. With mixtures simulating spent sulfite liquor and a hardboard mill effluent, yields of 76 to 84% of theoretical were obtained with a wild-type strain, which increased to 83 to 90% with a mutant selected for more rapid growth on D-galactose. A small but significant loss in yield was caused by the formation by both strains of acetate, xylitol and L-arabinitol. The loss was estimated to be in the range of 5 to 8.3% for the mutant and 7.1 to 12% for the wild-type. One conclusion drawn from these results was that the organism has the potential for use with a wide variety of hydrolysates, since the four sugars which could be efficiently fermented in the mixtures - D-mannose, D-xylose, D-glucose, and D-galactose - generally comprise more than 90% of those in polysaccharides from many biomass sources. The organism was also found to be capable of producing ethanol from, and surviving in, spent sulfite liquor. However, productivity decreased on recycling the cells, suggesting that strain improvement will be a necessary step in process development. 1 figure, 3 tables.

  12. Acute toxicity of binary and ternary mixtures of Cd, Cu, and Zn to Daphnia magna.

    PubMed

    Meyer, Joseph S; Ranville, James F; Pontasch, Mandee; Gorsuch, Joseph W; Adams, William J

    2015-04-01

    Standard static-exposure acute lethality tests were conducted with Daphnia magna neonates exposed to binary or ternary mixtures of Cd, Cu, and Zn in moderately hard reconstituted water that contained 3 mg dissolved organic carbon/L added as Suwannee River fulvic acid. These experiments were conducted to test for additive toxicity (i.e., the response to the mixture can be predicted by combining the responses obtained in single-metal toxicity tests) or nonadditive toxicity (i.e., the response is less than or greater than additive). Based on total metal concentrations (>90% dissolved) the toxicity of the tested metal mixtures could be categorized into all 3 possible additivity categories: less-than-additive toxicity (e.g., Cd-Zn and Cd-Cu-Zn mixtures and Cd-Cu mixtures when Cu was titrated into Cd-containing waters), additive toxicity (e.g., some Cu-Zn mixtures), or more-than-additive toxicity (some Cu-Zn mixtures and Cd-Cu mixtures when Cd was titrated into Cu-containing waters). Exposing the organisms to a range of sublethal to supralethal concentrations of the titrated metal was especially helpful in identifying nonadditive interactions. Geochemical processes (e.g., metal-metal competition for binding to dissolved organic matter and/or the biotic ligand, and possibly supersaturation of exposure waters with the metals in some high-concentration exposures) can explain much of the observed metal-metal interactions. Therefore, bioavailability models that incorporate those geochemical (and possibly some physiological) processes might be able to predict metal mixture toxicity accurately.

  13. Overview of human health and chemical mixtures: problems facing developing countries.

    PubMed Central

    Yáñ ez, Leticia; Ortiz, Deogracias; Calderón, Jaqueline; Batres, Lilia; Carrizales, Leticia; Mejía, Jesús; Martínez, Lourdes; García-Nieto, Edelmira; Díaz-Barriga, Fernando

    2002-01-01

    In developing countries, chemical mixtures within the vicinity of small-scale enterprises, smelters, mines, agricultural areas, toxic waste disposal sites, etc., often present a health hazard to the populations within those vicinities. Therefore, in these countries, there is a need to study the toxicological effects of mixtures of metals, pesticides, and organic compounds. However, the study of mixtures containing substances such as DDT (dichlorodiphenyltrichloroethane, an insecticide banned in developed nations), and mixtures containing contaminants such as fluoride (of concern only in developing countries) merit special attention. Although the studies may have to take into account simultaneous exposures to metals and organic compounds, there is also a need to consider the interaction between chemicals and other specific factors such as nutritional conditions, alcoholism, smoking, infectious diseases, and ethnicity. PMID:12634117

  14. Time-dependence in mixture toxicity prediction

    PubMed Central

    Dawson, Douglas A.; Allen, Erin M.G.; Allen, Joshua L.; Baumann, Hannah J.; Bensinger, Heather M.; Genco, Nicole; Guinn, Daphne; Hull, Michael W.; Il'Giovine, Zachary J.; Kaminski, Chelsea M.; Peyton, Jennifer R.; Schultz, T. Wayne; Pöch, Gerald

    2014-01-01

    The value of time-dependent toxicity (TDT) data in predicting mixture toxicity was examined. Single chemical (A and B) and mixture (A + B) toxicity tests using Microtox® were conducted with inhibition of bioluminescence (Vibrio fischeri) being quantified after 15, 30 and 45-min of exposure. Single chemical and mixture tests for 25 sham (A1:A2) and 125 true (A:B) combinations had a minimum of seven duplicated concentrations with a duplicated control treatment for each test. Concentration/response (x/y) data were fitted to sigmoid curves using the five-parameter logistic minus one parameter (5PL-1P) function, from which slope, EC25, EC50, EC75, asymmetry, maximum effect, and r2 values were obtained for each chemical and mixture at each exposure duration. Toxicity data were used to calculate percentage-based TDT values for each individual chemical and mixture of each combination. Predicted TDT values for each mixture were calculated by averaging the TDT values of the individual components and regressed against the observed TDT values obtained in testing, resulting in strong correlations for both sham (r2 = 0.989, n = 25) and true mixtures (r2 = 0.944, n = 125). Additionally, regression analyses confirmed that observed mixture TDT values calculated for the 50% effect level were somewhat better correlated with predicted mixture TDT values than at the 25 and 75% effect levels. Single chemical and mixture TDT values were classified into five levels in order to discern trends. The results suggested that the ability to predict mixture TDT by averaging the TDT of the single agents was modestly reduced when one agent of the combination had a positive TDT value and the other had a minimal or negative TDT value. PMID:25446331

  15. Ultracentrifuge for separating fluid mixtures

    DOEpatents

    Lowry, Ralph A.

    1976-01-01

    1. A centrifuge for the separation of fluid mixtures having light and heavy fractions comprising a cylindrical rotor, disc type end-plugs closing the ends of the rotor, means for mounting said rotor for rotation about its cylindrical axis, a housing member enclosing the rotor, a vacuum chamber in said housing about the central portion of the rotor, a collection chamber at each end of the housing, the innermost side of which is substantially formed by the outer face of the end-plug, means for preventing flow of the fluid from the collection chambers to said vacuum chamber, at least one of said end-plugs having a plurality of holes therethrough communicating between the collection chamber adjacent thereto and the inside of the rotor to induce countercurrent flow of the fluid in the centrifuge, means for feeding fluid to be processed into the centrifuge, means communicating with the collection chambers to extract the light and heavy separated fractions of the fluid, and means for rotating the rotor.

  16. Engineering preliminaries to obtain reproducible mixtures of atelocollagen and polysaccharides.

    PubMed

    Lefter, Cristina-Mihaela; Maier, Stelian Sergiu; Maier, Vasilica; Popa, Marcel; Desbrieres, Jacques

    2013-05-01

    The critical stage in producing blends of biomacromolecules consists in the mixing of component solutions to generate homogenous diluted colloidal systems. Simple experimental investigations allow the establishment of the design rules of recipes and the procedures for preparing homogenous and compositionally reproducible mixtures. Starting from purified solutions of atelocollagen, hyaluronan and native gellan, having as low as possible inorganic salts content, initial binary and ternary mixtures can be prepared up to a total dry matter content of 0.150 g/dL, in no co-precipitating conditions. Two pH manipulation ways are feasible for homogenous mixing: (i) unbuffered prior correction at pH 5.5, and (ii) "rigid" buffering at pH 9.0, using organic species. Atelocollagen including co-precipitates can be obtained in the presence of one or both polysaccharides, preferably in pH domains far from the isoelectric point of scleroprotein. A critical behavior has been observed in mixtures containing gellan, due to its macromolecular dissimilarities compared with atelocollagen. In optimal binary mixtures, the coordinates of threshold points on the phase diagrams are 0.028% w/w atelocollagen/0.025% w/w hyaluronan, and 0.022% w/w atelocollagen/0.020% w/w gellan. Uni- or bi-phasic ternary systems having equilibrated ratios of co-precipitated components can be prepared starting from initial mixtures containing up to 0.032 g/dL atelocollagen, associated with, for example, 0.040 g/dL hyaluronan and 0.008 g/dL gellan, following the first pH manipulation way.

