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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. Near azeotropic mixture substitute

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor)

    1996-01-01

    The present invention comprises a refrigerant mixture consisting of a first mole fraction of 1,1,1,2-tetrafluoroethane (R134a) and a second mole fraction of a component selected from the group consisting of a mixture of CHClFCF.sub.3 (R124) and CH.sub.3 CClF.sub.2 (R142b); a mixture of CHF.sub.2 CH.sub.3 (R152a) and CHClFCF.sub.3 (R124); a mixture of CHF.sub.2 CH.sub.3 (R152a) and CH.sub.3 CClF.sub.2 (R142b); and a mixture of CHClFCF.sub.3 (R124), CH.sub.3 CClF.sub.2 (R142b) and CHF.sub.2 CH.sub.3 (R152a).

  4. Nearly Azeotropic Mixtures To Replace Refrigerant 12

    NASA Technical Reports Server (NTRS)

    Jones, Jack A.

    1992-01-01

    Number of nearly azeotropic fluid mixtures have saturation pressures similar to Refrigerant 12 while being about 2 percent as damaging to ozone layer. Five mixtures of R134a, R152a, R124, and R142b have low boiling-point spreads, low toxicity, and low ozone-damaging capability, are nonflammable, and more compatible with conventional oils than R134a. Pressure of combinations nearly equal to R12, and mixtures may be good "drop-in substitutes". Overall composition not altered by leakage. Usable in commercial, automotive, and household refrigerators and air conditioners.

  5. Near azeotropic mixture substitute for dichlorodifluoromethane

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor)

    1998-01-01

    A refrigerant and a process of formulating thereof that consists of a mixture of a first mole fraction of CH.sub.2 FCF.sub.3 and a second mole fraction of a component selected from the group consisting of a mixture of CHClFCF.sub.3 and CH.sub.3 CClF.sub.2 ; a mixture of CHF.sub.2 CH.sub.3 and CH.sub.3 CClF.sub.2 ; and a mixture of CHClFCF.sub.3, CH.sub.3 CClF.sub.2 and CHF.sub.2 CH.sub.3.

  6. Near azeotropic mixture substitute for dichlorodifluoromethane

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor)

    1996-01-01

    The present invention comprises a refrigerant mixture having two halocarbon components. The first component is present in a mole fraction of about 0.7 to less than 1.0 while the second component is present in a mole fraction of more than 0.0 to about 0.3. The first component is CH.sub.2 FCF.sub.3. The second component can be CHClFCF.sub.3, CH.sub.3 CClF.sub.2, a mixture of CHClFCF.sub.3 and CH.sub.3 CClF.sub.2, a mixture of CHF.sub.2 CH.sub.3 and CHClFCF.sub.3, a mixture of CHF.sub.2 CH.sub.3 and CH.sub.3 CClF.sub.2, or a mixture of CHClFCF.sub.3, CH.sub.3 CClF.sub.2 and CHF.sub.2 CH.sub.3. The preferred embodiment of this invention comprises about 0.7 to less than 1.0 mole fraction CH.sub.2 FCF.sub.3, and more than 0.0 to about 0.3 mole fraction of a mixture of CHClFCF.sub.3 and CH.sub.3 CClF.sub.2. The most preferred embodiment of this invention comprises about 0.7 to less than 1.0 mole fraction CH.sub.2 FCF.sub.3 and more than 0.0 to about 0.3 mole fraction CH.sub.3 CClF.sub.2. The resulting refrigerant has a vapor pressure close to-that of CF.sub.2 Cl.sub.2, a nearly constant vapor pressure with evaporation, and is substantially less damaging to the Earth's ozone layer than CF.sub.2 Cl.sub.2.

  7. 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

  8. 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. PMID:21116474

  9. Expert system for the design of separation sequences for close-boiling and azeotropic mixtures

    SciTech Connect

    Simmrock, K.H.; Fried, A.; Welker, R.

    1993-10-01

    Formation of azeotropes, or occurrence of close boiling components in a mixture, precludes straightforward rectification as a method of separation. Instead, recourse must be taken to special distillation processes which overcome distillation boundaries by the admixture of an entrainer or solvent, or by exploitation of inherent system properties. While the choice of a suitable entrainer is almost the only important factor in the design of extractive rectification processes, to sort out the numerous possible variants is difficult, due to the different distillation properties of the azeotropic mixture. A satisfactory approach is offered by the use of heuristic knowledge in the form of a knowledge-based expert system to provide alternatives which correspond to the requirements of the process. Starting with a small amount of readily available physical property data for pure components and mixtures, rectification processes which are suitable for the separation of a close boiling or an azeotropic mixture are selected, and appropriate process structures are generated. The expert proposes entrainers, meeting the demands of the process under consideration. The present paper presents a detailed description of the structure and the operation of the expert system for selecting entrainers and for process generation. The system consists of modules for pressure change, homoazeotropic, heteroazeotropic, extractive, and multiple azeotropic rectification, procedural strategy, and explanatory components.

  10. Efficiency of vapor compression heat pumps based on non-azeotropic refrigerant mixtures

    NASA Astrophysics Data System (ADS)

    Mezentseva, N. N.

    2011-06-01

    The work presents the results of cycle computation for vapor compression pumps based on ozone-safe mixed refrigerants. Non-azeotropic binary refrugerants R32/R152a (30/70) and R32/R134a (30/70) were considere as working substances. Properties of non-azeotropic refrigerants were calculated according to the additivity method of thermodynamic functions and method of Lemmon and Jacobsen. Deviations in the values of thermophysical properties obtained with two methods have been determined. It is shown that at the use of nonazeotropic mixture R32/R152a (30/70), energy conversion ratio increases by 2.2-3.6 % compared with the results for R32/R134a (30/70) at temperature difference between the processes of boiling and condensation from 28 to 53 °C.

  11. Azeotropic distillation

    SciTech Connect

    Widagdo, S.; Seider, W.D.

    1996-01-01

    Recent and ongoing research in the distillation of nonideal mixtures is reviewed focusing on advances in the methodologies for the synthesis, design, analysis and control of separation sequences involving homogeneous and heterogeneous azeotropic towers. Maps of residue curves and distillation lines are examined, as well as geometric methods for the synthesis and design of separation sequences, trends in the steady-state and dynamic analysis of homogeneous and heterogeneous towers, the nonlinear behavior of these towers, and strategies for their control. Emphasis is placed on the methods of computing all of the azeotropes associated with a multicomponent mixture, on the features that distinguish azeotropic distillations from their zeotropic counterparts, on the potential for steady-state multiplicity, and on the existence of maximum and minimum reflux bounds. Important considerations in the selection of entrainers are examined. For the synthesis of separation trains, when determining the feasible production compositions, the graphical methods are clarified, especially the conditions under which distillation boundaries can be crossed and bounding strategies under finite reflux. The application of geometric theory to locate the fixed points, at minimum reflux, is reviewed in connection with homotopy-continuation algorithms for this purpose. The use of homotopy-continuation algorithms, especially for the steady-state simulation of heterogeneous azeotropic distillations, is justified. Methods for phase stability analysis are reviewed in connection with the location of real bifurcation points at phase transitions, an important feature of algorithms for the dynamic simulation of heterogeneous azeotropic distillations.

  12. Adsorption of binary gas mixtures in heterogeneous carbon predicted by density functional theory: on the formation of adsorption azeotropes.

    PubMed

    Ritter, James A; Pan, Huanhua; Balbuena, Perla B

    2010-09-01

    Classical density functional theory (DFT) was used to predict the adsorption of nine different binary gas mixtures in a heterogeneous BPL activated carbon with a known pore size distribution (PSD) and in single, homogeneous, slit-shaped carbon pores of different sizes. By comparing the heterogeneous results with those obtained from the ideal adsorbed solution theory and with those obtained in the homogeneous carbon, it was determined that adsorption nonideality and adsorption azeotropes are caused by the coupled effects of differences in the molecular size of the components in a gas mixture and only slight differences in the pore sizes of a heterogeneous adsorbent. For many binary gas mixtures, selectivity was found to be a strong function of pore size. As the width of a homogeneous pore increases slightly, the selectivity for two different sized adsorbates may change from being greater than unity to less than unity. This change in selectivity can be accompanied by the formation of an adsorption azeotrope when this same binary mixture is adsorbed in a heterogeneous adsorbent with a PSD, like in BPL activated carbon. These results also showed that the selectivity exhibited by a heterogeneous adsorbent can be dominated by a small number of pores that are very selective toward one of the components in the gas mixture, leading to adsorption azeotrope formation in extreme cases. PMID:20712330

  13. Heat transfer in pool boiling of binary and ternary non-azeotropic mixtures

    NASA Astrophysics Data System (ADS)

    Nahra, Ziad; Næss, Erling

    2009-05-01

    Heat transfer coefficients in nucleate pool boiling of binary and ternary non-azeotropic hydrocarbon mixtures were obtained experimentally using a vertical electrically heated cylindrical carbon steel surface at atmospheric pressure with several surface roughness. The fluids used were Methanol/1-Pentanol and Methanol/1-Pentanol/1,2-Propandiol at constant 1,2-Propandiol mole fraction of 30%. Heat fluxes were varied in the range 25-235 kW/m2. The cylindrical heater surface was polished to an average surface roughness of 0.2 μm, and sandblasted yielding surface roughness of 2.98 and 4.35 μm, respectively. The experimental results were compared to available prediction correlations, indicating that the correlations based on the boiling range are in better qualitative agreement than correlations based on the phase envelope. Increasing surface roughness resulted in an increase in the heat transfer coefficient, and the effect was observed to be dependent on the heat flux and fluid composition.

  14. Performance evaluation of two azeotropic refrigerant mixtures of HFC-134a with R-290 (propane) and R-600a (isobutane)

    SciTech Connect

    Kim, M.S.; Mulroy, W.J.; Didion, D.A. . Building and Fire Research Lab.)

    1994-06-01

    The reduction in chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) production and the scheduled phase-out of these ozone-depleting refrigerants require the development and determination of environmentally safe refrigerants for use in heat pumps, water chillers, air conditioners, and refrigerators. This paper presents a performance evaluation of a generic heat pump with two azeotropic refrigerant mixtures of HFC-134a (1,1,1,2-tetrachloroethane) with R-290 (propane) and R-600a (isobutane); R-290/134a (45/55 by mass percentage) and R-134a/600a (80/20 by mass percentage). The performance characteristics of the azeotropes were compared with pure CFC-12, HFC-134a, HCFC-22, and R-290 at the high temperature cooling and heating conditions including those using liquid-line/suction-line heat exchange. The coefficient of performance of R-290/134a is lower than that of HCFC-22 and R-290, and R-134a/600a shows higher coefficient of performance than CFC-12 and HFC-134a. The capacity for R-290/134a is higher than that for HCFC-22 and R-290, and R-134a/600a exhibits higher system capacity than CFC-12 and HFC-134a. Experimental results show that the discharge temperatures of the studied azeotropic mixtures are lower than those of the pure refrigerants, CFC-12 and HCFC-22.

  15. Performance of Pentaborane, Pentaborane - JP-4 Fuel Mixtures, and Trimethylborate Azeotrope Fuel in a Full-scale Turbojet Engine

    NASA Technical Reports Server (NTRS)

    Breitwiesser, Roland; Useller, James W.

    1956-01-01

    This report summarizes the full-scale engine tests of pentaborane, pentaborane - JP-4 fuel mixtures, and trimethylborate azeotrope fuel. The tests were conducted in a full-scale turbojet engine at a simulated altitude of 50,000 feet and Mach number of 0.08. Engine speeds were 90 to 100 percent of rated speed. Pentaborane reduced the the specific fuel consumption to two-thirds that of JP-4 fuel. However, because boron oxide collected in the engine, the performance deteriorated with continued operation of pentaborane in each of the short-duration tests reported.

  16. Theoretical Consideration on the Characteristics and the Performance Evaluation for a Heat Pump Cycle of Non-azeotropic Refrigerant Mixtures

    NASA Astrophysics Data System (ADS)

    Fujii, Tetsu; Koyama, Shigeru; Miyara, Akio

    The present paper treats a possibility of performance improvement and its evaluation method for a heat pump cycle of non-azeotropic refrigerant mixtures. Calculation is made for R22 + R114 and R22 + R11 mixtures under the conditions that the inlet temperature and flow rates of heat source fluids through a condenser and an evaporator of counter flow type, heat pump thermal output and FK-value (heat transfer area times average overall heat transfer coefficient) are given. It is graphically shown that the coefficient of performance (COP)h, pressures and volumetric flow rates at suction and discharge ports of a compressor depend on the FK-value and on the flow rate of heat source fluid as well as mixture composition. The characteristics of the heat pump cycle thus obtained are markedly different from those, in which the state points of the refrigerant mixture are fixed.

  17. 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...

  18. Electroosmotic Membrane Pump for the separation of water from azeotropic mixtures. Technical progress report, Phase 1

    SciTech Connect

    Lundstrom, J.E.

    1986-03-01

    The Electroosmotic Membrane (EOM) Pump is proposed as a process for saving energy during the separation of azeotropes of alcohol and water. The process is electrically driven and removes water from the process stream through ion-selective membranes by electroosmosis. A laboratory-scale Model Cell was constructed to test the EOM pump concept using commercially available ion exchange membranes. Tests were performed with the Model Cell at various (1) alcohol-water compositions, (2) feed molalities of lithium chloride and lithium bromide in water, (3) stack temperatures, and (4) other operating conditions, such as stack configuration and membrane thickness. As part of the integration of the EOM pump and distillation processes, the effect of salt injection into the reflux line of the distillation column was studied. A conclusion of the study is that the overhead composition can be substantially enriched in alcohol to essentially anhydrous alcohol with salt addition.

  19. Reliable computation of homogeneous azeotropes

    SciTech Connect

    Maier, R.W.; Brennecke, J.F.; Stadtherr, M.A.

    1998-08-01

    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 any and all homogeneous azeotropes for multicomponent mixtures is presented. The method also verifies the nonexistence of homogeneous azeotropes if none are present. The method is based on interval analysis, in particular an interval-Newton/generalized-bisection-algorithm providing a mathematical and computational guarantee that all azeotropes are located. This general-purpose technique can be applied in connection with any thermodynamic models. The technique is illustrated in several example problems using the Wilson, NRTL, and UNIQUAC activity-coefficient models.

  20. Two-Phase Flow and Energy Transfer of a Non-Azeotropic Mixture, R-407c, in a Micro-Fin Tube

    NASA Astrophysics Data System (ADS)

    Liu, Xin

    1996-11-01

    This study is to determine experimentally the two-phase flow and energy transfer characteristics of a non-azeotropic refrigerant mixture, R-407c (nominal composition: 23% R-32, 25% R-125, and 52% R-134a). R-407c is a fluid with zero ozone depletion potential and one of several alternatives to currently widely used pure refrigerant HCFC-22. As a non-azeotrope, R-407c has distinctly different characteristics from pure fluids. The phase change of a non-azeotrope under constant pressure does not proceed at a constant temperature but rather over a range of temperature. In addition, the momentum, energy transfer, and mass transfer processes are closely linked. The vapor-liquid interfacial mass transfer rate limits the evaporation or condensation rate, and in turns limits the energy transfer rate. The experiments are conducted in a test apparatus with a fluid sampling port to monitor the composition change of the mixture. The test section consists of six horizontal identical passes, constructed as double tube heat exchangers. Each pass is about 2.2 m long and are connected in order by 7.6 cm radius U-bends. The heated or cooled section of each pass is shorter than the pass length and is 1.8 meter long. The inner (mixture) tube of the test section is a nominal 3/8" inch (9.5 mm) copper tube of 0.348 mm wall thickness with 72 axial fins of 0.185 mm height on its inner surface. The apex angle of the fins is 15 deg. and the helix angle is 0. The annulus-side water, serving as heat source (evaporating mode) or heat sink (condensing mode), flows through the annular space between inner and outer tubes. The tests are conducted at 100 deg F dew point temperature and mass flux from 192,000 to 818,000 lb/hr-ft^2 for condensing, and 50 deg F dew point and mass flux from 70,000 to 394,000 lb/hr-ft^2 for evaporating. The experimental results show that, compared to R-22, two-phase flow frictional pressure gradients of R-407c are about 10% less than R-22. Due to the mass transfer resistance, its condensing coefficients are 15% to 30% lower and its evaporating coefficients are about 20% lower, relative to R-22.

  1. Evaluation of a locus of azeotropes by molecular simulation

    SciTech Connect

    Pandit, S.P.; Kofke, D.A.

    1999-10-01

    The technique proposed here for the evaluation of azeotrope lines by molecular simulation builds on ideas used to devise the Gibbs-Duhem integration (GDI) technique for evaluating phase equilibria by molecular simulation. Beginning with a known azeotropic state point, the method integrates a differential equation for the locus of azeotropes with a single semigrand-ensemble molecular simulation performed at each integration state point. Unlike the standard GDI method, fluctuation quantities are needed to conduct the integration. Although these quantities are measured less precisely than simple ensemble averages, the integration is not adversely affected by this difficulty. The method is demonstrated by applying to three model Lennard-Hones binaries. Among these mixtures in one in which the molecular diameter o one species is varied along the azeotrope line. This application shows how details of the intermolecular interactions affect azeotropic behavior. Such an understanding might be useful in formulating additives to break an azeotrope.

  2. 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)

  3. Spectra and structure of binary azeotropes VI-benzene-methanol

    NASA Astrophysics Data System (ADS)

    Jalilian, M. R.; Tayyari, S. F.

    2009-09-01

    Benzene and methanol make a minimum boiling point homogeneous binary azeotrope with the mole ratio 2:3. Some characteristic vibrational modes, as well as 1H NMR signals change due to the azeotrope formation. The extend of interaction of these molecules causes significant changes on some vibrational modes involved, and 1H NMR signals show some changes on their position. No IR, Raman, and NMR spectra have been reported for this constant boiling mixture, also there has not been any attempt to investigate the unit-structure of this azeotrope. In this work the FTIR, FT-Raman, and 1H NMR spectra of pure benzene, pure methanol, and corresponding azeotrope were recorded, mutual influences resulting from azeotrope formation have been analyzed, and spectral changes has been discussed. The unit-structure of cluster has been deduced based on mole ratio, boiling point depression of constituents, and comparison among the spectra obtained by FTIR, FT-Raman, and 1H NMR techniques.

  4. Application of the QSPR approach to the boiling points of azeotropes.

    PubMed

    Katritzky, Alan R; Stoyanova-Slavova, Iva B; Tämm, Kaido; Tamm, Tarmo; Karelson, Mati

    2011-04-21

    CODESSA Pro derivative descriptors were calculated for a data set of 426 azeotropic mixtures by the centroid approximation and the weighted-contribution-factor approximation. The two approximations produced almost identical four-descriptor QSPR models relating the structural characteristic of the individual components of azeotropes to the azeotropic boiling points. These models were supported by internal and external validations. The descriptors contributing to the QSPR models are directly related to the three components of the enthalpy (heat) of vaporization. PMID:21449551

  5. Spectra and structure of binary azeotropes VI-benzene-methanol.

    PubMed

    Jalilian, M R; Tayyari, S F

    2009-09-01

    Benzene and methanol make a minimum boiling point homogeneous binary azeotrope with the mole ratio 2:3. Some characteristic vibrational modes, as well as (1)H NMR signals change due to the azeotrope formation. The extend of interaction of these molecules causes significant changes on some vibrational modes involved, and (1)H NMR signals show some changes on their position. No IR, Raman, and NMR spectra have been reported for this constant boiling mixture, also there has not been any attempt to investigate the unit-structure of this azeotrope. In this work the FTIR, FT-Raman, and (1)H NMR spectra of pure benzene, pure methanol, and corresponding azeotrope were recorded, mutual influences resulting from azeotrope formation have been analyzed, and spectral changes has been discussed. The unit-structure of cluster has been deduced based on mole ratio, boiling point depression of constituents, and comparison among the spectra obtained by FTIR, FT-Raman, and (1)H NMR techniques. PMID:19477679

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Enzymatic synthesis of sorbitan esters using a low-boiling-point azeotrope as a reaction solvent.

    PubMed

    Sarney, D B; Barnard, M J; Virto, M; Vulfson, E N

    1997-05-20

    Sorbitan esters were prepared by controlled dehydration of sorbitol followed by lipase-catalyzed esterification of the resulting "sorbitan." The reaction was carried out in azeotropic mixtures of tert-butanol/n-hexane. A partial phase diagram to determine the temperature required for the distillation of the azeotrope at a given ratio of the solvents was constructed. The effect of varying concentrations of the two solvents on the rate of esterification and the monoester/diester ratio of the final product was investigated in detail. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 54: 351-356, 1997. PMID:18634102

  13. 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.

  14. 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...

  15. Hetero-azeotropic distillation: combining fungal dehydration and lipid extraction.

    PubMed

    Tough, A J; Isabella, B L; Beattie, J E; Herbert, R A

    2000-01-01

    A low-cost single-stage laboratory process combining fungal dehydration and lipid extraction was compared with a traditional two-stage method employing freeze-drying and subsequent mechanical disruption in the presence of solvent. The ability of a number of organic solvents to form hetero-azeotropes with water was exploited. Chloroform, cyclohexane and hexane were assessed in their abilities to both dry and extract lipid from the oleaginous phycomycete Mortierella alpina (ATCC 32222). Drying rate and lipid extraction were maximised under conditions that prevented fungal agglomeration. The total processing time was limited by the rate of dehydration rather than by the rate of lipid extraction. In all cases azeotropic distillation facilitated a greater rate of dehydration than was possible with freeze-drying. A consequent reduction in overall processing time was observed. Uniquely, both the solvent used and the mode of mixing employed controlled the morphology of the aggregates formed during distillation. In combination with mild mixing chloroform discouraged agglomeration whereas cyclohexane and hexane promoted aggregation. Successful lipid extraction was dependent on the use of dry biomass rather than on the application of heat to effect distillation. Neither the application of heat nor the solvent employed had any significant effect on the lipid composition of the extracted oil. PMID:16232815

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

    PubMed

    Starkl Renar, K; Pe?ar, 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

  17. Spectra and structure of binary azeotropes IV. Acetone-cyclohexane.

    PubMed

    Jalilian, M R

    2008-03-01

    Acetone and cyclohexane make a binary azeotrope with mole ratio 3:1. Some characteristic vibrational modes of acetone and cyclohexane change due to the azeotrope formation. The extend of interaction of these molecules causes significant changes on vibrational modes involved, and (1)H NMR signals show some changes on their position. FTIR and (1)H NMR spectra of pure substances and corresponding azeotrope were recorded, mutual influences resulting from azeotrope formation have been analyzed, spectral changes have been discussed. The unit-structure of cluster were deduced based on mole ratio, boiling point depression of constituents and comparison between spectra obtained by FTIR and (1)H NMR techniques. PMID:17644469

  18. Spectra and structure of binary azeotropes. I. Acetone-chloroform

    NASA Astrophysics Data System (ADS)

    Jalilian, M. R.; Alibabaei, L.

    2005-11-01

    Some characteristic vibrational modes of acetone and chloroform change due to the azeotrope formation. The extend of interaction of these molecules has significant effects on some vibrational modes involved, depending on unit structure in azeotrope cluster. Besides 1H NMR signals undergo some chemical shifts, which show the effect of oncoming molecules on the target molecule. FT-IR and 1H NMR spectra of pure substances and corresponding azeotrope were recorded, mutual influences due to azeotrope formation based on mole ratio, boiling point and spectral changes has been discussed. Unit structure of cluster deduced by investigating fundamental frequency shifts and 1H NMR chemical shifts.

  19. Spectra and structure of binary azeotropes I. Acetone-chloroform.

    PubMed

    Jalilian, M R; Alibabaei, L

    2005-11-01

    Some characteristic vibrational modes of acetone and chloroform change due to the azeotrope formation. The extend of interaction of these molecules has significant effects on some vibrational modes involved, depending on unit structure in azeotrope cluster. Besides (1)H NMR signals undergo some chemical shifts, which show the effect of oncoming molecules on the target molecule. FT-IR and (1)H NMR spectra of pure substances and corresponding azeotrope were recorded, mutual influences due to azeotrope formation based on mole ratio, boiling point and spectral changes has been discussed. Unit structure of cluster deduced by investigating fundamental frequency shifts and (1)H NMR chemical shifts. PMID:16257732

  20. Spectra and structure of binary azeotropes. IV. Acetone-cyclohexane

    NASA Astrophysics Data System (ADS)

    Jalilian, M. R.

    2008-03-01

    Acetone and cyclohexane make a binary azeotrope with mole ratio 3:1. Some characteristic vibrational modes of acetone and cyclohexane change due to the azeotrope formation. The extend of interaction of these molecules causes significant changes on vibrational modes involved, and 1H NMR signals show some changes on their position. FTIR and 1H NMR spectra of pure substances and corresponding azeotrope were recorded, mutual influences resulting from azeotrope formation have been analyzed, spectral changes have been discussed. The unit-structure of cluster were deduced based on mole ratio, boiling point depression of constituents and comparison between spectra obtained by FTIR and 1H NMR techniques.

  1. 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.

  2. EFFECTS IN HUMANS OF A VOLATILE ORGANIC COMPOUND MIXTURE: SENSORY

    EPA Science Inventory

    Time-course actions for symptoms of the sick building syndrome were derived from 66 healthy males exposed to clean air and a volatile organic (VOC) mixture in separate sessions. he mixture contained 22 VOCs (25 mg/m3 total concentration) commonly found air-borne in new or recentl...

  3. 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.

  4. 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 higher component systems and it can be easily incorporated into compositional multiphase flow models using only parameters from ternary systems.

  5. Spectra and structure of binary azeotropes V-acetone-cyclopentane

    NASA Astrophysics Data System (ADS)

    Jalilian, M. R.; Zahedi-Tabrizi, Mansoureh

    2008-01-01

    Acetone and cyclopentane make a minimum boiling homogeneous binary azeotrope with mole ratio 2:3. Some characteristic vibrational modes, as well as 1H NMR signals change due to the azeotrope formation. The extend of interaction of these molecules causes significant changes on some vibrational modes involved and 1H NMR signals show some changes on their position. In this work the FTIR and 1H NMR spectra of pure acetone, pure cyclopentane and corresponding azeotrope were recorded, mutual influences resulting from azeotrope formation have been analyzed, and spectral changes has been discussed. The unit-structure of cluster have been deduced, based on mole ratio, boiling point depression of constituents, and comparison between the spectra obtained by FTIR and 1H NMR techniques.

  6. Spectra and structure of binary azeotropes V-acetone-cyclopentane.

    PubMed

    Jalilian, M R; Zahedi-Tabrizi, Mansoureh

    2008-01-01

    Acetone and cyclopentane make a minimum boiling homogeneous binary azeotrope with mole ratio 2:3. Some characteristic vibrational modes, as well as (1)H NMR signals change due to the azeotrope formation. The extend of interaction of these molecules causes significant changes on some vibrational modes involved and (1)H NMR signals show some changes on their position. In this work the FTIR and (1)H NMR spectra of pure acetone, pure cyclopentane and corresponding azeotrope were recorded, mutual influences resulting from azeotrope formation have been analyzed, and spectral changes has been discussed. The unit-structure of cluster have been deduced, based on mole ratio, boiling point depression of constituents, and comparison between the spectra obtained by FTIR and (1)H NMR techniques. PMID:17521957

  7. PREDICTIONS OF AZEOTROPES FORMED FROM FLUORINATED ETHERS, ETHANES, AND PROPANES

    EPA Science Inventory

    The paper discusses an evaluation of the potential for azeotrope formation and performance for fluorinated ethers, ethanes, and propanes. (NOTE: The synthesis of new non-chlorinated refrigerants expands the base of alternatives for replacing ozone-depleting chlorofluorocarbons (O...

  8. Synthesis of Amorphous Monomeric Glass Mixtures for Organic Electronic Applications.

    PubMed

    Wu, You-Chi Mason; Molaire, Michel F; Weiss, David S; Angel, Felipe A; DeBlase, Catherine R; Fors, Brett P

    2015-12-18

    We report a divergent synthetic strategy and novel design concept that exploit molecular mixtures to create amorphous organic charge-transporting glasses. Using Suzuki-Miyaura cross-coupling reactions, we synthesized well-defined molecular mixtures in a single step. These solution-processable materials are noncrystalline and show good thermal and morphological stabilities. Moreover, they have robust hole and electron mobilities, which make them excellent candidate materials for organic light-emitting diodes. Our general strategy enables the facile synthesis of noncrystalline materials with well-controlled electronic properties. PMID:26560445

  9. 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.

  10. ACUTE TOXICITY OF ORGANIC CHEMICAL MIXTURES TO THE FATHEAD MINNOW

    EPA Science Inventory

    The acute joint toxicity of industrial organic chemicals to the fathead minnow was determined for binary and equitoxic multiple chemical mixtures. Results from binary tests were used to define isobole diagrams. The degree of joint toxic action was determined among 27 chemicals fr...

  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. 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. PMID:26428097

  13. Toxicity of thiocyanate, phenol, and their mixtures to freshwater aquatic organisms: A mixture modeling approach

    SciTech Connect

    Soboslay, E.G.

    1987-01-01

    Thiocyanate and phenol are two environmentally significant constituents of wastewater streams from coke production plants and coal conversion facilities. Acute and chronic toxicity experiments were conducted for thiocyanate and phenol with Daphnia magna at 20 C and Ceriodaphnia affinis/dubia at 25C in hard water to study their individual toxic effects on survival and reproduction. Statistical analysis of the dose response relationships for the individual chemicals indicated the type of combined effects that occur when thiocyanate and phenol are present simultaneously. Mixture models for toxicant interaction were used to predict joint toxic effects on survival and reproduction. The applicability of the mixture model was tested by performing joint toxicity experiments for specific thiocyanate and phenol mixtures to verify the model for toxic effects on specific whole organism performances. Neonate production and hatchability, two indices of reproduction, were selected to evaluate the chronic toxic effects of thiocyanate and phenol. The resulting dose response curves for mixtures were compared to curves predicted on the basis of the mathematical model for concentration addition. Low concentrations of thiocyanate, phenol and their mixtures generally caused a stimulation effect on D. magna and C. affinis/dubia reproduction.

  14. 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.

  15. 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.

  16. Survey of Binary Azeotropes as Physical Chemistry Lab Experiments with Attention to Cost, Safety, and the Environment

    NASA Astrophysics Data System (ADS)

    Glinski, Robert J.; Smith, Christopher W.; Cooke, Jason B.

    1999-02-01

    A survey is presented of possible binary azeotropic systems suitable for study in an undergraduate physical chemistry laboratory. From a range of sources, a list has been compiled of the most acceptable systems on the basis of health, safety, waste disposal, and practicability concerns. More than 80 systems were reviewed. For comparison purposes, the list was reduced to a table showing 5 high-boiling and 19 low-boiling azeotropes with their exposure limits, approximate costs, and some physical properties of the mixtures. Comments are made about the strengths and weaknesses of the choice of each. The paper should supply the instructor with sufficient data to choose a binary system for study and with literature sources for further information.

  17. 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.

  18. 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.

  19. 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.

  20. Adsorption of chromate/organic-acid mixtures in aquifer materials

    SciTech Connect

    Fish, W.; Palmer, C.D.

    1991-07-15

    The overall objective of this project is to develop a fuller understanding of the interactions of mixtures of anionic co-contaminants with oxide-mineral surfaces. Our specific focus is on the competitive interactions of chromate and oxalic acid on ferric oxyhydroxide and on natural aquifer materials. Chromate and oxalate are of practical interest as widespread contaminants at many DOE facilities. However, these anions also are excellent model adsorbates for elucidating fundamental aspects of ionic adsorption processes, particularly with respect to organic acids.

  1. Toxicity assessment of organic contaminants: evaluation of mixture effects in model industrial mixtures using 2n full factorial design.

    PubMed

    Parvez, Shahid; Venkataraman, Chandra; Mukherji, Suparna

    2008-10-01

    Toxic organic chemicals present in industrial effluents were screened to design mixtures for examining the significant main and interaction effects among mixture components. A set of five four-component mixtures was selected by examining effluents from organic chemical, textile-dye, pulp-paper and petroleum refinery industries. The screening was based on their discharge, solubility, toxicity and volatility. A 2(n) full factorial approach was used in designing the mixtures, containing components at two dose levels, EC(10)(-) and EC(40)(+). Each mixture resulted in 16 combinations. Mixture toxicity was measured using the Vibrio fischeri bioluminescence inhibition assay. The main effects and binary, ternary and quaternary interaction effects were determined and the significance of effects was evaluated using normal order score and multifactor ANOVA. The organic chemicals retained after screening included, acetaldehyde, aniline, n-butanol, p-cresol, catechol, ethylbenzene, naphthalene, phenol, 1,2,4 trimethylbenzene and o-xylene. In all mixtures, the magnitude of main effects was more significant than the interaction effects. The trend in the main effect of components in any mixture was affected by the trends in the physico-chemical properties of the components, i.e., partition coefficient, molecular size and polarity. In some mixtures, a component with significantly higher concentration and significantly lower toxicity was found to depict a relatively high main effect, as observed for acetaldehyde in mixture I and n-butanol in mixture III. Normal order score approach failed to identify the significant interaction effects that could be identified using multifactor ANOVA. In general, the binary interactions were more significant than the ternary and quaternary interactions. PMID:18789476

  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 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

  5. 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.

  6. Equilibrium liquid-vapor diagrams of ternary systems with three azeotropes

    NASA Astrophysics Data System (ADS)

    Raeva, V. M.; Serafimov, L. A.; Stepanov, V. N.

