Science.gov

Sample records for organic azeotropic mixtures

  1. Separation of organic azeotropic mixtures by pervaporation

    SciTech Connect

    Baker, R.W.

    1991-12-01

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

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

    SciTech Connect

    Baker, R.W.

    1991-12-01

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

  3. 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. Desolventizing of soybean oil/azeotrope mixtures using ceramic membranes.

    PubMed

    de Melo, Jonas R M; Tiggeman, Lidia; Rezzadori, Katia; Steffens, Juliana; Palliga, Marshall; Oliveira, J Vladimir; Di Luccio, Marco; Tres, Marcus V

    2017-08-01

    This work investigates the use of ceramic membranes with different molecular weight cut-offs (MWCOs: 5, 10 and 20 kDa) to desolventize azeotropic solvent mixtures (ethanol/n-hexane and isopropyl alcohol/n-hexane) from soybean oil/azeotrope micelles. Results show that a decrease in the MWCO of a membrane and an increase in the solvent mass ratio in the mixture resulted in a significant reduction in the permeate flux. The 20 kDa membrane presented the highest permeate flux, 80 and 60 kg/m(2)h for the soybean oil/n-hexane/isopropyl alcohol and soybean oil/n-hexane/ethanol azeotropes, respectively, for an oil to solvent ratio of 1:3 (w/w). The highest oil retention was found using the n-hexane/isopropyl alcohol azeotrope, around 25% in the membrane with the lowest MWCO, that is, 5 kDa. It is shown that the azeotropic mixtures provided intermediate characteristics compared to the original pure solvent behavior.

  6. 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.

  7. 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.

  8. 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

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

    DOEpatents

    Frazer, J.W.

    1961-12-19

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

  10. 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

    2010-09-07

    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.

  11. Decay rate of critical fluctuations in ethane+carbon dioxide mixtures near the critical line including the critical azeotrope

    SciTech Connect

    Chang, R.F.; Doiron, T.; Pegg, I.L.; Hanley, H.J.M.; Cezairliyan, A.

    1986-03-01

    Using the technique of photon correlation spectroscopy we have measured the decay rate of critical fluctuations in mixtures of ethane and carbon dioxide of various compositions including a near-azeotropic mixture. Our experimental data indicate that there is only one dominant mode of fluctuations and the decay rate is well described by the predictions of the mode-coupling theory with the exponent v=0.63 for all compositions. The decay rate, its background contributions, the shear viscosity, and the correlation length for the mixtures appear to interpolate simply between those of ethane and carbon dioxide.

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

    SciTech Connect

    Abe, Yoshiyuki; Iwasaki, Akira

    1999-07-01

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

  13. 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.

  14. Peculiar behavior of the critical loci of azeotropic binary mixtures: Case of perfluoromethylcyclohexane-isomeric hexane systems

    NASA Astrophysics Data System (ADS)

    Abbaci, Azzedine; Ladjama, Sabrina; Toumi, Adel

    2017-04-01

    In a previous publication [A. Abbaci, H.R. van den Berg, E. Sakonidou, J.V. Sengers, Int. J. Thermophys. 13, 1043 (1992)], a study of ethane-carbon dioxide mixture critical locus as a function of the mole fraction was presented in order to show the evidence of an abnormal behavior in the critical density curve. An update on the evaluation of the critical parameters of this same mixture was published by [J.V. Sengers, G.X. Jin, Int. J. Thermophys. 28, 1181 (2007)]. In this work, we generalize the study to the critical loci of five selected azeotropic mixtures of perfluoromethylcyclohexane-isomeric hexane systems that have been correlated using simple polynomials. It is generally assumed that an azeotropic mixture is a synonym of a peculiar behavior of the critical density of this mixture as a function of the mole fraction. The purpose of this correlation is to show that this is not the case. Finally, we show the consequences of this abnormal behavior if it exists on the behavior of certain thermodynamic properties of such mixtures.