  17. Automatic NMR-based identification of chemical reaction types in mixtures of co-occurring reactions.

    PubMed

    Latino, Diogo A R S; Aires-de-Sousa, João

    2014-01-01

    The combination of chemoinformatics approaches with NMR techniques and the increasing availability of data allow the resolution of problems far beyond the original application of NMR in structure elucidation/verification. The diversity of applications can range from process monitoring, metabolic profiling, authentication of products, to quality control. An application related to the automatic analysis of complex mixtures concerns mixtures of chemical reactions. We encoded mixtures of chemical reactions with the difference between the (1)H NMR spectra of the products and the reactants. All the signals arising from all the reactants of the co-occurring reactions were taken together (a simulated spectrum of the mixture of reactants) and the same was done for products. The difference spectrum is taken as the representation of the mixture of chemical reactions. A data set of 181 chemical reactions was used, each reaction manually assigned to one of 6 types. From this dataset, we simulated mixtures where two reactions of different types would occur simultaneously. Automatic learning methods were trained to classify the reactions occurring in a mixture from the (1)H NMR-based descriptor of the mixture. Unsupervised learning methods (self-organizing maps) produced a reasonable clustering of the mixtures by reaction type, and allowed the correct classification of 80% and 63% of the mixtures in two independent test sets of different similarity to the training set. With random forests (RF), the percentage of correct classifications was increased to 99% and 80% for the same test sets. The RF probability associated to the predictions yielded a robust indication of their reliability. This study demonstrates the possibility of applying machine learning methods to automatically identify types of co-occurring chemical reactions from NMR data. Using no explicit structural information about the reactions participants, reaction elucidation is performed without structure elucidation of

  18. Enthalpy characteristics of sodium phenylalaninate solvation in mixtures of water with ethanol at 298 K

    NASA Astrophysics Data System (ADS)

    Vandyshev, V. N.; Litova, N. A.

    2013-02-01

    The heat effects of mixing for aqueous solutions of sodium phenylalaninate (NaPheAla) with mixtures of water and ethanol are measured by calorimetry at 298.15 K. The standard enthalpies of transfer of a stoichiometric mixture of ions, and of an organic ion of α-PheAla- from water to water-alcohol mixtures are calculated. The enthalpy coefficients of binary and ternary ion-alcohol interactions are calculated using the McMillan-Mayer theory. The obtained enthalpy characteristics are compared with previously studied systems containing synthetic β- and natural α-alanine.

  19. Mixture Modeling of Individual Learning Curves

    ERIC Educational Resources Information Center

    Streeter, Matthew

    2015-01-01

    We show that student learning can be accurately modeled using a mixture of learning curves, each of which specifies error probability as a function of time. This approach generalizes Knowledge Tracing [7], which can be viewed as a mixture model in which the learning curves are step functions. We show that this generality yields order-of-magnitude…

  20. The Potential of Growth Mixture Modelling

    ERIC Educational Resources Information Center

    Muthen, Bengt

    2006-01-01

    The authors of the paper on growth mixture modelling (GMM) give a description of GMM and related techniques as applied to antisocial behaviour. They bring up the important issue of choice of model within the general framework of mixture modelling, especially the choice between latent class growth analysis (LCGA) techniques developed by Nagin and…

  1. Laser kinetic processes in dye mixtures

    SciTech Connect

    Lei Jie; Fu Honglang

    1988-11-01

    Radiation from rhodamine 6G+cresyl violet and rhodamine B+cresyl violet dye mixtures in ethyl alcohol pumped by N/sub 2/ laser light were studied. The rate constants of resonant transfer in the mixtures were determined. The radiative transfer processes are discussed.

  2. THE RECOVERY OF URANIUM FROM GAS MIXTURE

    DOEpatents

    Jury, S.H.

    1964-03-17

    A method of separating uranium from a mixture of uranium hexafluoride and other gases is described that comprises bringing the mixture into contact with anhydrous calcium sulfate to preferentially absorb the uranium hexafluoride on the sulfate. The calcium sulfate is then leached with a selective solvent for the adsorbed uranium. (AEC)

  3. Gas mixtures for spark gap closing switches

    DOEpatents

    Christophorou, Loucas G.; McCorkle, Dennis L.; Hunter, Scott R.

    1988-01-01

    Gas mixtures for use in spark gap closing switches comprised of fluorocarbons and low molecular weight, inert buffer gases. To this can be added a third gas having a low ionization potential relative to the buffer gas. The gas mixtures presented possess properties that optimized the efficiency spark gap closing switches.

  4. Process Dissociation and Mixture Signal Detection Theory

    ERIC Educational Resources Information Center

    DeCarlo, Lawrence T.

    2008-01-01

    The process dissociation procedure was developed in an attempt to separate different processes involved in memory tasks. The procedure naturally lends itself to a formulation within a class of mixture signal detection models. The dual process model is shown to be a special case. The mixture signal detection model is applied to data from a widely…

  5. Gas mixtures for spark gap closing switches

    DOEpatents

    Christophorou, L.G.; McCorkle, D.L.; Hunter, S.R.

    1987-02-20

    Gas mixtures for use in spark gap closing switches comprised of fluorocarbons and low molecular weight, inert buffer gases. To this can be added a third gas having a low ionization potential relative to the buffer gas. The gas mixtures presented possess properties that optimized the efficiency spark gap closing switches. 6 figs.

  6. Prediction of viscosity of dense fluid mixtures

    NASA Astrophysics Data System (ADS)

    Royal, Damian D.; Vesovic, Velisa; Trusler, J. P. Martin; Wakeham, William. A.

    The Vesovic-Wakeham (VW) method of predicting the viscosity of dense fluid mixtures has been improved by implementing new mixing rules based on the rigid sphere formalism. The proposed mixing rules are based on both Lebowitz's solution of the Percus-Yevick equation and on the Carnahan-Starling equation. The predictions of the modified VW method have been compared with experimental viscosity data for a number of diverse fluid mixtures: natural gas, hexane + hheptane, hexane + octane, cyclopentane + toluene, and a ternary mixture of hydrofluorocarbons (R32 + R125 + R134a). The results indicate that the proposed improvements make possible the extension of the original VW method to liquid mixtures and to mixtures containing polar species, while retaining its original accuracy.

  7. Mixture of Skewed α-Stable Distributions

    NASA Astrophysics Data System (ADS)

    Shojaei, S. R. Hosseini; Nassiri, V.; Mohammadian, Gh. R.; Mohammadpour, A.

    2011-03-01

    Expectation maximization (EM) algorithm and the Bayesian techniques are two approaches for statistical inference of mixture models [3, 4]. By noting the advantages of the Bayesian methods, practitioners prefer them. However, implementing Markov chain Monte Carlo algorithms can be very complicated for stable distributions, due to the non-analytic density or distribution function formulas. In this paper, we introduce a new class of mixture of heavy-tailed distributions, called mixture of skewed stable distributions. Skewed stable distributions belongs to the exponential family and they have analytic density representation. It is shown that skewed stable distributions dominate skew stable distribution functions and they can be used to model heavy-tailed data. The class of skewed stable distributions has an analytic representation for its density function and the Bayesian inference can be done similar to the exponential family of distributions. Finally, mixture of skewed stable distributions are compared to the mixture of stable distributions through a simulations study.

  8. Analysis of interaction in binary odorant mixtures.

    PubMed

    Smith, B H

    1998-12-01

    An understanding of the olfactory system of any animal must account for how odor mixtures are perceived and processed. The present experiments apply associationist models to the study of how elements are processed in binary odorant mixtures. Using experimental designs for Proboscis Extension Conditioning of honey bees, I show that learning about a pure odorant element is frequently affected by its occurrence in a mixture with a second odorant. Presence of a background odor when an odorant is associated with sucrose reinforcement decreases the rate and/or asymptotic level of associative strength that accumulates to that odorant. This interaction is in part due to synthetic qualities that arise in sensory transduction and initial processing. In addition, it involves an attention-like processing system like that involved in overshadowing. Therefore, a model that includes representations of the component and configural qualities of odorants in mixtures is needed to provide a more complete account of learning about odor mixtures. PMID:9877404

  9. Preferential Solvation in Binary and Ternary Mixtures.

    PubMed

    Pallewela, Gayani N; Smith, Paul E

    2015-12-24

    Preferential solvation has become a useful tool to help characterize and understand the properties of liquid mixtures. Here, we provide a new quantitative measure of preferential solvation in binary and ternary mixtures that uses Kirkwood-Buff integrals as input, but differs from traditional measures. The advantages of the new measure are highlighted and compared with established literature approaches. Molecular dynamics simulations are performed to further investigate the nature of binary mixtures, as described by the new and existing measures of preferential solvation. It is shown that the new measure of preferential solvation is rigorous, has a simple physical interpretation, can be easily related to the underlying thermodynamic properties of the mixture, and naturally leads to zero values for ideal mixtures.