    2013-07-01

    Forty-nine classes involving 222 types of ternary liquid-vapor systems with three azeotropes are revealed. The place of three-azeotrope systems in the thermodynamic classification of binary solutions is determined. Examples of phase portraits of liquid-vapor equilibrium with three azeotropes in various elements of the concentration triangle (binary components, internal region, and binary components and the internal region) are presented.

  7. THERMODYNAMIC EVALUATION OF PREDICTED FLUORINATED ETHER, ETHANE, AND PROPANE AZEOTROPES

    EPA Science Inventory

    The paper gives results of thermodynamic analyses, using basic thermophysical property data, to evaluate seven predicted fluorinated ether, ethane, and propane azeotropes: E125/RC270, E125/R134a, E143a/R134, R134a/E143a, E143a/ R152a, R134/R245cb, and R245cb/R227ea. he performanc...

  8. Spectra and structure of binary azeotropes. II. Acetone- n-pentane

    NASA Astrophysics Data System (ADS)

    Jalilian, M. R.

    2007-01-01

    Acetone and n-pentane from an azeotrope with the mole ratio of 1:3, respectively. As the result of this azeotrope formation, some characteristic vibrational modes in FT-IR and chemical shifts in 1H NMR changes. The amount of these band and signal changes is an indication of the extend of interaction between two components and their orientation in unit structure of the cluster. FT-IR and 1H NMR spectra of pure substances and their azeotrope were recorded, spectral changes analyzed. Unit structure of azeotrope was deduced based on mole ratio, boiling point changes of pure components, and spectral changes in fundamental frequency and chemical shifts.

  9. Rotary drum composting of different organic waste mixtures.

    PubMed

    Kalamdhad, Ajay S; Kazmi, Absar A

    2009-03-01

    The effects of three different mixtures of organic waste on composting in a rotary drum were examined by measuring changes in physico-chemical and biological parameters. It was observed that the time courses of the three mixtures: run A (grass cuttings, vegetable waste and food waste), run B (cattle manure, vegetable waste and sawdust) and run C (cattle manure, food waste, vegetable waste, paper waste and sawdust) were quite diverse. Run B, with initial C/N ratio 22 and containing a large proportion of cattle manure produced high quality and mature compost within 20 days. It showed a final total nitrogen (2.1%), final total phosphorus 3.52 g kg(-1), final total organic carbon (TOC) (24.8%) and final moisture content (44%). At the end of 20 days, higher degradation led to final chemical oxygen demand (COD) (454 mg L(- 1)), biochemical oxygen demand (BOD) (107 mg L(- 1)), fecal coliform (1.2 x 10(2) bacteria g(- 1)), fecal streptococci (85 bacteria g(-1)) and low electrical conductivity (1.658 dS m(-1)), respectively. Furthermore, run C with initial C/N ratio of 30 and containing a larger amount of food and vegetable waste produced good quality compost and resulted in 4.34% total nitrogen and 2.42% total phosphorus after 20 days, but, it had higher final fecal coliform 2.5 x 10(4) bacteria g( -1), fecal streptococci 2.1 x 10(4) bacteria g(-1), high TOC and NH(4)-N and a BOD/COD ratio of 0.63, which rendered it hygienically unsafe and immature. Finally, run A with initial C/N ratio of 15 showed a higher amount of EC (4.84 dS m(-1)), NH(4)-N, BOD/COD ratio of 0.4 with 15% nitrogen loss, which indicated an unstable product even after 20 days of composting. Therefore, it was found that rotary drum composting of a combination of cattle manure, vegetable waste and sawdust resulted in a primary stabilized compost within 20 days of composting. PMID:19244412

  10. 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.

  11. Behavioural evaluation of workers exposed to mixtures of organic solvents.

    PubMed Central

    Maizlish, N A; Langolf, G D; Whitehead, L W; Fine, L J; Albers, J W; Goldberg, J; Smith, P

    1985-01-01

    Reports from Scandinavia have suggested behavioural impairment among long term workers exposed to solvents below regulatory standards. A cross sectional study of behavioural performance was conducted among printers and spray painters exposed to mixtures of organic solvents to replicate the Scandinavian studies and to examine dose-response relationships. Eligible subjects consisted of 640 hourly workers from four midwestern United States companies. Of these, 269 responded to requests to participate and 240 were selected for study based on restrictions for age, sex, education, and other potentially confounding variables. The subjects tested had been employed on average for six years. Each subject completed an occupational history, underwent a medical examination, and completed a battery of behavioural tests. These included the Fitts law psychomotor task, the Stroop colour-word test, the Sternberg short term memory scanning test, the short term memory span test, and the continuous recognition memory test. Solvent exposure for each subject was defined as an exposed or non-exposed category based on a plant industrial hygiene walk-through and the concentration of solvents based on an analysis of full shift personal air samples by gas chromatography. The first definition was used to maintain consistency with Scandinavian studies, but the second was considered to be more accurate. The average full shift solvent concentration was 302 ppm for the printing plant workers and 6-13 ppm for the workers at other plants. Isopropanol and hexane were the major components, compared with toluene in Scandinavian studies. Performance on behavioural tests was analysed using multiple linear regression with solvent concentration as an independent variable. Other relevant demographic variables were also considered for inclusion. No significant (p greater than 0.05) relation between solvent concentration and impairment on any of the 10 behavioural variables was observed after controlling for confounding variables. Exposed/non-exposed comparisons showed a significantly poorer digit span among those exposed, but this has not been generally reported in the Scandinavian studies. The medical examination showed no abnormalities of clinical significance. The inability to replicate the findings of the Scandinavian studies could have been due to the shortness of the duration of workers' exposure, the type of solvents in the mixtures, use of different behavioural tests, or to selection factors. PMID:3876109

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

    EPA Science Inventory

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

  13. 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. PMID:24632362

  14. Retention capacity of an organic bio-mixture against different mixtures of fungicides used in vineyards.

    PubMed

    Monaci, Elga; Coppola, Laura; Casucci, Cristiano; Perucci, Piero; Vischetti, Costantino

    2009-09-01

    A laboratory experiment was carried out to test the efficiency of a bio-mixture made up of pruning residues at two (PR2) and five (PR5) years of composting and wheat straw (STW) in the biological cleaning of water contaminated by different mixtures of fungicides usually employed in vineyards. The experiment was conducted and reproduced at a scale of 1:100 of operating field conditions. Commercial formulates of penconazole (PC), (RS)-1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole), dimetomorph (DM), (EZ)-4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloyl]morpholine), azoxystrobin (AZ), (methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate), iprovalicarb (IP), (isopropyl 2-methyl-1-[(RS)-1-p-tolylethyl]carbamoyl-(S)-propylcarbamate), metalaxyl (MX), (methyl N-(methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate), fludioxonil (FL), (4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile) and cyprodinil (CY), (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine) were mixed in water and discharged into the bio-mixture following the time schedule of the treatments carried out in the grapevine in real field conditions. At each treatment, contaminated water with fungicides was circulated repeatedly through the bio-mixture to enhance the sorption of fungicides. In fact, it retained them between 98-100% with the exception of MX of which it was able to retain only 90.5%. The adsorption/desorption experiment showed that repeated circulation of water, instead of enhancing MX retention, can easily remove about 30% of MX already adsorbed by the bio-mixture. This finding suggests that water contaminated by very mobile pesticides should be discharged at the end of field treatments without re-circulating the water in order to avoid the release of pesticides weakly adsorbed on the bio-mixture. PMID:20183083

  15. Biodegradation of a mixture of chlorinated volatile organic compounds

    SciTech Connect

    Barnes, L.J.W.; Daniel, S.R.; Warner, J.B.

    1997-12-31

    A mixture of vinyl chloride, cis- and trans-1,2-dichloroethene (DCE), and 1,1-dichloroethane (DCA) was biodegraded at 20 C in static microcosms by a consortium of indigenous microorganisms from a Superfund site contaminated with a variety of halogenated compounds. Microcosms were set up with sand and groundwater from the site to model biodegradation under aquifer conditions and biodegradation with various amendments in batch cultures. Under aerobic conditions, vinyl chloride and cis- and trans-1,2-DCE biodegraded slowly, although there was no change in the concentration of 1,1-DCA. The biodegradation rates for all three chlorinated ethenes were greatly increased by enriching for methanotrophs in an aerobic environment, but this had little effect on the concentration of 1,1-DCA. DCA and the dichloroethene isomers decreased. The rate at which 1,1-DCA decreased from the VOC mixture correlated directly to the concentration of the chlorinated ethenes in that mixture. This relationship may be new in the literature and has important implications for the potential success for intrinsic bioremediation of sites contaminated with mixtures of chlorinated compounds.

  16. 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.

  17. 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 ...

  18. Spectra and structure of binary azeotropes. III. Acetone- n-hexane

    NASA Astrophysics Data System (ADS)

    Jalilian, M. R.

    2007-04-01

    Acetone and n-hexane form an azeotrope with the mole ratio 2:1. As a result of this phenomenon, some characteristic vibrational modes in FT-IR and some chemical shifts in 1H NMR spectra changes. The amount of these changes is an indication of the extension of interaction between two components and their orientation in unit structure of the cluster. FT-IR and 1H NMR spectra of pure substances and their azeotrope were recorded and spectral changes analyzed. Based on mole ratio of constituents, boiling point depressions, spectral changes in fundamental frequencies, and chemical shifts, unit structure of the azeotrope were deduced.

  19. Spectra and structure of binary azeotropes. III. Acetone-n-hexane.

    PubMed

    Jalilian, M R

    2007-04-01

    Acetone and n-hexane form an azeotrope with the mole ratio 2:1. As a result of this phenomenon, some characteristic vibrational modes in FT-IR and some chemical shifts in 1H NMR spectra changes. The amount of these changes is an indication of the extension of interaction between two components and their orientation in unit structure of the cluster. FT-IR and 1H NMR spectra of pure substances and their azeotrope were recorded and spectral changes analyzed. Based on mole ratio of constituents, boiling point depressions, spectral changes in fundamental frequencies, and chemical shifts, unit structure of the azeotrope were deduced. PMID:16920003

  20. 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...

  1. Parameters for the Pyrolysis of Organic Material - Perchlorate Mixtures

    NASA Astrophysics Data System (ADS)

    Steininger, Harald; Goesmann, Fred; Goetz, Walter

    2013-04-01

    The ESA-lead Mars rover ExoMars (launch in 2018) will carry a suit of instruments, one of the in-struments is the Mars Organic Molecule Analyzer MOMA. Organic material in the Martian soil will be either pyrolyzed at temperatures of up to 1000°C and separated by gas chromatography or volatilized with the help of an UV-laser. A mass spectrometer will be the detector for both methods. Chlorinated organics have been detected in pyroly-sis GC-MS experiments on Mars two times. The first time during the Viking mission in 1976 and a second time with the Sample Analysis on Mars (SAM) in-strument onboard the Curiosity rover in 2012. [1] [2] The presence of perchlorates found by the Phoenix mission in 2008 [3] lead to the discovery that organic molecules not only get oxidized during pyrolysis, but also chlorinated organic compounds can be pro-duced. [4] The parameters used for pyrolysis and the sample composition especially the distribution of organics and perchlorates within the sample and the concentrations of organics and perchlorate have a huge influence on the products created. It is possible to change the condi-tions of the pyrolysis by spatially separating the organ-ics from the perchlorates that the chloromethanes get the major product of the pyrolysis. This might help to understand the results of the (SAM) instrument yield-ing mono-, di- and trichloromethane and a chlorinated 4-hydrocarbon molecule. References: [1] Biemann K et al. (1977) JGR, 82, 4641-4658. [2] Grotzinger J. P et al. (2011) AGU Fall Meeting U13A-01 [3] Hecht M. H., et al. (2009) Science, 325 64-67. [4] Steininger H., Goesmann F., Goetz W. (2011) Planet. & Space Sci., 71, 9-17. Acknowledgments: This work was funded by DLR (FKZ 50QX1001)

  2. 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.

  3. ODOR AND IRRITATION EFFECTS OF A VOLATILE ORGANIC COMPOUND MIXTURE

    EPA Science Inventory

    Human exposure to volatile organic compounds elicits a variety ofsymptoms, many of which are thought to be mediated by the olfactoryand trigeminal systems. his report describes evidence indicatingthat perceived odor intensity diminishes during prolonged exposure,whearas irritatin...

  4. Spectra and structure of binary azeotropes II. Acetone-n-pentane.

    PubMed

    Jalilian, M R

    2007-01-01

    Acetone and n-pentane from an azeotrope with the mole ratio of 1:3, respectively. As the result of this azeotrope formation, some characteristic vibrational modes in FT-IR and chemical shifts in 1H NMR changes. The amount of these band and signal changes is an indication of the extend of interaction between two components and their orientation in unit structure of the cluster. FT-IR and 1H NMR spectra of pure substances and their azeotrope were recorded, spectral changes analyzed. Unit structure of azeotrope was deduced based on mole ratio, boiling point changes of pure components, and spectral changes in fundamental frequency and chemical shifts. PMID:16807080

  5. Dynamics and control of a heterogeneous azeotropic distillation column: Conventional control approach

    SciTech Connect

    Chien, I.L.; Wang, C.J.; Wong, D.S.H.

    1999-02-01

    In this work, bifurcation analysis and dynamic simulation were used to investigate the optimum conventional control strategy of an isopropyl alcohol (IPA), cyclohexane (CyH), and water (H{sub 2}O) heterogeneous azeotropic column. Steady-state process analysis shows that the optimal operation point should be located at a critical reflux, a transition point at which the distillation path switches from a route that passes through the IPA + H{sub 2}O azeotrope to one that passes through the IPA + CyH azeotrope. A good control strategy must be able to maintain a steady column temperature profile that shows a plateau near 70 C to ensure passage around the IPA + CyH azeotrope. An inverse double-loop control strategy is proposed based on principal component analysis. This scheme is capable of maintaining the desired column temperature profile given all kinds of feed disturbances, thus keeping the product IPA purity at the desired level.

  6. 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.

  7. Nature and prevalence of non-additive toxic effects in industrially relevant mixtures of organic chemicals.

    PubMed

    Parvez, Shahid; Venkataraman, Chandra; Mukherji, Suparna

    2009-06-01

    The concentration addition (CA) and the independent action (IA) models are widely used for predicting mixture toxicity based on its composition and individual component dose-response profiles. However, the prediction based on these models may be inaccurate due to interaction among mixture components. In this work, the nature and prevalence of non-additive effects were explored for binary, ternary and quaternary mixtures composed of hydrophobic organic compounds (HOCs). The toxicity of each individual component and mixture was determined using the Vibrio fischeri bioluminescence inhibition assay. For each combination of chemicals specified by the 2(n) factorial design, the percent deviation of the predicted toxic effect from the measured value was used to characterize mixtures as synergistic (positive deviation) and antagonistic (negative deviation). An arbitrary classification scheme was proposed based on the magnitude of deviation (d) as: additive (< or =10%, class-I) and moderately (10< d < or =30 %, class-II), highly (30< d < or =50%, class-III) and very highly (>50%, class-IV) antagonistic/synergistic. Naphthalene, n-butanol, o-xylene, catechol and p-cresol led to synergism in mixtures while 1, 2, 4-trimethylbenzene and 1, 3-dimethylnaphthalene contributed to antagonism. Most of the mixtures depicted additive or antagonistic effect. Synergism was prominent in some of the mixtures, such as, pulp and paper, textile dyes, and a mixture composed of polynuclear aromatic hydrocarbons. The organic chemical industry mixture depicted the highest abundance of antagonism and least synergism. Mixture toxicity was found to depend on partition coefficient, molecular connectivity index and relative concentration of the components. PMID:19344929

  8. 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

  9. Complex mixtures of air pollutants: Characterizing the cancer risk of polycyclic organic matter

    SciTech Connect

    Lewtas, J. )

    1993-04-01

    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 biomark(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. 41 refs., 8 figs.

  10. Resolving detailed molecular structures in complex organic mixtures and modeling their secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Goodman-Rendall, Kevin A. S.; Zhuang, Yang R.; Amirav, Aviv; Chan, Arthur W. H.

    2016-03-01

    Characterization of unresolved complex mixtures (UCMs) remains an ongoing challenge towards developing detailed and accurate inputs for modeling secondary organic aerosol (SOA) formation. Traditional techniques based on gas chromatography/electron impact-mass spectrometry induce excessive fragmentation, making it difficult to speciate and quantify isomers precisely. The goal of this study is to identify individual organic isomers by gas chromatography/mass spectrometry with supersonic molecular beam (SMB-GC/MS, also known as GC/MS with Cold EI) and to incorporate speciated isomers into an SOA model that accounts for the specific structures elucidated. Two samples containing atmospherically relevant UCMs are analyzed. The relative isomer distributions exhibit remarkably consistent trends across a wide range of carbon numbers. Constitutional isomers of different alkanes are speciated and individually quantified as linear, branched - for the first time by position of branching - multiply branched, or unsaturated - by degree of ring substitution and number of rings. Relative amounts of exact molecular structures are used as input parameters in an SOA box model to study the effects of molecular structures on SOA yields and volatility evolution. Highly substituted cyclic, mono-substituted cyclic, and linear species have the highest SOA yields while branched alkanes formed the least SOA. The rate of functionalization of a representative UCM is found to be in agreement with current volatility basis set (VBS) parameterizations based on detailed knowledge of composition and known oxidation mechanisms, confirming the validity of VBS parameters currently used in air quality models.

  11. EXPOSURE OF HUMANS TO VOLATILE ORGANIC MIXTURE. III. INFLAMMATORY RESPONSE

    EPA Science Inventory

    A set of symptoms has been described during the past two decades which has been called the "sick building syndrome." hese symptoms include eye, nose, and throat irritation; headache; mental fatigue; and respiratory distress. t is likely that volatile organic compounds (VOC) prese...

  12. 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...

  13. FLY ASH ORGANIC BYPRODUCT MIXTURE AS SOIL AMENDMENTS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Greenhouse studies were conducted to assess the potential of fly ash-organic waste co-disposal to enhance crop production. Two pot experiments, one using Sorghum Sudangrass (Sorghum vulgaris) and other using Collard greens (Brassica olreraceae) were conducted under greenhouse conditions. In addition...

  14. 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...

  15. 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.

  16. [Rapid detection of chlorinated organic mixture by laser Raman spectroscopy].

    PubMed

    Ma, Jing

    2014-07-01

    In order to realize the rapid, nondestructive detection of organic compounds, a two-dimensional analysis method based on technology of laser Raman spectroscopy was proposed. The results show that using 532 nm laser as excitation light source, the observation of 236.2, 348.9, 449.4 and 513.6 cm(-1), the four vibrational Raman spectra, and the intensity ratio of 6.4 : 1.7: 9.4 : 1.0 can determine the existence of tetrachloroethylene. The observation of 707.5, 1 087.9, 1 175.8 and 3 078.6 cm(-1), the four vibrational Raman spectra, and the intensity ratio of 9.6 : 6.4 : 1.0 : 3.9 can determine the existence of chlorobenzene. In other words, that through the comprehensive study of spectral lines and intensity ratio of some spectral lines, the presence of organic compounds in the mixed solution can be determined quickly. In the aspect of quantitative analysis, using multi-spectral analysis combined with least square fitting method can improve the reliability of the measurement, The accuracy of sample concentration was 98.4%. This spectral measurement method is a potential tool for organic component identification and concentration analysis which has a prosperous application prospects. PMID:25269297

  17. Dependences between the boiling point of binary aqueous-organic mixtures and their composition

    NASA Astrophysics Data System (ADS)

    Preobrazhenskii, M. P.; Rudakov, O. B.

    2015-01-01

    The optimum three-parametric regression basis set that reflects the properties of permutation symmetry and takes into account the specificity of isobars of aqueous-organic mixtures is constructed. The optimum algorithm for the calculation of the regression parameters of the boiling point isobars is proposed. The parameters are calculated for a series of systems. The accuracy of the method proposed for the regression description of the dependence of the boiling point of binary aqueous-organic mixtures on the composition is determined by empirical inaccuracies and is sufficient for the most part of practical applications. Methods for increasing the accuracy of the regression description of equilibrium homogeneous systems are formulated.

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. PRENEOPLASTIC TRANSFORMATION OF RESPIRATORY EPITHELIAL CELLS BY COMPLEX ORGANIC MIXTURES IN A CLONAL ASSAY

    EPA Science Inventory

    In the study complex organic mixtures that were extracts of particulate emissions from 3 heating sources were tested for the presence of agents that induce preneoplastic transformation of rat tracheal epithelial (RTE) cells in an in vitro clonal assay. The samples were derived fr...

  3. MIXTURE EFFECTS IN THE CATALYTIC OXIDATION OF VOCS (VOLATILE ORGANIC COMPOUNDS) IN AIR

    EPA Science Inventory

    The report gives results of a study of the deep oxidation of organic mixtures over a heterogeneous catalyst in an attempt to explain earlier observations concerning the apparent inhibition or enhancement of destruction of some components to establish a scientific basis for the de...

  4. 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. PMID:24719347

  5. Lanolin-derived lipid mixtures mimic closely the lipid composition and organization of vernix caseosa lipids.

    PubMed

    Rissmann, Robert; Oudshoorn, Marion H M; Kocks, Elise; Hennink, Wim E; Ponec, Maria; Bouwstra, Joke A

    2008-10-01

    The aim of the present study was to use semi-synthetic lipid mixtures to mimic the complex lipid composition, organization and thermotropic behaviour of vernix caseosa (VC) lipids. As VC shows multiple protecting and barrier supporting properties before and after birth, it is suggested that a VC substitute could be an innovative barrier cream for barrier deficient skin. Lanolin was selected as the source of the branched chain sterol esters and wax esters--the main lipid classes of VC. Different lipid fractions were isolated from lanolin and subsequently mixed with squalene, triglycerides, cholesterol, ceramides and fatty acids to generate semi-synthetic lipid mixtures that mimic the lipid composition of VC, as established by high-performance thin-layer chromatography. Differential scanning calorimetry and Fourier transform infrared spectroscopy investigations revealed that triglycerides play an important role in the (lateral) lipid organization and thermotropic behaviour of the synthetic lipid mixtures. Excellent resemblance of VC lipids was obtained when adding unsaturated triglycerides. Moreover, these lipid mixtures showed similar long range ordering as VC. The optimal lipid mixture was evaluated on tape-stripped hairless mouse skin in vivo. The rate of barrier recovery was increased and comparable to VC lipid treatment. PMID:18655769

  6. 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 the previous model version. The new parameterisation of AIOMFAC agrees well with a large number of experimental datasets and enables the calculation of activity coefficients of a wide variety of different aqueous/water-free organic solutions down to the low temperatures present in the upper troposphere.

  7. Evidence for liquid-like and nonideal behavior of a mixture of organic aerosol components

    PubMed Central

    Cappa, Christopher D.; Lovejoy, Edward R.; Ravishankara, A. R.

    2008-01-01

    The condensation, evaporation, and repartitioning of semivolatile organic compounds (SVOCs) in the atmosphere depends both on the phase of condensed material and the effective condensed phase vapor pressures of the SVOCs. Although direct measurements of vapor pressures of individual SVOCs exist, there are limited measurements of how the properties of a given compound changes in mixtures of multiple components that exist in the atmosphere. Here, the evaporation behavior of mixtures of dicarboxylic acids, which are common atmospheric aerosol constituents, is investigated. These measurements demonstrate that complex mixtures of the individually solid organic compounds take on liquid-like properties. Additionally, the vapor pressures of individual components show strong, identity-dependent deviations from ideality (i.e., Raoult's Law), with the vapor pressures of the smaller, more volatile compounds decreased significantly in the mixtures. The addition of an inorganic compound (NaNO3) further influences the nonideal behavior, again in a compound-specific manner. These results suggest that nonideal behavior of particle-phase compounds influences the abundances of organic aerosol observed in the atmosphere and in the laboratory. PMID:19020087

  8. Laboratory measurements of the oxidation kinetics of organic aerosol mixtures using a relative rate constants approach

    NASA Astrophysics Data System (ADS)

    Huff Hartz, Kara E.; Weitkamp, Emily A.; Sage, Amy M.; Donahue, Neil M.; Robinson, Allen L.

    2007-02-01

    Organic aerosols in the atmosphere are exposed to oxidants, but the oxidation kinetics are largely unknown. We investigate the decay of organic species in laboratory-generated organic aerosols exposed to atmospherically relevant ozone concentrations in a smog chamber. The experiments were conducted using five different organic aerosols, varying in complexity from three to twelve components. These mixtures include alkenoic acids, alkanoic acids, alkanedioic acids, n-alkanes, and sterols and are designed to simulate meat cooking emissions. A relative rate constants approach was used to compare reaction rates of individual organic species and to compare the reaction rates of the aerosol species to gas phase tracers. Significant decay was observed for all species (except for the n-alkanes) in at least one of the experimental systems. By relating the decomposition of condensed phase alkenoic acids to gas phase alkenes, we show that the reaction rate constants of oleic acid and palmitoleic acid evolve as the aerosol is processed, decreasing by a factor of ˜10 over the course of a 4-hour experiment. The decay rate constants of cholesterol, oleic acid, and palmitic acid all depend strongly on aerosol composition, with more than an order of magnitude change in the effective rate constants depending on mixture composition. Effects of aerosol composition are likely to be even more significant in atmospheric aerosol, where particle compositions are highly variable. The data presented here indicate these mixture effects are complicated, making it difficult to extrapolate from simple laboratory systems to atmospherically relevant conditions.

  9. Methods of analysis for complex organic aerosol mixtures from urban emission sources of particulate carbon

    SciTech Connect

    Mazurek, M.A. ); Hildemann, L.M. . Dept. of Civil Engineering); Cass, G.R.; Rogge, W.F. . Dept. of Environmental Engineering Science); Simoneit, B.R.T. . Coll. of Oceanography)

    1990-04-01

    Extractable organic compounds having between 6 to 40 carbon atoms comprise an important mass fraction of the fine particulate matter samples from major urban emission sources. Depending on the emission source type, this solvent-soluble fraction accounts for <20% to 100% of the total organic aerosol mass, as measured by quantitative high-resolution has chromatography (HRGC) with flame ionization detection. In addition to total extract quantitation, HRGC can be applied to further analyses of the mass distributions of elutable organics present in the complex aerosol extract mixtures, thus generating profiles that serve as fingerprints'' for the sources of interest. This HRGC analytical method is applied to emission source samples that contain between 7 to 12,000 {mu}g/filter organic carbon. It is shown to be a sensitive technique for analysis of carbonaceous aerosol extract mixtures having diverse mass loadings and species distributions. This study describes the analytical chemical methods that have been applied to: the construction of chemical mass balances based on the mass of fine organic aerosol emitted for major urban sources of particulate carbon; and the generation of discrete emission source chemical profiles derived from chromatographic characteristics of the organic aerosol components. 21 refs., 1 fig., 2 tabs.

  10. 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 (?2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

  11. 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 (?2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

  12. Separation and molecular-level segregation of complex alkane mixtures in metal-organic frameworks.

    PubMed

    Dubbeldam, David; Galvin, Casey J; Walton, Krista S; Ellis, Donald E; Snurr, Randall Q

    2008-08-20

    In this computational work we explore metal-organic frameworks (MOFs) for separating alkanes according to the degree of branching. We show that the structure MOF-1 shows an adsorption hierarchy for a 13-component light naphtha mixture precisely as desired for increasing the research octane number of gasoline. In addition we report an unusual molecular-level segregation of molecules based on their degree of branching. PMID:18651737

  13. Determination of benzene and toluene in soils and plant material by azeotropic distillation

    SciTech Connect

    Kozloski, R.P.

    1985-01-01

    The suspected dumping of gasoline near a garden resulted in the need for a method that would measure trace amounts of benzene and toluene in both soil and plant samples. In this report the authors show that a method involving methanolic extraction and azeotropic distillation is a highly sensitive technique that eliminated the contamination of the GC column by non-volatile material.

  14. 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. PMID:25421649

  15. 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.

  16. 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

  17. 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

  18. Organic biowastes blend selection for composting industrial eggshell by-product: experimental and statistical mixture design.

    PubMed

    Soares, Micaela A R; Andrade, Sandra R; Martins, Rui C; Quina, Margarida J; Quinta-Ferreira, Rosa M

    2012-01-01

    Composting is one of the technologies recommended for pre-treating industrial eggshells (ES) before its application in soils, for calcium recycling. However, due to the high inorganic content of ES, a mixture of biodegradable materials is required to assure a successful procedure. In this study, an adequate organic blend composition containing potato peel (PP), grass clippings (GC) and wheat straw (WS) was determined by applying the simplex-centroid mixture design method to achieve a desired moisture content, carbon: nitrogen ratio and free air space for effective composting of ES. A blend of 56% PP, 37% GC and 7% WS was selected and tested in a self heating reactor, where 10% (w/w) of ES was incorporated. After 29 days of reactor operation, a dry matter reduction of 46% was achieved and thermophilic temperatures were maintained during 15 days, indicating that the blend selected by statistical approach was adequate for composting of ES. PMID:22592462

  19. 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 quantification of compounds possessing these groups in complex mixtures.

  20. 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 comparison to the previous model version, when both versions are compared to our database of experimentally determined activity coefficients and related thermodynamic data. When comparing the previous and new AIOMFAC model parameterisations to the subsets of experimental data with all temperatures below 274 K or all temperatures above 322 K (i.e. outside a 25 K margin of the reference temperature of 298 K), applying the new parameterisation leads to 37% improvement in each of the two temperature ranges considered. The new parameterisation of AIOMFAC agrees well with a large number of experimental data sets. Larger model-measurement discrepancies were found particularly for some of the systems containing multi-functional organic compounds. The affected systems were typically also poorly represented at room temperature and further improvements will be necessary to achieve better performance of AIOMFAC in these cases (assuming the experimental data are reliable). The performance of the AIOMFAC parameterisation is typically better for systems containing relatively small organic compounds and larger deviations may occur in mixtures where molecules of high structural complexity such as highly oxygenated compounds or molecules of high molecular mass (e.g. oligomers) prevail. Nevertheless, the new parameterisation enables the calculation of activity coefficients for a wide variety of different aqueous/water-free organic solutions down to the low temperatures present in the upper troposphere.

  1. 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.

  2. 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.

  3. PROCEDURES FOR THE DERIVATION OF EQUILIBRIUM PARTITIONING SEDIMENT BENCHMARKS (ESBS) FOR THE PROTECTION OF BENTHIC ORGANISMS: 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 the ...

  4. 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 vacuum ultraviolet (VUV) photo-ionization. Chapters 3 and 4 describe this new analytical technique and its initial application to determine the structures of unknown compounds and formerly unresolvable mixtures, including a complete description of the chemical composition of two common petroleum products related to anthropogenic emissions: diesel fuel and motor oil. The distribution of hydrocarbon isomers in these mixtures - found to be mostly of branched, cyclic, and saturated -- is described with unprecedented detail. Instead of measuring average bulk aerosol properties, the methods developed and applied in this work directly measure the polarity, volatility, and structure of individual components to allow a mechanistic understanding of oxidation processes. Novel characterizations of these complex mixtures are used to elucidate the role of structure and functionality in particle-phase oxidation, including in Chapter 4 the first measurements of relative reaction rates in a complex hydrocarbon particle. Molecular structure is observed to influence particle-phase oxidation in unexpected and important ways, with cyclization decreasing reaction rates by ~30% and branching increasing reaction rates by ~20-50%. The observed structural dependence is proposed to result in compositional changes in anthropogenic organic aerosol downwind of urban areas, which has been confirmed in subsequent work by applying the techniques described here. Measurement of organic aerosol components is extended to ambient environments through the development of instrumentation with the unprecedented capability to measure hourly concentrations and gas/particle partitioning of individual highly oxygenated organic compounds in the atmosphere. Chapters 5 and 6 describe development of new procedures and hardware for the calibration and analysis of oxygenates using the Semi-Volatile Thermal desorption Aerosol Gas chromatograph (SV-TAG), a custom instrument for in situ quantification of gas- and particle-phase organic compounds in the atmosphere. High time resolution measurement of oxygenated compounds is achieved through a reproducible and quantitative methodology for in situ "derivatization" -- replacing highly polar functional groups that cannot be analyzed by traditional gas chromatography with less polar groups. Implementation of a two-channel sampling system for the simultaneous collection of particle-phase and total gas-plus-particle phase samples allows for the first direct measurements of gas/particle partitioning in the atmosphere, significantly advancing the study of atmospheric composition and variability, as well as the processes governing condensation and re-volatilization. This work presents the first in situ measurements of a large suite of highly oxygenated biogenic oxidation products in both the gas- and particle-phase. Isoprene, the most ubiquitous biogenic emission, oxidizes to form 2-methyltetrols and C5 alkene triols, while α-pinene, the most common monoterpene, forms pinic, pinonic, hydroxyglutaric, and other acids. These compounds are reported in Chapter 7 with unprecedented time resolution and are shown for the first time to have a large gas-phase component, contrary to typical assumptions. Hourly comparisons of these products with anthropogenic aerosol components elucidate the interaction of human and natural emissions at two rural sites: the southeastern, U.S. and Amazonia, Brazil. Anthropogenic influence on SOA formation is proposed to occur through the increase in liquid water caused by anthropogenic sulfate. Furthermore, these unparalleled observations of gas/particle partitioning of biogenic oxidation products demonstrate that partitioning of oxygenates is unexpectedly independent of volatility: many volatile, highly oxygenated compounds have a large particle-phase component that is poorly described by traditional models. These novel conclusions are reached in part by applying the new frameworks developed in previous chapters to understand the properties of unidentified compounds, demonstrating the importance of detailed characterization of atmospheric organic mixtures. Comprehensive analysis of anthropogenic and biogenic emissions and oxidation product mixtures is coupled in this work with high time-resolution measurement of individual organic components to yield significant insights into the transformations of organic aerosols. Oxidation chemistry is observed in both laboratory and field settings to depend on molecular properties, volatility, and atmospheric composition. However, this work demonstrates that these complex processes can be understood through the quantification of individual known and unidentified compounds, combined with their classification into descriptive frameworks.