  15. Peculiar behavior of the critical loci of azeotropic binary mixtures: Case of perfluoromethylcyclohexane-isomeric hexane systems

    NASA Astrophysics Data System (ADS)

    Abbaci, Azzedine; Ladjama, Sabrina; Toumi, Adel

    2016-08-01

    In a previous publication [A. Abbaci, H.R. van den Berg, E. Sakonidou, J.V. Sengers, Int. J. Thermophys. 13, 1043 (1992)], a study of ethane-carbon dioxide mixture critical locus as a function of the mole fraction was presented in order to show the evidence of an abnormal behavior in the critical density curve. An update on the evaluation of the critical parameters of this same mixture was published by [J.V. Sengers, G.X. Jin, Int. J. Thermophys. 28, 1181 (2007)]. In this work, we generalize the study to the critical loci of five selected azeotropic mixtures of perfluoromethylcyclohexane-isomeric hexane systems that have been correlated using simple polynomials. It is generally assumed that an azeotropic mixture is a synonym of a peculiar behavior of the critical density of this mixture as a function of the mole fraction. The purpose of this correlation is to show that this is not the case. Finally, we show the consequences of this abnormal behavior if it exists on the behavior of certain thermodynamic properties of such mixtures.

  16. 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.

  17. 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.

  18. 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...

  19. 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...

  20. Recovery of organic carbon from atmospheric particulate matter using soxhlet extraction with the benzene/methanol azeotrope

    SciTech Connect

    Barkenbus, B.D.; Griest, W.H.; Huntzicker, J.J.; Heyerdahl, E.K.; MacDougall, C.S.

    1983-01-01

    The extraction efficiency of the benzene/methanol azeotrope for organic carbon in atmospheric particulate matter was determined using a carbon types analyzer and also radio-labeled tracers and liquid scintillation spectroscopy. A twenty-four hour Soxhlet extraction with the azeotrope extracts 76 percent of the organic carbon, 15 percent of the elemental carbon, and 61 percent of the total carbon. Nonpolar and moderately polar organic compounds such as dotriacontane, benzo(a)pyrene, and stearic acid are extracted with 95 percent recovery. Highly polar oxygenated species such as succinic acid are extracted with an efficiency of 82 percent. The Soxhlet extractor was more efficient than ultrasonication for the extraction of highly polar species.

  1. Thermodynamic performance limit and evaporator design considerations for NARM-based domestic refrigerator-freeze systems. Rept. for Aug 89-May 90. [Non-Azeotropic Refrigerant Mixtures

    SciTech Connect

    Smith, M.K.; Heun, M.C.; Crawford, R.R.; Newell, T.A.

    1990-01-01

    The paper gives results of an investigation of non-azeotropic refrigerant mixtures (NARMs) for a two-temperature-level heat exchange process found in a domestic refrigerator-freezer. Ideal (constant air temperature) heat exchange processes are assumed. The results allow the effects of intercooling between the evaporator refrigerant stream and the condenser outlet stream to be examined systematically. Three refrigerant pairs, R22/R142b, R22/R123, and R32/R142b, were studied, but the results for only R22/R123 are presented because of its unique temperature glide curvature. Practical implementation of a Lorenz cycle constrains evaporator design. An evaporator module design is presented which meets the NARM system constraints.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  3. 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)

  4. Study of a non-ideal liquid mixture in the hydrodynamic regime. Rayleigh-Brillouin spectra, sound propagation and damping in the CH 3CN-CCl 4 system at the azeotropic composition

    NASA Astrophysics Data System (ADS)

    Sassi, Paola; D'Elia, Valerio; Cataliotti, Rosario Sergio

    2003-01-01

    The hydrodynamic behaviour in the GHz frequency region has been analzsed for the non-ideal CH 3CN-CCl 4 liquid mixture around the azeotropic composition. Rayleigh-Brillouin spectra have been measured as a function of temperature and composition, at fixed value of transferred wave vector in the 90° scattering geometry, and also at different scattering angles to study dispersion with frequency of the spectral observables. These measurements have been complemented by those of refractive index, density and viscosity at the same temperatures and mole fraction values. Very interesting behaviour of the classic Brillouin spectral observables, such as the hypersonic propagation speeds and the acoustic absorption coefficients, has been revealed near the azeotropic composition of the mixture at the investigated temperatures, namely 15°C, 25°C, 40°C and 60°C. These effects have been interpreted at the light of the Mountain and Deutch theory of binary solutions and the forecast behaviour of the intermolecular forces around the azeotropic point composition of these very different molecular liquids.

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

    PubMed

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

    2015-04-01

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

  6. Azeotropic dehydration process for treating bituminous froth

    SciTech Connect

    Filby, J. E.