  10. Chemical contaminants on DOE lands and selection of contaminant mixtures for subsurface science research

    SciTech Connect

    Riley, R.G.; Zachara, J.M.

    1992-04-01

    This report identifies individual contaminants and contaminant mixtures that have been measured in the ground at 91 waste sites at 18 US Department of Energy (DOE) facilities within the weapons complex. The inventory of chemicals and mixtures was used to identify generic chemical mixtures to be used by DOE`s Subsurface Science Program in basic research on the subsurface geochemical and microbiological behavior of mixed contaminants (DOE 1990a and b). The generic mixtures contain specific radionuclides, metals, organic ligands, organic solvents, fuel hydrocarbons, and polychlorinated biphenyls (PCBs) in various binary and ternary combinations. The mixtures are representative of in-ground contaminant associations at DOE facilities that are likely to exhibit complex geochemical behavior as a result of intercontaminant reactions and/or microbiologic activity stimulated by organic substances. Use of the generic mixtures will focus research on important mixed contaminants that are likely to be long-term problems at DOE sites and that will require cleanup or remediation. The report provides information on the frequency of associations among different chemicals and compound classes at DOE waste sites that require remediation.

  11. Chemical contaminants on DOE lands and selection of contaminant mixtures for subsurface science research

    SciTech Connect

    Riley, R.G.; Zachara, J.M. )

    1992-04-01

    This report identifies individual contaminants and contaminant mixtures that have been measured in the ground at 91 waste sites at 18 US Department of Energy (DOE) facilities within the weapons complex. The inventory of chemicals and mixtures was used to identify generic chemical mixtures to be used by DOE's Subsurface Science Program in basic research on the subsurface geochemical and microbiological behavior of mixed contaminants (DOE 1990a and b). The generic mixtures contain specific radionuclides, metals, organic ligands, organic solvents, fuel hydrocarbons, and polychlorinated biphenyls (PCBs) in various binary and ternary combinations. The mixtures are representative of in-ground contaminant associations at DOE facilities that are likely to exhibit complex geochemical behavior as a result of intercontaminant reactions and/or microbiologic activity stimulated by organic substances. Use of the generic mixtures will focus research on important mixed contaminants that are likely to be long-term problems at DOE sites and that will require cleanup or remediation. The report provides information on the frequency of associations among different chemicals and compound classes at DOE waste sites that require remediation.

  12. Environmental complex mixture toxicity assessment.

    PubMed

    Gardner, H S; Brennan, L M; Toussaint, M W; Rosencrance, A B; Boncavage-Hennessey, E M; Wolfe, M J

    1998-12-01

    Trichloroethylene (TCE) was found as a contaminant in the well supplying water to an aquatic testing laboratory. The groundwater was routinely screened by a commercial laboratory for volatile and semivolatile compounds, metals, herbicides, pesticides, and polychlorinated biphenyls using U.S. Environmental Protection Agency methods. Although TCE was the only reportable peak on the gas chromatograph, with average concentrations of 0.200 mg/l, other small peaks were also present, indicating the possibility that the contamination was not limited to TCE alone. A chronic 6-month carcinogenicity assay was conducted on-site in a biomonitoring trailer, using the Japanese medaka fish (Oryzias latipes) in an initiation-promotion protocol, with diethylnitrosamine (DEN) as the initiator and the TCE-contaminated groundwater as a promoter. Study results indicated no evidence of carcinogenic potential of the groundwater without initiation. There was, however, a tumor-promotional effect of the groundwater after DEN initiation. A follow-up laboratory study was conducted using reagent grade TCE added to carbon-filtered groundwater to simulate TCE concentrations comparable to those found in the contaminated groundwater. Study results indicated no promotional effects of TCE. These studies emphasize the necessity for on-site bioassays to assess potential environmental hazards. In this instance, chemical analysis of the groundwater identified TCE as the only reportable contaminant, but other compounds present below reportable limits were noted and may have had a synergistic effect on tumor promotion observed with the groundwater exposure. Laboratory toxicity testing of single compounds can produce toxicity data specific to that compound for that species but cannot take into account the possible toxic effects of mixtures of compounds.

  13. Environmental complex mixture toxicity assessment.

    PubMed Central

    Gardner, H S; Brennan, L M; Toussaint, M W; Rosencrance, A B; Boncavage-Hennessey, E M; Wolfe, M J

    1998-01-01

    Trichloroethylene (TCE) was found as a contaminant in the well supplying water to an aquatic testing laboratory. The groundwater was routinely screened by a commercial laboratory for volatile and semivolatile compounds, metals, herbicides, pesticides, and polychlorinated biphenyls using U.S. Environmental Protection Agency methods. Although TCE was the only reportable peak on the gas chromatograph, with average concentrations of 0.200 mg/l, other small peaks were also present, indicating the possibility that the contamination was not limited to TCE alone. A chronic 6-month carcinogenicity assay was conducted on-site in a biomonitoring trailer, using the Japanese medaka fish (Oryzias latipes) in an initiation-promotion protocol, with diethylnitrosamine (DEN) as the initiator and the TCE-contaminated groundwater as a promoter. Study results indicated no evidence of carcinogenic potential of the groundwater without initiation. There was, however, a tumor-promotional effect of the groundwater after DEN initiation. A follow-up laboratory study was conducted using reagent grade TCE added to carbon-filtered groundwater to simulate TCE concentrations comparable to those found in the contaminated groundwater. Study results indicated no promotional effects of TCE. These studies emphasize the necessity for on-site bioassays to assess potential environmental hazards. In this instance, chemical analysis of the groundwater identified TCE as the only reportable contaminant, but other compounds present below reportable limits were noted and may have had a synergistic effect on tumor promotion observed with the groundwater exposure. Laboratory toxicity testing of single compounds can produce toxicity data specific to that compound for that species but cannot take into account the possible toxic effects of mixtures of compounds. Images Figure 2 PMID:9860885

  14. Surface and Interfacial Properties of Nonaqueous-Phase Liquid Mixtures Released to the Subsurface at the Hanford Site

    SciTech Connect

    Nellis, Scott; Yoon, Hongkyu; Werth, Charlie; Oostrom, Martinus; Valocchi, Albert J.

    2009-05-01

    Surface and interfacial tensions that arise at the interface between different phases are key parameters affecting Nonaqueous Phase Liquid (NAPL) movement and redistribution in the vadose zone after spill events. In this study, the impact of major additive components on surface and interfacial tensions for organic mixtures and wastewater was investigated. Organic mixture and wastewater compositions are based upon carbon tetrachloride (CT) mixtures released at the Hanford site, where CT was discharged simultaneously with dibutyl butyl phosphonate (DBBP), tributyl phosphate (TBP), dibutyl phosphate (DBP), and a machining lard oil (LO). A considerable amount of wastewater consisting primarily of nitrates and metal salts was also discharged. The tension values measured in this study revealed that the addition of these additive components caused a significant lowering of the interfacial tension with water or wastewater and the surface tension of the wastewater phase in equilibrium with the organic mixtures, compared to pure CT, but had minimal effect on the surface tension of the NAPL itself. These results lead to large differences in spreading coefficients for several mixtures, where the additives caused both a higher (more spreading) initial spreading coefficient and a lower (less spreading) equilibrium spreading coefficient. This indicates that if these mixtures migrate into uncontaminated areas, they will tend to spread quickly, but form a higher residual NAPL saturation after equilibrium, as compared to pure CT. Over time, CT likely volatilizes more rapidly than other components in the originally disposed mixtures and the lard oil and phosphates would become more concentrated in the remaining NAPL, resulting in a lower interfacial tension for the mixture. Spreading coefficients are expected to increase and perhaps change the equilibrated organic mixtures from nonspreading to spreading in water-wetting porous media. These results show that the behavior of organic

  15. Purification of metal-organic framework materials

    SciTech Connect

    Farha, Omar K.; Hupp, Joseph T.