  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. Capillary chromatography based on tube radial distribution of aqueous-organic mixture carrier solvents.

    PubMed

    Jinno, Naoya; Itano, Minoru; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

    2009-10-15

    A capillary chromatography system was developed using open capillary tubes made of fused-silica, polyethylene, or poly(tetrafluoroethylene), and an aqueous-organic mixture (water-acetonitrile-ethyl acetate mixture) as a carrier solution. Model analyte mixture solutions, such as 2,6-naphthalenedisulfonic acid and 1-naphthol, Eosin Y and perylene, bis[N,N-bis(carboxymethyl)aminomethyl]fluorescein and 1,1'-bi-2-naphthol, and 2,7-naphthalenedisulfonic acid and p-nitroaniline, were injected into the capillary tube by a gravity method. The analyte solutions were subsequently delivered through the capillary tube with the carrier solution by a micro-syringe pump. The system worked under laminar flow conditions. The analytes were separated through the capillary tube and detected on-capillary by an absorption detector. For example, 2,6-naphthalenedisulfonic acid and 1-naphthol were detected in this order with a carrier solution of water-acetonitrile-ethyl acetate (volume ratio 15:3:2), while they were detected in the reverse order with a carrier solution of water-acetonitrile-ethyl acetate (volume ratio 2:9:4). The other analyte solutions were similarly separated by the system. The elution times of the analytes could be easily reversed by changing the component ratio of the solvents in the carrier solution. PMID:19635369

  7. Effects of immunological and hematological parameter in mice exposed to mixture of volatile organic compounds.

    PubMed

    Wang, Fan; Liu, Fei; Liu, Haifang; Chen, Wanguang; Si, Xianli; Ma, Xiuying

    2016-03-01

    Exposure to some kinds of volatile organic compounds (VOCs) leads to immune system disorders, liver and kidney damage, hematological change. However, there is little information about the effect of VOCs mixture on immune system and hematological parameter. In this study, 50 Kunming male mice were exposed in five similar chambers, 0 (control) and four different doses of VOCs mixture (G1-4) for consecutively 10 days at 2 h/day. The concentrations of VOCs mixture were as follows: formaldehyde, benzene, toluene and xylene 1.0 + 1.1 + 2.0 + 2.0, 3.0 + 3.3 + 6.0 + 6.0, 5.0 + 5.5 + 10.0 + 10.0 and 10.0 + 11.0 + 20.0 + 20.0 mg/m(3), respectively, which corresponded to 10, 30, 50 and 100 times of indoor air quality standard in china. One day following VOCs exposure, spleen T lymphocyte subpopulation, serum biochemical markers and peripheral blood cells in mice were analyzed, respectively. VOCs exposure decreased significantly erythrocyte count (RBC), platelet (PLT) in peripheral blood in mice. While aspartate aminotransaminase (AST), alanine aminotransaminase (ALT), alkaline phosphatase (ALP) and creatinine (CREA) in serum increased significantly in G4 mice versus controls. Flow cytometry analysis showed that the number of splenic lymphocyte subpopulation cells decreased significantly in G2, 3 and 4 mice in comparison with normal Kunming mice. These results indicate inhalation of VOCs mixture affects CD4/8 subpopulations, liver, kidney function and some hematological parameters in mice. PMID:26986951

  8. 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.

  9. 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 known to affect VOC exposures, many personal, environmental, and socioeconomic determinants remain to be identified, and the significance and applicability of the determinants reported in the literature are uncertain. To help answer these unresolved questions and overcome limitations of previous analyses, this project used several novel and powerful statistical modeling and analysis techniques and two large data sets. The overall objectives of this project were (1) to identify and characterize exposure distributions (including extreme values), (2) evaluate mixtures (including dependencies), and (3) identify determinants of VOC exposure. METHODS VOC data were drawn from two large data sets: the Relationships of Indoor, Outdoor, and Personal Air (RIOPA) study (1999–2001) and the National Health and Nutrition Examination Survey (NHANES; 1999–2000). The RIOPA study used a convenience sample to collect outdoor, indoor, and personal exposure measurements in three cities (Elizabeth, NJ; Houston, TX; Los Angeles, CA). In each city, approximately 100 households with adults and children who did not smoke were sampled twice for 18 VOCs. In addition, information about 500 variables associated with exposure was collected. The NHANES used a nationally representative sample and included personal VOC measurements for 851 participants. NHANES sampled 10 VOCs in common with RIOPA. Both studies used similar sampling methods and study periods. Specific Aim 1 To estimate and model extreme value exposures, extreme value distribution models were fitted to the top 10% and 5% of VOC exposures. Health risks were estimated for individual VOCs and for three VOC mixtures. Simulated extreme value data sets, generated for each VOC and for fitted extreme value and lognormal distributions, were compared with measured concentrations (RIOPA observations) to evaluate each model’s goodness of fit. Mixture distributions were fitted with the conventional finite mixture of normal distributions and the semi-parametric Dirichlet process mixture (DPM) of normal distributions for three individual VOCs (chloroform, 1,4-DCB, and styrene). Goodness of fit for these full distribution models was also evaluated using simulated data. Specific Aim 2 Mixtures in the RIOPA VOC data set were identified using positive matrix factorization (PMF) and by toxicologic mode of action. Dependency structures of a mixture’s components were examined using mixture fractions and were modeled using copulas, which address correlations of multiple components across their entire distributions. Five candidate copulas (Gaussian, t, Gumbel, Clayton, and Frank) were evaluated, and the performance of fitted models was evaluated using simulation and mixture fractions. Cumulative cancer risks were calculated for mixtures, and results from copulas and multivariate lognormal models were compared with risks based on RIOPA observations. Specific Aim 3 Exposure determinants were identified using stepwise regressions and linear mixed-effects models (LMMs). RESULTS Specific Aim 1 Extreme value exposures in RIOPA typically were best fitted by three-parameter generalized extreme value (GEV) distributions, and sometimes by the two-parameter Gumbel distribution. In contrast, lognormal distributions significantly underestimated both the level and likelihood of extreme values. Among the VOCs measured in RIOPA, 1,4-dichlorobenzene (1,4-DCB) was associated with the greatest cancer risks; for example, for the highest 10% of measurements of 1,4-DCB, all individuals had risk levels above 10−4, and 13% of all participants had risk levels above 10−2. Of the full-distribution models, the finite mixture of normal distributions with two to four clusters and the DPM of normal distributions had superior performance in comparison with the lognormal models. DPM distributions provided slightly better fit than the finite mixture distributions; the advantages of the DPM model were avoiding certain convergence issues associated with the finite mixture distributions, adaptively selecting the number of needed clusters, and providing uncertainty estimates. Although the results apply to the RIOPA data set, GEV distributions and mixture models appear more broadly applicable. These models can be used to simulate VOC distributions, which are neither normally nor lognormally distributed, and they accurately represent the highest exposures, which may have the greatest health significance. Specific Aim 2 Four VOC mixtures were identified and apportioned by PMF; they represented gasoline vapor, vehicle exhaust, chlorinated solvents and disinfection byproducts, and cleaning products and odorants. The last mixture (cleaning products and odorants) accounted for the largest fraction of an individual’s total exposure (average of 42% across RIOPA participants). Often, a single compound dominated a mixture but the mixture fractions were heterogeneous; that is, the fractions of the compounds changed with the concentration of the mixture. Three VOC mixtures were identified by toxicologic mode of action and represented VOCs associated with hematopoietic, liver, and renal tumors. Estimated lifetime cumulative cancer risks exceeded 10−3 for about 10% of RIOPA participants. The dependency structures of the VOC mixtures in the RIOPA data set fitted Gumbel (two mixtures) and t copulas (four mixtures). These copula types emphasize dependencies found in the upper and lower tails of a distribution. The copulas reproduced both risk predictions and exposure fractions with a high degree of accuracy and performed better than multivariate lognormal distributions. Specific Aim 3 In an analysis focused on the home environment and the outdoor (close to home) environment, home VOC concentrations dominated personal exposures (66% to 78% of the total exposure, depending on VOC); this was largely the result of the amount of time participants spent at home and the fact that indoor concentrations were much higher than outdoor concentrations for most VOCs. In a different analysis focused on the sources inside the home and outside (but close to the home), it was assumed that 100% of VOCs from outside sources would penetrate the home. Outdoor VOC sources accounted for 5% (d-limonene) to 81% (carbon tetrachloride [CTC]) of the total exposure. Personal exposure and indoor measurements had similar determinants depending on the VOC. Gasoline-related VOCs (e.g., benzene and methyl tert-butyl ether [MTBE]) were associated with city, residences with attached garages, pumping gas, wind speed, and home air exchange rate (AER). Odorant and cleaning-related VOCs (e.g., 1,4-DCB and chloroform) also were associated with city, and a residence’s AER, size, and family members showering. Dry-cleaning and industry-related VOCs (e.g., tetrachloroethylene [or perchloroethylene, PERC] and trichloroethylene [TCE]) were associated with city, type of water supply to the home, and visits to the dry cleaner. These and other relationships were significant, they explained from 10% to 40% of the variance in the measurements, and are consistent with known emission sources and those reported in the literature. Outdoor concentrations of VOCs had only two determinants in common: city and wind speed. Overall, personal exposure was dominated by the home setting, although a large fraction of indoor VOC concentrations were due to outdoor sources. City of residence, personal activities, household characteristics, and meteorology were significant determinants. Concentrations in RIOPA were considerably lower than levels in the nationally representative NHANES for all VOCs except MTBE and 1,4-DCB. Differences between RIOPA and NHANES results can be explained by contrasts between the sampling designs and staging in the two studies, and by differences in the demographics, smoking, employment, occupations, and home locations. A portion of these differences are due to the nature of the convenience (RIOPA) and representative (NHANES) sampling strategies used in the two studies. CONCLUSIONS Accurate models for exposure data, which can feature extreme values, multiple modes, data below the MDL, heterogeneous interpollutant dependency structures, and other complex characteristics, are needed to estimate exposures and risks and to develop control and management guidelines and policies. Conventional and novel statistical methods were applied to data drawn from two large studies to understand the nature and significance of VOC exposures. Both extreme value distributions and mixture models were found to provide excellent fit to single VOC compounds (univariate distributions), and copulas may be the method of choice for VOC mixtures (multivariate distributions), especially for the highest exposures, which fit parametric models poorly and which may represent the greatest health risk. The identification of exposure determinants, including the influence of both certain activities (e.g., pumping gas) and environments (e.g., residences), provides information that can be used to manage and reduce exposures. The results obtained using the RIOPA data set add to our understanding of VOC exposures and further investigations using a more representative population and a wider suite of VOCs are suggested to extend and generalize results. PMID:25145040

  10. 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.

  11. 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

  12. Oxidation From the "Bottom Up" of Organics on Sodium Nitrite/Sodium Chloride Mixtures

    NASA Astrophysics Data System (ADS)

    Dilbeck, C. W.; Karagulian, F.; Finlayson-Pitts, B. J.

    2008-12-01

    Sea salt and other particles in air are believed to be coated at least in part with organics. Oxidation of the coating can change the properties of the particles, including their water uptake and growth which affects visibility, their radiative properties and potentially health effects. We report here a new mechanism of oxidation of adsorbed organics by OH generated by the photolysis of nitrite ions in the underlying substrate. The UV photolysis in air of a mixture of NaNO2 and NaCl coated with 1-oleoyl-2-palmitoyl-sn- glycero-3-phosphocholine (OPPC) was followed using diffuse reflection infrared Fourier transform spectrometry (DRIFTS) at 296 K, both with and without added water vapor. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry was used to confirm the identification of the products. Organic nitrates and carbonyl compounds were observed as products and in the absence of added water vapor, carboxylate ions were also formed. These experiments show that the generation of O- and OH in the photolysis of nitrite ions in and on solids leads to oxidation of organics adsorbed on the salt surface. Similar chemistry is likely to occur for nitrate ions which also photolyze to generate O- and OH. This suggests a new mechanism of oxidation of organics on surfaces in air that have co-adsorbed nitrite or nitrate ions.

  13. 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.

  14. Microbial detection of mutagenic nitro-organic compounds in filtrates of coal fly ash

    SciTech Connect

    Wei, C.; Raabe, O.G.; Rosenblatt, L.S.

    1982-01-01

    The presence of mutagenic nitro-organic compounds on coal fly ash was indicated by the greatly reduced microbial mutagenicity of the ash filtrates with nitroreductase-deficient strains of Salmonella typhimurium compared to their corresponding parental strains. Addition of the liver S-9 microsomal enzyme preparation significantly increased the mutagenic activities of the ash extracts. Extracts of fly ash mutagens were prepared with horse serum, dimethyl sulfoxide, or azeotropic benzene/methanol mixture. The data were normalized to net revertants per 10/sup 8/ Salmonella typhimurium cells per milligram of ash used. This normalization procedure is essential for interpretation of comparative results. Both four-way and three-way analyses of variance were used to simultaneously evaluate the differences between solvent extracts, fly ash mutagen, S-9 activation, and nitroreductase-deficient strains and their parental strains. Of the three extraction systems tested, benzene/methanol azeotropic mixture was generally found to have the highest extraction power, and horse serum was the lowest. The results show that overall 87.5% (+/- 1.8 SE) of the mutagenic activity of the fly ash was associated with nitro-organic compounds.

  15. Importance of Aqueous-phase Secondary Organic Aerosol Formation from Aromatics in an Atmospheric Hydrocarbon Mixture

    NASA Astrophysics Data System (ADS)

    Parikh, H. M.; Carlton, A. G.; Vizuete, W.; Zhang, H.; Zhou, Y.; Chen, E.; Kamens, R. M.

    2010-12-01

    Two new secondary organic aerosol (SOA) modeling frameworks are developed, one based on an aromatic gas and particle-phase kinetic mechanism and another based on a parameterized SOA model used in conjunction with an underlying gas-phase mechanism, both of which simulate SOA formation through partitioning to two stable liquid phases: one hydrophilic containing particle aqueous-phase and the other hydrophobic comprising mainly organic components. The models were evaluated against outdoor smog chamber experiments with different combinations of initial toluene, o-xylene, p-xylene, toluene and xylene mixtures, NOx, non-SOA-forming hydrocarbon mixture, initial seed type, and humidity. Aerosol data for experiments with either ammonium sulfate or initial background seed particles, in the presence of an atmospheric hydrocarbon mixture, NOx and in sunlight under a dry atmosphere (RH = 6 to 10%) show reduced SOA formation when compared to experiments with similar initial gas and particle concentrations at higher relative humidities (RH = 40 to 90%). Both frameworks simulated reasonable fits to the total observed SOA concentrations under all conditions. For both dry and wet experiments with low initial seed, semi-volatile product partitioning in particle organic-phase is mass-transfer limited and is modeled using a dynamic gas-particle partitioning algorithm with accommodation coefficient as the primary pseudo-transport parameter. Further, the modeled SOA product distributions for both frameworks clearly show the importance of the contribution of aqueous-phase SOA particularly under conditions of low initial seed concentrations and high-humidity. For both models, under these conditions, aqueous-phase SOA from uptake of glyoxal, methylglyoxal and related polar products to particle water phase dominates as compared to the partitioning of semi-volatiles to particle organic phase. Interestingly, both the kinetic and parameterized SOA frameworks simulate similar amounts of aqueous-phase SOA for each experiment. For wet experiments with initial ammonium sulfate seed, the modeled fraction of aqueous-phase SOA is up to 82% of the total ammonium sulfate mass and for wet experiment with initial background seed this fraction is as high as 60% of the total particle mass formed for the duration of the experiments. This suggests that aqueous-phase SOA from oxidation of toluene and xylene, under atmospherically relevant conditions, is significant and should be part of kinetic or parameterized SOA modeling frameworks in current air quality models.

  16. 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.

  17. 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.

  18. 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. PMID:25394187

  19. Multi-Atlas Segmentation for Abdominal Organs with Gaussian Mixture Models

    PubMed Central

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

    2015-01-01

    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. PMID:25914508

  20. 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, Ji?í; 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-?B) 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

  1. Polymer coated quartz crystal microbalance sensors for detection of volatile organic compounds in gas mixtures.

    PubMed

    Si, Pengchao; Mortensen, John; Komolov, Alexei; Denborg, Jens; Møller, Preben Juul

    2007-08-01

    By coating different conducting polymers of thiophene and its derivatives on quartz crystal microbalance (QCM) sensor surfaces, new novel QCM gas sensors have been produced in two simple ways, which could classify testing gas samples of volatile organic compounds (VOCs) gases. Principle components analysis (PCA) has been performed based on the QCM measurement results, which shows that our QCM sensors array has very good utilizing potential on sensing both polar and low-polar/nonpolar VOC gases. The sensitivity, selectivity, reproducibility and detection limit of QCM sensors have also been discussed. Quantitative variation of sensitivity response with the increasing concentration has been studied. (PLS) analysis and prediction of concentrations of single gas in mixtures have been carried out. PMID:17683733

  2. Extraction of betulin, trimyristin, eugenol and carnosic acid using water-organic solvent mixtures.

    PubMed

    Lugemwa, Fulgentius N

    2012-01-01

    A solvent system consisting of ethyl acetate, ethyl alcohol and water, in the volume ratio of 4.5:4.5:1, was developed and used to extract, at room temperature, betulin from white birch bark and antioxidants from spices (rosemary, thyme, sage, and oregano) and white oak chips. In addition, under reflux conditions, trimyristin was extracted from nutmeg using the same solvent system, and eugenol from olives was extracted using a mixture of salt water and ethyl acetate. The protocol demonstrates the use of water in organic solvents to extract natural products from plants. Measurement of the free-radical scavenging activity using by 2,2-diphenyl-1-picrylhydrazyl (DPPH) indicated that the extraction of plant material using ethyl acetate, ethyl alcohol and water (4.5:4.5:1, v/v/v) was exhaustive when carried out at room temperature for 96 h. PMID:22864237

  3. 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.

  4. 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.

  5. Mixture designs in the optimisation of PLGA nanoparticles: influence of organic phase composition on ?-aescin encapsulation.

    PubMed

    Ven, H Van de; Vandervoort, J; Weyenberg, W; Apers, S; Ludwig, A

    2012-01-01

    The objective of this study was to enhance the encapsulation of the antileishmanial saponin aescin in poly(D,L-lactide-co-glycolide) (PLGA) nanoparticles (NPs). We prepared the NPs by the O/W and W/O/W combined emulsification solvent evaporation/salting-out technique and investigated the influence of organic phase composition on the NPs' size, zeta potential and entrapment efficiency (EE%) using mixture designs. The obtained NPs were monodispersed with Z(ave)<300?nm and exhibited negative zeta potentials. For the single emulsion, the co-solvent concentration was shown to be the primary determinant of drug entrapment. The EE% increased from 14% to 22% by decreasing the amount of DMSO from 80% to 25% (v/v) in the organic polymer solution. For the double emulsion, EE% was 22% on average and independent of the organic phase composition. The double-emulsion technique did not enhance the aescin encapsulation as expected due to its amphiphilic nature. The optimised aescin-loaded NPs meet the requirements for further in vitro activity tests. PMID:22047548

  6. 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 mix. The plate also has two brass holders (Fig. 1C) which contain 10-mm diameter discs of high purity, sterilised gold foil (also at low temperature). During the impact, the plasma will condense onto the cold surfaces of the gold foil. One of the gold foils is pointed directly at the ice mixture, the other is pointed backwards into the gun's target chamber (and thus acts as a control). The gold discs can then be removed (Fig. 1D) and mounted onto stubs for analyses using Raman spectroscopy, SEM-EDX, GC-MS as required. Preliminary Results: Several trial shots have been performed using this system and residues have been found. The initial analysis of these residues is now underway and the results will be presented at the conference. If successful, this collection and analysis methodology will greatly speed up the number of experiments that can be done, allowing us to explore a large parameter space and determine the efficiency of shock syntheses of complex organics as a function of impact speed (peak shock pressure) and target composition.

  7. IUPAC-NIST Solubility Data Series. 99. Solubility of Benzoic Acid and Substituted Benzoic Acids in Both Neat Organic Solvents and Organic Solvent Mixtures

    NASA Astrophysics Data System (ADS)

    Acree, William E.

    2013-09-01

    Solubility data are compiled and reviewed for benzoic acid and 63 substituted benzoic acids dissolved in neat organic solvents and well-defined binary and ternary organic solvent mixtures. The compiled solubility data were retrieved from the published chemical and pharmaceutical literature covering the period from 1900 to the beginning of 2013.

  8. A neurological evaluation of workers exposed to mixtures of organic solvents.

    PubMed Central

    Maizlish, N A; Fine, L J; Albers, J W; Whitehead, L; Langolf, G D

    1987-01-01

    Workers with long term exposure to mixtures of organic solvents below regulatory limits have been reported to experience mild, but clinically detectable, sensory or sensorimotor polyneuropathies. In conjuction with a cross sectional study of behavioural performance a clinical neurological evaluation was conducted among printers and spray painters to examine dose response relations. All 240 subjects completed an occupational history and symptom questionnaire and underwent a clinical neurological examination. On average, subjects had been employed on their current job for six years. Classification of solvent exposure for each subject was based on exposed versus non-exposed job titles and observations during an industrial hygiene walk-through or on the measured concentration of solvents in full shift personal air samples. The average full shift solvent concentration was 302 ppm for printing plant workers and 6-13 ppm for workers at other plants. Isopropanol and hexane were the major constituents. Neurological abnormalities consistent with mild polyneuropathy were found in 16% of subjects; none was clinically significant. Exposed/non-exposed comparisons showed slightly higher frequency of symptoms in the exposed subjects which was not related to solvent level. Subjects categorised as exposed during the walk- through survey also had poorer vibratory sensation measured at the foot and diminished ankle reflexes. In multiple linear regression models, however, controlling for age, sex, alcohol intake, and examiner, no significant (p less than 0.05) relation was found between solvent concentration and poor neurological function except for two point discrimination measured at the foot. This investigation has not provided evidence for dose related adverse neurological effects from exposure to moderately low levels of solvent mixtures for a relatively short duration, although this may be due to the shortness of exposure duration, the type of solvent exposure, or to selection factors. PMID:3814530

  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. PMID:26550706

  10. 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 ?m). 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

  11. IUPAC-NIST Solubility Data Series. 98. Solubility of Polycyclic Aromatic Hydrocarbons in Pure and Organic Solvent Mixtures: Revised and Updated. Part 1. Binary Solvent Mixtures

    NASA Astrophysics Data System (ADS)

    Acree, William E.

    2013-03-01

    This work updates Vols. 54, 58, and 59 in the IUPAC Solubility Data Series and presents solubility data for polycyclic aromatic hydrocarbon solutes dissolved in binary organic solvent mixtures. Published solubility data for anthracene, naphthalene, phenanthrene, phenothiazine, and pyrene that appeared in the primary literature between 1995 to the end of 2011 are compiled and critically evaluated. Experimental solubility data for 360 different solute-binary solvent systems are included in the volume. Solubility data published prior to 1995 were contained in three earlier volumes (Vols. 54, 58, and 59) and are not repeated in this volume.

  12. IUPAC-NIST Solubility Data Series. 98. Solubility of Polycyclic Aromatic Hydrocarbons in Pure and Organic Solvent Mixtures: Revised and Updated. Part 2. Ternary Solvent Mixtures

    NASA Astrophysics Data System (ADS)

    Acree, William E.

    2013-03-01

    This work updates Vols. 54, 58, and 59 in the IUPAC Solubility Data Series and presents solubility data for polycyclic aromatic hydrocarbon solutes dissolved in ternary organic solvent mixtures. Published solubility data for anthracene, phenanthrene, and pyrene that appeared in the primary literature between 1995 to the end of 2011 are compiled and critically evaluated. Experimental solubility data for 119 different solute-ternary solvent systems are included in the volume. Solubility data published prior to 1995 were contained in three earlier volumes (Vols. 54, 58, and 59) and are not repeated here.

  13. 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...

  14. COMPARISON OF SORPTION ENERGETICS 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. he enthalpy-entropy compensation model was used to infer that the hydrophobic sorptive mecha...

  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. 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.

  17. Alterations in lung function due to mixtures of organic solvents used in floor laying.

    PubMed

    Angerer, P; Marstaller, H; Bahemann-Hoffmeister, A; Römmelt, H; Höppe, P; Kessel, R

    1991-01-01

    To determine the short-term and long-term effects of organic solvents on the respiratory tract, 26 male floorlayers exposed to organic solvents were compared with 36 persons unexposed to such substances. The investigation primarily included a detailed history, determination of solvent concentration in the air inhaled by the workers, long-term ECG during the entire shift and lung-function test (vital capacity, forced expiratory volume in one second, flow volume curve) as well as non-specific bronchial inhalation challenge using a 3% acetylcholine aerosol before and after the shift. The floorlayers were primarily subjected to inhalative exposure to adhesives containing mixtures of toluene, petroleum hydrocarbons, ethyl acetate, methanol and acetone or one of these substances alone. This frequently resulted in short-term value limit excesses, especially in the MAK value (standardised threshold concentration in Germany) for toluene, which is a prime component of neoprene glue. Of the 26 floorlayers, 6 complained of breathlessness and coughing, whereas 13 suffered from nasal discharge and blockage--symptoms closely related to work. The smokers in this group showed a decline in lung function during the shift--especially in the forced expiratory volume in 1 s (FEV1)--as compared with the non-smokers in this group and the persons in the control group. This probably due to the combination of noxious substances. A strong correlation between occupational age and changes in lung function was observed: the occupationally youngest workers demonstrated the highest decrease in values during the course of the shift. There was no evidence of either obstructive or restrictive respiratory disorders or of marked deviation from the European Community for Coal and Steel (ECCS) references.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1856023

  18. 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.

  19. Modeling competitive adsorption of mixtures of volatile organic compounds in a fixed-bed of beaded activated carbon.

    PubMed

    Tefera, Dereje Tamiru; Hashisho, Zaher; Philips, John H; Anderson, James E; Nichols, Mark

    2014-05-01

    A two-dimensional mathematical model was developed to study competitive adsorption of n-component mixtures in a fixed-bed adsorber. The model consists of an isotherm equation to predict adsorption equilibria of n-component volatile organic compounds (VOCs) mixture from single component isotherm data, and a dynamic adsorption model, the macroscopic mass, energy and momentum conservation equations, to simulate the competitive adsorption of the n-components onto a fixed-bed of adsorbent. The model was validated with experimentally measured data of competitive adsorption of binary and eight-component VOCs mixtures onto beaded activated carbon (BAC). The mean relative absolute error (MRAE) was used to compare the modeled and measured breakthrough profiles as well as the amounts of adsorbates adsorbed. For the binary and eight-component mixtures, the MRAE of the breakthrough profiles was 13 and 12%, respectively, whereas, the MRAE of the adsorbed amounts was 1 and 2%, respectively. These data show that the model provides accurate prediction of competitive adsorption of multicomponent VOCs mixtures and the competitive adsorption isotherm equation is able to accurately predict equilibrium adsorption of VOCs mixtures. PMID:24670053

  20. 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 reliable compositional characterization. PMID:25347814

  1. Energy efficient membrane processes for the separation of organic liquids: Part 1: Final report, September 28, 1982--December 31, 1986

    SciTech Connect

    Cabasso, I.; Acharya, H.R.; Korngold, E.; Liu, Z.; Stern, S.A.; Li, W.; Makenzie, T.; Poda, E.

    1987-10-01

    The potential usefulness of two membrane processes, namely, pervaporation and perstraction, for separating azeotropic mixtures of aromatic and aliphatic hydrocarbons was studied theoretically and experimentally. A third membrane process, osmotic phase-separation, was investigated experimentally. The separation of an azeotropic mixture of benzene and cyclohexane was used as an example. Part II of this report will discuss membrane processes for the separation of alcohol/water mixtures. Mathematical models of pervaporation and perstraction were developed for computer simulations of the processes. The perstraction model presented herein is the first of its kind. Additionally, the energy requirements and capital investments costs for the separation of an azeotropic benzene/cyclohexane mixture were determined and compared with those for extractive distillation. 31 refs., 64 figs., 19 tabs.

  2. Optimal coating selection for the analysis of organic vapor mixtures with polymer-coated surface acoustic wave sensor arrays.

    PubMed

    Zellers, E T; Batterman, S A; Han, M; Patrash, S J

    1995-03-15

    A method for determining the optimal set of polymer sensor coatings to include in a surface acoustic wave (SAW) sensor array for the analysis of organic vapors is described. The method combines an extended disjoint principal components regression (EDPCR) pattern recognition analysis with Monte Carlo simulations of sensor responses to rank the various possible coating selections and to estimate the ability of the sensor array to identify any set of vapor analytes. A data base consisting of the calibrated responses of 10 polymer-coated SAW sensors to each of six organic solvent vapors from three chemical classes was generated to demonstrate the method. Responses to the individual vapors were linear over the concentration ranges examined, and coatings were stable over several months of operation. Responses to binary mixtures were additive functions of the individual component responses, even for vapors capable of strong hydrogen bonding. The EDPCR-Monte Carlo method was used to select the four-sensor array that provided the least error in identifying the six vapors, whether present individually or in binary mixtures. The predicted rate of vapor identification (87%) was experimentally verified, and the vapor concentrations were estimated within 10% of experimental values in most cases. The majority of errors in identification occurred when an individual vapor could not be differentiated from a mixture of the same vapor with a much lower concentration of a second component. The selection of optimal coating sets for several ternary vapor mixtures is also examined. Results demonstrate the capabilities of polymer-coated SAW sensor arrays for analyzing of solvent vapor mixtures and the advantages of the EDPCR-Monte Carlo method for predicting and optimizing performance. PMID:7717524

  3. Pervaporative dehydration characteristics of an ethanol/water azeotrope through various chitosan membranes.

    PubMed

    Uragami, Tadashi; Saito, Tomoyuki; Miyata, Takashi

    2015-04-20

    The permeation and separation characteristics of an ethanol/water azeotrope through chitosan membranes of different molecular weights and degrees of deacetylation during pervaporation were investigated. The normalized permeation rate decreased with increasing molecular weight up to 90 kDa, but at over 90 kDa, the rate increased. On the other hand, the water/ethanol selectivity increased with increasing molecular weight up to 90 kDa but decreased at over 90 kDa. With increasing degree of deacetylation, the water/ethanol permselectivity increased significantly, but the normalized permeation rate decreased. The characteristics of chitosan membranes are discussed based on their chemical and physical structures such as the contact angle, density, degree of swelling, and glass transition temperature. PMID:25662680

  4. Flow boiling heat transfer coefficients at cryogenic temperatures for multi-component refrigerant mixtures of nitrogen-hydrocarbons

    NASA Astrophysics Data System (ADS)

    Ardhapurkar, P. M.; Sridharan, Arunkumar; Atrey, M. D.

    2014-01-01

    The recuperative heat exchanger governs the overall performance of the mixed refrigerant Joule-Thomson cryocooler. In these heat exchangers, the non-azeotropic refrigerant mixture of nitrogen-hydrocarbons undergoes boiling and condensation simultaneously at cryogenic temperature. Hence, the design of such heat exchanger is crucial. However, due to lack of empirical correlations to predict two-phase heat transfer coefficients of multi-component mixtures at low temperature, the design of such heat exchanger is difficult.

  5. Screening Metal-Organic Frameworks by Analysis of Transient Breakthrough of Gas Mixtures in a Fixed Bed Adsorber

    SciTech Connect

    Krishna, Rajamani; Long, Jeffrey R.

    2011-07-07

    Metal–organic frameworks (MOFs) offer considerable potential for separating a variety of mixtures that are important in applications such as CO? capture and H? purification. In view of the vast number of MOFs that have been synthesized, there is a need for a reliable procedure for comparing screening and ranking MOFs with regard to their anticipated performance in pressure swing adsorption (PSA) units. For this purpose, the most commonly used metrics are the adsorption selectivity and the working capacity. Here, we suggest an additional metric for comparing MOFs that is based on the analysis of the transient response of an adsorber to a step input of a gaseous mixture. For a chosen purity of the gaseous mixture exiting from the adsorber, a dimensionless breakthrough time ?{sub break} can be defined and determined; this metric determines the frequency of required regeneration and influences the productivity of a PSA unit. The values of ?{sub break} are dictated both by selectivity and by capacity metrics .By performing transient adsorber calculations for separation of CO?/H?, CO?/CH?, CH?/H?, and CO?/CH?/H? mixtures, we compare the values of ?break to highlight some important advantages of MOFs over conventionally used adsorbents such as zeolite NaX. For a given separation duty, such comparisons provide a more realistic ranking of MOFs than afforded by either selectivity or capacity metrics alone. We conclude that breakthrough calculations can provide an essential tool for screening MOFs.

  6. 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 ...

  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. 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.

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

    PubMed

    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

  10. 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

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

    NASA Astrophysics Data System (ADS)

    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

    2015-06-01

    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.

  12. The influence of cellulose complexite swelling on its protolytic properties in aqueous-organic mixtures

    NASA Astrophysics Data System (ADS)

    Miroshnik, L. V.; Korovnikova, N. I.; Aleksandrov, A. V.; Dubyna, A. M.