    1985-04-30

    Bituminous froths, typically obtained from the known Hot Water Method of extraction treatment of oil sands, are processed to remove water and part of the coarse mineral solids contained in the froth. In the process, the froth feed stock from the Hot Water Method treatment is mixed with a naphtha diluent, preferably naphtha which is derived from upgrading or refining of separated bitumen, in preferably the minimum amount sufficient to effectively remove all water by azeotropic distillation, while providing a workable feed viscosity. The mixture of naphtha and froth is treated to remove coarse solids and part of the water in a settling device, heated to a temperature sufficient to cause vaporization of the naphtha and remaining water as an azeotrope and flashed to substantially separate all water and naphtha from the bitumen. The dry bitumen with remaining solids, is normally not suitable for passing to a refinery but rather is sent to upgrading at a typical oil sands mining upgrading complex. Naphtha is recovered and recycled. The naphtha, in addition to its azeotrope forming feature, makes the froth more homogenous, less viscous, easier to handle and less fouling in heat exchangers, facilitates separation of coarse solids, and eliminates severe foaming when the froth is heated.

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

    ERIC Educational Resources Information Center

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

    2016-01-01

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

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

    ERIC Educational Resources Information Center

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

    2016-01-01

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

  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. Nonlinear ultrasonic nature of organic liquid and organic liquid mixture.

    PubMed

    Lu, Yi-gang; Zhang, Yang; Dong, Yan-wu

    2006-12-22

    Based on Jacobson's molecular free length theory in liquids and the relationship between ultrasonic velocity and the molecular free length in organic liquids, this paper deduces the equations for pressure coefficient and temperature coefficient of ultrasonic velocity and nonlinear acoustic parameter B/A in both of organic liquid and organic liquid binary mixtures. These nonlinear acoustic parameters are evaluated against the measured results and data from other sources. The equations reveal the connections between the nonlinear acoustic parameters and some internal structural of the medium or mixtures e.g. the sizes of molecule, several thermodynamic physical parameters and outside status e.g. condition of pressure and temperature of the liquid or liquid mixture. With the equations the nonlinear acoustic parameter B/A of organic liquid binary mixtures, which is impossible to know without the nonlinear acoustic parameter B/A of the tow components before, can be calculated based on the structural and physical parameters of organic liquid and organic liquid binary mixtures.

  13. 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...

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

    PubMed

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

    2015-09-28

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

  16. SECONDARY ORGANIC AEROSOL FORMATION FROM MIXTURES OF BIOGENIC HYDROCARBONS

    EPA Science Inventory

    In this work the influence of hydrocarbon mixtures on the overall Secondary Organic Aerosol yield is investigated. Photochemical reaction experiments were conducted using mixtures of a-pinene, isoprene and propene in the presence of NOx. Results of the experiments show...

  17. 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.

  18. Lateral organization of complex lipid mixtures from multiscale modeling

    NASA Astrophysics Data System (ADS)

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

    2010-02-01

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

  19. 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.

  20. 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.

  1. Estimation of interfacial tension between organic liquid mixtures and water.

    PubMed

    Yoon, Hongkyu; Oostrom, Mart; 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 ternarysystems 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

  2. 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

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

    PubMed

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

    2002-04-05

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

  4. 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.

  5. 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.

  6. Influence of organic solvent mixtures on biological membranes.

    PubMed Central

    Gustafson, C; Tagesson, C

    1985-01-01

    A simple experimental model was used to study the influence of organic solvents and solvent mixtures on the integrity of biological membranes. Radiolabelled membranes were prepared biosynthetically by growing Escherichia coli in the presence of 14C-oleic acid; the bulk of the radioactivity was incorporated into 14C-phosphatidylethanolamine, the predominant phospholipid species in E coli membranes. The radiolabelled bacteria were incubated at 37 degrees C in the presence of solvent, and the mixture filtrated through a Millipore 0.45 micron filter. This filtration retained radiolabel associated with the bacteria, and only radiolabel released as a result of solvent action was allowed through the filter. The radioactivity in the filtrate was then counted and expressed as a percentage of the total radioactivity. Results showed that aliphatic alcohols released membrane constituents in relation to their hydrocarbon chain length (1-propanol greater than 2-propanol greater than ethanol greater than methanol); the effects of aliphatic alcohols were potentiated by acetone, ethyl methyl ketone, ethylene glycol, and N,N'-dimethylformamide, and the effects of ethanol were potentiated by 1-butanol, benzyl alcohol, and ethylacetate. These findings point to the possibility that certain mixtures of organic solvents are more damaging to membranes than the components of the mixture would indicate, and suggest that the experimental model used might help in showing mixtures that are particularly harmful. PMID:3899160

  7. 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.