    2015-06-30

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  16. Purification of metal-organic framework materials

    SciTech Connect

    Farha, Omar K.; Hupp, Joseph T.

    2012-12-04

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  17. Analysis and computer tools for separation processes involving nonideal mixtures. Progress report, December 1, 1992--November 30, 1993

    SciTech Connect

    Lucia, A.

    1993-07-12

    This research is concerned with developing mathematical analysis, numerical analysis, and computer tools for separation processes involving nonideal, homogeneous, and heterogeneous multi-component mixtures. Progress, organized in terms of mathematical analysis, numerical analysis, and algorithmic development, is summarized.

  18. Single and mixture toxicity of pharmaceuticals and chlorophenols to freshwater algae Chlorella vulgaris.

    PubMed

    Geiger, Elisabeth; Hornek-Gausterer, Romana; Saçan, Melek Türker

    2016-07-01

    Organisms in the aquatic environment are exposed to a variety of substances of numerous chemical classes. The unintentional co-occurrence of pharmaceuticals and other contaminants of emerging concern may pose risk to non-target organisms. In this study, individual and binary mixture toxicity experiments of selected pharmaceuticals (ibuprofen and ciprofloxacin) and chlorophenols (2.4-dichlorophenol (2,4-DCP) and 3-chlorophenol (3-CP)) have been performed with freshwater algae Chlorella vulgaris. All experiments have been carried out according to the 96-h algal growth inhibition test OECD No. 201. Binary mixture tests were conducted using proportions of the respective IC50s in terms of toxic unit (TU). The mixture concentration-response curve was compared to predicted effects based on both the concentration addition (CA) and the independent action (IA) model. Additionally, the Combination Index (CI)-isobologram equation method was used to assess toxicological interactions of the binary mixtures. All substances individually tested had a significant effect on C. vulgaris population density and revealed IC50 values <100mgL(-1) after exposure period of 96-h. The toxic ranking of these four compounds to C. vulgaris was 2,4-DCP>ciprofloxacin>3-CP>ibuprofen. Generally, it can be concluded from this study that toxic mixture effects of all tested chemicals to C. vulgaris are higher than the individual effect of each mixture component. It could be demonstrated that IC50 values of the tested mixtures predominately lead to additive effects. The CA model is appropriate to estimate mixture toxicity, while the IA model tends to underestimate the joint effect. The CI-isobologram equation method predicted the mixtures accurately and elicited synergism at low effect levels for the majority of tested combinations. PMID:27045919

  19. DETERMINATION AND QUANTIFICATION OF NON-AQUEOUS PHASE LIQUID MIXTURES IN ENVIRONMENTAL MEDIA

    SciTech Connect

    Rucker, G

    2006-09-22

    It is important to recognize the presence of Non-Aqueous Phase Liquids (NAPLs) in soils at a waste site in order to design and construct a successful remediation system. NAPLs often manifest as a complex, multi-component mixture of organic compounds that can occur in environmental media, such as vadose zone soil, where the mixture will partition and equilibrate with soil particles, pore vapor, and pore water. Complex organic mixtures can greatly complicate the determination and quantification of NAPL in soil due to inter-media transfer. NAPL thresholds can also change because of mixture physical properties and can disguise the presence of NAPL. A unique analytical method and copyrighted software have been developed at the Department of Energy's Savannah River Site that facilitates solution of this problem. The analytical method uses a classic chemistry approach and applies the principals of solubility limit theory, Raoult's Law, and equilibrium chemistry to derive an accurate estimation of NAPL presence and quantity. The method is unique because it calculates an exact result that is mass balanced for each physical state, chemical mixture component, and mixture characteristics. The method is also unique because the solution can be calculated on both a wet weight and dry weight basis--a factor which is often overlooked. The software includes physical parameters for 300 chemicals in a database that self-loads into the model to save time. The method accommodates up to 20 different chemicals in a multi-component mixture analysis. A robust data display is generated including important parameters of the components and mixture including: NAPL thresholds for individual chemical components within the mixture, mass distribution in soil for each physical state, molar fractions, density, vapor pressure, solubility, mass balance, media concentrations, residual saturation, and modest graphing capabilities. This method and software are power tools to simplify otherwise tedious

  20. Evaluating the similarity of complex drinking-water disinfection by-product mixtures: overview of the issues.

    PubMed

    Rice, Glenn E; Teuschler, Linda K; Bull, Richard J; Simmons, Jane E; Feder, Paul I

    2009-01-01

    Humans are exposed daily to complex mixtures of environmental chemical contaminants, which arise as releases from sources such as engineering procedures, degradation processes, and emissions from mobile or stationary sources. When dose-response data are available for the actual environmental mixture to which individuals are exposed (i.e., the mixture of concern), these data provide the best information for dose-response assessment of the mixture. When suitable data on the mixture itself are not available, surrogate data might be used from a sufficiently similar mixture or a group of similar mixtures. Consequently, the determination of whether the mixture of concern is "sufficiently similar" to a tested mixture or a group of tested mixtures is central to the use of whole mixture methods. This article provides an overview for a series of companion articles whose purpose is to develop a set of biostatistical, chemical, and toxicological criteria and approaches for evaluating the similarity of drinking-water disinfection by-product (DBPs) complex mixtures. Together, the five articles in this series serve as a case study whose techniques will be relevant to assessing similarity for other classes of complex mixtures of environmental chemicals. Schenck et al. (2009) describe the chemistry and mutagenicity of a set of DBP mixtures concentrated from five different drinking-water treatment plants. Bull et al. (2009a, 2009b) describe how the variables that impact the formation of DBP affect the chemical composition and, subsequently, the expected toxicity of the mixture. Feder et al. (2009a, 2009b) evaluate the similarity of DBP mixture concentrates by applying two biostatistical approaches, principal components analysis, and a nonparametric "bootstrap" analysis. Important factors for determining sufficient similarity of DBP mixtures found in this research include disinfectant used; source water characteristics, including the concentrations of bromide and total organic carbon

  1. Foaming of mixtures of pure hydrocarbons

    NASA Technical Reports Server (NTRS)

    Robinson, J. V.; Woods, W. W.

    1950-01-01

    Mixtures of pure liquid hydrocarbons are capable of foaming. Nine hydrocarbons were mixed in pairs, in all possible combinations, and four proportions of each combination. These mixtures were sealed in glass tubes, and the foaming was tested by shaking. Mixtures of aliphatic with other aliphatic hydrocarbons, or of alkyl benzenes with other alkyl benzenes, did not foam. Mixtures of aliphatic hydrocarbons with alkyl benzenes did foam. The proportions of the mixtures greatly affected the foaming, the maximum foaming of 12 of 20 pairs being at the composition 20 percent aliphatic hydrocarbon, 80 percent alkyl benzene. Six seconds was the maximum foam lifetime of any of these mixtures. Aeroshell 120 lubricating oil was fractionated into 52 fractions and a residue by extraction with acetone in a fractionating extractor. The index of refraction, foam lifetime, color, and viscosity of these fractions were measured. Low viscosity and high index fractions were extracted first. The viscosity of the fractions extracted rose and the index decreased as fractionation proceeded. Foam lifetimes and color were lowest in the middle fractions. Significance is attached to the observation that none of the foam lifetimes of the fractions or residue is as high as the foam lifetime of the original Aeroshell, indicating that the foaming is not due to a particular foaming constituent, but rather to the entire mixture.

  2. A computer simulation study of racemic mixtures

    NASA Astrophysics Data System (ADS)

    Largo, J.; Vega, C.; MacDowell, L. G.; Solana, J. R.