    2008-09-01

    The swellability of cellulose complexite containing hydroxamic acid and amidoxime groups and its matrix (grafted copolymer of cellulose and polyacrylonitrle) in variable-composition water-methanol and water-dimethylsulfoxide mixtures was studied by pH metry, refractometry, and atomic absorption spectroscopy over the pH range 5.30 12.87 corresponding to the dissociation of the functional groups of fibers. The solvation characteristics of fibers, including specific volume, degree of sorption, and interphase distribution coefficients of mixture components, were determined experimentally. The Gibbs energies of sample swelling and the dissociation constants of complexite groups were calculated taking into account the contribution of the solvation parameter. The suggestion was made that the acid properties of the polymer were determined by the predominant influence of the specific solvation of its matrix caused by the formation of H-bonds in complexite-solvent systems.

  13. Absorption of a mixture of volatile organic compounds (VOCs) in aqueous solutions of soluble cutting oil.

    PubMed

    Lalanne, Franck; Malhautier, Luc; Roux, Jean-Claude; Fanlo, Jean-Louis

    2008-04-01

    A semi-industrial bioscrubber was developed to treat a complex mixture of VOCs: oxygenated, aromatic and chlorinated compounds. In order to optimize the VOCs mass transfer, an original washing agent made up of water and cutting oil was tested, and the impact of this washing agent on bioscrubbing performances was investigated. The results obtained with a laboratory unit show that the addition of oil strongly increases the quantity of transferred aromatics. For these compounds, the apparent mass transfer coefficient k(L)a is lower than with water alone. In term of bioscrubbing performances, comparison of the results obtained with the water-oil mixture and water alone showed that the removal efficiency for aromatics is enhanced: from 12% to 36% (applied load of 852 g VOCs m(-3)h(-1)); the elimination of chlorinated compounds is slightly improved. The addition of oil does not seem to lead to any dysfunction of the microbial communities that metabolize the transferred compounds. PMID:17513105

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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 ([P666,14+][Cl-]) 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 xIL ? 0.1. Then, the mixture goes through gradual structural changes from methanol-like to the IL-like for 0.1 < xIL ? 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 xIL > 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.

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

    PubMed

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

    2015-04-01

    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 ([P666,14 (+)][Cl(-)]) 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 xIL ? 0.1. Then, the mixture goes through gradual structural changes from methanol-like to the IL-like for 0.1 < xIL ? 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 xIL > 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. PMID:25854249

  17. Separation of 2-propanol-water mixture with capillary porous plates

    SciTech Connect

    Abu Al-Rub, F.A.; Datta, R.

    1999-03-01

    Distillation of the 2-propanol-water mixture of different compositions was experimentally studied in a continuous distillation column equipped with polar and nonpolar porous plates as well as normal sieve plates. The results showed that while no separation was achieved in a distillation column with porous carbon plates or with conventional stages, the azeotropic point of this system was broken in a distillation column with polar sintered stainless steel porous plates. A distillate of about 80.0 mol% 2-propanol was obtained for a feed of azeotropic composition, i.e., 68.0 mol% 2-propanol. These results showed that the main factors affecting the separation efficiency in a given porous plate are the polarization of the pure liquids and porous plates as well as the polarization difference between the mixture components.

  18. 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 & Sons, Ltd. PMID:26939986

  19. A kinetic study of the crystallization of zeolite ZSM-5 in organic solvent/water mixture systems

    NASA Astrophysics Data System (ADS)

    Narita, E.

    1986-10-01

    The rates of crystallization of zeolite ZSM-5 from a reaction mixture containing small amounts of ZSM-5 seed crystals and organic solvents such as acetone and 1,4-dioxane (i.e., ( a = 0.10-0.20)Na 2O-( b = 0.005-0.02)Al 2O 3-SiO 2-46H 2O-0.7 (orga nic solvent)-seed system; a and b values indicate the molar Na 2O/SiO 2 and Al 2O 3/SiO 2 ratios, respectively) were investigated. The crystallization of ZSM-5 began immediately after the addition of the seed crystals without any induction period. The degree of crystallization and the uniformity of the crystal shape and size were advanced with the addition of the organic solvent. After the start of the crystallization of ZSM-5, it decomposed and the more stable phase, ?-quartz, was subsequently crystallized, depending on the composition of the reaction mixture. The apparent activation energies for ZSM-5 crystal growth were 76 ( a = 0.15) and 42 ( a = 0.02) kJ mol -1 for the acetone mixed system, and 71 ( a = 0.15) and 45 ( a = 0.20) kJ mol -1 for the 1,4-dioxane mixed system. The accelerated crystallization of ZSM-5 with the addition of an organic solvent is thought to be caused by the increased fluidity of the reaction mixture thus increasing also the diffusion rate of the ZSM-5 species.

  20. Study of binary and ternary azeotropes formed by 1,4-butylene glycol and diethylene glycol with alcohols and hydrocarbons

    SciTech Connect

    Shleinikova, M.V.; Smirnova, T.N.; Kushner, T.M.

    1988-04-10

    The azeotropic parameters in the 1,4-BG-C/sub 9/C/sub 15/ alcohol series at 13.33 kPa and the DEG-C/sub 9/-C/sub 16/ alcohol series at 2.67 kPa were experimentally determined. Azeotropy was experimentally studied in 14 1,4-BG-alcohol-hydrocarbon ternary systems. It was found that C/sub 8/ and C/sub 15/ alcohols are the alcohols with the lowest and highest molecular weights which form ternary azeotropes with 1,4-BG, and they are C/sub 8/ and C/sub 16/ alcohols for DEG. 1,4-BG is recommended as a separating agent for purification of hydrocarbons from the C/sub 17/-C/sub 20/ fraction of alcohols by the method of heteroazeotropic rectification.

  1. Titan in a Fume Hood: Room-Temperature Simulation of a Titan Evaporite Playa Using a Multi-Component Mixture of Organic Compounds

    NASA Astrophysics Data System (ADS)

    Malaska, M.; Radebaugh, J.; Barnes, J.; Mitchell, K.

    2012-03-01

    A multi-component mixture of organic compounds in heptanes was evaporated to simulate the formation of an evaporite playa on Titan. The deposition sequence of the analog materials and their implications for Titan geology will be presented.

  2. 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...

  3. Adsorption of chromate/organic-acid mixtures in aquifer materials. Technical progress report, 1 July 1990--30 June 1991

    SciTech Connect

    Fish, W.; Palmer, C.D.

    1991-07-15

    The overall objective of this project is to develop a fuller understanding of the interactions of mixtures of anionic co-contaminants with oxide-mineral surfaces. Our specific focus is on the competitive interactions of chromate and oxalic acid on ferric oxyhydroxide and on natural aquifer materials. Chromate and oxalate are of practical interest as widespread contaminants at many DOE facilities. However, these anions also are excellent model adsorbates for elucidating fundamental aspects of ionic adsorption processes, particularly with respect to organic acids.

  4. Hazardous and Corrosive Gas Production in the Radiolysis of Water/Organic Mixtures in Model TRU Waste

    SciTech Connect

    LaVerne, Jay A.

    2005-06-01

    Experiments in combination with diffusion-kinetic modeling incorporating track structure simulations are used to examine the radiation chemistry of aqueous systems containing chlorinated hydrocarbons. Irradiations with both Co-60 gamma rays and alpha particles are employed in order to simulate typical mixed radiation environments encountered in waste management. The goal is to determine fundamental mechanisms, kinetics, and yields for the formation of potentially explosive gases and corrosive agents, such as H2 and HCl, respectively, in the radiolysis of water-organic mixtures. The radiation chemical systems studied are found throughout the DOE portfolio and are important in radioactive waste remediation and management.

  5. Parameterization of thermal properties of aging secondary organic aerosol produced by photo-oxidation of selected terpene mixtures.

    PubMed

    Emanuelsson, Eva U; Mentel, Thomas F; Watne, Agot K; Spindler, Christian; Bohn, Birger; Brauers, Theo; Dorn, Hans-Peter; Hallquist, Asa M; Häseler, Rolf; Kiendler-Scharr, Astrid; Müller, Klaus-Peter; Pleijel, Håkan; Rohrer, Franz; Rubach, Florian; Schlosser, Eric; Tillmann, Ralf; Hallquist, Mattias

    2014-06-01

    Formation and evolution of secondary organic aerosols (SOA) from biogenic VOCs influences the Earth's radiative balance. We have examined the photo-oxidation and aging of boreal terpene mixtures in the SAPHIR simulation chamber. Changes in thermal properties and chemical composition, deduced from mass spectrometric measurements, were providing information on the aging of biogenic SOA produced under ambient solar conditions. Effects of precursor mixture, concentration, and photochemical oxidation levels (OH exposure) were evaluated. OH exposure was found to be the major driver in the long term photochemical transformations, i.e., reaction times of several hours up to days, of SOA and its thermal properties, whereas the initial concentrations and terpenoid mixtures had only minor influence. The volatility distributions were parametrized using a sigmoidal function to determine TVFR0.5 (the temperature yielding a 50% particle volume fraction remaining) and the steepness of the volatility distribution. TVFR0.5 increased by 0.3±0.1% (ca. 1 K), while the steepness increased by 0.9±0.3% per hour of 1×10(6) cm(-3) OH exposure. Thus, aging reduces volatility and increases homogeneity of the vapor pressure distribution, presumably because highly volatile fractions become increasingly susceptible to gas phase oxidation, while less volatile fractions are less reactive with gas phase OH. PMID:24810838

  6. Correlation between free-volume properties and pervaporative flux of polyurethane-zeolite composites on organic solvent mixtures.

    PubMed

    Lue, Shingjiang Jessie; Su, I-Ming; Lee, Da-Tung; Chen, Hsin-Yi; Shih, Chao-Ming; Hu, Chien-Chieh; Jean, Y C; Lai, Juin-Yih

    2011-03-31

    Micron-sized zeolite particles were incorporated into a polyurethane (PU) matrix to prepare ethylbenzene-selective membranes. The resulting composite membranes were used in the pervaporation (PV) of ethylbenzene/styrene (EB/ST) mixtures. The sorption, diffusion, and PV permeation behaviors as a result of zeolite addition were elucidated. Zeolite is less chemically compatible with organic solvents than PU and the PU-zeolite composites, which exhibited suppressed solvent solubilities compared with pristine PU. However, these membranes favor EB transport by diffusion selectivity. The diffusivity and permeation flux increases in parallel with the enlarged radius of the free-volume hole size (R(4) increasing from 3.46 to 3.64 Å using positron annihilation lifetime spectroscopy analysis) by increasing the zeolite content from 0 to 23%. The enlarged free volume at a zeolite loading of 23% promoted pure solvent diffusivities by 10% higher than that of the unfilled film. During the PV operation on the EB/ST mixture, a significant diffusion-coupling was observed, and the permeant diffusion coefficients from the binary mixture exceeded the pure solvent diffusivity. The permeation flux was greatly improved (up to 0.72 kg/m(2)·h) by zeolite addition without any detrimental effect on the separation efficiency. PMID:21375225

  7. 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. PMID:26772051

  8. 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. PMID:23637306

  9. Photonic Crystal Based Sensor for Organic Solvents and for Solvent-Water Mixtures

    PubMed Central

    Fenzl, Christoph; Hirsch, Thomas; Wolfbeis, Otto S.

    2012-01-01

    Monodisperse polystyrene nanoparticles with a diameter of 173 nm were incorporated into a polydimethylsiloxane matrix where they display an iridescent color that can be attributed to the photonic crystal effect. The film is of violet color if placed in plain water, but turns to red in the presence of the non-polar solvent n-hexane. Several solvents were studied in some detail. We show that such films are capable of monitoring the water content of ethanol/water mixtures, where only 1% (v/v) of water leads to a shift of the peak wavelength of reflected light by 5 nm. The method also can be applied to determine, both visually and instrumentally, the fraction of methanol in ethanol/methanol mixtures. Here, a fraction of 1% of methanol (v/v) results in a wavelength shift of 2 nm. The reflected wavelength is not influenced by temperature changes nor impeded by photobleaching. The signal changes are fully reversible and response times are <1 s. PMID:23235441

  10. 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.

  11. 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

  12. 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): ?-pinene, ?-pinene, ?3-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 ?-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 ?-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.

  13. EXPOSURE OF HUMANS TO A VOLATILE ORGANIC MIXTURE: I. BEHAVIORAL ASSESSMENT

    EPA Science Inventory

    Subjective reactions of discomfort, impaired air quality, irritation of mucosal membranes, and impaired memory have been reported to chemically sensitive subjects during exposure to volatile organic compounds (VOC's) found in new buildings. 6 normal healthy male subjects aged 18-...

  14. NEUROTOXIC EFFECTS OF CONTROLLED EXPOSURE TO A COMPLEX MIXTURE OF VOLATILE ORGANIC COMPOUNDS

    EPA Science Inventory

    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 (VOC's) found in new buildings. 6 normal healthy male subjects aged 18-...

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

    DOEpatents

    Pekala, Richard W. (Pleasant Hill, CA)

    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.

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

    DOEpatents

    Pekala, Richard W. (Pleasant Hill, CA)

    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.

  17. 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.

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

    DOEpatents

    Pekala, Richard W. (Pleasant Hill, CA)

    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.

  19. 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.

  20. 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.

  1. 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...

  2. 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.

  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. KINETICS AND SELECTIVITY OF DEEP CATALYTIC OXIDATION OF VOLATILE ORGANIC COMPOUND MIXTURES

    EPA Science Inventory

    The paper gives results of a fundamental study of low-temperature deep (complete) oxidation of n-hexane, benzene, and ethyl-acetate over a 0.1% Pt, 3% Ni/gamma-AL203 catalyst. (NOTE: Deep catalytic combustion of volatile organic compounds--VOCs--is emerging as an important emissi...

  5. Complex rhamnolipid mixture characterization and its influence on DPPC bilayer organization.

    PubMed

    Haba, E; Pinazo, A; Pons, R; Pérez, L; Manresa, A

    2014-03-01

    Rhamnolipids (RL) are one of the most important classes of biosurfactants produced by microorganisms using a wide range of carbon sources, from a simple carbon source like glucose to complex wastes such as the used cooking oils used in this work. The objective of this work was to learn about the rhamnolipid-phospholipid dipalmitoyl phosphatidyl choline (DPPC) molecular interactions through the behaviour observed in the neat products and four RL/DPPC mixtures. Size and z-potential were used to characterize the size and the charge of the vesicles, and small angle X-ray scattering (SAXS) was used to measure the vesicle bilayer characteristics, and the release of carboxyfluorescein to study the bilayer disrupting effect promoted by rhamnolipids. The results show that rhamnolipids are disposed in ordered bilayers with long repeating distances, which are stabilized by the charging of the bilayer and also by a strong fluidity of the bilayers. The ability of rhamnolipids to increase the fluidity of DPPC bilayers may be related with the strong haemolytic power of these molecules. PMID:24239913

  6. Testing secondary organic aerosol models using smog chamber data for complex precursor mixtures: influence of precursor volatility and molecular structure

    NASA Astrophysics Data System (ADS)

    Jathar, S. H.; Donahue, N. M.; Adams, P. J.; Robinson, A. L.

    2014-06-01

    We use secondary organic aerosol (SOA) production data from an ensemble of unburned fuels measured in a smog chamber to test various SOA formation models. The evaluation considered data from 11 different fuels including gasoline, multiple diesels, and various jet fuels. The fuels are complex mixtures of species; they span a wide range of volatility and molecular structure to provide a challenging test for the SOA models. We evaluated three different versions of the SOA model used in the Community Multiscale Air Quality (CMAQ) model. The simplest and most widely used version of that model only accounts for the volatile species (species with less than or equal to 12 carbons) in the fuels. It had very little skill in predicting the observed SOA formation (R2 = 0.04, fractional error = 108%). Incorporating all of the lower-volatility fuel species (species with more than 12 carbons) into the standard CMAQ SOA model did not improve model performance significantly. Both versions of the CMAQ SOA model over-predicted SOA formation from a synthetic jet fuel and under-predicted SOA formation from diesels because of an overly simplistic representation of the SOA formation from alkanes that did not account for the effects of molecular size and structure. An extended version of the CMAQ SOA model that accounted for all organics and the influence of molecular size and structure of alkanes reproduced the experimental data. This underscores the importance of accounting for all low-volatility organics and information on alkane molecular size and structure in SOA models. We also investigated fitting an SOA model based solely on the volatility of the precursor mixture to the experimental data. This model could describe the observed SOA formation with relatively few free parameters, demonstrating the importance of precursor volatility for SOA formation. The exceptions were exotic fuels such as synthetic jet fuel that expose the central assumption of the volatility-dependent model that most emissions consist of complex mixtures with similar distribution of molecular classes. Despite its shortcomings, SOA formation as a function of volatility may be sufficient for modeling SOA formation in chemical transport models.

  7. 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.

  8. Dehydration of water-pyridine mixtures by pervaporation

    SciTech Connect

    Kujawski, W. Centre National de la Recherche Scientifique-UA 494, Nancy ); Nguyen, T.Q.; Neel, J. )

    1991-08-01

    The pervaporation technique, in which the liquid feed mixture is maintained in contact with one side of a nonporous membrane and the permeate is continuously removed from the other side as a vapor, is one of the new methods to attain separation of azeotropic mixtures, structural isomers, or even to displace the equilibrium of chemical reactions. Several ion-exchange and neutral membranes were examined in the pervaporation of water-pyridine mixtures. Carboxylic and sulfonic ion-exchange membranes were used with hydrogen counterion and additionally with trimethylammonium, triethylammonium, and tributylammonium counterions. All membranes were selective to water, but the transport mode and selectivity properties of membranes were dependent on both the character of the ion-exchange group and the ionic form of the membrane. The results obtained suggest that pervaporation of water-pyridine mixtures could be used with standard distillation in the large-scale dehydration process of pyridine.

  9. Photocatalytic oxidation of toxic organohalides with TiO2/UV: the effects of humic substances and organic mixtures.

    PubMed

    Lin, Chitsan; Lin, Kuen-Song

    2007-01-01

    TiO2/UV photocatalytic oxidation of DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane), 1,2,3-trichlorobenzene and 4-chlorophenol were examined in aqueous solution in the presence of humic substances and organic mixtures to study if the degradation rates were affected. Both commercial and natural humic substances were observed to retard the photodegradation rates, with a greater effect from the natural humic substances. Acetonitrile and isopropanol also caused significant retardation of 4-chlorophenol photodegradation. The overall retardation can be attributed to the combination of light attenuation, inhibition and competition effects. Moreover, the TiO2/UV system favors the decomposition of compounds that have stronger adsorption onto the TiO2 surface. To engineer effective treatment facilities that use the TiO2/UV system for the treatment of toxic substances in wastewater, the methodology must allow for concerns about adventitious species which are present. PMID:17084883

  10. Secondary Organic Aerosol Formation in Aerosol Water by Photochemical Reactions of Gaseous Mixture of Monoterpene and Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Lim, H.; Yi, S.; Park, J.; Cho, H.; Jung, K.

    2011-12-01

    There exist large uncertainties in model predictions for climate change and regional air quality. It could be caused by incomplete integration of secondary organic aerosol (SOA) formation in atmospheric chemical models. Recent laboratory studies have found SOA formation through chemical reactions on aerosol surface and in aerosol water. Water soluble organics formed by photochemical degradation of biogenic organics including isoprene and anthropogenic aromatics are predicted to form substantial amount of SOA through the newly found pathways. Although SOA formation in bulk aqueous solution was reported for laboratory experiments of various precursors (e.g., water soluble carbonyls and phenols), little is known for SOA formation in real aerosol water. In this study, photochemical reactions of the gaseous mixture of monoterpene and hydrogen peroxide were examined to investigate SOA formation through reactions in real aerosol phase water. SOA formation was conducted using a flow tube reactor (ID 30 cm x L 150 cm, FEP) and a smog chamber using FEP film in the presence of dry and wet seed particles. Acidity and chemical composition of seed aerosol were also controlled as important parameters influencing SOA formation. Particle size distribution and aerosol composition were analyzed to account for differences in SOA formation mechanisms and yields for dry and wet particles. The differences might be mainly associated with SOA formation in aerosol phase water. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2011-0000221).

  11. Methods of analysis for complex organic aerosol mixtures from urban emission sources of particulate carbon

    SciTech Connect

    Mazurek, M.A. ); Hildemann, L.M. . Dept. of Civil Engineering); Cass, G.R.; Rogge, W.F. ); Simoneit, B.R.T. . Coll. of Oceanography)

    1990-10-01

    Organic aerosols comprise approximately 30% by mass of the total fine particulate matter present in urban atmospheres. The chemical composition of such aerosols is complex and reflects input from multiple sources of primary emissions to the atmosphere, as well as from secondary production of carbonaceous aerosol species via photochemical reactions. To identify discrete sources of fine carbonaceous particles in urban atmospheres, analytical methods must reconcile both bulk chemical and molecular properties of the total carbonaceous aerosol fraction. This paper presents an overview of the analytical protocol developed and used in a study of the major sources of fine carbon particles emitted to an urban atmosphere. 23 refs., 1 fig., 2 tabs.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. Accumulation and effects of natural mixtures of persistent organic pollutants (POP) in Zebrafish after two generations of exposure.

    TOXLINE Toxicology Bibliographic Information

    Berg V; Lyche JL; Karlsson C; Stavik B; Nourizadeh-Lillabadi R; Hårdnes N; Skaare JU; Alestrøm P; Lie E; Ropstad E

    2011-01-01

    Effects of exposure to environmentally realistic mixtures of persistent organic pollutants (POP) harvested from aquatic ecosystems in Norway were studied in an in vivo zebrafish model. POP were extracted from burbot (Lota lota) liver from two separate lakes, Lake Losna and Lake Mjøsa, and exposed to zebrafish through the diet in a two-generation study. Effects on survival, growth, sex ratio, and timing of puberty were investigated. In addition, the biomarkers 7-ethoxyresorufin O-deethylase (EROD) and vitellogenin (Vtg) were measured. The ratios of contaminant levels in extracts collected from Lake Mjøsa:Lake Losna were 6, 10, and 270 for polychlorinated biphenyls (PCB), dichlorodiphenyltrichloroethanes (DDT), and polybrominated diphenyl ethers (PBDE), respectively. The concentration range of POP measured in zebrafish was lower than in burbot originating from Lake Mjøsa, but comparable to concentrations previously reported in humans and wildlife. The results showed that exposure to environmentally realistic mixtures of POP exerted a negative effect on survival of fish in both generations. The marked drop in survival during 9-20 days post fertilization (dpf) suggested that this period may be a critical window for development. In both generations an earlier onset of puberty was observed and a higher proportion of males than females was noted in exposed fish compared to controls. Suprising effects of exposure were found on body weight. In the first generation (F(0)), body weight was significantly higher in both exposure groups compared to controls, while in the next generation (F(1)) the same exposures were associated with a decrease in body weight. Zebrafish exposed to relatively low quantities of POP showed a significant induction of biomarkers (EROD and Vtg), while fish exposed to higher exposure doses did not demonstrate induction.

  18. Accumulation and effects of natural mixtures of persistent organic pollutants (POP) in Zebrafish after two generations of exposure.

    PubMed

    Berg, Vidar; Lyche, Jan L; Karlsson, Camilla; Stavik, Benedicte; Nourizadeh-Lillabadi, Rasoul; Hårdnes, Nina; Skaare, Janneche Utne; Alestrøm, Peter; Lie, Elisabeth; Ropstad, Erik

    2011-01-01

    Effects of exposure to environmentally realistic mixtures of persistent organic pollutants (POP) harvested from aquatic ecosystems in Norway were studied in an in vivo zebrafish model. POP were extracted from burbot (Lota lota) liver from two separate lakes, Lake Losna and Lake Mjøsa, and exposed to zebrafish through the diet in a two-generation study. Effects on survival, growth, sex ratio, and timing of puberty were investigated. In addition, the biomarkers 7-ethoxyresorufin O-deethylase (EROD) and vitellogenin (Vtg) were measured. The ratios of contaminant levels in extracts collected from Lake Mjøsa:Lake Losna were 6, 10, and 270 for polychlorinated biphenyls (PCB), dichlorodiphenyltrichloroethanes (DDT), and polybrominated diphenyl ethers (PBDE), respectively. The concentration range of POP measured in zebrafish was lower than in burbot originating from Lake Mjøsa, but comparable to concentrations previously reported in humans and wildlife. The results showed that exposure to environmentally realistic mixtures of POP exerted a negative effect on survival of fish in both generations. The marked drop in survival during 9-20 days post fertilization (dpf) suggested that this period may be a critical window for development. In both generations an earlier onset of puberty was observed and a higher proportion of males than females was noted in exposed fish compared to controls. Suprising effects of exposure were found on body weight. In the first generation (F(0)), body weight was significantly higher in both exposure groups compared to controls, while in the next generation (F(1)) the same exposures were associated with a decrease in body weight. Zebrafish exposed to relatively low quantities of POP showed a significant induction of biomarkers (EROD and Vtg), while fish exposed to higher exposure doses did not demonstrate induction. PMID:21391088

  19. 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

  20. 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. PMID:26070163

  1. 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. PMID:23598091

  2. 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

    The Control of Substances Hazardous to Health (COSHH) Essentials model was evaluated using full-shift exposure measurements of five chemical components in a mixture [acetone, ethylbenzene, methyl ethyl ketone, toluene, and xylenes] at a medium-sized plant producing paint materials. Two tasks, batch-making and bucket-washing, were examined. Varying levels of control were already established in both tasks and the average exposures of individual chemicals were considerably lower than the regulatory and advisory 8-h standards. The average exposure fractions using the additive mixture formula were also less than unity (batch-making: 0.25, bucket-washing: 0.56) indicating the mixture of chemicals did not exceed the combined occupational exposure limit (OEL). The paper version of the COSHH Essentials model was used to calculate a predicted exposure range (PER) for each chemical according to different levels of control. The estimated PERs of the tested chemicals for both tasks did not show consistent agreement with exposure measurements when the comparison was made for each control method and this is believed to be because of the considerably different volatilities of the chemicals. Given the combination of health hazard and exposure potential components, the COSHH Essentials model recommended a control approach ‘special advice’ for both tasks, based on the potential reproductive hazard ascribed to toluene. This would not have been the same conclusion if some other chemical had been substituted (for example styrene, which has the same threshold limit value as toluene). Nevertheless, it was special advice, which had led to the combination of hygienic procedures in place at this plant. The probability of the combined exposure fractions exceeding unity was 0.0002 for the batch-making task indicating that the employees performing this task were most likely well protected below the OELs. Although the employees involved in the bucket-washing task had greater potential to 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

  3. 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/...

  4. 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 find that basal attachments at the chamber edge no longer form. Rather, bundles become unstable and interact in bulk by merging, extending, buckling, breaking, and recombining. These interactions lead to the emergence of a steady-state bulk mixing process that causes the super-diffusive transport of tracer particles and enhanced mixing of fluid. This mixing bears some resemblance to other mixing processes, including the biological example of cytoplasmic streaming. Finally, we show that a qualitatively new example of self-organization occurs when these active mixtures are put into water droplets in oil-water emulsions. The MT bundles migrate to the oil-water interface, forming a 2D active nematic. This active nematic exhibits a host of emergent properties, including the unbinding of +1/2 and -1/2 nematic defects from each other. The internal stresses of these active nematics also cause droplets to be self-propelled, leading to the possibility of studying a system of spherical swimmers, where new examples of self-organized behavior may occur.

  5. Self-organization of mixtures of fluorocarbon and hydrocarbon amphiphilic thiolates on the surface of gold nanoparticles.

    PubMed

    Posocco, Paola; Gentilini, Cristina; Bidoggia, Silvia; Pace, Alice; Franchi, Paola; Lucarini, Marco; Fermeglia, Maurizio; Pricl, Sabrina; Pasquato, Lucia

    2012-08-28

    Self-assembled monolayers composed of a mixture of thiolate molecules, featuring hydrocarbon or perfluorocarbon chains (H- and F-chains) terminating with a short poly(oxoethylene) (PEG) moiety, are the most extreme example of surfactant immiscibility on gold nanoparticles reported so far. The phase segregation between H-chains and F-chains and the consequent, peculiar folding of PEG chains are responsible for the increased affinity of a selected radical probe for the fluorinated region, which increases as the size of the fluorinated domains decrease, independently of the shape of such domains. This feature has been revealed by ESR measurements and an in silico innovative multiscale molecular simulations approach in explicit water. Our results reveal an underlying mechanism of a transmission of the organization of the monolayer from the inner region close to the gold surface toward the external hydrophilic PEG region. Moreover, this study definitively proves that a mixed monolayer is a complex system with properties markedly different from those characterizing the parent homoligand monolayers. PMID:22804477

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

    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.

  8. 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.

  9. Modeling of non-additive mixture properties using the Online CHEmical database and Modeling environment (OCHEM)

    PubMed Central

    2013-01-01

    The Online Chemical Modeling Environment (OCHEM, http://ochem.eu) is a web-based platform that provides tools for automation of typical steps necessary to create a predictive QSAR/QSPR model. The platform consists of two major subsystems: a database of experimental measurements and a modeling framework. So far, OCHEM has been limited to the processing of individual compounds. In this work, we extended OCHEM with a new ability to store and model properties of binary non-additive mixtures. The developed system is publicly accessible, meaning that any user on the Web can store new data for binary mixtures and develop models to predict their non-additive properties. The database already contains almost 10,000 data points for the density, bubble point, and azeotropic behavior of binary mixtures. For these data, we developed models for both qualitative (azeotrope/zeotrope) and quantitative endpoints (density and bubble points) using different learning methods and specially developed descriptors for mixtures. The prediction performance of the models was similar to or more accurate than results reported in previous studies. Thus, we have developed and made publicly available a powerful system for modeling mixtures of chemical compounds on the Web. PMID:23321019

  10. 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 variable. The data also suggest that each extraction method samples a separate component of soil-pore water. Consequently, centrifugation can be used with good success, particularly for efficient sampling of large areas. Azeotropic distillation is more appropriate when strict qualitative and quantitative data for desorption, desorption, and various types of kinetic studies are needed.

  11. 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.

  12. The use of growth and behavioral endpoints to assess the effects of pesticide mixtures upon aquatic organisms.

    PubMed

    Hasenbein, Simone; Lawler, Sharon P; Geist, Juergen; Connon, Richard E

    2015-05-01

    Aquatic communities are often subject to complex contaminant mixtures, usually at sublethal concentrations, that can cause long-term detrimental effects. Chemicals within mixtures can effectively interact, resulting in synergism, antagonism or additivity. We investigated the tertiary mixture effects of two pyrethroids, lambda-cyhalothrin and permethrin, and the organophosphate chlorpyrifos, evaluating sublethal endpoints; immobility and growth, on Chironomus dilutus in 10-day exposures. We utilized a toxic units (TU) approach, based on median lethal concentrations (LC50) for each compound. The concepts of independent action and concentration addition were used to compare predicted mixture toxicity to observed mixture toxicity. Increased immobility resulted from mixture concentrations ?1 TU (7.45 ng/L lambda-cyhalothrin × 24.90 ng/L permethrin × 129.70 ng/L chlorpyrifos), and single pesticides concentrations ?0.25 TU (5.50 ng/L lambda-cyhalothrin, 24.23 ng/L permethrin, 90.92 ng/L chlorpyrifos, respectively). Growth was inhibited by pesticide mixtures ?0.125 TU (1.04 ng/L lambda-cyhalothrin × 3.15 ng/L permethrin × 15.47 ng/L chlorpyrifos), and singly by lambda-cyhalothrin ?0.25 TU (5.50 ng/L), and permethrin ?0.167 TU (18.21 ng/L). The no observed effect concentrations (NOEC) for immobility and growth, for both mixture and single-pyrethroid exposure, were up to 8.0 and 12.0 times respectively lower than the corresponding NOEC for survival. The median effective concentrations (EC50) for growth (mixture and single-pyrethroid exposure) were up to 7.0 times lower than the respective LC50. This study reinforces that the integration of sublethal endpoints in monitoring efforts is powerful in discerning toxic effects that would otherwise be missed by solely utilizing traditional toxicity assessments. PMID:25630500

  13. 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...

  14. CONTRIBUTIONS OF TOLUENE AND ? -PINENE TO SOA FORMED IN AN IRRADIATED TOLUENE/?-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 ?-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydro...

  15. 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

  16. 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.

  17. Applicability of 0.05 mol kg(-1) potassium hydrogen phthalate as reference value pH standard in water-organic solvent mixtures.