  8. 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.

  9. 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.

  10. How will Primary and Secondary Organic Mixtures Impact CCN?

    NASA Astrophysics Data System (ADS)

    Asa-Awuku, A. A.; Donahue, N. M.; Robinson, A. L.

    2009-12-01

    As organic particles age, they may enhance their ability to uptake water, activate and form cloud droplets. These particles that activate are called cloud condensation nuclei (CCN). Understanding the chemical and thermodynamic properties that control CCN activity and droplet growth is necessary for constraining impacts on the hydrological cycle and uncertainties from the aerosol indirect effect. In particular, quantifying the effects of changes in partitioning and aging are important for predicting CCN concentrations. In our study we investigate changes in the CCN activity of biogenic secondary organic aerosol (SOA) modified by the presence of two anthropogenic two types of primary organic aerosol (POA) that are emitted by anthropogenic sources; POA from a flash vaporized mixture of motor-oil and fuel and POA emitted by a diesel engine. The aerosol are sampled from a 12 meter-cubed chamber and an Aerodyne quadrapole aerosol mass spectrometer (Q-AMS) measures changes in aerosol chemical composition and a continuous flow thermal gradient CCN counter measures CCN activity at different instrument supersaturations. We present the CCN activity of alpha-pinene SOA, motor-oil fuel and diesel exhaust POA and their subsequent mixtures. Alpha-pinene SOA is moderately CCN active and the POA that contain lubricating oil components are significantly less active. CCN measurements are compared with mass spectra to identify correlations in the data sets. CCN concentrations are predicted using Q-AMS chemical composition data; particle time of flight data is used to infer the aerosol mixing state and size-resolved CCN predictions are compared to measurements. The assumption that CCN properties are additive is tested by applying CCN properties of individual species to data from mixing experiments.

  11. 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.

  12. 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

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

    PubMed

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

    2016-06-29

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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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

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

    PubMed

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

    1985-09-01

    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

  20. 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.

  1. 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.

  2. 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.

  3. Processes of Heat Transfer in Rheologically Unstable Mixtures of Organic Origin

    NASA Astrophysics Data System (ADS)

    Tkachenko, S. I.; Pishenina, N. V.; Rumyantseva, T. Yu.

    2014-05-01

    The dependence of the coefficient of heat transfer from the heat-exchange surface to a rheologically unstable organic mixture on the thermohydrodynamic state of the mixture and its prehistory has been established. A method for multivariant investigation of the process of heat transfer in compound organic mixtures has been proposed; this method makes it possible to evaluate the character and peculiarities of change in the rheological structure of the mixture as functions of the thermohydrodynamic conditions of its treatment. The possibility of evaluating the intensity of heat transfer in a biotechnological system for production of energy carriers at the step of its designing by multivariant investigation of the heat-transfer intensity in rheologically unstable organic mixtures with account of their prehistory has been shown.

  4. 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 ...

  5. 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 ...

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

    PubMed

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

    2016-11-15

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

  7. 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...

  8. 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...

  9. 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)

  10. Nanofiltration properties of PTMSP in binary organic solvents mixtures

    NASA Astrophysics Data System (ADS)

    Yushkin, A. A.; Kossov, A. A.; Volkov, V. V.

    2016-09-01

    In this study, the stability and nanofiltration performance of poly[1-(trimethylsilyl)- 1-propyne] (PTMSP) in ethanol solutions of butylaldehyde, 1-decanal, 1-hexene, 1-decene was evaluated. It was found that PTMSP was insoluble in all aldehyde solutions, but it was soluble at olefin concentration of 80% or higher. Nanofiltration experiments demonstrate that binary mixtures of 1-decanal and ethanol viscosity are not the parameter affecting on membrane permeability and rejection of solute as well as swelling degree. In the case of decanol/ethanol solutions both solution viscosity and molar volume demonstrate the best fit of experimental data. It was shown that with the decrease of ethanol content in the feed, the rejection of anionic solute Remazol Brilliant Blue R (MW 626) increases from 94 up to 97%.