    A simple model for a chiral molecule is proposed. The model consists of a central atom bonded to four different atoms in tetrahedral coordination. Two different potentials were used to describe the pair potentials between atoms: the hard sphere potential and the Lennard-Jones potential. For both the hard sphere and the Lennard-Jones chiral models, computer simulations have been performed for the pure enantiomers and also for the racemic mixture. The racemic mixture consisted of an equimolar mixture of the two optically active enantiomers. It is found that the equations of state are the same, within statistical uncertainty, for the pure enantiomer fluid and for the racemic mixture. Only at high pressures does the racemic mixture seem to have a higher density, for a given pressure, than the pure enantiomer. Concering the structure, no difference is found in the site-site correlation functions between like and unlike molecules in the racemic mixture either at low or at high densities. However, small differences are found for the site-site correlations of the pure enantiomer and those of the racemic mixtures. In the Lennard-Jones model, similar conclusions are drawn. The extension of Wertheim's first-order perturbation theory, denoted bonded hard sphere theory (ARCHER, A. L., and JACKSON, G., 1991, Molec. Phys. , 73 , 881; AMOS, M. D., and JACKSON, G., 1992, J. chem. Phys. , 96 , 4604), successfully reproduces the simulation results for the hard chiral model. Virial coefficients of the hard chiral model up to the fourth have also been evaluated. Again, no differences are found between virial coefficients of the pure fluid and of the racemic mixture. All the results of this work illustrate the quasi-ideal behaviour of racemic mixtures in the fluid phase.

  3. Estrogenic activity of UV filter mixtures

    SciTech Connect

    Kunz, Petra Y. . E-mail: petra.kunz@fhnw.ch; Fent, Karl . E-mail: karl.fent@bluewin.ch

    2006-11-15

    UV-absorbing chemicals (UV filters) are widely used for protection against UV radiation in sunscreens and in a variety of cosmetic products and materials. Depending on the breadth and factor of UV protection, they are added as single compounds or as a combination thereof. Some UV filters have estrogenic activity, but their activity and interactions in mixtures are largely unknown. In this work, we analyzed 8 commonly used UV filters, which are pure or partial hER{alpha} agonists, for their estrogenic activity in equieffective mixtures in a recombinant yeast assay carrying the human estrogen receptor alpha (hER{alpha}). Mixtures of two, four and eight UV filters alone, or in combination with 17 {beta} estradiol (E2), were assessed at different effect levels and no-observed-effect-concentrations (NOEC). Predictions of the joint effects of these mixtures were calculated by employing the concentration addition (Canada) and independent action (IA) model. Most binary mixtures comprising of pure hER{alpha} agonists showed a synergistic activity at all mixture combinations. Only in combination with benzophenone-1, antagonistic activity was observed at some effect levels. All mixtures of four or eight, pure or pure and partial hER{alpha} agonists, alone or including E2, showed synergistic activity at concentrations giving an increase of 10% of basal activity (BC10). This occurred even at concentrations that were at the NOEC level of each single compound. Hence, there were substantial mixture effects even though each UV filter was present at its NOEC level. These results show that significant interactions occur in UV filter mixtures, which is important for the hazard and risk assessments of these personal care products.

  4. SEPARATION OF POLONIUM, PROTACTINIUM OR MIXTURES THEREOF IN AQUEOUS SOLUTION FROM BISMUTH, LEAD, ZIRCONIUM AND/OR COLUMBIUM VALUES

    DOEpatents

    Van Winkle, Q.; Kraus, K.A.

    1959-10-27

    A process is presented for separating polonium, protactinium, or mixtures thereof in aqueous solution from bismuth, zirconium, lead, and niobium values contained in the solution. The method comprises providing hydrochloric acid in the solution in a concentration of at least 5N. contacting the aqueous solution with a substantially waterimmiscible organic solvent such as diisopropyl ketone, and separating the aqueous phase containing the bismuth, zirconium, lead, and niobium from the organic extract phase containing the polonium, protactinium, or mixture thereof.

  5. APPARATUS FOR HANDLING MIXTURES OF SOLID MATERIALS

    DOEpatents

    Hubbell, J.P.

    1959-08-25

    An apparatus is described for handling either a mixture of finely subdivided materials or a single material requiring a compacting action thereon preparatory to a chemical reducing process carried out in a crucible container. The apparatus is designed to deposit a mixture of dust-forming solid materials in a container while confining the materials against escape into the surrounding atmosphere. A movable filling tube, having a compacting member, is connected to the container and to a covered hopper receiving the mixture of materials. The filling tube is capable of reciprocating in the container and their relative positions are dependent upon the pressure established upon the material by the compacting member.

  6. Quantitative NIR Raman analysis in liquid mixtures.

    PubMed

    Sato-Berrú, R Ysacc; Medina-Valtierra, Jorge; Medina-Gutiérrez, Cirilo; Frausto-Reyes, Claudio

    2004-08-01

    The capability to obtain quantitative information of a simple way from Raman spectra is a subject of considerable interest. In this work, this is demonstrated for mixtures of ethanol with water and rhodamine-6G (R-6G) with methanol, which were analyzed directly in glass vessel. The Raman intensities and a simple mathematical model have been used and applied for the analysis of liquid samples. It is starting point to generate a general expression, from the experimental spectra, as the sum of the particular expression for each pure compound allow us to obtain an expression for the mixtures which can be used for determining concentrations, from the Raman spectrum, of the mixture.

  7. Flashpoint prediction for ternary mixtures of alcohols with water for CFD simulation of unsteady flame propagation during explosion

    NASA Astrophysics Data System (ADS)

    Skřínský, Jan; Vereš, Ján; Ševčíková, Silvie Petránková

    2016-06-01

    Aqueous solutions of binary and ternary mixtures of alcohols are of considerable interest for a wide range of scientists and technologists. Simple dimensionless experimental formulae based on rational reciprocal and polynomial functions are proposed for correlation of the flashpoint data of binary mixtures of two components. The formulae are based on data obtained from flashpoint experiments and predictions. The main results are the derived experimental flashpoint values for ternary mixtures of two aqueous-organic solutions and the model prediction of maximum explosion pressure values for the studied mixtures. Potential application for the results concerns the assessment of fire and explosion hazards, and the development of inherently safer designs for chemical processes containing binary and ternary partially miscible mixtures of an aqueous-organic system. The goal of this article is to present the results of modelling using these standard models and to demonstrate its importance in the area of CFD simulation.

  8. Phenol and cresol mixture degradation by the yeast Trichosporon cutaneum.

    PubMed

    Alexieva, Z; Gerginova, M; Manasiev, J; Zlateva, P; Shivarova, N; Krastanov, A

    2008-11-01

    Most industrial wastes contain different organic mixtures, making important the investigation on the microbial destruction of composite substrates. The capability of microbes to remove harmful chemicals from polluted environments strongly depends on the presence of other carbon and energy substrates. The effect of mixtures of phenol- and methyl-substituted phenols (o-, m-, p-cresol) on the growth behaviour and degradation capacity of Trichosporon cutaneum strain was investigated. The cell-free supernatants were analysed by HPLC. It was established that the presence of o-, m- and p- cresol has not prevented complete phenol assimilation but had significant delaying effect on the phenol degradation dynamics. The mutual influence of phenol and p-cresol was investigated. We developed the kinetic model on the basis of Haldane kinetics, which used model parameters from single-substrate experiments to predict the outcome of the two-substrate mixture experiment. The interaction coefficients indicating the degree to which phenol affects the biodegradation of p-cresol and vice versa were estimated. Quantitative estimation of interaction parameters is essential to facilitate the application of single or mixed cultures to the bio-treatment of hazardous compounds.

  9. Genotoxicity of complex mixtures: CHO cell mutagenicity assay

    SciTech Connect

    Frazier, M.E.; Samuel, J.E.

    1985-02-01

    A Chinese hamster ovary (CHO) mammalian cell assay was used to evaluate the genotoxicity of complex mixtures (synthetic fuels). The genotoxicity (mutagenic potency) of the mixtures increased as the temperature of their boiling range increased. Most of the genotoxicity in the 750/sup 0/F+ boiling-range materials was associated with the neutral polycyclic aromatic hydrocarbon (PAH) fractions. Chemical analysis data indicate that the PAH fractions of high-boiling coal liquids contain a number of known chemical carcinogens, including five- and six-ring polyaromatics (e.g., benzo(a)pyrene) as well as four- and five-ring alkyl-substituted PAH (e.g., methylchrysene and dimethylbenzanthracenes); concentrations are a function of boiling point (bp). In vitro genotoxicity was also detected in fractions of nitrogen-containing polyaromatic compounds, as well as in those with aliphatics of hydroxy-containing PAH. Mutagenic activity of some fractions was detectable in the CHO assay in the absence of an exogenous metabolic activation system; in some instances, addition of exogenous enzymes and cofactors inhibited expression of the direct-acting mutagenic potential of the fraction. These data indicate that the organic matrix of the chemical fraction determines whether, and to what degree, various mutagens are expressed in the CHO assay. Therefore, the results of biological assays of these mixtures must be correlated with chemical analyses for proper interpretation of these data. 29 references, 16 figures, 4 tables.