    PubMed

    Izutsu, K; Yamamoto, H

    1998-12-01

    The applicability of 0.05 mol kg(-1) potassium hydrogen phthalate (KHPh(S), S=the solvent under study) as reference value pH standard (RVS) was studied in water-organic solvent mixtures. Phthalic acid in various aqueous organic solvent mixtures was titrated potentiometrically with Bu(4)NOH (MeOH), using a pH-ISFET and a glass electrode as pH-sensors, and the buffer capacity of the HPh(-) solution was roughly estimated from the difference between the first and second half-neutralization potentials. The influence of potassium ion to the buffer capacity was also studied, titrating KHPh and Et(4)NHPh with CF(3)SO(3)H and Bu(4)NOH (MeOH) and comparing the titration curves. The KHPh solution loses its buffer capacity if the solvent mixture has an aprotic property. For aqueous mixtures of protophilic aprotic solvents (e.g. DMSO and DMF), it is unsuitable as RVS if the water content is less than ca. 40 (v/v)%. The necessity of selecting subsidiary pH standard(s) is suggested for the solvent systems in which KHPh is inapplicable. PMID:18967421

  18. 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 assembly process include THF/water ratio, PS block length, the type and amount of organic counterions, and the mixing pathway. Their formation mechanism has been investigated from three aspects: (i) the chain structure of organic counterions, including spacer length, chain hydrophobicity between ionizable groups and the number of ionizable groups (amine group); (ii) molecular structure of the triblock copolymer, including block length of polystyrene and chain architecture; (iii) relative variation of the components, such as different ratios of THF to water and the different ratios of amine groups to acid groups. The first example of a novel micelle formed was the toroidal micelle. The toroidal micelle morphology, which is theoretically predicted but rarely observed, has been produced by the self assembly of PAA99- b-PMA73-b-PS66 in combination with 2,2-(ethylenedioxy)diethylamine (EDDA) and mixed THF/H2O solvent. It was found that toroids can be constructed by two mechanisms: elimination of energetically unfavored cylindrical micelle endcaps or perforation of disk-like micelles. Three-fold junctions were formed as intermediate structures to facilitate toroidal formation from cylindrical micelles. In order to construct toroids from cylindrical micelles, three requirements must be met: lower bending modulus (flexibility of cylinders), selfattraction between cylinders, and extra endcapping energy originating from chain packing frustration. Extremely high energy spheres can also fuse into toroids. Disk-like micelles can transform into a toroidal morphology when cylindrical packing geometry was initiated along the rims of disk-like micelles via solvent mixing that eventually perforated the disk center. The toroidal morphology can be kinetically trapped by either ridding the system of organic solvent or chemically crosslinking the PAA corona with EDDA via addition of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide (DPEM). The interaction of positively-charged, multivalent organic amines with the negatively-charged PAA corona plays a decisive role in the formation of these micelles. Inter-chain binding from the interaction of the two amine end groups of diamines with acid groups from different PAA corona blocks governs the final assembled structures. Diamines with hydrophilic spacers induced the formation of micelles with larger interfacial curvature as the spacer length increased. Disk-like micelles, cylindrical micelles or spherical micelles were observed with the gradual increase of hydrophilic spacer length. Diamines with variable hydrophobic spacers showed a similar effect when the spacer length was less than six methylene units. Application of longer hydrophobic diamines had a reverse effect on the interfacial curvature. This effect was attributed to the interaction of hydrophobic diamine hydrocarbon linking chains with the PMA-b-PS hydrophobic core. These findings indicate an easy method to tune micelle structure with multivalent organic counterions. (Abstract shortened by UMI.)

  19. 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.

  20. Densities and isobaric vapor-liquid equilibria for the mixtures formed by four butyl esters and 1-butanol

    SciTech Connect

    Gonzalez, E.; Ortega, J.

    1996-01-01

    Densities of 298.15 K and the vapor-liquid equilibria for 1-butanol + butyl methanoate, + butyl ethanoate, + butyl propanoate, and + butyl butanoate have been measured at 101.32 kPa in small capacity ebulliometer. All results were found to be thermodynamically consistent with a point-to-point test. The mixtures containing butyl methanoate and butyl ethanoate show azeotropes at T = 379.14 K, x = 0.871 and T = 389.64 K, x = 0.222, respectively. Different group-contribution methods were applied to these mixtures.

  1. Theoretical analysis for condensation heat transfer of binary refrigerant mixtures with annular flow in horizontal mini-tubes

    NASA Astrophysics Data System (ADS)

    Zhang, Hui-Yong; Li, Jun-Ming; Sun, Ji-Liang; Wang, Bu-Xuan

    2016-01-01

    A theoretical model is developed for condensation heat transfer of binary refrigerant mixtures in mini-tubes with diameter about 1.0 mm. Condensation heat transfer of R410A and R32/R134a mixtures at different mass fluxes and saturated temperatures are analyzed, assuming that the phase flow pattern is annular flow. The results indicate that there exists a maximum interface temperature at the beginning of condensation process for azeotropic and zeotropic mixtures and the corresponding vapor quality to the maximum value increases with mass flux. The effects of mass flux, heat flux, surface tension and tube diameter are analyzed. As expected, the condensation heat transfer coefficients increase with mass flux and vapor quality, and increase faster in high vapor quality region. It is found that the effects of heat flux and surface tension are not so obvious as that of tube diameter. The characteristics of condensation heat transfer of zeotropic mixtures are consistent to those of azeotropic refrigerant mixtures. The condensation heat transfer coefficients increase with the concentration of the less volatile component in binary mixtures.

  2. Phase diagrams of binary mixtures of patchy colloids with distinct numbers and types of patches: The empty fluid regime

    NASA Astrophysics Data System (ADS)

    Heras, Daniel de las; Tavares, José Maria; da Gama, Margarida M. Telo

    2011-03-01

    We investigate the effect of distinct bonding energies on the onset of criticality of low functionality fluid mixtures. We focus on mixtures of particles with two and three patches as this includes the mixture where "empty" fluids were originally reported. In addition to the number of patches, the species differ in the type of patches or bonding sites. For simplicity, we consider that the patches on each species are identical: one species has three patches of type A and the other has two patches of type B. We have found a rich phase behavior with closed miscibility gaps, liquid-liquid demixing, and negative azeotropes. Liquid-liquid demixing was found to pre-empt the "empty" fluid regime, of these mixtures, when the AB bonds are weaker than the AA or BB bonds. By contrast, mixtures in this class exhibit "empty" fluid behavior when the AB bonds are stronger than at least one of the other two. Mixtures with bonding energies ?BB = ?AB and ?AA < ?BB, were found to exhibit an unusual negative azeotrope.

  3. Phase diagrams of binary mixtures of patchy colloids with distinct numbers and types of patches: the empty fluid regime.

    PubMed

    de las Heras, Daniel; Tavares, José Maria; da Gama, Margarida M Telo

    2011-03-14

    We investigate the effect of distinct bonding energies on the onset of criticality of low functionality fluid mixtures. We focus on mixtures of particles with two and three patches as this includes the mixture where "empty" fluids were originally reported. In addition to the number of patches, the species differ in the type of patches or bonding sites. For simplicity, we consider that the patches on each species are identical: one species has three patches of type A and the other has two patches of type B. We have found a rich phase behavior with closed miscibility gaps, liquid-liquid demixing, and negative azeotropes. Liquid-liquid demixing was found to pre-empt the "empty" fluid regime, of these mixtures, when the AB bonds are weaker than the AA or BB bonds. By contrast, mixtures in this class exhibit "empty" fluid behavior when the AB bonds are stronger than at least one of the other two. Mixtures with bonding energies ?(BB) = ?(AB) and ?(AA) < ?(BB), were found to exhibit an unusual negative azeotrope. PMID:21405190

  4. Theoretical analysis for condensation heat transfer of binary refrigerant mixtures with annular flow in horizontal mini-tubes

    NASA Astrophysics Data System (ADS)

    Zhang, Hui-Yong; Li, Jun-Ming; Sun, Ji-Liang; Wang, Bu-Xuan

    2015-06-01

    A theoretical model is developed for condensation heat transfer of binary refrigerant mixtures in mini-tubes with diameter about 1.0 mm. Condensation heat transfer of R410A and R32/R134a mixtures at different mass fluxes and saturated temperatures are analyzed, assuming that the phase flow pattern is annular flow. The results indicate that there exists a maximum interface temperature at the beginning of condensation process for azeotropic and zeotropic mixtures and the corresponding vapor quality to the maximum value increases with mass flux. The effects of mass flux, heat flux, surface tension and tube diameter are analyzed. As expected, the condensation heat transfer coefficients increase with mass flux and vapor quality, and increase faster in high vapor quality region. It is found that the effects of heat flux and surface tension are not so obvious as that of tube diameter. The characteristics of condensation heat transfer of zeotropic mixtures are consistent to those of azeotropic refrigerant mixtures. The condensation heat transfer coefficients increase with the concentration of the less volatile component in binary mixtures.

  5. Energy efficient membrane processes for the separation of organic liquids: Part 3 (Supplement report): Final report, September 28, 1982--December 31, 1986

    SciTech Connect

    Cabasso, I.; Acharya, H.R.; Korngold, E.; Liu, Z.; Stern, S.A.; Li, W.; Makenzie, T.; Poda, E.

    1987-10-01

    In this supplemental report, two pilot plants are described. The first is air purge pervaporation (or air sweep pervaporation hollow fiber system) for the separation of azeotropic aqueous liquids. The second describes pilot plant construction and operation for the perstraction process. Several configurations for the air purge pervaporation process were studied and were shown to yield high purity products e.g., isopropanol from the azeotropic mixture with water was enriched to 99.9%. Parallel and U-module configuration were used and durability experiments up to 120 days were carried out successfully. The report describes the first successful low scale pilot plant unit and elements for perstraction process. The conclusion and outcome of this study are two fold. First, membrane systems in a pilot plant unit proved to be very efficient in upgrading nonpermeable components in a membrane system and especially when dealing with azeotropic mixtures. For example, more than 99% isopropanol can be produced from a feed liquid which is 88% i-PrOH (azeotropic mixture with water). The membrane system proved to be durable within the time limit of the experiments (120 days). Second, all parameters including the various configurations of the pilot plants (which are still being studied) are available for chemical, petroleum, and other US industries. 3 refs., 22 figs., 2 tabs.

  6. Evaluation of the risk of mixtures of paddy insecticides and their transformation products to aquatic organisms in the Sakura River, Japan.

    PubMed

    Iwafune, Takashi; Yokoyama, Atsushi; Nagai, Takashi; Horio, Takeshi

    2011-08-01

    To assess the risk of mixtures of six paddy insecticides and their transformation products (TPs) to aquatic organisms in the Sakura River, Japan, their concentrations in the river water were monitored during the rice cultivation season in 2008 and 2009, and acute toxicity tests for Cheumatopsyche brevilineata (caddisflies) and Daphnia magna (daphnids), surrogate test species for caddisflies and cladocerans, respectively, were conducted. The mixture of fipronil, applied in the rice nursery box, and its desulfinyl, sulfide, and sulfone TPs were detected in the river for several months after transplanting, and they were more toxic to C. brevilineata than the other tested compounds. The toxicities of the parent compound and its TPs, such as fipronil and its TPs, may be related to their hydrophobicities. Risk quotients for mixtures (RQ(mix)) of only parent compounds did not exceed 1, but, in mid-June 2009, the RQ(mix) of parent compounds and TPs for caddisflies exceeded 1. Diazinon, fenitrothion, and fenthion sprayed on the rice crop and their TPs posed a sporadic risk for cladocerans, depending on the application timing, whereas fipronil TPs contributed to the RQ(mix) for caddisflies for several months after transplanting. The risk of mixtures of insecticides and their TPs differed seasonally between caddisflies and cladocerans, depending on insecticide application timing and the persistence and toxicity of TPs. PMID:21560145

  7. 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.

  8. The performance of a residential heat pump operating with a nonazeotropic binary refrigerant mixture

    NASA Astrophysics Data System (ADS)

    Didion, D.; Mulroy, W.

    Results of laboratory measurement of the performance change of a substantially unmodified residential heat pump designed for 222 when charged with a non azeotropic, binary mixture of R1381 and R152a is presented. Results are presented for various sizes of fixed expansion devices. The effect of gliding temperature in the saturation zone was found to be small. The effect of compositions shift by flash distillation in the accumulator was found to measurably improve low temperature heating performance. It was further observed that some system modification (such as the addition of a receiver) could have further enhanced this low temperature heating performance improvement.

  9. Closed-loop phase diagrams, vaporization, and multicriticality in binary liquid mixtures

    NASA Astrophysics Data System (ADS)

    Caflisch, Robert G.; Walker, James S.

    1983-09-01

    The coupled Potts-Ising models of Walker and Vause, which successfully describe closed-loop phase diagrams in hydrogen-bonding mixtures, are generalized to encompass the vapor phase, and are studied using position-space renormalization-group techniques. Global phase diagrams are generated, exhibiting such features as miscibility-immiscibility criticality, liquid-vapor critical points, critical end points, and bicritical and tricritical points. In addition, new types of phase diagrams are found, involving upper and lower azeotropes, for example, which are expected to be physically realizable in experimental systems.

  10. 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.

  11. A Combined Kinetic and Volatility Basis Set Approach to Model Secondary Organic Aerosol from Toluene and Diesel Exhaust/Meat Cooking Mixtures

    NASA Astrophysics Data System (ADS)

    Parikh, H. M.; Carlton, A. G.; Zhang, H.; Kamens, R.; Vizuete, W.

    2011-12-01

    Secondary organic aerosol (SOA) is simulated for 6 outdoor smog chamber experiments using a SOA model based on a kinetic chemical mechanism in conjunction with a volatility basis set (VBS) approach. The experiments include toluene, a non-SOA-forming hydrocarbon mixture, diesel exhaust or meat cooking emissions and NOx, and are performed under varying conditions of relative humidity. SOA formation from toluene is modeled using a condensed kinetic aromatic mechanism that includes partitioning of lumped semi-volatile products in particle organic-phase and incorporates particle aqueous-phase chemistry to describe uptake of glyoxal and methylglyoxal. Modeling using the kinetic mechanism alone, along with primary organic aerosol (POA) from diesel exhaust (DE) /meat cooking (MC) fails to simulate the rapid SOA formation at the beginning hours of the experiments. Inclusion of a VBS approach with the kinetic mechanism to characterize the emissions and chemistry of complex mixture of intermediate volatility organic compounds (IVOCs) from DE/MC, substantially improves SOA predictions when compared with observed data. The VBS model includes photochemical aging of IVOCs and evaporation of POA after dilution. The relative contribution of SOA mass from DE/MC is as high as 95% in the morning, but substantially decreases after mid-afternoon. For high humidity experiments, aqueous-phase SOA fraction dominates the total SOA mass at the end of the day (approximately 50%). In summary, the combined kinetic and VBS approach provides a new and improved framework to semi-explicitly model SOA from VOC precursors in conjunction with a VBS approach that can be used on complex emission mixtures comprised with hundreds of individual chemical species.

  12. Large-scale enzymatic production of natural flavour esters in organic solvent with continuous water removal.

    PubMed

    Gubicza, L; Kabiri-Badr, A; Keoves, E; Belafi-Bako, K

    2001-11-30

    A new, large-scale process was developed for the enzymatic production of low molecular weight flavour esters in organic solvent. Solutions for the elimination of substrate and product inhibitions are presented. The excess water produced during the process was continuously removed by hetero-azeotropic distillation and esters were produced at yields of over 90%. PMID:11090691

  13. 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.

  14. 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

    2016-04-15

    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

  15. 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.

  16. 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.

  17. 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...

  18. 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

  19. 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. PMID:24463251

  20. New approach to complex organic compounds mixtures analysis based on gas chromatography-atmospheric pressure photoionization-mass-spectrometry.

    TOXLINE Toxicology Bibliographic Information

    Revelsky IA; Yashin YS

    2012-12-15

    The mass-spectra of a number of different hydrocarbons were obtained using atmospheric pressure photoionization (APPhI) and photochemical ionization (APPhCI) mass-spectrometry. The respective mass-spectra consisted mainly of molecular (M(+)) or quasimolecular (MH(+)) ion peaks or both. The composition of aromatic hydrocarbons in straight-run gasoline was investigated using standard PIONA method, based on capillary GC and retention time indexes, and GC/MS (APPhI). 56 aromatic hydrocarbons were identified using GC/MS (APPhI) and 43-using standard PIONA method. The opportunities of MS (APPHCI) for determination of impurities in pure hydrocarbons and for direct analysis of complex mixtures without separation were demonstrated when MS (APPhCI) analysis for GC standards of benzene and toluene was carried out (main component vapor was reagent gas). The targeted PAHs and phtalates were registered selectively in 44 component model mixture of semivolatiles with partial or without separation of the components, using GC/MS (APPhI).

  1. New approach to complex organic compounds mixtures analysis based on gas chromatography-atmospheric pressure photoionization-mass-spectrometry.

    PubMed

    Revelsky, I A; Yashin, Yu S

    2012-12-15

    The mass-spectra of a number of different hydrocarbons were obtained using atmospheric pressure photoionization (APPhI) and photochemical ionization (APPhCI) mass-spectrometry. The respective mass-spectra consisted mainly of molecular (M(+)) or quasimolecular (MH(+)) ion peaks or both. The composition of aromatic hydrocarbons in straight-run gasoline was investigated using standard PIONA method, based on capillary GC and retention time indexes, and GC/MS (APPhI). 56 aromatic hydrocarbons were identified using GC/MS (APPhI) and 43-using standard PIONA method. The opportunities of MS (APPHCI) for determination of impurities in pure hydrocarbons and for direct analysis of complex mixtures without separation were demonstrated when MS (APPhCI) analysis for GC standards of benzene and toluene was carried out (main component vapor was reagent gas). The targeted PAHs and phtalates were registered selectively in 44 component model mixture of semivolatiles with partial or without separation of the components, using GC/MS (APPhI). PMID:23182582

  2. Development of cellulose acetate propionate membrane for separation of ethanol and ethyl tert-butyl ether mixtures

    SciTech Connect

    Luo, G.S.; Niang, M.; Schaetzel, P.

    1997-04-01

    For pervaporation separation of ethanol and ethyl tert-butyl ether mixtures, a cellulose acetate propionate membrane was chosen as the experimental membrane because of its high selectivity and good mass fluxes. The properties of the membranes were evaluated by the pervaporation separation of mixtures of ethyl tert-butyl ether/ethanol and the sorption experiments. The experimental results showed that the selectivity and the permeates depend on the ethanol concentration in the feed and the experimental temperature. With increases of the ethanol weight fraction in the feed and the temperature, the total and partial mass fluxes increased. With respect to the temperature, ethanol mass flux obeys the Arrhenius equation. The selectivity of this membrane decreases as the temperature and the ethanol concentration in the feed increase. This membrane shows special characteristics at the azeotropic composition. In the vicinity of the azeotropic point, minimum values of ethanol concentration in the permeate and in sorption solution are obtained. The swelling ratios increase when temperature and the ethanol concentration in the feed are increasing. The ethanol concentration in the sorption solution is also influenced by the temperature and the mixture`s composition. When the temperature increases, the sorption selectivity of the membrane decreases.

  3. In vitro study on the effect of organic acids on Campylobacter jejuni/coli populations in mixtures of water and feed.

    PubMed

    Chaveerach, P; Keuzenkamp, D A; Urlings, H A P; Lipman, L J A; van Knapen, F

    2002-05-01

    Gastroenteritis caused by Campylobacter spp. infection has been recognized as one of the important public health problems in the developed countries. Outbreaks mostly originate from the consumption of contaminated poultry or infected water. The aim of this study was to determine the bactericidal activity on Campylobacter spp. of organic acids individually and in combinations at different pH levels and times and to compare bactericidal activities with activities of commercially available products. Ten strains of Campylobacter spp. were added in a mixture of water with commercial broiler feed, separately adjusted by four acids: formic, acetic, propionic, and hydrochloric acids, into pH 4.0, 4.5, 5.0, and 5.5. A combination of three organic acids was used in two different formulation ratios: formic:acetic:propionic at 1:2:3 and 1:2:5, at pH 4.0, 4.5, 5.0, and 5.5. All organic acids showed the strongest bactericidal effect on Campylobacter at pH 4.0. In contrast, at pH 5.0 and 5.5, the bactericidal activity of the four acids was low. The combination of organic acids showed a synergistic bactericidal activity at pH 4.5. Interestingly, the effect of the combined organic acids was stronger than the commercial products. Morphological cell changes were studied by transmission electron microscopy to determine the effect of the organic acids on the cell structure of Campylobacter. Some loss of outer membranes of the bacteria could be found in treated groups. Therefore, it can be concluded that organic acids, individually or in combination, have a strong bactericidal effect on Campylobacter spp. Routine application of organic acids to the water supply on poultry farms could prevent or diminish Campylobacter transmission. PMID:12033410

  4. Application of Steam Flushing to Removal of a DNAPL Mixture of Volatile and Very Low Volatility Organic Compounds

    NASA Astrophysics Data System (ADS)

    Sleep, B. E.; Zhang, Z.

    2009-05-01

    A laboratory study was performed to assess the effectiveness of steam flushing for removal of a dense nonaqueous phase liquid (DNAPL) mixture of monochlorobenzene (MCB) and DDT. MCB has a boiling point of 131 C, while DDT has a melting point of approximately 110 C, but is soluble in MCB. In the study 600 mL of a MCB-DDT DNAPL mixture was injected into a medium sand layer above a capillary barrier (silt) in a cell of dimension 110 cm long by 60 cm high by 10 cm thick. After the DNAPL became immobilized as a pool on the capillary barrier steam was flushed through the system at an inlet temperature of 135 C and a pressure of 100 kPa, to represent removal of DNAPL from approximately 10 m below the water table. Approximately 3.5 pore volumes of steam (as condensate) were flushed through the DNAPL zone above the capillary barrier over an 11 hour period. Temperatures in the DNAPL zone exceeded the melting point of pure DDT and reached the boiling point of MCB. Initial DNAPL removal was due to hydraulic displacement (as indicated by DNAPL composition close to the source DNAPL composition), followed by primarily MCB removal by steam distillation. A total of 255 mL of DNAPL was recovered. Soil sampling following steam flushing showed levels of both MCB and DDT remaining in the original DNAPL zone that were consistent with the presence of DNAPL. Significant levels of MCB and DDT were also found below the capillary barrier, indicating that downward movement of MCB and DDT occurred, likely due to desaturation of the capillary barrier during steam flushing. In addition, heating to temperatures associated with significant depths below the water table enhances the mobility of the MCB-DDT DNAPL by reducing the DNAPL viscosity and preventing the solidification of DDT that might otherwise occur with MCB removal.

  5. Crystal nucleation in binary hard sphere mixtures: A Monte Carlo simulation study

    NASA Astrophysics Data System (ADS)

    Punnathanam, S.; Monson, P. A.

    2006-07-01

    We present calculations of the nucleation barrier during crystallization in binary hard sphere mixtures under moderate degrees of supercooling using Monte Carlo simulations in the isothermal-isobaric semigrand ensemble in conjunction with an umbrella sampling technique. We study both additive and negatively nonadditive binary hard sphere systems. The solid-fluid phase diagrams of such systems show a rich variety of behavior, ranging from simple spindle shapes to the appearance of azeotropes and eutectics to the appearance of substitutionally ordered solid phase compounds. We investigate the effect of these types of phase behavior upon the nucleation barrier and the structure of the critical nucleus. We find that the underlying phase diagram has a significant effect on the mechanism of crystal nucleation. Our calculations indicate that fractionation of the species upon crystallization increases the difficulty of crystallization of fluid mixtures and in the absence of fractionation (azeotropic conditions) the nucleation barrier is comparable to pure fluids. We also calculate the barrier to nucleation of a substitutionally ordered compound solid. In such systems, which also show solid-solid phase separation, we find that the phase that nucleates is the one whose equilibrium composition is closer to the composition of the fluid phase.

  6. Crystal nucleation in binary hard sphere mixtures: a Monte Carlo simulation study.

    PubMed

    Punnathanam, S; Monson, P A

    2006-07-14

    We present calculations of the nucleation barrier during crystallization in binary hard sphere mixtures under moderate degrees of supercooling using Monte Carlo simulations in the isothermal-isobaric semigrand ensemble in conjunction with an umbrella sampling technique. We study both additive and negatively nonadditive binary hard sphere systems. The solid-fluid phase diagrams of such systems show a rich variety of behavior, ranging from simple spindle shapes to the appearance of azeotropes and eutectics to the appearance of substitutionally ordered solid phase compounds. We investigate the effect of these types of phase behavior upon the nucleation barrier and the structure of the critical nucleus. We find that the underlying phase diagram has a significant effect on the mechanism of crystal nucleation. Our calculations indicate that fractionation of the species upon crystallization increases the difficulty of crystallization of fluid mixtures and in the absence of fractionation (azeotropic conditions) the nucleation barrier is comparable to pure fluids. We also calculate the barrier to nucleation of a substitutionally ordered compound solid. In such systems, which also show solid-solid phase separation, we find that the phase that nucleates is the one whose equilibrium composition is closer to the composition of the fluid phase. PMID:16848593

  7. ASSESSING THE INTERACTIONS OF ORGANIC COMPOUNDS DURING BIODEGRADATION OF COMPLEX WASTE MIXTURES BY NATURALLY OCCURRING BACTERIAL ASSEMBLAGES

    EPA Science Inventory

    Selected organic chemicals were tested to determine the minimum concentrations at which complete inhibition of microbial degradative processes occurred. omplete inhibition did not occur at less than 2 g/L phenols 10 g/L toluene or n-butanol, and 100 g/L acetone, benzene or methan...

  8. 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. PMID:25572270

  9. 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. PMID:22178276

  10. Organic light-emitting devices with a mixture emitting layer of tris-(8-hydroxyquinoline) aluminum and 4,4'-bis(carbazol-9-yl)-biphenyl

    NASA Astrophysics Data System (ADS)

    Chen, B. J.; Sun, X. W.; Sarma, K. R.

    2006-06-01

    Organic light-emitting devices with a mixture of tris-(8-hydroxyqunoline) aluminum (Alq3) and 4,4'-bis(carbazol-9-yl)-biphenyl (CBP) as the emitting layer have been fabricated. The devices were fabricated in the same run with a standard device without CBP for comparison, with an identical structure of indium tin oxide (ITO)/m-MTDATA (80nm)/NPB (20nm)/CBP:Alq3 (40nm)/BCP (10nm)/Alq3 (60nm)/Mg:Ag (200nm), where m-MTDATA is 4,4',4?-tris(N-3-methylphenyl-N-phenyl-amino) triphenylamine, which is used to improve hole injection; NPB is N ,N'-di(naphth-2-yl)-N ,N'-diphenyl-benzidine; and BCP is 2,9-Dimethyl-4,7-diphenyl-1,110-phenanthorline. The ratio of CBP to Alq3 in mixture was varied from 0 to 2. For device with a ratio of 0.5, the current efficiency and power efficiency were significantly improved by 35% and 32%, respectively, compared to the standard device with Alq3 only as emitting layer. By increasing the ratio to 2, the current efficiency and power efficiency were dropped by 20% and 11%, respectively. The electroluminescence spectra showed a slight blueshift with the increase of CBP to Alq3 ratio.

  11. 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

  12. IUPAC-NIST Solubility Data Series. 98. Solubility of Polycyclic Aromatic Hydrocarbons in Pure and Organic Solvent Mixtures--Revised and Updated. Part 3. Neat Organic Solvents

    NASA Astrophysics Data System (ADS)

    Acree, William E.

    2013-03-01

    This work updates Vols. 54, 58, and 59 in the IUPAC Solubility Data Series and presents solubility data for polycyclic aromatic hydrocarbon solutes dissolved in neat organic solvents. Published solubility data for acenaphthene, anthracene, biphenyl, carbazole, dibenzofuran, dibenzothiophene, fluoranthene, fluorene, naphthalene, phenanthrene, phenothiazine, pyrene, thianthrene, and xanthene that appeared in the primary literature from 1995 to the end of 2011 are compiled and critically evaluated. Experimental solubility data for more than 550 different solute-organic solvent systems are included. Solubility data published prior to 1995 were contained in three earlier volumes (Vols. 54, 58, and 59) and are not repeated in this volume.

  13. Determination of the H isotopic composition of individual components in fine-scale mixtures of organic matter and phyllosilicates with the nanoscale secondary ion mass spectrometry.

    PubMed

    Piani, Laurette; Remusat, Laurent; Robert, François

    2012-12-01

    When organic matter is mixed on a nanometer scale with clay minerals, the individual D/H ratios of the two H-bearing phases cannot be directly measured even with the nominal spatial resolution of nanoscale secondary ion mass spectrometry (NanoSIMS, 50-100 nm). To overcome this limitation, a new analytical protocol is proposed based on the deconvolution of the D(-)/H(-) and (16)OD(-)/(16)OH(-) ionic ratios measured by NanoSIMS. Indeed, since the yields of H(-) and (16)OH(-) are different for organics and clays, it should be theoretically possible to determine the mixing ratio of these two components in the area analyzed by the ion probe. Using organics with different D/H ratios, the interdependence of the D(-)/H(-) and (16)OD(-)/(16)OH(-) ionic ratios was determined in pure samples. Then using the H(-) and (16)OH(-) yields and the isotopic ratios measured on pure organic matter and clays, the expected D(-)/H(-) and (16)OD(-)/(16)OH(-) variations as a function of the mixing proportions were determined. These numerical predictions are consistent with measurements on laboratory prepared mixtures of D-rich organic matter and D-poor phyllosilicates, validating both the proposed experimental protocol and its use for meteorites. With an improvement of the precision of the ionic ratios by a factor of 10, it should possible to expend this protocol to samples having natural terrestrial D/H variations. Such an improvement could be attainable with the development of synthetic deuterated reference samples. PMID:23121456

  14. 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

  15. 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. PMID:1574610

  16. 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 by the increased parasitic refrigerant-side pressure drop utiortunately resulting from tkbrication requirements of the identical order circuiting.

  17. Heat transfer in nucleate boiling of R134a/R152a mixtures

    NASA Astrophysics Data System (ADS)

    Shi, Kehong; Spindler, Klaus; Hahne, Erich

    2010-11-01

    Heat transfer coefficients were measured on a horizontal platinum wire and converted to data on horizontal copper tubes. The measurements spanned a large region of pressures p* = p/pcrit = 0.05-0.50 and heat fluxes of q = 103-1.5 × 105 W/m2. The preparation of the test equipment is described. The effects of pressure and concentration on the heat transfer coefficients are shown. The mixture behaves very much like an azeotropic mixture; concentration has only a small effect, the heat transfer coefficients can be obtained from the heat transfer coefficients of the pure components according to their molar fractions. The conversion steps from wire- to tube-data are presented. A comparison of wire-data with correlations given in literature is shown. It renders good agreement.

  18. A high performance membrane for sorption and pervaporation separation of ethyl tert-butyl ether and ethanol mixtures

    SciTech Connect

    Luo, G.S.; Niang, M.; Schaetzel, P.

    1999-02-01

    A new kind of membrane was prepared by blending 5 wt% poly(1-vinylpyrrolidone-co-acrylic acid) with cellulose acetate propionate for the separation of ethyl tert-butyl ether and ethanol mixtures. The membrane properties were evaluated by pervaporation and sorption of mixtures of ethyl tert-butyl ether/ethanol. The experimental results show that the selectivity and the fluxes of this membrane depend upon the feed composition and upon the temperature. The minimum values of ethanol concentration in the permeate and in the sorption solution were obtained in the vicinity of the azeotropic point. Compared with the pure CAP membrane, the new membrane shows high performance for the separation of ETBE and EtOH mixtures, especially under high temperature conditions.

  19. 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. PMID:26845181

  20. Aggregation behavior of sodium lauryl ether sulfate with a positively bicharged organic salt and effects of the mixture on fluorescent properties of conjugated polyelectrolytes.

    PubMed

    Tang, Yongqiang; Liu, Zhang; Zhu, Linyi; Han, Yuchun; Wang, Yilin

    2015-02-24

    The aggregation behavior of anionic single-chain surfactant sodium lauryl ether sulfate containing three ether groups (SLE3S) with positively bicharged organic salt 1,2-bis(2-benzylammoniumethoxy)ethane dichloride (BEO) has been investigated in aqueous solution, and the effects of the BEO/SLE3S aggregate transitions on the fluorescent properties of anionic conjugated polyelectrolyte MPS-PPV with a larger molecular weight and cationic conjugated oligoelectrolyte DAB have been evaluated. Without BEO, SLE3S does not affect the fluorescent properties of MPS-PPV and only affects the fluorescent properties of DAB at a higher SLE3S concentration. With the addition of BEO, SLE3S and BEO form gemini-like surfactant (SLE3S)2-BEO. When the BEO/SLE3S molar ratio is fixed at 0.25, with increasing the BEO/SLE3S concentration, the BEO/SLE3S mixture forms large, loosely arranged aggregates and then transforms to closely packed spherical aggregates and finally to long thread-like micelles. The photoluminescence (PL) intensity of MPS-PPV varies with the morphologies of the BEO/SLE3S aggregates, while the PL intensity of DAB is almost independent of the aggregate morphologies. The results demonstrate that gemini-like surfactants formed through intermolecular interactions can effectively adjust the fluorescent properties of conjugated polyelectrolytes. PMID:25641198

  1. 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

  2. Modeling secondary organic aerosol formation from xylene and aromatic mixtures using a dynamic partitioning approach incorporating particle aqueous-phase chemistry (II)

    NASA Astrophysics Data System (ADS)

    Parikh, Harshal M.; Carlton, Annmarie G.; Zhou, Yang; Zhang, Haofei; Kamens, Richard M.; Vizuete, William

    2012-09-01

    Formation of secondary organic aerosol (SOA) is simulated for 14 outdoor smog chamber experiments using condensed gas-phase regulatory mechanisms and a new SOA framework. This framework is based on empirical parameterizations of independent chamber experiments and includes role of glyoxal and methylglyoxal in formation of particle aqueous-phase. To evaluate for regulatory applications, the chamber experiments include an urban non-SOA VOC mixture and NOx, with either injections of o/p-xylenes or toluene. The experiments are performed under varying conditions of relative humidity (RH) and in the presence of low initial background seed. Gas-particle partitioning of semi-volatile products into particle organic-phase is modeled using a dynamic partitioning approach with reactive uptake coefficient as the principal transport and kinetic parameter. Aqueous-phase SOA is predicted using formulations that describe the irreversible loss of both glyoxal and methylglyoxal to particle aqueous-phase. The predicted SOA mass in the new framework is evaluated using two regulatory gas-phase mechanisms - CB05 or SAPRC07 and, two regulatory parameterization schemes to predict semi-volatile product formation - an Odum-type two-product model and volatility basis-set (VBS). Predictions from the new SOA framework reproduce SOA mass within the uncertainty range of observations, irrespective of the choice of gas-phase mechanism and SOA parameterization scheme (root mean square error [RMSE] range of 0.18-3.08 ?g m-3). Further, model results suggest strong possibility of dominance of bulk-process under low seed conditions and surface-uptake process under high seed for aqueous-phase SOA formation. Sensitivity analysis to the hygroscopic nature of aqueous-phase SOA indicates an uncertainty of a factor of 2 in bulk-process and surface-uptake rates. In summary, the results strongly point to considering mass-transfer and kinetic limitations in regulatory air quality models at low ambient seed concentrations and highlight the importance of aqueous-phase SOA for aromatics under high-RH conditions.