  10. Biodegradability of chlorophenols and mixtures of chlorophenols in seawater

    SciTech Connect

    Lindgaard-Jorgensen, P.

    1989-04-01

    Laboratory studies using chemical concentrations comparable to those found in nature have provided considerable knowledge of microbial transformations in nature. Although the number of studies performed is increasing rapidly, the effects of low substrate levels on growth, enzyme induction, enzyme activity, and the use of mixtures of substrates have not yet been clarified. Likewise, studies at low concentrations in seawater are lacking. This paper describes a study of the rates of degradation of chlorophenols 4-chlor-2-methylphenol, 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol at concentrations ranging from 2 to 18 micrograms/liter. The compounds were tested separately, in a mixture, and in waste water containing other organics. The obtained rates of 2,4-DCP in seawater were comparable to those found in fresh water. Also, the rates were in general agreement with a kinetic model proposed for degradation of chlorophenols. The rates of degradation of chlorophenols in the mixture were comparable to those found when tested separately. In the waste, very low rates were observed. It is suggested that this might be explained by a toxic effect, caused by other substances in the waste water, on the microorganisms considered to be active in degrading the chlorophenols at low concentrations.

  11. Assessing exposures to inhaled complex mixtures.

    PubMed Central

    Leaderer, B P; Lioy, P J; Spengler, J D

    1993-01-01

    In the course of daily activities, individuals spend varying amounts of time in different spaces where they are exposed to a complex mixture of gas, vapor, and particulate contaminants. The term complex is used in this paper to refer to binary mixtures as well as truly complex mixtures of three or more constituents. The diversity of the environments where pollution may occur, the number of pollutants that may be present, and the nature of the activity in the environment combine to pose a challenge to investigators of the health effects of air pollutants. This article discusses several methods of measuring or assessing exposure to complex mixture air contaminants that include time-activity assessments, personal monitoring, biomarkers of exposure, and microenvironmental models that can be employed singly or in combination in a protocol for exposure assessment. The use of nested designs, involving more intensive data collection from samples or subjects, is also considered. PMID:8206025

  12. Titration of phosphonic acid derivatives in mixtures.

    PubMed

    Wittmann, Z

    1980-01-01

    An analytical procedure is described for the determination of the weak acids phosphonomethyliminodiacetic acid and phosphonomethyliminoacetic acid in their mixtures, and the dissociation constants of phosphonomethyliminoacetic acid are reported.

  13. Robust clustering using exponential power mixtures.

    PubMed

    Zhang, Jian; Liang, Faming

    2010-12-01

    Clustering is a widely used method in extracting useful information from gene expression data, where unknown correlation structures in genes are believed to persist even after normalization. Such correlation structures pose a great challenge on the conventional clustering methods, such as the Gaussian mixture (GM) model, k-means (KM), and partitioning around medoids (PAM), which are not robust against general dependence within data. Here we use the exponential power mixture model to increase the robustness of clustering against general dependence and nonnormality of the data. An expectation-conditional maximization algorithm is developed to calculate the maximum likelihood estimators (MLEs) of the unknown parameters in these mixtures. The Bayesian information criterion is then employed to determine the numbers of components of the mixture. The MLEs are shown to be consistent under sparse dependence. Our numerical results indicate that the proposed procedure outperforms GM, KM, and PAM when there are strong correlations or non-Gaussian components in the data. PMID:20163406

  14. Transcriptional responses to complex mixtures - A review

    EPA Science Inventory

    Exposure of people to hazardous compounds is primarily through complex environmental mixtures, those that occur through media such as air, soil, water, food, cigarette smoke, and combustion emissions. Microarray technology offers the ability to query the entire genome after expos...

  15. Quantiles for Finite Mixtures of Normal Distributions

    ERIC Educational Resources Information Center

    Rahman, Mezbahur; Rahman, Rumanur; Pearson, Larry M.

    2006-01-01

    Quantiles for finite mixtures of normal distributions are computed. The difference between a linear combination of independent normal random variables and a linear combination of independent normal densities is emphasized. (Contains 3 tables and 1 figure.)

  16. Predicting skin permeability from complex chemical mixtures

    SciTech Connect

    Riviere, Jim E. . E-mail: Jim_Riviere@ncsu.edu; Brooks, James D.

    2005-10-15

    Occupational and environmental exposure to topical chemicals is usually in the form of complex chemical mixtures, yet risk assessment is based on experimentally derived data from individual chemical exposures from a single, usually aqueous vehicle, or from computed physiochemical properties. We present an approach using hybrid quantitative structure permeation relationships (QSPeR) models where absorption through porcine skin flow-through diffusion cells is well predicted using a QSPeR model describing the individual penetrants, coupled with a mixture factor (MF) that accounts for physicochemical properties of the vehicle/mixture components. The baseline equation is log k {sub p} = c + mMF + a{sigma}{alpha} {sub 2} {sup H} + b{sigma}{beta} {sub 2} {sup H} + s{pi} {sub 2} {sup H} + rR {sub 2} + vV {sub x} where {sigma}{alpha} {sub 2} {sup H} is the hydrogen-bond donor acidity, {sigma}{beta} {sub 2} {sup H} is the hydrogen-bond acceptor basicity, {pi} {sub 2} {sup H} is the dipolarity/polarizability, R {sub 2} represents the excess molar refractivity, and V {sub x} is the McGowan volume of the penetrants of interest; c, m, a, b, s, r, and v are strength coefficients coupling these descriptors to skin permeability (k {sub p}) of 12 penetrants (atrazine, chlorpyrifos, ethylparathion, fenthion, methylparathion, nonylphenol, {rho}-nitrophenol, pentachlorophenol, phenol, propazine, simazine, and triazine) in 24 mixtures. Mixtures consisted of full factorial combinations of vehicles (water, ethanol, propylene glycol) and additives (sodium lauryl sulfate, methyl nicotinate). An additional set of 4 penetrants (DEET, SDS, permethrin, ricinoleic acid) in different mixtures were included to assess applicability of this approach. This resulted in a dataset of 16 compounds administered in 344 treatment combinations. Across all exposures with no MF, R{sup 2} for absorption was 0.62. With the MF, correlations increased up to 0.78. Parameters correlated to the MF include refractive

  17. Diffusion method of seperating gaseous mixtures

    DOEpatents

    Pontius, Rex B.

    1976-01-01

    A method of effecting a relatively large change in the relative concentrations of the components of a gaseous mixture by diffusion which comprises separating the mixture into heavier and lighter portions according to major fraction mass recycle procedure, further separating the heavier portions into still heavier subportions according to a major fraction mass recycle procedure, and further separating the lighter portions into still lighter subportions according to a major fraction equilibrium recycle procedure.

  18. Thermodynamics of wax precipitation in petroleum mixtures

    SciTech Connect

    Lira-Galeana, C.; Firoozabadi, A.; Prausnitz, J.M. |

    1996-01-01

    A thermodynamic framework is developed for calculating wax precipitation in petroleum mixtures over a wide temperature range. The framework uses the experimentally supported assumption that precipitated wax consists of several solid phases; each solid phase is described as a pure component or pseudocomponent that does not mix with other solid phases. Liquid-phase properties are obtained from an equation of state. Calculated wax-precipitation data are in excellent agreement with experimental results for binary and multicomponent hydrocarbon mixtures, including petroleum.

  19. Thermodynamics of wax precipitation in petroleum mixtures

    SciTech Connect

    Firoozabadi, A.; Lira-Galeana, C.L.; Prausnitz, J.M.

    1995-12-01

    A thermodynamic framework is developed for calculating wax precipitation in petroleum mixtures over a wide temperature range. The framework assumes that the precipitated wax consists of several solid phases; each solid-phase is described as a pure component or pseudocomponent which does not mix with other solid phases. Liquid-phase properties are obtained from an equation of state. Calculated wax precipitation data are in excellent agreement with experimental results for binary and multicomponent hydrocarbon mixtures, including petroleum.

  20. Further gas mixtures with low environment impact

    NASA Astrophysics Data System (ADS)

    Liberti, B.; Aielli, G.; Camarri, P.; Cardarelli, R.; Di Ciaccio, A.; Di Stante, L.; Pastori and, E.; Santonico, R.

    2016-09-01

    Further gas mixtures with low environment impact have been tested. For the best RPC performance the main effort was to look for a mixture giving a comfortable avalanche-streamer separation and a gas density ensuring sufficient primary ionization. The measurements have been carried out on small size chambers at cosmic ray rates using the waveforms recorded on the oscilloscope. Efficiencies and distributions of amplitude and charge will be presented.

  1. Flash evaporation of liquid monomer particle mixture

    DOEpatents

    Affinito, John D.; Darab, John G.; Gross, Mark E.

    1999-01-01

    The present invention is a method of making a first solid composite polymer layer. The method has the steps of (a) mixing a liquid monomer with particles substantially insoluble in the liquid monomer forming a monomer particle mixture; (b) flash evaporating the particle mixture and forming a composite vapor; and (c) continuously cryocondensing said composite vapor on a cool substrate and cross-linking the cryocondensed film thereby forming the polymer layer.

  2. Flash evaporation of liquid monomer particle mixture

    DOEpatents

    Affinito, J.D.; Darab, J.G.; Gross, M.E.

    1999-05-11

    The present invention is a method of making a first solid composite polymer layer. The method has the steps of (a) mixing a liquid monomer with particles substantially insoluble in the liquid monomer forming a monomer particle mixture; (b) flash evaporating the particle mixture and forming a composite vapor; and (c) continuously cryocondensing said composite vapor on a cool substrate and cross-linking the cryocondensed film thereby forming the polymer layer. 3 figs.

  3. ODE constrained mixture modelling: a method for unraveling subpopulation structures and dynamics.

    PubMed

    Hasenauer, Jan; Hasenauer, Christine; Hucho, Tim; Theis, Fabian J

    2014-07-01

    Functional cell-to-cell variability is ubiquitous in multicellular organisms as well as bacterial populations. Even genetically identical cells of the same cell type can respond differently to identical stimuli. Methods have been developed to analyse heterogeneous populations, e.g., mixture models and stochastic population models. The available methods are, however, either incapable of simultaneously analysing different experimental conditions or are computationally demanding and difficult to apply. Furthermore, they do not account for biological information available in the literature. To overcome disadvantages of existing methods, we combine mixture models and ordinary differential equation (ODE) models. The ODE models provide a mechanistic description of the underlying processes while mixture models provide an easy way to capture variability. In a simulation study, we show that the class of ODE constrained mixture models can unravel the subpopulation structure and determine the sources of cell-to-cell variability. In addition, the method provides reliable estimates for kinetic rates and subpopulation characteristics. We use ODE constrained mixture modelling to study NGF-induced Erk1/2 phosphorylation in primary sensory neurones, a process relevant in inflammatory and neuropathic pain. We propose a mechanistic pathway model for this process and reconstructed static and dynamical subpopulation characteristics across experimental conditions. We validate the model predictions experimentally, which verifies the capabilities of ODE constrained mixture models. These results illustrate that ODE constrained mixture models can reveal novel mechanistic insights and possess a high sensitivity. PMID:24992156

  4. Toxicity evaluation of PAH mixtures using Microtox

    SciTech Connect

    Thompkins, J.; Guthrie, E.; Pfaender, F.

    1995-12-31

    Polycyclic aromatic hydrocarbons (PAH) are produced from both natural and anthropogenic combustion processes. PAHs are known to be toxic and carcinogenic, are prevalent at many hazardous waste sites, and pose a potential risk to both ecological and human health. To date, few researchers have assessed the toxicity of polycyclic aromatic hydrocarbon (PAH) mixtures. The toxicity of chrysene, anthracene, pyrene, phenanthrene, fluoranthrene, acenaphthene, fluorene, and naphthalene were evaluated using Microtox, and acute toxicity assay that uses bioluminescent bacteria, Photobacterium phosphoreum, to measure toxicity. In this study, the toxicities of 2, 3, and 4 ring PAHs were determined for individual compounds. Synergistic or additive effects of PAH mixtures was assessed by comparing the toxicity of mixtures with that of pure compounds. Each PAH or mixture was evaluated at their respective water solubility concentrations, For individual PAHs tested, the toxicity of PAHs is inversely related to water solubility. Mixtures of two and three PAHs with disparate water solubilities resulted in synergistic interactions. Antagonistic interactions, a decrease in toxicity, were observed for mixtures of similar water solubilities.

  5. Phase equilibria for complex fluid mixtures

    SciTech Connect

    Prausnitz, J.M.

    1983-04-01

    After defining complex mixtures, attention is given to the canonical procedure used for the thermodynamics of fluid mixtures: first, we establish a suitable, idealized reference system and then we establish a perturbation (or excess function) which corrects the idealized system for real behavior. For complex mixtures containing identified components (e.g. alcohols, ketones, water) discussion is directed at possible techniques for extending to complex mixtures our conventional experience with reference systems and perturbations for simple mixtures. Possible extensions include generalization of the quasi-chemical approximation (local compositions) and superposition of chemical equilibria (association and solvation) on a physical equation of state. For complex mixtures containing unidentified components (e.g. coal-derived fluids), a possible experimental method is suggested for characterization; conventional procedures can then be used to calculate phase equilibria using the concept of pseudocomponents whose properties are given by the characterization data. Finally, as an alternative to the pseudocomponent method, a brief introduction is given to phase-equilibrium calculations using continuous thermodynamics.

  6. Homogeneous cooling of mixtures of particle shapes

    NASA Astrophysics Data System (ADS)

    Hidalgo, R. C.; Serero, D.; Pöschel, T.

    2016-07-01

    In this work, we examine theoretically the cooling dynamics of binary mixtures of spheres and rods. To this end, we introduce a generalized mean field analytical theory, which describes the free cooling behavior of the mixture. The relevant characteristic time scale for the cooling process is derived, depending on the mixture composition and the aspect ratio of the rods. We simulate mixtures of spherocylinders and spheres using a molecular dynamics algorithm implemented on graphics processing unit (GPU) architecture. We systematically study mixtures composed of spheres and rods with several aspect ratios and varying the mixture composition. A homogeneous cooling state, where the time dependence of the system's intensive variables occurs only through a global granular temperature, is identified. We find cooling dynamics in excellent agreement with Haff's law, when using an adequate time scale. Using the scaling properties of the homogeneous cooling dynamics, we estimated numerically the efficiency of the energy interchange between rotational and translational degrees of freedom for collisions between spheres and rods.

  7. Relationship inference based on DNA mixtures.

    PubMed

    Kaur, Navreet; Bouzga, Mariam M; Dørum, Guro; Egeland, Thore

    2016-03-01

    Today, there exists a number of tools for solving kinship cases. But what happens when information comes from a mixture? DNA mixtures are in general rarely seen in kinship cases, but in a case presented to the Norwegian Institute of Public Health, sample DNA was obtained after a rape case that resulted in an unwanted pregnancy and abortion. The only available DNA from the fetus came in form of a mixture with the mother, and it was of interest to find the father of the fetus. The mother (the victim), however, refused to give her reference data and so commonly used methods for paternity testing were no longer applicable. As this case illustrates, kinship cases involving mixtures and missing reference profiles do occur and make the use of existing methods rather inconvenient. We here present statistical methods that may handle general relationship inference based on DNA mixtures. The basic idea is that likelihood calculations for mixtures can be decomposed into a series of kinship problems. This formulation of the problem facilitates the use of kinship software. We present the freely available R package relMix which extends on the R version of Familias. Complicating factors like mutations, silent alleles, and θ-correction are then easily handled for quite general family relationships, and are included in the statistical methods we develop in this paper. The methods and their implementations are exemplified on the data from the rape case.

  8. Novel anisole mixture and gasoline containing the same

    DOEpatents

    Singerman, Gary M.

    1982-01-26

    A novel anisole mixture containing anisole and a mixture of alkyl anisoles and liquid hydrocarbon fuels containing said novel anisole mixture in an amount sufficient to increase the octane number of said liquid fuel composition.

  9. Chemical mixtures in untreated water from public-supply wells in the U.S.--occurrence, composition, and potential toxicity.