  3. A Thermodynamic Property Model for R-125/143a Mixtures Based on a New Cubic Equation of State

    NASA Astrophysics Data System (ADS)

    Zhang, Heng-Liang; Tada, Satoru; Waranabe, Koichi

    The binary mixture of two hydrofluorocarbons, R-125 and R-143a, behaves almost like an azeotrope and has been considered as a promising refrigerant to substitute R-502. In this paper, we present a thermodynamic property model for the R-125/143a system, which was developed on the basis of a new cubic equation of state proposed in our previous publications. The essential thermodynamic properties such as PVTx properties, vapor-liquid equilibrium, enthalpy, entropy, isobaric specific heat, and speed of sound are well represented simultaneously by the new model in the entire fluid-phase of theR-125/143a system including the pure components.The model is valid for any composition with thermodynamic consistency to cover a range broad enough for refrigeration engineering applications. A pressure-enthalpy diagram for the R-125/143a mixture with 50 mass% R-125 is also presented.

  4. 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. PMID:25287741

  5. 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 ?-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 ?-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 ?-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 ?M ?-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. PMID:26159488

  6. 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 (?p) 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 (?h) 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

  7. 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. PMID:26845107

  8. 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

  9. 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

  10. 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

    2015-12-01

    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. PMID:26456707

  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.

    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

  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

    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.

  13. Influence of catalyticity of a porous medium on the concentration limit of filtration combustion of a water-organic mixture in a reversible flow reactor

    NASA Astrophysics Data System (ADS)

    Dobrego, K. V.; Koznacheev, I. A.

    2012-09-01

    The problem on oxidation purification of water in a reversible flow reactor with the use of a catalyst has been studied by numerical methods. We have made comparative studies of the concentration limits of mixture combustion attained in inert and catalytic porous media reactors at varied values of the liquid flow rate, the reactor length, the heat loss coefficient, and the size of the packed bed. It has been established that the use of a catalyst leads to an insignificant decrease in the concentration limit: 11.6% against 13.4% (adiabatic case) and 12.5% against 13.9% (standard insulation).

  14. PH-metric log P 11. pKa determination of water-insoluble drugs in organic solvent-water mixtures.

    PubMed

    Avdeef, A; Box, K J; Comer, J E; Gilges, M; Hadley, M; Hibbert, C; Patterson, W; Tam, K Y

    1999-08-01

    The apparent acid dissociation constants (p(s)Ka) of two water-insoluble drugs, ibuprofen and quinine, were determined pH-metrically in acetonitrile water, dimethylformamide water, dimethylsulfoxide water, 1,4-dioxane-water, ethanol water, ethylene glycol-water, methanol water and tetrahydrofuran water mixtures. A glass electrode calibration procedure based on a four-parameter equation (pH = alpha + SpcH + jH[H+]+jOH[OH-]) was used to obtain pH readings based on the concentration scale (pcH). We have called this four-parameter method the Four-Plus technique. The Yasuda Shedlovsky extrapolation (p(s)Ka + log [H2O] = A/epsilon + B) was used to derive acid dissociation constants in aqueous solution (pKa). It has been demonstrated that the pKa values extrapolated from such solvent water mixtures are consistent with each other and with previously reported measurements. The suggested method has also been applied with success to determine the pKa values of two pyridine derivatives of pharmaceutical interest. PMID:10704132

  15. In situ removal of arsenic from groundwater by using permeable reactive barriers of organic matter/limestone/zero-valent iron mixtures.

    PubMed

    Gibert, O; de Pablo, J; Cortina, J-L; Ayora, C

    2010-08-01

    In this study, two mixtures of municipal compost, limestone and, optionally, zero-valent iron were assessed in two column experiments on acid mine treatment. The effluent solution was systematically analysed throughout the experiment and precipitates from both columns were withdrawn for scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry analysis and, from the column containing zero-valent iron, solid digestion and sequential extraction analysis. The results showed that waters were cleaned of arsenic, metals and acidity, but chemical and morphological analysis suggested that metal removal was not due predominantly to biogenic sulphide generation but to pH increase, i.e. metal (oxy)hydroxide and carbonate precipitation. Retained arsenic and metal removal were clearly associated to co-precipitation with and/or sorption on iron and aluminum (oxy)hydroxides. An improvement on the arsenic removal efficiency was achieved when the filling mixture contained zero-valent iron. Values of arsenic concentrations were then always below 10 microg/L. PMID:20387094

  16. Six interaction profiles for simple mixtures.

    PubMed

    Pohl, Hana R; Roney, Nickolette; Wilbur, Sharon; Hansen, Hugh; De Rosa, Christopher T

    2003-10-01

    The Agency for Toxic Substances and Disease Registry (ATSDR) has a program for chemical mixtures that encompasses research on chemical mixtures toxicity, health risk assessment, and development of innovative computational methods. ATSDR prepared a guidance document that instructs users on how to conduct health risk assessment on chemical mixtures (Guidance Manual for the Assessment of Joint Toxic Action of Chemical Mixtures). ATSDR also developed six interaction profiles for chemical mixtures. Two profiles were developed for persistent environmental chemicals that are often found in contaminated fish and also can be detected in human breast milk. The mixture included chlorinated dibenzo-p-dioxins, hexachlorobenzene, dichlorodiphenyl dichloroethane, methyl mercury, and polychlorinated biphenyls. Two profiles each were developed for mixtures of metals and mixtures of volatile organic chemicals (VOCs) that are frequently found at hazardous waste sites. The two metal profiles dealt with (a) lead, manganese, zinc, and copper; and (b) arsenic, cadmium, chromium, and lead; the two VOCs mixtures dealt with (a) 1,1,1-trichloroethane, 1,1-dichloroethane, trichloroethylene, and tetrachloroethylene; and (b) benzene, ethylbenzene, toluene, and xylenes (BTEX). Weight-of-evidence methodology was used to assess the joint toxic action for most of the mixtures. Physiologically based pharmacokinetic modeling was used for BTEX. In most cases, a target-organ toxicity dose modification of the hazard index approach is recommended for conducting exposure-based assessments of noncancer health hazards. PMID:12892681

  17. 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 experimental data were obtained at atmospheric pressure with the test section oriented horizontally. The effect of subcooling in pool boiling of mixtures is another area that has received limited attention. Therefore, experimental data were obtained for the water-propylene glycol and water-ethylene glycol systems for subcoolings ranging from 0 to 30 C. The experimental data showed that boiling heat transfer coefficients were found to have significant degradation due to the mixture effect for each of the water-glycol systems examined. This result is consistent with previous studies which examined water-hydrocarbon mixtures with large boiling ranges. The Turbo BIII surface was found to significantly increase heat transfer in each mixture and pure component in comparison to that for the smooth surface.

  18. CHEMICAL MIXTURES: CONSEQUENCES FOR WATER QUALITY

    EPA Science Inventory

    Chemicals have the potential to occur as mixtures in sediment, as well as bioaccumulate in aquatic organisms, sometimes resulting in adverse toxicological effects. Presently, assessments of contaminated sediment are based upon single chemical toxicological studies with the assump...

  19. DETERMINATION OF 2-METHYL TETROLS AND 2-METHYLGLYCERIC ACID IN SECONDARY ORGANIC AEROSOL FROM LABORATORY IRRADIATED ISOPRENE/NO X/SO 2/AIR MIXTURES

    EPA Science Inventory

    This presentation addresses recent work performed at EPA to evaluate the potential for the photooxidation of isoprene to produce secondary organic aerosol. Analysis of the samples for methyl tetrols and 2-methylglyceric acid were performed at EPA and the University of Antwerp. T...

  20. Sorption of organics and water on starch

    SciTech Connect

    Westgate, P.J.; Ladisch, M.R. . Lab. of Renewable Resources Engineering)

    1993-08-01

    Starch is a well-established adsorption agent for drying ethanol. This work examines its potential for other gas-phase drying applications. Results from gas chromatography studies confirm that starch separates water from organic acids, alcohols, ketones, ethers, and aromatics, many of which form azeotropes with water. Trends in organics with respect to size and functional group show that the efficiency of this separation is related to both transport properties and strength of interaction between the organic components and starch. Small, polar molecules such as methanol and formic acid that have rapid mass-transfer characteristics and relatively strong interactions with starch are retained to a greater degree and are more difficult to separate from water than either compounds of higher molecular weight or decreased polarity. The large number of possible separations indicates that starch is a versatile material for use in sorbents for vapor-phase separations.

  1. 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). PMID:25464998

  2. 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)

  3. Mixtures Research at NIEHS: An Evolving Program

    PubMed Central

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

    2014-01-01

    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. PMID:23146757

  4. 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

  5. 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

  6. New model that describes adsorption of laterally interacting gas mixtures on random heterogeneous surfaces. 2: Correlation of complex binary and prediction of multicomponent adsorption equilibria

    SciTech Connect

    Al-Muhtaseb, S.A.; Ritter, J.A.

    1999-10-26

    The model developed in part 1 of this series for correlating single component and rather ideal binary adsorption equilibria demonstrated a remarkable ability for correlating complex binary adsorption equilibria, including adsorption azeotropes and sigmoidal-shaped x-y diagrams, using a single binary fitting parameter. This model was also extended successfully for predicting multicomponent adsorption equilibria on a heterogeneous adsorbent surface with a uniform distribution of Henry's law constant using single component adsorption isotherm parameters, along with one binary fitting parameter from each of the binary pairs in the multicomponent mixture. Overall, the results from this new model generally showed a marked improvement in the correlation of binary and prediction of multicomponent adsorption equilibria compared to that obtained with the multicomponent Langmuir model, which used only single component isotherm parameters, and compared to that obtained with two-dimensional fluid and loading ratio correlation models that also utilized binary fitting parameters.

  7. 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. PMID:24930096

  8. First direct observation of secondary organic aerosol formation during cloud condensation-evaporation cycles in isoprene photo-oxidation reacting mixtures (CUMULUS project)

    NASA Astrophysics Data System (ADS)

    Brégonzio-Rozier, Lola; Siekmann, Frank; Giorio, Chiara; Temime-Roussel, Brice; Pangui, Edouard; Morales, Sébastien; Ravier, Sylvain; Monod, Anne; Doussin, Jean-François

    2014-05-01

    Several field observations, laboratory and model studies suggest a potentially important role of cloud droplets in forming additional secondary organic aerosol (SOA) (Sorooshian et al., 2007; Altieri et al., 2008; Couvidat et al., 2013). While this SOAaq hypothesis seems to be robust and is considered quite established, so far, no direct observations of such a process have been provided. Recently a consortium of five laboratories has joined theirs efforts in a series of experimental simulation experiments to try to bring a direct confirmation of this hypothesis: the CUMULUS project (CloUd MULtiphase chemistry of organic compoUndS in the troposphere). The aim of the present work is to study SOA formation from isoprene photo-oxidation during cloud condensation-evaporation cycles. The chemistry occurring in the gaseous, particulate and aqueous phases, and the exchange between these phases were investigated through an original multiphase approach in a simulation chamber. Experiments were performed in the CESAM chamber (Wang et al., 2011) which was designed to investigate multiphase processes under realistic actinic flux, and accurate control of both temperature and relative humidity. A protocol was designed to generate cloud events in the simulation chamber, it has allowed us to generate clouds lasting for ca. 10 minutes in the presence of light and many clouds could be generated in a single experiment. Connected to the chamber, a large panel of instruments was used to monitor the gas-phase and the particulate phase during experiments. Gas-phase composition was analyzed in-situ via a Fourier Transform Infrared Spectrometer (FTIR) and a Proton Transfer Reaction Mass Spectrometer (PTR-TOF-MS) as well as NOx and O3 analyzers. A Scanning Mobility Particle Sizer (SMPS) measured dried SOA size distributions and total concentrations inside the chamber. An Aerodyne High Resolution Time-Of-Flight Aerosol Mass Spectrometer (HR-TOF-AMS) was also used to investigate aerosol composition. Cloud droplets size distributions were measured by a white light Optical Particle Counter (OPC). In each experiment, around 800 ppb of isoprene was injected in the chamber together with HONO under dry conditions before irradiation. In all experiments, the impact of the cloud generation on the gaseous and particulate phases has been highlighted, suggesting a significant production of SOA from isoprene photo-oxidation by interactions with cloud droplets. The overall results in additional SOA mass production, the dynamic of its mass concentration and some insight of its chemical composition will be presented. Altieri, K. et al. (2008). Atmospheric Environment 42(7): 1476-1490. Couvidat, F. et al. (2013). Environmental Science & Technology 47(2): 914-922. Sorooshian, A. et al. (2007). Environmental Science & Technology 41(13): 4647-4654. Wang, J. et al. (2011). Atmospheric Measurement Techniques 4(11): 2465-2494.

  9. 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. PMID:23992500

  10. 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.

  11. Strategies for toxicological evaluation of mixtures.

    PubMed

    Eide, I

    1996-01-01

    Different strategies for the toxicological evaluation of mixtures are presented. The purpose is to determine the effects of each component (variable) in the mixture, and possible interactions between variables. The examples presented have 3-5 predictor variables and 1-3 responses, and are based on statistical experimental design, multivariate data analysis and modelling. The following examples are presented: (1) inhalation experiments with synthetic vapour mixtures of hydrocarbons formulated by means of mixture design at different vapour concentrations (the experimental) region covers both partial and complete evaporation of the liquid mixtures); (2) combination of refinery streams for fuel blending by means of mixture design with constraints, followed by engine tests and determination of exhaust particles; (3) fractionation of organic extracts of diesel exhaust particles, and recombination of the extracts by means of mixture design, followed by mutagenicity testing of the recombined extracts in the Ames Salmonella assay; (4) spiking complex mixtures with individual compounds using factorial design, and subsequent mutagenicity testing. The data obtained from these four examples were analysed by means of Projections to Latent Structures (PLS). The effects of each variable and possible interactions, were quantified by means of PLS regression coefficients. Furthermore, the empirical models obtained were evaluated by means of correlation coefficients, cross validation and predictions. PMID:9119328

  12. 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.

  13. 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

  14. 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.

  15. Investigations of reversible thermochromic mixtures

    NASA Astrophysics Data System (ADS)

    MacLaren, Douglas C.

    Three-component organic thermochromic systems have potential applications in reversible, rewritable thermal printing. In principle, such mixtures could maintain a coloured or non-coloured state at ambient temperature depending on their thermal treatment. These systems generally consist of a functional dye (1--3 mol%), a weakly acidic colour developer (5--25 mol%), and a high-melting organic solvent (75--90 mol%). Colour development occurs at the fusion temperature of the mixture, which triggers the interaction of the dye and developer. Slow cooling of the melt results in an equilibrium state with low colour density, whereas rapid cooling of the melt results in a metastable state with high colour density. The metastable state can be decoloured by heating to an intermediate decolourisation temperature at which the coloured state becomes unstable. Barriers to the widespread use of reversible, rewritable thermochromic materials include problems with colour contrast, colour stability, and decolourisation rates. Development is hindered by a lack of detailed knowledge of the interactions between components in these systems. In this study the developer-dye and developer-solvent interactions were examined for an archetypal dye/developer/solvent thermochromic system. Vibrational spectroscopy, NMR, and thermal analysis were used to examine compounds formed in developer/dye and developer/solvent binary mixtures. Rewritable thermochromic properties such as metastable colour density, equilibrium colour density, and decolourisation rates were examined and discussed in terms of the thermodynamics of the developer/dye and developer/solvent interactions. Observed thermochromic properties are shown to be strongly correlated to a competition between the dye and the solvent for interaction with the developer. Increasing the attractive interaction between the solvent and developer results in enhanced rewritable thermochromic properties.

  16. Fuel mixture control system

    SciTech Connect

    Drews, U.; Gloss, E.; Kirn, D.; Moder, H.; Schnurle, H.; Steinbrenner, U.; Streit, K.; Werner, P.

    1980-06-03

    A fuel mixture control apparatus for an electronic fuel injection system for internal combustion engines is disclosed. In a warm-up controller, the fuel injection control pulses are lengthened for enrichment of the fuel-air mixture during engine warm-up on the basis of signals supplied by a temperature transducer. In order to make the warm-up enrichment dependent on prevailing engine states, for example on the conditions of idling and partial or full load, circuitry is provided to sense these conditions and to suitably alter the enrichment factor. A further circuit suppresses the dependence or enrichment on engine status during engine starting. Various embodiments are presented.

  17. 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 performance to cost ratio of this machine lends significant credence to the economic viability of small-scale, low-temperature ORCs. The experimental campaign covered two heat source temperatures, the full range of pump and expander speeds, a full range of heat source and heat sink fluid flow rates, and various charge levels for the three working fluids. This resulted in 366 steady-state measurements. The steady state measurements are used to develop a detailed ORC model. The model is based on multi-fluid performance maps for the pump and expander and a robust moving-boundary heat exchanger model. It is validated against the measured data and predicts the net power output of the tested ORC with a mean absolute percent error of 7.16%. Comparisons made with the detailed model confirm the predictions of the design-stage model. Using a conservative estimate of the condenser fan power, 19.1% improvement of the ZRC over the baseline ORC is indicated for a source temperature of 80 °C. For a 100 °C source temperature, 13.8% improvement is indicated. A key feature of the detailed ORC model is that it calculates the charge inventory of the working fluid in each heat exchanger and line set. Total system charge can also be specified as a model input. The model can represent the total charge well for R134a at low measured charge levels. As the measured charge level increases, the model becomes less accurate. Reasons for the deviation of the model at higher charge are investigated. It is expected that a charge tuning scheme could be employed to improve the accuracy of model-predicted charge.

  18. Theory of phase equilibria for model mixtures of n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock surfactants

    NASA Astrophysics Data System (ADS)

    Dos Ramos, María Carolina; Blas, Felipe J.

    2007-05-01

    An extension of the SAFT-VR equation of state, the so-called hetero-SAFT approach [Y. Peng, H. Zhao, and C. McCabe, Molec. Phys. 104, 571 (2006)], is used to examine the phase equilibria exhibited by a number of model binary mixtures of n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock surfactants. Despite the increasing recent interest in semifluorinated alkanes (or perfluoroalkylalkane diblock molecules), the phase behaviour of mixtures involving these molecules with n-alkanes or perfluoroalkanes is practically unknown from the experimental point of view. In this work, we use simple molecular models for n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock molecules to predict, from a molecular perspective, the phase behaviour of selected model mixtures of perfluoroalkylalkanes with n-alkanes and perfluoroalkanes. In particular, we focus our interest on the understanding of the microscopic conditions that control the liquid-liquid separation and the stabilization of these mixtures. n-Alkanes and perfluoroalkanes are modelled as tangentially bonded monomer segments with molecular parameters taken from the literature. The perfluoroalkylalkane diblock molecules are modelled as heterosegmented diblock chains, with parameters for the alkyl and perfluoroalkyl segments developed in earlier work. This simple approach, which was proposed in previous work [P. Morgado, H. Zhao, F. J. Blas, C. McCabe, L. P. N. Rebelo, and E. J. M. Filipe, J. Phys. Chem. B, 111, 2856], is now extended to describe model n-alkane (or perfluoroalkane) + perfluroalkylalkane binary mixtures. We have obtained the phase behaviour of different mixtures and studied the effect of the molecular weight of n-alkanes and perfluoroalkanes on the type of phase behaviour observed in these mixtures. We have also analysed the effect of the number of alkyl and perfluoroalkyl chemical groups in the surfactant molecule on the phase behaviour. In addition to the usual vapour-liquid phase separation, liquid-liquid, positive azeotropes, and Bancroft points are found for different mixtures. This rich phase behaviour is a consequence of a delicate balance between the alkyl-alkyl, perfluoroalkyl-perfluoroalkyl, and alkyl-perfluoroalkyl interactions in different molecules. We used the SAFT-VR microscopic description of chain-like systems to analyse the conditions that n-alkane (or perfluoroalkane) + perfluoroalkyalkane mixtures should posses in order to exhibit complete liquid miscibility. Although the model proposed here is chosen to reproduce most of the quantitative features of the phase equilibria of some pure perfluoroalkylalkane diblock surfactants and their mixtures with n-alkanes, this is the first time the SAFT approach has been used to predict the phase behaviour of the mixtures considered here. The lack of experimental data for these systems does not allow us to test the accuracy of our theoretical predictions directly. However, since SAFT has proven to be an excellent approach for the prediction of the phase behaviour of complex mixtures, we expect that the theory will reproduce the most important qualitative trends exhibited by real mixtures.

  19. Volcanology: Messy magma mixtures

    NASA Astrophysics Data System (ADS)

    Eichelberger, John

    2010-09-01

    Andesite magmas were once thought to be simple melts derived from a subducting oceanic slab or the mantle. Analysis of lavas at Mount Hood shows that instead andesites are a complex mixture of magmas formed in the continental crust just before eruption.

  20. Photoisomerization- and photopolymerization-induced phase transitions in mixtures of photoresponsive chromophores and reactive mesogens

    NASA Astrophysics Data System (ADS)

    Kim, Namil

    Phase diagram of various blend systems containing photochromophores and reactive mesogenic diacrylate monomers has been constructed both experimentally and theoretically. Differential scanning calorimetry was commonly utilized to determine phase transition temperature, and theoretical curve was obtained by solving self-consistently the combined free energy of Flory-Huggins, Maier-Saupe, and phase field theory. Depending on the system, it exhibited various single and coexistence phases including crystal, nematic, crystal + isotropic, nematic + isotropic, crystal + nematic, and crystal + crystal. Guided by the phase diagram, we further investigated (i) self-motion of azobenzene chromophore (AC) in triacrylate (TA) solution, (ii) photoisomerization-induced phase transition of liquid crystalline azobenzene (LCAC) and spiropyran (SP) chromophore in its mixtures with reactive mesogenic diacrylate (RMDA), and (iii) photopolymerization-induced phase separation of RMDA/low molecular weight liquid crystal (LMWLC) blends. Self-motion of AC single crystal in TA solution was investigated in relation to the solid-liquid phase diagram. Upon thermal quenching from the isotropic melt to the crystal + liquid gap, the concentration gradient that formed as the result of TA expulsion induced convective flows and generated spatial variability of surface tension usually responsible for Marangoni effect. A stationary rhomboidal crystal was also shown to swim upon irradiation with UV light due to mechanical torque generated by trans-cis isomerization. The trans-cis photoisomerization of LCAC not only exerted a dramatic effect on the mesophase transitions, but also on the stratification on the crystal morphology. The phase diagram of photoisomerized mixtures displayed a significant depression of nematic ordering. Meanwhile, spiropyran-merocyanine molecular shape change induced the I-N phase transition, which was infusible. Upon photopolymerization of RMDA/LMWLC blends, the homogeneous 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.

  1. Hydrodynamic gas mixture separation

    SciTech Connect

    Stolyarov, A.A.

    1982-02-10

    The separation of gas mixtures is the basis of many chemical, petrochemical, and gas processes. Classical separation methods (absorption, adsorption, condensation, and freezing) require cumbersome and complex equipment. No adequate solution is provided by the cheapening and simplification of gas-processing apparatus and separation methods by hydration and diffusion. For example, an apparatus for extracting helium from natural gas by diffusion has a throughput of gas containing 0.45% helium of 117,000 m/sup 3//h and in the first stage has teflon membranes working at a pressure difference of 63.3x10/sup 5/ Pa of area 79,000 m/sup 2/, and the specific cost of the apparatus was 8500 dollars per m/sup 3//h of helium. Therefore, vigorous studies are being conducted on new ways of efficient separation of gas mixtures that are cheaper and simpler. Here we consider a novel method of physically essentially reversible separation of gas mixtures, which involves some features of single-phase supersonic flows.

  2. Development of more efficacious TC-99M organ imaging agents for use in nuclear medicine by analytical characterization of radiopharmaceutical mixtures. Progress report, May 1, 1983-April 1, 1984

    SciTech Connect

    Heineman, W.R.

    1984-01-01

    It has been demonstrated that formulation variables (pH, TcO/sub 4//sup -/ concentration, and ligand-to-metal ratio) influence the chromatographic distribution of the components of a Tc-hydroxyethylidene diphosphonate (HEDP) mixture prepared by the NaBH/sub 4/ reduction of TcO/sub 4//sup -/ in the presence of HEDP. The use of alternate reductants for TcO/sub 4//sup -/ (i.e., SnCl/sub 2/, and electrode) not only alters the relative proportion of the Tc-HEDP components formed, but produces new complexes not previously seen (based on chromatographic retention time data). Thus, a systematic evaluation has been undertaken of the SnCl/sub 2/ and electrochemical reduction preparations that is similar to that conducted for Tc(NaBH/sub 4/)-HEDP mixtures. High performance liquid chromatography with electrochemical detection has been utilized to separate components of a Tc(NaBH4)-methylene diphosphonate mixture. All Tc components of the mixture are reducible at a mercury electrode and hydrodynamic voltammetric data is being generated. Stripping chronocoulometry has been developed as a novel variation of anodic stripping voltammetry in order to increase precision in the analytical determination of TcO/sub 4//sup -/ in aqueous solution. Pilot studies to evaluate the operating parameters of /sup 99/Mo//sup 99m/Tc/ generators and to investigate two new diphosphonate ligands in the preparation of technetium skeletal imaging radiopharmaceutical analogs have been initiated.

  3. Perception of odor blending mixtures in the newborn rabbit.

    PubMed

    Coureaud, Gérard; Thomas-Danguin, Thierry; Le Berre, Elodie; Schaal, Benoist

    2008-09-01

    In adult mammals, the processing of complex odor mixtures is elemental or configural. Here, we challenged these processes in newborn rabbits, in evaluating their perception of a binary odor mixture for which perceptual blending occurs in humans. This model of newborn animal was interesting since general questions remain on how odor cues are processed in immature organisms, and since rabbit pups present abilities of rapid odor learning. In the present study, we first demonstrated (Exp. 1) that rabbit pups rapidly acquired the odor of the binary mixture through associative conditioning (when the mammary pheromone was used as unconditioned stimulus). Then, we compared how they responded to the mixture, its components and the mammary pheromone, after they had learned the mixture or one of its constituents. After they had learned the odor of the mixture, they responded to its odor and the odor of its constituents (Exp. 2). However, after they had learned one constituent's odor, they responded to this odor but not to the mixture's odor (Exp. 3). The response to the mixture appeared nevertheless when pups successively acquired the odor of the two components (Exp. 4). Therefore, both elemental and configural processing of the mixture seem to be displayed by rabbit pups, suggesting that neonatal perception of a simple odor mixture may involve more than the perception of its constituents. PMID:18586286

  4. Assessment of intakes of mixtures of radionuclides.

    PubMed

    O'Brien, R S

    2003-01-01

    Australia has several uranium mines and a large number of mineral sand mines, with associated processing facilities. Exposures resulting from these mining and processing operations usually involve intakes of mixtures of radionuclides. This work describes the development of a suite of first order, linear compartment models, based on the ICRP Publication 66 respiratory tract model, and an analytical solution to the decay equations, for assessing the consequences of such intakes. The computer programs based on these models directly compute excretion, organ retention and organ and whole-body doses for intakes of either single radionuclides or any mixture of radionuclides belonging to the same radioactive decay chain. The intake can be via inhalation, ingestion or injection, and can be acute, chronic or of limited duration. The starting concentration and degree of secular (dis)equilibrium can be specified for each radionuclide. No assumptions need to be made about the relative magnitudes of the radioactive half-lives of the different nuclides. PMID:14526935

  5. Transport coefficients of fluid mixtures

    SciTech Connect

    Castillo, R.; de Haro, M.L.; Martina, E.

    1986-07-01

    On the basis of the successful description of the equilibrium properties of simple fluids and fluid mixtures using perturbation theory, the consequences of including density- and temperature-dependent diameters in the formulas for the transport coefficients of dense hard-sphere fluid mixtures are investigated. The advantages and limitations of this approach for the correlation of the experimental data of real mixtures, together with numerical estimates for particular mixtures, are discussed. On the other hand, recent mean field kinetic theories which include the effect of the attractive tail in the intermolecular potential are employed to derive transport coefficients for mixtures. Numerical results are presented and comparison with other theories is also made.

  6. Binomial Gaussian mixture filter

    NASA Astrophysics Data System (ADS)

    Raitoharju, Matti; Ali-Löytty, Simo; Piché, Robert

    2015-12-01

    In this work, we present a novel method for approximating a normal distribution with a weighted sum of normal distributions. The approximation is used for splitting normally distributed components in a Gaussian mixture filter, such that components have smaller covariances and cause smaller linearization errors when nonlinear measurements are used for the state update. Our splitting method uses weights from the binomial distribution as component weights. The method preserves the mean and covariance of the original normal distribution, and in addition, the resulting probability density and cumulative distribution functions converge to the original normal distribution when the number of components is increased. Furthermore, an algorithm is presented to do the splitting such as to keep the linearization error below a given threshold with a minimum number of components. The accuracy of the estimate provided by the proposed method is evaluated in four simulated single-update cases and one time series tracking case. In these tests, it is found that the proposed method is more accurate than other Gaussian mixture filters found in the literature when the same number of components is used and that the proposed method is faster and more accurate than particle filters.

  7. 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.

  8. Mutation spectra of complex environmental mixtures

    SciTech Connect

    DeMarini, D.M.

    1997-10-01

    Bioassay-directed chemical analysis of complex environmental mixtures has indicated that much of the genotoxic activity of mixtures is due to the presence of one or a few classes or chemicals within the mixture. We have extended this observation to the molecular level by using colony probe hybridization and PCR/DNA sequence analysis to determine the mutation spectra of {approximately}8,000 revertants induced by a variety of complex mixtures and their chemical fractions in TA100 and TA98 of Salmonella. For urban air, >80% of mutagenic activity was due to a base/neutral fraction that contained primarily PAHs. The mutation spectrum induced by unfractionated urban air was not significantly different from that produced by a model PAH, B(a)P. The mutation spectrum induced by organic extracts of chlorinated drinking water were similar to those produced by the chlorinated furanone MX, which accounted for {approximately}20% of the mutagenic activity of the samples. The base/neutral fraction of municipal waste incinerator emissions accounted for the primary class of mutations induced by the emissions, and a polar neutral fraction accounted for the secondary class of mutations induced by the emissions. The primary class of mutations induced by cigarette smoke condensate in TA100 (GC {yields} TA) is also the primary class of mutations in the p53 gene of lung tumors of cigarette smokers. These results confirm at the molecular level that the mutations induced by a complex mixture reflect the dominance of one or a few classes of chemicals within the mixture.

  9. 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 achieve this goal. PMID:17888717

  10. Energy efficient membrane processes for the separation of organic liquids: Part 2: Final report, September 28, 1982--December 31, 1986

    SciTech Connect

    Cabasso, I.; Acharya, H.R.; Korngold, E.; Liu, Z.; Stern, S.A.; Li, W.; Makenzie, T.; Poda, E.

    1987-10-01

    The present report demonstrates the use of membrane technology for dehydration processes concentrating on two examples: azeotropic separation of isopropanol-water, and separation of ethanol-water mixtures (starting at 84.5 wt. % ethanol where separation by distillation begins to be progressively more energy intensive). The principles of the membrane separation processes employed in such separations were discussed in Part I of the report. The advantage of the membrane processes is that they do not require the addition of a third component and separation is a continuous process. Pervaporation, perstraction, and air-sweep pervaporation were thoroughly studied for these separations. An urgent need for the identification of the appropriate membrane was realized. This study has revealed that ion-exchange membranes are suited for these separations. Results are discussed. 9 refs., 68 figs., 33 tabs.

  11. 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

  12. Bayesian mixture analysis for metagenomic community profiling

    PubMed Central

    Morfopoulou, Sofia; Plagnol, Vincent

    2015-01-01

    Motivation: Deep sequencing of clinical samples is now an established tool for the detection of infectious pathogens, with direct medical applications. The large amount of data generated produces an opportunity to detect species even at very low levels, provided that computational tools can effectively profile the relevant metagenomic communities. Data interpretation is complicated by the fact that short sequencing reads can match multiple organisms and by the lack of completeness of existing databases, in particular for viral pathogens. Here we present metaMix, a Bayesian mixture model framework for resolving complex metagenomic mixtures. We show that the use of parallel Monte Carlo Markov chains for the exploration of the species space enables the identification of the set of species most likely to contribute to the mixture. Results: We demonstrate the greater accuracy of metaMix compared with relevant methods, particularly for profiling complex communities consisting of several related species. We designed metaMix specifically for the analysis of deep transcriptome sequencing datasets, with a focus on viral pathogen detection; however, the principles are generally applicable to all types of metagenomic mixtures. Availability and implementation: metaMix is implemented as a user friendly R package, freely available on CRAN: http://cran.r-project.org/web/packages/metaMix Contact: sofia.morfopoulou.10@ucl.ac.uk Supplementary information: Supplementary data are available at Bionformatics online. PMID:26002885

  13. 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.

  14. Global fluid phase behavior in binary mixtures of rodlike and platelike molecules

    NASA Astrophysics Data System (ADS)

    Varga, Szabolcs; Galindo, Amparo; Jackson, George

    2002-10-01

    The phase behavior of a liquid-crystal forming model colloidal system containing hard rodlike and platelike particles is studied using the Parsons-Lee scaling [J. D. Parsons, Phys. Rev. A 19, 1225 (1979); S. D. Lee, J. Chem. Phys. 87, 4972 (1987)] of the Onsager theory. The rod and plate molecules are both modeled as hard cylinders. All of the mixtures considered correspond to cases in which the volume of the plate is orders of magnitude larger that the volume of the rod, so that an equivalence can be made where the plates are colloidal particles while the rods play the role of a depleting agent. A combined analysis of the isotropic-nematic bifurcation transition and spinodal demixing is carried out to determine the geometrical requirements for the stabilization of a demixing transition involving two isotropic phases. Global phase diagrams are presented in which the boundaries of isotropic phase demixing are indicated as functions of the molecular parameters. Using a parameter z which corresponds to the product of the rod and plate aspect ratios, it is shown that the isotropic phase is unstable relative to a demixed state for a wide range of molecular parameters of the constituting particles due to the large excluded volume associated with the mixing of the unlike particles. However, the stability analysis indicates that for certain aspect ratios, the isotropic-nematic phase equilibria always preempts the demixing of the isotropic phase, irrespective of the diameters of the particles. When isotropic-isotropic demixing is found, there is an upper bound at large size ratios (Asakura and Oosawa limit), and a lower bound at small size ratios (Onsager limit) beyond which the system exhibits a miscible isotropic phase. It is very gratifying to find both of these limits within a single theoretical framework. We test the validity of the stability analysis proposed by calculating a number of phase diagrams of the mixture for selected molecular parameters. As the hard rod particles promote an effective attractive interaction between the hard-plate colloidal particles, the isotropic-isotropic demixing usually takes place between two rod-rich fluids. As far as the isotropic-nematic transition is concerned, a stabilization as well as a destabilization of the nematic phase relative to the isotropic phase is seen for varying rod-plate size ratios. Moreover, isotropic-nematic azeotropes and re-entrant phenomena are also observed in most of the mixtures studied. We draw comparisons between the predicted regions of stability for isotropic demixing and recent experimental observations.

  15. 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 levels of biological organization and life stages when assessing contaminant interactions. Environ Toxicol Chem 2016;35:953-965. © 2015 SETAC. PMID:26561986

  16. 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 levels of biological organization and life stages when assessing contaminant interactions.

  17. 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...

  18. Choice of basis mixtures for the prediction of vapor-liquid equilibria using the UNIFAC model

    SciTech Connect

    Kushner, T.M.; Fainburg, G.D.; Vitman, T.A.; Serafimov, L.A.

    1988-07-01

    A link was established between the accurate prediction of vapor-liquid equilibria and azeotropes using the UNIFAC group model and the choice of the basis information. The component activity coefficients are plotted as functions of composition for all the sets of data in each binary system. The activity coefficients at infinite dilution are determined as graphical extrapolations of these plots. The plot for the butanol-hydrocarbon system is shown. It is shown that azeotrope parameters can be used as the basis information to predict vapor-liquid equilibria for several sets of systems.

  19. Zwanzig model of multi-component mixtures of biaxial particles: y3 theory re-visited

    NASA Astrophysics Data System (ADS)

    Sokolova, E. P.; Tumanyan, N. P.; Vlasov, A. Yu.; Masters, A. J.

    The paper considers the thermodynamic and phase ordering properties of a multi-component Zwanzig mixture of hard rectangular biaxial parallelepipeds. An equation of state (EOS) is derived based on an estimate of the number of arrangements of the particles on a three- dimensional cubic lattice. The methodology is a generalization of the Flory-DiMarzio counting scheme, but, unlike previous work, this treatment is thermodynamically consistent. The results are independent of the order in which particles are placed on the lattice. By taking the limit of zero lattice spacing, a translationally continuous variant of the model (the off-lattice variant) is obtained. The EOS is identical to that obtained previously by a wide variety of different approaches. In the off-lattice limit, it corresponds to a third-level y-expansion and, in the case of a binary mixture of square platelets, it also corresponds to the EOS obtained from fundamental measure theory. On the lattice it is identical to the EOS obtained by retaining only complete stars in the virial expansion. The off-lattice theory is used to study binary mixtures of rods (R1 - R2) and binary mixtures of platelets (P1 - P2). The particles were uniaxial, of length (thickness) L and width D. The aspect ratios ?i = Li/Di of the components were kept constant (?1R = 15, ?1P = 1/15 and ?2R = 150, ?2P = 1/150), so the second virial coefficient of R1 was identical to P1 and similarly for R2 and P2. The volume ratio of particles 1 and 2, v1/v2, was then varied, with the constraints that viR = viP and ILM0001. Results on nematic-isotropic (N - I) phase coexistence at an infinite dilution of component 2, are qualitatively similar for rods and platelets. At small values of the ratio v1/v2, the addition of component 2 (i.e. a thin rod (e.g. a polymer) or a thin plate) results in the stabilization of the nematic phase. For larger values of v1/v2, however, this effect is reversed and the addition of component 2 destabilizes the nematic. For similar molecular volumes of the two components strong fractionation is observed: shorter rods and thicker platelets congregate in the isotropic phase. In general, the stabilization of the ordered phase and the fractionation between the phases are both weaker in the platelet mixtures. The calculated spinodal curves for isotropic-isotropic demixing are noticeably different between the R1 - R2 and the P1 - P2 systems. The platelet mixtures turn out to be stable with respect to de-mixing up to extremely high densities. The values of the consolute points for the R1 - R2 blends are remarkably similar to those obtained using the Parsons-Lee approximation for bi-disperse mixtures of freely rotating cylinders with similar aspect ratios [S. Varga. A. Galindo, G. Jackson, Mol. Phys., 101, 817 (2003)]. In a number of R1 - R2 mixtures, phase diagrams exhibiting both N - I equilibrium and I - I de-mixing were calculated. The latter is pre-empted by nematic ordering in all the cases studied. Calculations show the possible appearance of azeotropes in the N - I coexistence domain.

  20. 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.

  1. 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...

  2. RISK ASSESSMENT OF COMPLEX MIXTURES

    EPA Science Inventory

    Quantitative carcinogenic assessment of complex mixtures is complicated by the variability of the mixtures. Different samples of effluents from the same source may vary in their carcinogenic potency. A multiplicative effect could be produced by the action of different fractions o...

  3. Thermobaric investigation of coal mixtures

    SciTech Connect

    Kosinskii, V.A.

    1983-01-01

    An examination of the dynamics of gas emission during the heating in vacuo of different grades of Donbass coal included a study of binary and ternary mixtures of these coals. Discrete gas emission was established at temperatures depending principally on the ratio of coals within the mixtures. The data obtained could be used as a basis for commercial processes.

  4. Latent Classiness and Other Mixtures

    PubMed Central

    Neale, Michael C.

    2014-01-01

    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

  5. 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

  6. POTENTIAL EMISSIONS OF HAZARDOUS ORGANIC COMPOUNDS FROM SEWAGE SLUDGE INCINERATION

    EPA Science Inventory

    Laboratory thermal decomposition studies were undertaken to evaluate potential organic emissions from sewage sludge incinerators. Precisely controlled thermal decomposition experiments were conducted on sludge spiked with mixtures of hazardous organic compounds, on the mixtures o...

  7. Development of more efficacious Tc-99m organ imaging agents for use in nuclear medicine by analytical characterization of radiopharmaceutical mixtures. Progress report, May 1, 1980-April 30, 1981. [/sup 99m/Tc(NaBH/sub 4/)HEDP

    SciTech Connect

    Heineman, W. R.; Deutsch, E. A.

    1980-12-01

    High performance liquid chromatography (HPLC) was used to efficiently separate and detect the individual components in a radiopharmaceutical mixture. A procedure for separating Tc(NaBH/sub 4/)HEDP radiopharmaceutical analogues by anion exchange HPLC with uv-visible and ..gamma.. detection was developed. Such preparations consist of as many as 7 Tc-containing components, the relative quantities of which are highly dependent on the conditions during preparation and subsequent handling. The in vivo distributions of 3 of the isolated Tc-HEDP species were evaluated as skeletal imaging agents in normal rats. The chromatographically separated Tc-HEDP components exhibit distinctly different biodistributions which are related to the chromatographic characteristics of the individual components. These same Tc-HEDP components were evaluated for uptake in myocardial infarcts using the isoproterenol-induced necrosis model in the rat. The relative uptake of the various components in the infarcted heart parallels the skeletal uptake. An optically transparent thin layer electrochemical flow cell was developed and characterized. This cell enables optical and electrochemical measurements to be made simultaneously on individual Tc-HEDP complexes as they elute from the HPLC. These results demonstrate the potential presence of numerous technetium complexes in radiopharmaceuticals and the efficacy of HPLC as a mode of separation and detection of these complexes. One particular component in the Tc(NaBH/sub 4/)HEDP radiopharmaceutical analogue is more effective than the others for both skeletal and myocardial infarct uptake. This is strongly suggestive that a more efficacious radiopharmaceutical would result from the administration of this single component.

  8. Water-enhanced solvation of organic solutes in ketone and ester solvents

    SciTech Connect

    Lee, J.H.; Brunt, V. van; King, C.J. . Dept. of Chemical Engineering Lawrence Berkeley Lab., CA )

    1994-05-01

    Previous research has shown that the solubilities of dicarboxylic acids in certain electron-donor solvents are substantially increased in the presence of water. Information on solubilities, liquid-liquid equilibria and maximum-boiling ternary azeotropes was screened so as to identify other systems where codissolved water appears to enhance solvation of organic solutes in solvents. Several carboxylic acids, an alcohol, diols, and phenols were selected for examination as solutes in ketone and ester solvents. Effects of water upon solute solubilities and volatilities were measured. Results showed that water-enhanced solvation is greatest for carboxylic acids. Solute activity coefficients decreased by factors of 2--3, 6--8, and 7--10 due to the presence of water for mono-, di and tricarboxylic acids, respectively. Activity coefficients decreased by a factor of about 1.5 for ethanol and 1,2-propanediol as solutes. Water-enhanced solvation of phenols is small, when existent.

  9. Thermobaric investigations of coal mixtures

    SciTech Connect

    Kosinskii, V.A.

    1983-01-01

    The dynamics of the evolution of gas when coals of various types from the Donbass and binary and ternary mixtures of them are heated have been studied. The discrete nature of the evolution of gas has been established, the temperature intervals of which depend primarily on the ratio of the coals in the mixtures. The possibility of using the results obtained in determining rational schemes for the industrial processing of coals is suggested.

  10. Process for separating relatively pure fractions of methane and carbon dioxide from gas mixtures

    SciTech Connect

    Goddin, C.S. Jr.; McGalliard, R.L.

    1983-01-25

    Standard Oil's cryogenic liquids-removal and purification process uses lean oil as the absorbent, thus preventing the formation of solid CO/sub 2/ in the apparatus and CO/sub 2/-ethane azeotropes. Suitable for gas streams containing 20-95 mol % CO/sub 2/, the process provides a convenient way of obtaining foolproof operation in the methane separation step.

  11. 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. PMID:25809105

  12. Predicting the toxicity of metal mixtures.

    PubMed

    Balistrieri, Laurie S; Mebane, Christopher A

    2014-01-01

    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. PMID:23973545

  13. 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)

  14. 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...

  15. Modeling and analysis of personal exposures to VOC mixtures using copulas

    PubMed Central

    Su, Feng-Chiao; Mukherjee, Bhramar; Batterman, Stuart

    2014-01-01

    Environmental exposures typically involve mixtures of pollutants, which must be understood to evaluate cumulative risks, that is, the likelihood of adverse health effects arising from two or more chemicals. This study uses several powerful techniques to characterize dependency structures of mixture components in personal exposure measurements of volatile organic compounds (VOCs) with aims of advancing the understanding of environmental mixtures, improving the ability to model mixture components in a statistically valid manner, and demonstrating broadly applicable techniques. We first describe characteristics of mixtures and introduce several terms, including the mixture fraction which represents a mixture component's share of the total concentration of the mixture. Next, using VOC exposure data collected in the Relationship of Indoor Outdoor and Personal Air (RIOPA) study, mixtures are identified using positive matrix factorization (PMF) and by toxicological mode of action. Dependency structures of mixture components are examined using mixture fractions and modeled using copulas, which address dependencies of multiple variables across the entire distribution. Five candidate copulas (Gaussian, t, Gumbel, Clayton, and Frank) are evaluated, and the performance of fitted models was evaluated using simulation and mixture fractions. Cumulative cancer risks are calculated for mixtures, and results from copulas and multivariate lognormal models are compared to risks calculated using the observed data. Results obtained using the RIOPA dataset showed four VOC mixtures, representing gasoline vapor, vehicle exhaust, chlorinated solvents and disinfection by-products, and cleaning products and odorants. Often, a single compound dominated the mixture, however, mixture fractions were generally heterogeneous in that the VOC composition of the mixture changed with concentration. Three mixtures were identified by mode of action, representing VOCs associated with hematopoietic, liver and renal tumors. Estimated lifetime cumulative cancer risks exceeded 10?3 for about 10% of RIOPA participants. Factors affecting the likelihood of high concentration mixtures included city, participant ethnicity, and house air exchange rates. The dependency structures of the VOC mixtures fitted Gumbel (two mixtures) and t (four mixtures) copulas, types that emphasize tail dependencies. Significantly, the copulas reproduced both risk predictions and exposure fractions with a high degree of accuracy, and performed better than multivariate lognormal distributions. Copulas may be the method of choice for VOC mixtures, particularly for the highest exposures or extreme events, cases that poorly fit lognormal distributions and that represent the greatest risks. PMID:24333991

  16. Modeling and analysis of personal exposures to VOC mixtures using copulas.

    PubMed

    Su, Feng-Chiao; Mukherjee, Bhramar; Batterman, Stuart

    2014-02-01

    Environmental exposures typically involve mixtures of pollutants, which must be understood to evaluate cumulative risks, that is, the likelihood of adverse health effects arising from two or more chemicals. This study uses several powerful techniques to characterize dependency structures of mixture components in personal exposure measurements of volatile organic compounds (VOCs) with aims of advancing the understanding of environmental mixtures, improving the ability to model mixture components in a statistically valid manner, and demonstrating broadly applicable techniques. We first describe characteristics of mixtures and introduce several terms, including the mixture fraction which represents a mixture component's share of the total concentration of the mixture. Next, using VOC exposure data collected in the Relationship of Indoor Outdoor and Personal Air (RIOPA) study, mixtures are identified using positive matrix factorization (PMF) and by toxicological mode of action. Dependency structures of mixture components are examined using mixture fractions and modeled using copulas, which address dependencies of multiple variables across the entire distribution. Five candidate copulas (Gaussian, t, Gumbel, Clayton, and Frank) are evaluated, and the performance of fitted models was evaluated using simulation and mixture fractions. Cumulative cancer risks are calculated for mixtures, and results from copulas and multivariate lognormal models are compared to risks calculated using the observed data. Results obtained using the RIOPA dataset showed four VOC mixtures, representing gasoline vapor, vehicle exhaust, chlorinated solvents and disinfection by-products, and cleaning products and odorants. Often, a single compound dominated the mixture, however, mixture fractions were generally heterogeneous in that the VOC composition of the mixture changed with concentration. Three mixtures were identified by mode of action, representing VOCs associated with hematopoietic, liver and renal tumors. Estimated lifetime cumulative cancer risks exceeded 10(-3) for about 10% of RIOPA participants. Factors affecting the likelihood of high concentration mixtures included city, participant ethnicity, and house air exchange rates. The dependency structures of the VOC mixtures fitted Gumbel (two mixtures) and t (four mixtures) copulas, types that emphasize tail dependencies. Significantly, the copulas reproduced both risk predictions and exposure fractions with a high degree of accuracy, and performed better than multivariate lognormal distributions. Copulas may be the method of choice for VOC mixtures, particularly for the highest exposures or extreme events, cases that poorly fit lognormal distributions and that represent the greatest risks. PMID:24333991

  17. 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

  18. 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…

  19. Gaussian-mixture umbrella sampling

    PubMed Central

    van der Vaart, Arjan; Karplus, Martin

    2009-01-01

    We introduce the Gaussian-mixture umbrella sampling method (GAMUS), a biased molecular dynamics technique based on adaptive umbrella sampling that efficiently escapes free energy minima in multi-dimensional problems. The prior simulation data are reweighted with a maximum likelihood formulation, and the new approximate probability density is fit to a Gaussian-mixture model, augmented by information about the unsampled areas. The method can be used to identify free energy minima in multi-dimensional reaction coordinates. To illustrate GAMUS, we apply it to the alanine dipeptide (2D reaction coordinate) and tripeptide (4D reaction coordinate). PMID:19284746

  20. 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.

  1. Separating mixtures by exploiting molecular packing effects in microporous materials.

    PubMed

    Krishna, Rajamani

    2015-01-01

    We examine mixture separations with microporous adsorbents such as zeolites, metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs), operating under conditions close to pore saturation. Pore saturation is realized, for example, when separating bulk liquid phase mixtures of polar compounds such as water, alcohols and ketones. For the operating conditions used in industrial practice, pore saturation is also attained in separations of hydrocarbon mixtures such as xylene isomers and hexane isomers. Separations under pore saturation conditions are strongly influenced by differences in the saturation capacities of the constituent species; the adsorption is often in favor of the component with the higher saturation capacity. Effective separations are achieved by exploiting differences in the efficiency with which molecules pack within the ordered crystalline porous materials. For mixtures of chain alcohols, the shorter alcohol can be preferentially adsorbed because of its higher saturation capacity. With hydrophilic adsorbents, water can be selectively adsorbed from water-alcohol mixtures. For separations of o-xylene-m-xylene-p-xylene mixtures, the pore dimensions of MOFs can be tailored in such a manner as to allow optimal packing of the isomer that needs to be adsorbed preferentially. Subtle configurational differences between linear and branched alkane isomers result in significantly different packing efficiencies within the pore topology of MFI, AFI, ATS, and CFI zeolites. A common characteristic feature of most separations that are reliant on molecular packing effects is that adsorption and intra-crystalline diffusion are synergistic; this enhances the separation efficiencies in fixed bed adsorbers. PMID:25377790

  2. 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...

  3. 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”...

  4. 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”...

  5. 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...

  6. 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...

  7. 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”...

  8. 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”...

  9. 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”...

  10. 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).

  11. 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.

  12. Theory of phase equilibria and closed-loop liquid-liquid immiscibility for model aqueous solutions of associating chain molecules: Water +alkanol mixtures

    NASA Astrophysics Data System (ADS)

    Green, Daron G.; Jackson, George

    1992-12-01

    In this work we examine the phase equilibria exhibited by a number of model binary mixtures of water+alkanols. The water molecules are modeled as hard spheres with four off-center square-well hydrogen-bonding sites representing the two hydrogen atoms and the two electron lone pairs on the oxygen atom. Dispersion forces are included and are treated within the mean-field approximation. Each alkanol is modeled as a chain molecule formed from fused hard spheres with dispersion forces and two hydrogen-bonding sites. Thus water-water, water-alkanol, and alkanol-alkanol association is allowed. A simple thermodynamic perturbation theory is used to develop an augmented van der Waals equation of state which treats the asymmetry in the attractions which arise because of the directional hydrogen-bonding sites, and the asymmetry in the repulsions caused by the molecular shape of the chains. The effects of chain length and association on the global phase equilibria are studied. As well as the usual gas-liquid phase separation, liquid-liquid and gas-gas phase separation, positive, negative, and double azeotropes, and Bancroft points are found. Closed-loop liquid-liquid immiscibility corresponding to the type VI classification of Scott and van Konynenburg is seen for water+alkanol mixtures with intermediate chain lengths and bonding energies. We also discuss our serious reservations about the type VI behavior claimed to have been found in some recent work. Although the potential parameters used in our work were not chosen to model any specific systems, it is gratifying to see that the theory can reproduce the types of phase behavior exhibited by aqueous solutions of alkanols.

  13. Mixtures of (Constrained) Ultrametric Trees.

    ERIC Educational Resources Information Center

    Wedel, Michel; DeSarbo, Wayne S.

    1998-01-01

    Presents a method for the estimation of ultrametric trees calibrated on subjects' pairwise proximity judgments of stimuli, capturing subject heterogeneity using a finite mixture formulation. An empirical example from published data shows the ability to deal with external constraints on the tree topology. (Author/SLD)

  14. Electrochemical signatures of multivitamin mixtures.

    PubMed

    Mohan, A M Vinu; Brunetti, Barbara; Bulbarello, Andrea; Wang, Joseph

    2015-10-26

    The ability of cyclic square wave voltammetry to identify distinct fingerprints of multiple vitamins, in a single voltammetric run, is demonstrated. This method represents an efficient alternative to more common techniques for fast screening of complex vitamin mixtures or commercial tablets due to its low cost, high speed and sensitivity. PMID:26473173

  15. Genetic Analysis of Plant Mixtures

    PubMed Central

    Griffing, B.

    1989-01-01

    Plant mixtures are difficult to analyze genetically because of possible interactions between neighboring plants (i.e., between plants in the same biological group). However, a genetic modeling scheme has been devised which, theoretically, can accommodate such interactions. This study was an attempt to put the theoretical modeling procedure to an experimental test. To this end an experimental procedure was devised that generated biological groups from a well defined base population. A cultural system was used which permitted growing plant mixtures in controlled environmental facilities. This allowed the experiment to be conducted over a wide range of temperature and nutrient conditions. Application of the theoretical gene model to the experimental data permitted identification of those classes of gene effects that were responsible for genetic variation exhibited by the mixtures. Adequacy of the genetic modeling description was corroborated by precise prediction of an independent genetic response. The genetic analyses also identified statistically significant temperature-and nutrient-dependent forms of heterosis. It was concluded that the study demonstrated the suitability of the theoretical group gene model for describing complexities inherent in plant mixtures. PMID:17246509

  16. 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.

  17. 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.

  18. PREDICTION OF THE SOLUBILITY OF HYDROPHOBIC COMPOUNDS IN NONIDEAL SOLVENT MIXTURES

    EPA Science Inventory

    The solubility of hydrophobic organic chemicals (HOCs) in partially-miscible solvent mixtures was investigated. In agreement with previous findings, it was observed that there is a limited domain in which nonideality effects are important; appreciable concentrations of partially-...

  19. Gas adsorption and gas mixture separations using mixed-ligand MOF material

    DOEpatents

    Hupp, Joseph T. (Northfield, IL); Mulfort, Karen L. (Chicago, IL); Snurr, Randall Q. (Evanston, IL); Bae, Youn-Sang (Evanston, IL)

    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.

  20. 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...

  1. Proteomic analysis of a model fish species exposed to individual pesticides and a binary mixture

    EPA Science Inventory

    Aquatic organisms are often exposed to multiple pesticides simultaneously. Due to the relatively poor characterization of mixture constituent interactions and the potential for highly complex exposure scenarios, there is considerable uncertainty in understanding the toxicity of m...

  2. Medium-term bioassays for carcinogenicity of chemical mixtures.

    PubMed Central

    Ito, N; Imaida, K; Hirose, M; Shirai, T

    1998-01-01

    Carcinogenic effects of chemical mixtures were examined with a medium-term liver bioassay for carcinogens or a multiorgan medium-term bioassay using male F344 rats. In the medium-term liver bioassay, rats were initially treated with diethylnitrosamine (DEN) at 200 mg/kg body weight, i.p.; after 2 weeks they received chemical mixtures such as 10 different heterocyclic amines at one-tenth or one-hundredth the dose levels used in carcinogenicity studies and the mixtures of 20 different pesticides, each at acceptable daily intake (ADI) levels or a mixture of 100 times ADI levels. All animals were subjected to two-thirds partial hepatectomy at week 3 and were sacrificed at week 8. The number and areas of glutathione S-transferase placental form (GST-P) positive foci (preneoplastic lesions in the liver) were compared between respective groups. When 10 heterocyclic amines were mixed in the diet at one-tenth dose level, clear synergism was observed, but no combined effects were evident with the one-hundredth dose levels. In the pesticide experiment, treatment of rats with the 20-pesticide mixture at the ADI dose level did not enhance GST-P-positive foci. In contrast, a mixture of 100 times the ADI significantly increased those values. In a multiorgan bioassay of 28 weeks, mixtures of 40 high-volume compounds and 20 pesticides (suspected carcinogens) added together at their respective ADI levels did not enhance carcinogenesis in any organs initiated by five different carcinogens (DEN, N-methylnitrosourea, dimethylhydrazine, N-butyl-N-(4-hydroxybutyl)nitrosamine, and dihydroxy-di-n-propylnitrosamine) in combination. The combination effect of low dietary levels of five antioxidants, butylated hydroxyanisole, caffeic acid, sesamol, 4-methoxyphenol, and catechol, were also examined using the multiorgan bioassay. The incidence of forestomach papillomas was significantly increased only in the combination group and the results indicate that combination of the five antioxidants can exert additive/synergistic effects on tumorigenesis in the multiorgan bioassay. These results indicate that chemical mixtures at very low doses did not enhance preneoplastic lesions synergistically but the mixtures at certain doses show synergism in the target organ. The medium-term bioassays are particularly useful tools for this purpose. Images Figure 1 Figure 2 Figure 3 PMID:9860889

  3. MULTIVARIATE KERNEL PARTITION PROCESS MIXTURES.

    PubMed

    Dunson, David B

    2010-10-10

    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

  4. Maxwell Stress in Fluid Mixtures

    NASA Astrophysics Data System (ADS)

    Sakaue, Takahiro; Ohta, Takao

    2012-02-01

    We examine the structure of Maxwell stress in binary fluid mixtures under an external electric field and discuss its consequence. In particular, we show that, in immiscible blends, it is intimately related to the statistics of domain structure. This leads to a compact formula, which may be useful in the investigation of electrorheological effects in such systems. The stress tensor calculated in a phase separated fluid under a steady electric field is in a good agreement with recent experiments.

  5. 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 on priority mixtures--priority being determined by (estimated) health risk (= toxicity and exposure). PMID:12634116

  6. 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. PMID:19505754

  7. Simultaneous De Novo Identification of Molecules in Chemical Mixtures by Doubly Indirect Covariance NMR Spectroscopy

    PubMed Central

    Zhang, Fengli; Bruschweiler-Li, Lei; Brüschweiler, Rafael

    2010-01-01

    The detailed characterization of complex molecular mixtures plays a key role in many areas of modern Chemistry. Here we report a novel NMR spectroscopic method that deconvolutes a complex mixture of organic molecules simultaneously into individual components and depicts their chemical structure without requiring physical separation of the components. Doubly indirect covariance spectroscopy is introduced and applied to 2D 13C-1H HSQC and 2D 1H-1H COSY spectra, which results in a 13C-13C 2D spectrum with unprecedented high resolution. This reconstituted spectrum is indeed a carbon-connectivity map that can be directly analyzed with basic graph theory to obtain the skeletal structures of individual mixture components or their fragments. The method is demonstrated for a model mixture and a natural product mixture extracted from cancer cells. Its suitability for automation makes this approach attractive for the analysis of a broad range of mixtures of natural or synthetic products. PMID:21062057

  8. 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

  9. 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.

  10. 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.

  11. CLUSTERING CRITERIA AND MULTIVARIATE NORMAL MIXTURES

    EPA Science Inventory

    New clustering criteria for use when a mixture of multivariate normal distributions is an appropriate model are presented. They are derived from maximum likelihood and Bayesian approaches corresponding to different assumptions about the covariance matrices of the mixture componen...

  12. 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. PMID:23816361

  13. 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…

  14. 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)

  15. 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…

  16. 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... STANDARDS: NORMAL, UTILITY, ACROBATIC, AND COMMUTER CATEGORY AIRPLANES Powerplant Powerplant Controls and Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a...

  17. 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...

  18. 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...

  19. 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...

  20. 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... STANDARDS: NORMAL, UTILITY, ACROBATIC, AND COMMUTER CATEGORY AIRPLANES Powerplant Powerplant Controls and Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a...

  1. 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...

  2. 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...

  3. 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...

  4. 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...

  5. 21 CFR 82.6 - Certifiable mixtures.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 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 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...

  7. 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...

  8. 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...

  9. 21 CFR 82.6 - Certifiable mixtures.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 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,...

  10. 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...

  11. 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...

  12. 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...

  13. 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...

  14. 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,...

  15. 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...

  16. 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.

  17. Sorption of BTX mixtures to contaminated and uncontaminated site soils

    SciTech Connect

    Uchrin, C.G.; Koshy, K.; Wojtenko, I.

    1995-12-31

    Both adsorption and desorption studies are being performed examining benzene, toluene, and meta-xylene (BTX) as single components, binary mixtures, and trinary mixture onto both existing contaminated soils as well as some uncontaminated reference soils. The contaminated soils were obtained from an oil refinery site and another industrial site in New Jersey. The oil refinery site soil did not exhibit significant amounts of either benzene, toluene or xylene but was contaminated with other compounds while the other industrial site soil was contaminated with toluene among other compounds. The organic carbon content of the soils ranged from 0.14 to 2.91 percent. Preliminary adsorption studies showed BTX to strongly sorb to these soils. The adsorption studies onto the reference soils also demonstrated the effect of organic matter on adsorption. Sequential batch desorption studies show the BTX to desorb quickly, reaching equilibrium within 48 hours. Long-term uptake and release were not noted with these soil/contaminant systems.

  18. 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).

  19. Engine fuel mixture control system

    SciTech Connect

    Hufton, A.G.

    1981-11-24

    An internal combustion engine fuel mixture control system is provided for use with an engine having a fuel supply and an intake air supply connected to the engine wherein the fuel and air mix to provide a combustible fuel/air mixture for the combustion engine. A fuel flow sensor is connected to the fuel supply line for the engine while an air flow sensor is similarly connected to the air intake of the engine and the outputs from the sensors are fed to a proportionator which provides an output signal representative of the instant fuel/air ratio for the engine and this output is coupled to one input of a differential amplifier. The other input of the differential amplifier is connected to a fuel/air ratio reference so that the output from the differential amplifier is representative of the difference between the reference and the actual fuel/air ratio for the engine. The output fromm the differential amplifier is used to vary the fuel flow to the engine.

  20. 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.

  1. Effect of Cement on Emulsified Asphalt Mixtures

    NASA Astrophysics Data System (ADS)

    Oruc, Seref; Celik, Fazil; Akpinar, M. Vefa

    2007-10-01

    Emulsified asphalt mixtures have environmental, economical, and logistical advantages over hot mixtures. However, they have attracted little attention as structural layers due to their inadequate performance and susceptibility to early life damage by rainfall. The objective of this article is to provide an improved insight into how the mechanical properties of emulsion mixtures may be improved and to determine the influence of cement on emulsified asphalt mixtures. Laboratory tests on strength, temperature susceptibility, water damage, creep and permanent deformation were implemented to evaluate the mechanical properties of emulsified asphalt mixtures. The test results showed that mechanical properties of emulsified asphalt mixtures have significantly improved with Portland cement addition. This experimental study suggested that cement modified asphalt emulsion mixtures might be an alternate way of a structural layer material in pavement.

  2. Sample preparation for semivolatile organics analysis of Hanford single-shell tank waste with high nitrate/nitrite and water content

    SciTech Connect

    Stromatt, R.W.; Hoppe, E.W.; Steele, M.J.

    1993-11-01

    This report describes research work carried out to solve sample preparation problems associated with applying gas chromatography with mass spectrometric detection (GC/MS) to the analysis of single shell tank (SST) samples from Hanford for semivolatile organic compounds. Poor performance was found when applying the procedures based on the U.S. Environmental Protection Agency (EPA), Contract Laboratory Program, Statement of Work (CLP SOW). Analysis work was carried out on simulated drainable liquid modeled after the SST core samples which had evidenced analysis problems. Some work was also conducted on true SST samples. It was found that the pH range was too broad in the original procedure. It was also found that by decreasing the amount of methanol used in the extraction process, problems associated with the formation of an azeotrope phase could be avoided. The authors suggest a new procedure, whose eventual application to a wide array of SST samples will lend itself to better quality control limits.

  3. Toxicity of four antifouling biocides and their mixtures on the brine shrimp Artemia salina.

    PubMed

    Koutsaftis, A; Aoyama, I

    2007-11-15

    Zinc pyrithione (ZPT), Copper pyrihione (CPT), Chlorothalonil and Diuron are four of the most widely used as alternative to tributlytin (TBT) antifouling biocides in boat paints. As most previous laboratory bioassays for these biocides have been conducted solely based on acute tests with a single compound, information on the possible combined toxicity of these common biocides to marine organisms are limited. In this study, the toxicity of binary (in several proportions), ternary and quaternary mixtures were evaluated using the brine shrimp Artemia salina as test organism. Mixture toxicities were studied using the concentration addition model (isobolograms and toxic unit summation), and the mixture toxicity index (MTI). The ZPT-CPT combination had a strictly synergistic effect which requires attention because the coexistence of ZPT and CPT in the marine environment, due to transchelation of ZPT, may occur. The binary mixtures of Diuron with the metal pyrithiones exhibited various interactive effects (synergistic, antagonistic or additive) depending on concentration ratios, whereas all binary mixtures that contained Chlorothalonil exhibited antagonistic effects. The different types of combined effects subsequent to proportion variation of binary mixtures underline the importance of the combined toxicity characterization for various ratios of concentrations. The four ternary mixtures tested, also exhibited various interactive effects, and the quaternary mixture exhibited synergism. The models applied were in agreement in most cases. The observed synergistic interactions underline the requirement to review water quality guidelines, which are likely underestimating the adverse combined effects of these chemicals. PMID:17765949

  4. Diffusion in the Micellar and Hexagonal Phases of the C{_{12}}EO{_6}/H{_2}O Mixture: A Directional-Growth Study

    NASA Astrophysics Data System (ADS)

    Sallen, L.; Oswald, P.; Sotta, P.