    PubMed

    Toccalino, Patricia L; Norman, Julia E; Scott, Jonathon C

    2012-08-01

    Chemical mixtures are prevalent in groundwater used for public water supply, but little is known about their potential health effects. As part of a large-scale ambient groundwater study, we evaluated chemical mixtures across multiple chemical classes, and included more chemical contaminants than in previous studies of mixtures in public-supply wells. We (1) assessed the occurrence of chemical mixtures in untreated source-water samples from public-supply wells, (2) determined the composition of the most frequently occurring mixtures, and (3) characterized the potential toxicity of mixtures using a new screening approach. The U.S. Geological Survey collected one untreated water sample from each of 383 public wells distributed across 35 states, and analyzed the samples for as many as 91 chemical contaminants. Concentrations of mixture components were compared to individual human-health benchmarks; the potential toxicity of mixtures was characterized by addition of benchmark-normalized component concentrations. Most samples (84%) contained mixtures of two or more contaminants, each at concentrations greater than one-tenth of individual benchmarks. The chemical mixtures that most frequently occurred and had the greatest potential toxicity primarily were composed of trace elements (including arsenic, strontium, or uranium), radon, or nitrate. Herbicides, disinfection by-products, and solvents were the most common organic contaminants in mixtures. The sum of benchmark-normalized concentrations was greater than 1 for 58% of samples, suggesting that there could be potential for mixtures toxicity in more than half of the public-well samples. Our findings can be used to help set priorities for groundwater monitoring and suggest future research directions for drinking-water treatment studies and for toxicity assessments of chemical mixtures in water resources.

  10. Primordial soup was edible: abiotically produced Miller-Urey mixture supports bacterial growth

    PubMed Central

    Xie, Xueshu; Backman, Daniel; Lebedev, Albert T.; Artaev, Viatcheslav B.; Jiang, Liying; Ilag, Leopold L.; Zubarev, Roman A.

    2015-01-01

    Sixty years after the seminal Miller-Urey experiment that abiotically produced a mixture of racemized amino acids, we provide a definite proof that this primordial soup, when properly cooked, was edible for primitive organisms. Direct admixture of even small amounts of Miller-Urey mixture strongly inhibits E. coli bacteria growth due to the toxicity of abundant components, such as cyanides. However, these toxic compounds are both volatile and extremely reactive, while bacteria are highly capable of adaptation. Consequently, after bacterial adaptation to a mixture of the two most abundant abiotic amino acids, glycine and racemized alanine, dried and reconstituted MU soup was found to support bacterial growth and even accelerate it compared to a simple mixture of the two amino acids. Therefore, primordial Miller-Urey soup was perfectly suitable as a growth media for early life forms. PMID:26412575

  11. Impact of Organic Contamination on Some Aquatic Organisms

    PubMed Central

    Yasser, El-Nahhal; Shawkat, El-Najjar; Samir, Afifi

    2015-01-01

    Background: Contamination of water systems with organic compounds of agricultural uses pose threats to aquatic organisms. Carbaryl, chlorpyrifos, and diuron were considered as model aquatic pollutants in this study. The main objective of this study was to characterize the toxicity of organic contamination to two different aquatic organisms. Materials and Methods: Low concentrations (0.0–60 µmol/L) of carbaryl, diuron and very low concentration (0.0–0.14 µmol/L) of chlorpyrifos and their mixtures were tested against fish and Daphnia magna. Percentage of death and immobilization were taken as indicators of toxicity. Results: Toxicity results to fish and D. magna showed that chlorpyrifos was the most toxic compound (LC50 to fish and D. magna are 0.08, and 0.001 µmol/L respectively), followed by carbaryl (LC50 to fish and D. magna are 43.19 and 0.031 µmol/L), while diuron was the least toxic one (LC50 values for fish and D. magna are 43.48 and 32.11 µmol/L respectively). Mixture toxicity (binary and tertiary mixtures) showed antagonistic effects. Statistical analysis showed a significant difference among mixture toxicities to fish and D. magma. Conclusion: Fish and D. magam were sensitive to low concentrations. These data suggest potent threats to aquatic organisms from organic contamination. PMID:26862260

  12. Modeling joint effects of mixtures of chemicals on microorganisms using quantitative structure activity relationships. Annual report, 20 August 1991-19 August 1992

    SciTech Connect

    Nirmalakhandan, N.; Mohsin, M.; Arulgnanendran, V.; Bangxin, S.; Cadena, F.

    1992-01-01

    Toxicity of 50 organic chemicals to microorganisms was determined using the respirometeric approach. Using this experimental database, models for predicting toxicity (IC50 values) were developed using QSAR techniques. Toxicity measurements were also made for ten binary mixtures, and sixteen multi-component mixtures. The joint effects of organic chemicals in mixtures were analyzed by three different approaches. Using the QSAR model developed from single chemical studies, an approach was developed to analyze and predict joint effects of chemicals in mixtures. The results of this study indicate that the joint effects could be considered simply additive for the different classes of chemicals tested.

  13. Prediction of sweetness intensity for equiratio aspartame/sucrose mixtures.

    PubMed

    Schifferstein, H N

    1995-04-01

    The Equiratio Mixture Model predicts the responses to a series of equiratio mixtures on the basis of the psychophysical functions for the unmixed components. The model predicts the sweetness of mixtures of sugars and sugar-alcohols successfully, but is unable to predict mixture intensity for substances with different dynamic ranges. In this paper, the equi-intensity concept is introduced in the Equiratio Mixture Model by transforming the physical concentrations expressed in molarity into units that produce approximately equi-intense sensations. An empirical test using aspartame/sucrose mixtures shows that the modified Equiratio Mixture Model yields good predictions of mixture intensities.

  14. Measuring Vapor Pressure with an Isoteniscope: A Hands-on Introduction to Thermodynamic Concepts

    ERIC Educational Resources Information Center

    Chen, Wenqian; Haslam, Andrew J.; Macey, Andrew; Shah, Umang V.; Brechtelsbauer, Clemens

    2016-01-01

    Characterization of the vapor pressure of a volatile liquid or azeotropic mixture, and its fluid phase diagram, can be achieved with an isoteniscope and an industrial grade digital pressure sensor using the experimental method reported in this study. We describe vapor-pressure measurements of acetone and n-hexane and their azeotrope, and how the…

  15. Prebiotic hydrocarbon synthesis in impacting reduced astrophysical icy mixtures

    DOE PAGES

    Koziol, Lucas; Goldman, Nir

    2015-04-21

    We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extendedmore » structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Lastly, our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.« less

  16. Prebiotic Hydrocarbon Synthesis in Impacting Reduced Astrophysical Icy Mixtures

    NASA Astrophysics Data System (ADS)

    Koziol, Lucas; Goldman, Nir

    2015-04-01

    We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extended structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.

  17. Prebiotic hydrocarbon synthesis in impacting reduced astrophysical icy mixtures

    NASA Astrophysics Data System (ADS)

    Goldman, Nir; Koziol, Lucas

    2015-06-01

    We present results of prebiotic organic synthesis in shock compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium time-scales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impact on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon and nitrogen bonded extended structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Our results help provide a bottom-up understanding for hydrocarbon impact synthesis on early Earth and its role in producing life building molecules from simple starting materials. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  18. Prebiotic hydrocarbon synthesis in impacting reduced astrophysical icy mixtures

    SciTech Connect

    Koziol, Lucas; Goldman, Nir

    2015-04-21

    We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extended structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Lastly, our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.

  19. PREBIOTIC HYDROCARBON SYNTHESIS IN IMPACTING REDUCED ASTROPHYSICAL ICY MIXTURES

    SciTech Connect

    Koziol, Lucas; Goldman, Nir E-mail: ngoldman@llnl.gov

    2015-04-20

    We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extended structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.

  20. Method of photocatalytic conversion of C-H organics

    DOEpatents

    Camaioni, Donald M.; Lilga, Michael A.

    1998-01-01

    The present invention is the addition of a semiconductor material and energy to the reaction mixture of organic, acid (for example, trifluoroacetate), and oxygen. A transition metal ion may be added to the reaction mixture. The semiconductor material converts energy to oxidants thereby promoting oxidation of the organic. Alternatively, using metal in combination with exposure to light may be used.