    1997-01-01

    We studied in directional growth the Mullins-Sekerka instability at the interface between the hexagonal H? phase and the micellar phase of the lyotropic mixture C{12}EO6 + water. We first worked at the azeotropic concentration (50wt% of surfactant). When the C{12}EO6 is pure, the mixture behaves as a pure compound and the Mullins-Sekerka instability disappears. It reappears when the soap degrades by radical oxidation in the presence of light and heat. We measured as a function of impurity concentration and of column orientation, the critical velocity, wavelength, and drift velocity in growth and in melting. From these experimental data, we deduced the mean diffusion coefficients of impurities in the micellar phase (D^i_L) and in the hexagonal phase, parallel (D^i_{allel}) and perpendicularly (D^i_{perp}) to the molecular columns. We then shifted a bit from the azeotropic concentration, taking care to avoid surfactant degradation. Similar experiments in growth and in melting allowed us to determine the three diffusion coefficients D_L, D_{allel} and D_{perp} of the surfactant concentration field. The values found differ from the values obtained for impurities and are compared to the individual diffusion coefficients of the water and of the C{12}EO6 measured by NMR. Finally, we measured the kinetic coefficient for molecular attachment at the interface. We found that kinetics are linear and symmetrical in growth and in melting. Nous avons étudié en croissance directionnelle l'instabilité de Mullins-Sekerka à l'interface entre la phase hexagonale H? et la phase micellaire du mélange lyotrope C{12}EO6+eau. Nous avons d'abord travaillé à la concentration azéotrope (50% de surfactant en poids). Lorsque le C{12}EO6 est pur, le mélange se comporte comme un corps pur et l'instabilité de Mullins-Sekerka disparaît. Elle réapparaît lorsque le savon se dégrade par oxydation radicalaire à la lumière et à la chaleur. Nous avons mesuré en fonction de la concentration en impuretés et de l'orientation des colonnes moléculaires, la vitesse critique, la longueur d'onde et la vitesse de dérive des cellules en croissance et en fusion. De ces données expérimentales, nous avons déduit les trois coefficients de diffusion moyens des impuretés dans la phase micellaire (D^i_L) et dans la phase hexagonale, parallèlement (D^i_{allel}) et perpendiculairement (D^i_{perp}) aux colonnes moléculaires. Nous nous sommes ensuite écartés légèrement de la concentration azéotrope en prenant soin d'éviter la dégradation du surfactant. Des expériences analogues en croissance et en fusion nous ont permis de déterminer les trois coefficients de diffusion D_L, D_{allel} et D_{perp} du champ de concentration en surfactant. Les valeurs trouvées diffèrent de celles obtenues pour les impuretés et sont comparées aux coefficients de diffusion individuels de l'eau et du C{12}EO6 mesurés par RMN. Enfin, nous avons mesuré le coefficient cinétique d'attachement moléculaire à l'interface. Nous avons trouvé que la cinétique est linéaire et symétrique en croissance et en fusion.

  5. 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 ?g 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 responses and gene expression alterations, which along with several interactions between each mixture component on each biomarker confirm the susceptibility of mussels to API mixtures. PMID:24630142

  6. 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

  7. 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

  8. 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. PMID:11911491

  9. Sparse multivariate gaussian mixture regression.

    PubMed

    Weruaga, Luis; Vía, Javier

    2015-05-01

    Fitting a multivariate Gaussian mixture to data represents an attractive, as well as challenging problem, in especial when sparsity in the solution is demanded. Achieving this objective requires the concurrent update of all parameters (weight, centers, and precisions) of all multivariate Gaussian functions during the learning process. Such is the focus of this paper, which presents a novel method founded on the minimization of the error of the generalized logarithmic utility function (GLUF). This choice, which allows us to move smoothly from the mean square error (MSE) criterion to the one based on the logarithmic error, yields an optimization problem that resembles a locally convex problem and can be solved with a quasi-Newton method. The GLUF framework also facilitates the comparative study between both extremes, concluding that the classical MSE optimization is not the most adequate for the task. The performance of the proposed novel technique is demonstrated on simulated as well as realistic scenarios. PMID:25029490

  10. Symmetrical mixtures in external fields.

    PubMed

    Materniak, S; Patrykiejew, A

    2013-07-01

    We have studied the behavior of symmetrical binary mixtures of Lennard-Jones particles in contact with strongly adsorbing walls using Monte Carlo simulation methods in the grand canonical and semi-grand canonical ensembles. Two types of the surface potential have been applied. The first depends on the distance from the surface only, while the second involves periodic modulations in the directions parallel to the wall. In the latter case, it has been assumed that the solid substrate is a fcc crystal with the surface being the (100) face. We have considered the systems in which the surface potential is strong enough to induce the layer-by-layer adsorption at low temperatures and discussed the interplay between the demixing transition and the structure of thin films for several systems characterized by different parameters describing the interactions in the system. PMID:23822318

  11. 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).

  12. What contributes to the combined effect of a complex mixture?

    PubMed

    Altenburger, Rolf; Walter, Helge; Grote, Matthias

    2004-12-01

    The effect of a mixture of 10 compounds, which have previously been identified in an effect-directed analysis as potentially relevant for a specific contaminated riverine sediment (Brack et al. Arch. Environ. Contam. Toxicol. 1999, 37, 164), were investigated for the underlying joint effect. Components identified in an organic sediment extract included several PAHs (benzo[ghi]fluoranthene, benz[a]anthracene, fluoranthene, pyrene, 2-phenylnaphthalene, anthracene, and phenanthrene) plus prometryn, N-phenyl-2-naphthylamine, and parathion-methyl. Experiments were performed using a one-generation algal bioassay with the unicellular green algae Scenedesmus vacuolatus as well as chlorophyll fluorescence quenching analysis to describe the effects of the components and mixtures thereof. Analysis of the mixture effects based on concentration-response modeling of the effect data reveals that indeed effect contributions of several components can be expected although the mixture ratio is not equitoxic and the individual components vary greatly with respect to biological effect. Comparing predicted and observed mixture effects, the combined effect may not be attributed to a joint narcotic effect of the mixture components. Evidently, some of the components act specifically and dissimilar and may therefore be best described in their combined effect by response addition while for others a similar mode of action seems plausible. Chlorophyll fluorescence quenching analysis supports to discriminate between prometryn, N-phenyl-2-naphthylamine, and PAHs. A joint model for calculating the combined effect using concentration addition for the suspected unspecifically acting components in algae (PAHs and parathion-methyl) and subsequently response addition for this group and the other components clearly improves the description of the observed combined effect. Allocation of effect contributions to specific components using toxic units or effect contributions lead to different judgments. The observed combined effect of a 3-compound mixture of prometryn, N-phenyl-2-naphthylamine, and benzo[ghi]fluoranthene is indistinguishable from the effects of the original 10-compound mixture, demonstrating the need in site-specific assessment of complex contamination to account for the mode of action of contaminants. Implications forthe confirmation step in effect-directed analysis of substances causing effects in complex contaminated samples are discussed. PMID:15597892

  13. 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.

  14. 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 performance based design procedure. Finally, the developed guidelines with easy-to-use flow charts for the integrated mix design methodology are presented.

  15. 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

  16. 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. PMID:25336231

  17. 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.

  18. 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.

  19. 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.

  20. Mixture toxicity assessment of wood preservative pesticides in the freshwater amphipod Gammarus pulex (L.).

    PubMed

    Adam, Olivier; Badot, Pierre-Marie; Degiorgi, François; Crini, Grégorio

    2009-02-01

    All over the world, insecticides and fungicides are used to protect wood against pathogens. To document the environmental toxicity of wood preservative mixtures, freshwater amphipods Gammarus pulex (L.) were submitted to organic pesticides given independently or in mixtures. When given independently at environmentally realistic concentrations, propiconazole and tebuconazole (triazoles fungicides) were not toxic for G. pulex, 3-iodo-2-propinyl butyl carbamate (IPBC, fungicide) was moderately toxic, and cypermethrin (pyrethroid insecticide) was extremely toxic. 96-h LC50 were, respectively, 4703, 1643, 604, and 0.09 microg L(-1). When amphipods were submitted to a mixture mimicking the composition of a commercial solution (18.2% of cypermethrin, 45.8% propiconazole, 17.2% tebuconazole, 18.8% IPBC), the overall toxicity was equal to that of the most toxic component, namely cypermethrin. But, when organisms were submitted to the real commercial mixture containing pesticides, solvents and additives, the toxic effects were markedly higher. Moreover, a third mixture with only 0.002% cypermethrin showed lethality 2.5-18-fold higher than those predicted by the commonly used models. The present results show that toxicity of wood preservative mixtures cannot be assessed starting only from the toxicities of each single component. Furthermore, the present data strongly suggest that the environmental impacts of wood preservative mixtures might be frequently underestimated. PMID:18768221

  1. 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

  2. Limit of miscibility and nanophase separation in associated mixtures.

    PubMed

    Artola, P A; Raihane, A; Crauste-Thibierge, C; Merlet, D; Emo, M; Alba-Simionesco, C; Rousseau, B

    2013-08-22

    We present a detailed analysis of the mixing process in an associating system, the water-tert-butanol (2-methyl-2-propanol) mixture. Using molecular dynamics simulations, together with neutron, X-ray diffraction experiments, and pulsed gradient spin-echo NMR, we study the local structure and dynamic properties over the full concentration range, and thereby provide quantitative data that reveal relationships between local structure and macroscopic behavior. For an alcohol-rich mixture, diffraction patterns from both neutron and X-ray experiments exhibit a peak at low wavelength vector (q ≈ 0.7 Å(-1)) characteristic of supermolecular structures. On increasing the water content, this "prepeak" progressively flattens and shifts to low wave vector . We identify hydrogen bonds in the system as the driving force for the specific organization that appears in mixtures, and provide an analysis of the variation of the cluster size distribution with composition. We find that the sizes of local hydrogen-bonded clusters observed in alcohol-rich mixtures become larger as the mole fraction, x(w), of water is increased; a nanophase separation is seen for x(w) in the range 0.6-0.7. This corresponds to several changes in some macroscopic properties of the liquid mixture. Thus, we propose a microscopic description of the effect of water addition in alcohol, which is in agreement with both neutron diffraction pattern and mobility of water and alcohol species. In summary we present a full and comprehensive description of miscibility at its limit in an associated system. PMID:23937163

  3. Toxicological evaluation of complex mixtures: fingerprinting and multivariate analysis.

    PubMed

    Eide, Ingvar; Neverdal, Gunhild; Thorvaldsen, Bodil; Arneberg, Reidar; Grung, Bjørn; Kvalheim, Olav M

    2004-11-01

    The present paper describes a strategy for toxicological evaluation of complex mixtures based on chemical "fingerprinting" followed by pattern recognition (multivariate data analysis). The purpose is to correlate chemical fingerprints to measured toxicological endpoints, identify all major contributors to toxicity, and predict toxicity of additional mixtures. The strategy is illustrated with organic extracts of exhaust particles which are characterized by full scan gas chromatography-mass spectrometry (GC-MS). The complex GC-MS data are resolved into peaks and spectra for individual compounds using an automated curve resolution procedure. Projections to latent structures (PLS) is used for the regression modeling to correlate the GC-MS data to the measured responses; mutagenicity in the Ames Salmonella assay. The regression model identifies those peaks that co-vary with the observed mutagenicity. These peaks may be identified chemically from their spectra. Furthermore, the regression model can be used to predict mutagenicity from GC-MS chromatograms of additional samples. PMID:21782741

  4. 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.

  5. 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.

  6. 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…

  7. 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.

  8. Gas mixtures for spark gap closing switches

    DOEpatents

    Christophorou, Loucas G. (Oak Ridge, TN); McCorkle, Dennis L. (Knoxville, TN); Hunter, Scott R. (Oak Ridge, TN)

    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.

  9. 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…

  10. RENAL CANCER STUDIES OF DRINKING WATER MIXTURES

    EPA Science Inventory

    Current default risk assessments for chemical mixtures assume additivity of carcinogenic effects but this may under or over represent the actual biological response. A rodent model of hereditary renal cancer (Eker rat) was used to evaluate the carcinogenicity of a mixture of DBPs...

  11. 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)

  12. 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…

  13. COMPLEX MIXTURES AND GROUND WATER 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...

  14. Novel critical transitions in ternary fluid mixtures

    SciTech Connect

    Sadus, R.J.

    1992-06-25

    In this paper, in ternary fluid mixtures, the critical transition results in the emergence of a different type of equilibrium depending upon whether gas-liquid or lower or upper critical solution equilibria are involved. This may be responsible for the tricritical equilibria of ternary mixtures or quasi-binary fluids. 32 refs., 5 figs., 1 tab.

  15. Relativistic mixtures of charged and uncharged particles

    NASA Astrophysics Data System (ADS)

    Kremer, Gilberto M.

    2014-01-01

    Mixtures of relativistic gases within the framework of Boltzmann equation are analyzed. Three systems are considered. The first one refers to a mixture of uncharged particles by using Grad's moment method, where the relativistic mixture is characterized by the moments of the distribution functions: particle four-flows, energy-momentum tensors, and third-order moment tensors. In the second Fick's law for a mixture of relativistic gases of non-disparate rest masses in a Schwarzschild metric are derived from an extension of Marle and McCormack model equations applied to a relativistic truncated Grad's distribution function, where it is shown the dependence of the diffusion coefficient on the gravitational potential. The third one consists in the derivation of the relativistic laws of Ohm and Fourier for a binary mixtures of electrons with protons and electrons with photons subjected to external electromagnetic fields and in presence of gravitational fields by using the Anderson and Witting model of the Boltzmann equation.

  16. 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.

  17. 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. PMID:26619142

  18. 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.

  19. Development and optimization of methodologies for analysis of complex hydrocarbon mixtures. Summary of progress, 1 January-31 August, 1980

    SciTech Connect

    Laub, R.J.

    1980-01-01

    This progress report describes studies designed to explore and to clarify the a priori prediction of optimum conditions for the chromatographic separation of complex mixtures of organic compounds of significance to the Department of Energy.

  20. Dynamic flow synthesis of porous organic cages.

    PubMed

    Briggs, Michael E; Slater, Anna G; Lunt, Neil; Jiang, Shan; Little, Marc A; Greenaway, Rebecca L; Hasell, Tom; Battilocchio, Claudio; Ley, Steven V; Cooper, Andrew I

    2015-12-21

    The dynamic covalent synthesis of two imine-based porous organic cages was successfully transferred from batch to continuous flow. The same flow reactor was then used to scramble the constituents of these two cages in differing ratios to form cage mixtures. Preparative HPLC purification of one of these mixtures allowed rapid access to a desymmetrised cage molecule. PMID:26463103

  1. 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

  2. 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 chemical mixtures should be accounted for in numerical flow and transport models.

  3. 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

  4. The influence of equilibrium chemical reactions on vapor-liquid phase diagrams

    SciTech Connect

    Barbosa, D.; Doherty, M.F.

    1986-01-01

    Phase diagrams for simultaneous chemical reaction and phase equilibrium are presented for ideal and non-ideal systems. It is shown that reactive-azeotropes can occur for ideal mixtures. The conditions for formation of reactive-azeotropes in constant volatility systems are derived. These conditions show that for such systems reactive-azeotropes can occur only when the volatiles of the reactants are either all higher or all lower than the volatilities of the products.

  5. 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 calculations and eliminate guesswork for site characterizations.

  6. Environmental quality standards for mixtures: a case study with a herbicide mixture tested in outdoor mesocosms.

    PubMed

    Knauer, Katja; Hommen, Udo

    2013-03-01

    Traces of pesticides are frequently detected in surface waters. As a consequence, specific environmental quality criteria (EQS) for a set of single pesticides in surface waters were defined by the environmental authorities in several countries. In this context, the aim of this study was to investigate if the sum of the five percentile hazard concentration (?HC(5-95 percent), meaning that 5 percent of the aquatic assemblage remains affected considering a 95 percent confidence interval) of three herbicides with the same mode of action derived from a species sensitivity distribution based on acute toxicity data (EC(50) values) of the most sensitive taxonomic group is a suitable EQS for surface water addressing the occurrence of herbicide mixtures as common exposure scenario. Therefore, an outdoor mesocosm study was performed with three replicates per treatment for a period of 173 days. Results demonstrated that a constant long-term exposure over 35 days to the HC(5-95 percent) of a mixture of three PSII inhibitors did not lead to adverse effects on the aquatic community in this field mesocosm study. Neither adverse effects on very sensitive functional endpoints such as photosynthesis measurements of algae and macrophytes nor adverse effects on structural endpoints such as abundance data and species composition were determined. In contrast and as a positive control, the HC(30) treatment affected statistically significant all investigated endpoints and it was demonstrated that the PSII inhibitors acted additive on various level of organization (Knauert et al., 2008). This study is filling the gap that no empirical evidence is published indicating that the chronic exposure at the HC(5-95 percent) estimate is leading to no adverse effects for the aquatic community and is therefore a suitable EQS for surface waters in the agriculture landscape. PMID:23273621

  7. 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.

  8. Estrogenic activity of UV filter mixtures.

    PubMed

    Kunz, Petra Y; Fent, Karl

    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 hERalpha agonists, for their estrogenic activity in equieffective mixtures in a recombinant yeast assay carrying the human estrogen receptor alpha (hERalpha). 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 (CA) and independent action (IA) model. Most binary mixtures comprising of pure hERalpha 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 hERalpha 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. PMID:17027055

  9. 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.

  10. SOLVENT EXTRACTION OF ORGANIC WATER POLLUTANTS

    EPA Science Inventory

    Based on experiments with model systems of known organic water pollutants and environmental samples, conclusions are reached concerning the best general solvent for extraction and the most appropriate methods for related manipulations. Chloroform, methylene chloride-ether mixture...

  11. Hormesis in mixtures -- can it be predicted?

    PubMed

    Belz, Regina G; Cedergreen, Nina; Sørensen, Helle

    2008-10-01

    Binary mixture studies are well established for mixtures of pollutants, pesticides, or allelochemicals and sound statistical methods are available to evaluate the results in relation to reference models. The majority of mixture studies are conducted to investigate the effect of one compound on the inhibitory action of another. However, since stimulatory responses to low concentrations of chemicals are gaining increased attention and improved statistical models are available to describe this phenomenon of hormesis, scientists are challenged by the question of what will happen in the low concentration range when all or some of the chemicals in a mixture induce hormesis? Can the mixture effects still be predicted and can the size and concentration range of hormesis be predicted? The present study focused on binary mixtures with one or both compounds inducing hormesis and evaluated six data sets of root length of Lactuca sativa L. and areal growth of Lemna minor L., where substantial and reproducible hormetic responses to allelochemicals and herbicides have been found. Results showed that the concentration giving maximal growth stimulatory effects (M) and the concentration where the hormetic effect had vanished (LDS) could be predicted by the most-used reference model of concentration addition (CA), if the growth inhibitory concentrations (EC50) followed CA. In cases of deviations from CA at EC50, the maximum concentration M and the LDS concentration followed the same deviation patterns, which were described by curved isobole models. Thus, low concentration mixture effects as well as the concentration range of hormesis can be predicted applying available statistical models, if both mixture partners induce hormesis. Using monotonic concentration-response models instead of biphasic concentration-response models for the prediction of joint effects, thus ignoring hormesis, slightly overestimated the deviation from CA at EC20 and EC50, but did not alter the general conclusion of the mixture study in terms of deviation from the reference model. Mixture effects on the maximum stimulatory response were tested against the hypothesis of a linear change with mixture ratio by constructing 95% prediction intervals based on the single concentration-response curves. Four out of the six data sets evaluated followed the model of linear interpolation reasonably well, which suggested that the size of the hormetic growth stimulation can be roughly predicted in mixtures from knowledge of the concentration-response relationships of the individual chemicals. PMID:18640701

  12. Viscosity of Mixtures of ?-Tocopherol Acetate + Mesitylene

    NASA Astrophysics Data System (ADS)

    Szwajczaka, El?bieta; Stagraczy?ski, Ryszard; Herba, Henryk; ?wiergielb, Jolanta; Jad?yn, Jan

    2009-08-01

    The paper presents results of the share viscosity measurements performed as a function of temperature and concentration for mixtures of ?-tocopherol acetate (vitamine E acetate) and mesitylene, two liquids of essentially different viscosity (four order of magnitude difference at 280 K). The viscosity/ temperature dependence for pure ?-tocopherol acetate as well as for the mixtures studied can be well described with the Vogel-Fulcher-Tammann equation. The viscosities of the mixtures exhibit a strong negative deviation from the rule of additive dependence on concentration and for increasing temperature the maximum value of the deviation shows an exponential decreasing.

  13. Viscosity of multicomponent partially ionized gas mixtures

    NASA Technical Reports Server (NTRS)

    Armaly, B. F.; Sutton, K.

    1980-01-01

    An approximate method is proposed for predicting the viscosity of partially ionized gas mixtures. This technique expresses the viscosity of a mixture in terms of the viscosities of the individual pure components, is simple in form, and does not require large computer run times or storage. Thus, the technique is suitable for use with complex flowfields and heat-transfer calculations. Results for gas mixtures which are representative of the atmospheres of Jupiter, Earth, and Venus, are presented and it is shown that the results compare favorably with detailed kinetic-theory analyses.

  14. Uptake and toxicity of Cd, Cu and Pb mixtures in the isopod Asellus aquaticus from waterborne exposure.

    PubMed

    Van Ginneken, M; De Jonge, M; Bervoets, L; Blust, R

    2015-12-15

    The present study evaluated interactions of waterborne Cd, Cu and Pb mixtures on metal uptake rates in the isopod Asellus aquaticus and related this to mixture effects on toxicity. Secondly, it was assessed whether observed mixture effects were better related to isopod body concentrations compared to exposure concentrations. Isopods were exposed for 10 days to single, binary and tertiary mixtures including five different concentrations of Cd (0.107 to 277 ?g L(-1)), Cu (3.35 to 2117 ?g L(-1)) and Pb (0.782 to 443 ?g L(-1)). Mortality was assessed every day while isopod body concentrations, growth (biomass) and energy reserves (glycogen, lipid and protein reserves) were assessed at the end of the experiment. Synergistic interactions of combined Cd and Pb exposure on Cd and Pb uptake as well as on growth rates and mortality rates were observed. Mixture effects of combined Cd and Pb exposure on toxicity endpoints were directly related to increased Cd uptake in the Cd+Pb treatment. No mixture interactions of Cu on Cd or Pb uptake (and vice versa), nor on toxicity endpoints were observed. All toxicity endpoints were related to body concentrations. However, mixture effects disappeared when growth and mortality rates were expressed on body concentrations instead of exposure concentrations. By combining information of mixture effects on metal uptake with mixture toxicity data, the present study provides more insight in the way metal mixtures interfere with aquatic organisms and how they can induce toxic effects. PMID:26282750

  15. 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.

  16. 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.

  17. Correlating Thermal-Conductivity Data for Ternary Liquid Mixtures

    NASA Astrophysics Data System (ADS)

    Focke, Walter W.

    2008-08-01

    The performance of several semi-empirical expressions for correlating the temperature, pressure and composition dependence of the thermal conductivity (?) of pure organic liquids and mixtures was investigated. The temperature and pressure dependence is adequately represented by Chisholm approximants of order (1, 1) or (2, 1) with five and eight adjustable constants, respectively. The fully predictive Vredeveld equation uses mass fractions as the composition variable. It significantly underestimated ? values for the R32 + R125 + R134a ternary refrigerant system. Binary predictive models with one or two adjustable parameters include the quadratic Scheffé polynomial and its corresponding Padé approximant, the cubic “Margules” model and the theoretical Wassiljewa equation. It was found that the Padé (2, 2) approximant and the Wassiljewa equation satisfactorily correlated the extensive ternary mixture data published by Rowley and coworkers. Best results were obtained when the mole fraction was used as a composition variable. The predictive capability of the models was checked using the R32 + R125 + R134a ternary refrigerant system. Combining rules were used for cross parameters such that the temperature and pressure dependence was incorporated via the pure fluid properties. Model parameters were fixed using binary data alone. In this case, the quadratic Scheffé, Padé (2, 2), and Wassiljewa (with temperature- and pressure-independent parameters) all provided satisfactory predictions for ternary mixtures.

  18. Toxicity of phenanthrene and lindane mixtures to marine invertebrates.

    PubMed

    Evans, A D; Nipper, M

    2007-10-01

    Surface waters near industrialized and agricultural areas are contaminated with hundreds of different pollutants from a variety of sources. Methods for measurement of sediment, surface water, and porewater toxicity in marine environments include the sea urchin (Arbacia punctulata) fertilization and embryological development tests and copepod (Schizopera knabeni) survival and hatching success assessment. The concentration addition model was applied to determine whether toxicity of two compounds, phenanthrene (polycyclic aromatic hydrocarbon) and lindane (organochlorine pesticide), when combined can be accurately assessed because of similar modes of action. Mixture analysis determined the sea urchin fertilization test to exhibit additivity (TU(mix) = 1.13), while the copepod test exhibited a synergistic effect (TU(mix) = 0.22). Mixture toxicity data for the sea urchin embryological test were not conclusive because of the lack of toxicity of the individual chemicals. The synergistic effect to copepods is a concern as it indicates that greater toxic effects may occur when the compounds are present in mixtures. Results from this research suggest that increased toxicity to some categories of organisms should be expected near agricultural and industrial areas where pesticides and other types of compounds may occur simultaneously. PMID:17696137

  19. Method of photocatalytic conversion of C-H organics

    DOEpatents

    Camaioni, D.M.; Lilga, M.A.

    1998-01-13

    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.

  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.

  1. ODE Constrained Mixture Modelling: A Method for Unraveling Subpopulation Structures and Dynamics

    PubMed Central

    Hasenauer, Jan; Hasenauer, Christine; Hucho, Tim; Theis, Fabian J.

    2014-01-01

    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

  2. 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

  3. 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

  4. Separation of gas mixtures including hydrogen

    SciTech Connect

    Krishnamurthy, R.; Lerner, S.L.; Shukla, Y.; Stokley, A.G.

    1993-08-10

    A process is described of separating a gas mixture comprising at least three components into three different fractions by pressure swing adsorption, comprising repeatedly performing a cycle including: passing said gas mixture sequentially through first and second adsorptive regions on each of which a second component of the mixture is more strongly adsorbed than a first component, but less strongly adsorbed than a third component; withdrawing a first fraction enriched in said first component from the downstream end of the second adsorptive region; stopping admission of the said gas mixture to the first adsorptive region; withdrawing a second fraction enriched in the second component from the downstream end of the first adsorptive region and from the upstream end of the second adsorptive region into a common pipeline; and withdrawing a third fraction enriched in the third component from the upstream end of the first adsorptive region.

  5. Uncertainty in Mixtures and Cumulative Risk Assessment

    EPA Science Inventory

    Uncertainty in Mixtures and Cumulative Risk Assessment JC Lipscomb and GE Rice U.S. Environmental Protection Agency, Office of Research and Development, National Center for Environmental Assessment, Cincinnati, Ohio, USA Humans and environmental species are rarely exposed to sing...

  6. Terahertz spectroscopy for quantifying refined oil mixtures.

    PubMed

    Li, Yi-nan; Li, Jian; Zeng, Zhou-mo; Li, Jie; Tian, Zhen; Wang, Wei-kui

    2012-08-20

    In this paper, the absorption coefficient spectra of samples prepared as mixtures of gasoline and diesel in different proportions are obtained by terahertz time-domain spectroscopy. To quantify the components of refined oil mixtures, a method is proposed to evaluate the best frequency band for regression analysis. With the data in this frequency band, dualistic linear regression fitting is used to determine the volume fraction of gasoline and diesel in the mixture based on the Beer-Lambert law. The minimum of regression fitting R-Square is 0.99967, and the mean error of fitted volume fraction of 97# gasoline is 4.3%. Results show that refined oil mixtures can be quantitatively analyzed through absorption coefficient spectra in terahertz frequency, which it has bright application prospects in the storage and transportation field for refined oil. PMID:22907017

  7. 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...

  8. 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.)

  9. Picosecond reorientational dynamics of polar dye probes in binary aqueous mixtures

    NASA Astrophysics Data System (ADS)

    Dutt, G. B.; Doraiswamy, S.

    1992-02-01

    Picosecond time dependent fluorescence method has been used to measure the rotational reorientation times (?r) of three kinds of dye probes—oxazine 720 (a monocation), nile red (neutral but polar), and resorufin (a monoanion)—in a series of binary mixtures of water-amides, water-dipolar aprotics, and water-alcohols at 298 K. Most of the binary mixtures are characterized by the fact that at a particular composition (between 25% to 40% of the organic solvent in water), the viscosity (?) of the solution reaches a maximum value that is higher than the viscosities of the two solvents. As a consequence, the viscosity profile of the solution as a function of the organic solvent exhibits a bivaluedness, the extent of which is more, if the liquids are nearly isoviscous. The dielectric properties of the solution also change across the composition range. All the dyes show a near linear behavior of ?r vs ? in formamide-water, N-methylformamide-water, and methanol-water mixtures. A dual-valued profile for ?r vs ? is obtained for the cation oxazine 720 in the three dipolar aprotic mixtures (N, N-dimethylformamide-water, N, N-dimethylacetamide-water, and dimethylsulphoxide-water), with the rotational reorientation times being higher in the organic solvent-rich zone, compared to the corresponding isoviscous point in the water-rich zone. However, the anion resorufin shows a bivalued profile of ?r vs ? only in dimethylsulphoxide-water mixtures, while the neutral nile red shows a linear behavior in all the dipolar-aprotic water mixtures. A hook-type profile of ?r vs ? is seen for the anion resorufin in ethanol-, 1-propanol-, and 2-propanol-water mixtures and for the cation oxazine 720 in 1-propanol- and 2-propanol-water mixtures; but nile red shows no departure from linear behavior even in alcohol-water mixtures. The rotational dynamics of the cation oxazine 720 in dipolar aprotic-water mixtures is explained in terms of solvation since the dielectric friction is minimal in these solutions. While the concept of dielectric friction model seems to be adequate to understand the nonhydrodynamic behavior of the oxazine 720, the additional contribution due to solvation effects has to be necessarily taken into account to explain the rotational dynamics of the anion resorufin in alcohol-water mixtures.

  10. Predicting skin permeability from complex chemical mixtures.

    PubMed

    Riviere, Jim E; 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(p) = c + mMF + a sigma alpha2(H) + b sigma beta2(H) + s pi2(H) + rR2 + vV(x) where sigma alpha2(H) is the hydrogen-bond donor acidity, sigma beta2(H) is the hydrogen-bond acceptor basicity, pi2(H) is the dipolarity/polarizability, R2 represents the excess molar refractivity, and V(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(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, R2 for absorption was 0.62. With the MF, correlations increased up to 0.78. Parameters correlated to the MF include refractive index, polarizability and log (1/Henry's Law Constant) of the mixture components. These factors should not be considered final as the focus of these studies was solely to determine if knowledge of the physical properties of a mixture would improve predicting skin permeability. Inclusion of multiple mixture factors should further improve predictability. The importance of these findings is that there is an approach whereby the effects of a mixture on dermal absorption of a penetrant of interest can be quantitated in a standard QSPeR model if physicochemical properties of the mixture are also incorporated. PMID:16183383

  11. 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 index, polarizability and log (1/Henry's Law Constant) of the mixture components. These factors should not be considered final as the focus of these studies was solely to determine if knowledge of the physical properties of a mixture would improve predicting skin permeability. Inclusion of multiple mixture factors should further improve predictability. The importance of these findings is that there is an approach whereby the effects of a mixture on dermal absorption of a penetrant of interest can be quantitated in a standard QSPeR model if physicochemical properties of the mixture are also incorporated.

  12. Flash evaporation of liquid monomer particle mixture

    DOEpatents

    Affinito, John D. (Kennewick, WA); Darab, John G. (Richland, WA); Gross, Mark E. (Pasco, WA)

    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.

  13. 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.

  14. 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.

  15. Amphiphile Meets Amphiphile: Beyond the Polar-Apolar Dualism in Ionic Liquid/Alcohol Mixtures.

    PubMed

    Russina, Olga; Sferrazza, Alessio; Caminiti, Ruggero; Triolo, Alessandro

    2014-05-15

    The mesoscopic morphology of binary mixtures of ethylammonium nitrate (EAN), the protic ionic liquid par excellence, and methanol is explored using neutron/X-ray diffraction and computational techniques. Both compounds are amphiphilic and characterized by an extended hydrogen bonding network: surprisingly, though macroscopically homogeneous, these mixtures turn out to be mesoscopically highly heterogeneous. Our study reveals that even in methanol-rich mixtures, a wide distribution of clusters exists where EAN preserves its bulk, sponge-like morphology. Accordingly methanol does not succeed in fully dissociating the ionic liquid that keeps on organizing in a bulk-like fashion. This behavior represents the premises to the more dramatic phenomenology observed with longer alcohols that eventually phase separate from EAN. These results challenge the commonly accepted polar and apolar moieties segregation in ionic liquids/molecular liquids mixtures and the current understanding of technologically relevant solvation processes. PMID:26270376

  16. 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

  17. Primordial soup was edible: abiotically produced Miller-Urey mixture supports bacterial growth.

    PubMed

    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

  18. 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. PMID:22687436

  19. 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.

  20. 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. PMID:26541994