  11. Nanostructural organization and anion effects in the optical Kerr effect spectra of binary ionic liquid mixtures.

    PubMed

    Xiao, Dong; Rajian, Justin Rajesh; Hines, Larry G; Li, Shengfu; Bartsch, Richard A; Quitevis, Edward L

    2008-10-23

    This article reports a study of the effect of anions on the optical Kerr effect (OKE) spectra of binary ionic liquid mixtures with one mixture comprising the 3-methyl-1-pentylimidazolium ([C 5mim] (+)) cation and the anions PF 6 (-) and CF 3CO 2 (-) (TFA (-)), and another mixture comprising the [C 5mim] (+) cation and the anions Br (-) and bis(trifluomethanesulfonyl)imide (NTf 2 (-)). The spectra were obtained by the use of optical heterodyne-detected Raman-induced Kerr Effect Spectroscopy at 295 K. The OKE spectra of the mixtures are compared with the calculated mole-fraction weighted sum of the normalized OKE spectra of the neat liquids. The OKE spectra are nearly additive for [C 5mim]Br/[C 5mim][NTf 2] mixtures, but nonadditive for [C 5mim][PF 6]/[C 5mim][TFA] mixtures. In the case of the equimolar [C 5mim][PF 6]/[C 5mim][TFA] mixture, the nonadditivity is such that the experimental OKE spectrum is narrower than the calculated OKE spectrum. The additivity or nonadditivity of OKE spectra for IL mixtures can be explained by assuming ionic liquids are nanostructurally organized into nonpolar regions and ionic networks. The ionic networks in mixtures will be characterized by "random co-networks" for anions that are nearly the same in size (PF 6 (-) and TFA (-)) and by "block co-networks" for anions that differ greatly in size (Br (-) and NTf 2 (-)).

  12. 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

  13. 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...

  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. Passivity and breakdown of carbon steel in organic solvent mixtures of propylene carbonate and dimethoxyethane

    SciTech Connect

    Shifler, D.A.; Kruger, J.; Moran, P.J.

    1998-07-01

    The passivity and breakdown of passivity of 1018 carbon steel in propylene carbonate (PC) and 1,2-dimethoxyethane (DME) mixtures with 0.5 molar lithium hexafluoroarsenate supporting electrolyte were examined via several electrochemical and surface analytical methods. The PC-DME/0.5 M LiAsF{sub 6} mixtures ranged from 10 to 90 mol % PC. The results from the PC/DME mixtures were compared to passivating mechanisms found in pure PC and DME solutions. In PC-rich mixtures, the breakdown of passivity occurred near the oxidation potentials of either organic solvent. Premature breakdown of the carbon steel in PC-DME mixtures occurred at sulfide inclusions as was observed earlier in PC/0.5 M LiAsF{sub 6} solutions although passive films attempted to form at these inclusion sites in mixtures containing at least 10 mol % DME. As the DME content increased in the PC-DME mixtures, the passive films formed on bare steel surfaces possessed an increasing polymer film character. In 50 and 70 mol % DME solutions nonprotective polymer films were formed. The nonprotective nature of these films indicated that PC passivation mechanisms competed and interfered with the DME mechanism of electropolymerized film formation. Only in 10 mol % PC-90 mol % DME mixtures were protective electropolymerized films formed on 1018 carbon steel.

  16. Secondary organic aerosol from VOC mixtures in an oxidation flow reactor

    NASA Astrophysics Data System (ADS)

    Ahlberg, Erik; Falk, John; Eriksson, Axel; Holst, Thomas; Brune, William H.; Kristensson, Adam; Roldin, Pontus; Svenningsson, Birgitta

    2017-07-01

    The atmospheric organic aerosol is a tremendously complex system in terms of chemical content. Models generally treat the mixtures as ideal, something which has been questioned owing to model-measurement discrepancies. We used an oxidation flow reactor to produce secondary organic aerosol (SOA) mixtures containing oxidation products of biogenic (α-pinene, myrcene and isoprene) and anthropogenic (m-xylene) volatile organic compounds (VOCs). The resulting volume concentration and chemical composition was measured using a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. The SOA mass yield of the mixtures was compared to a partitioning model constructed from single VOC experiments. The single VOC SOA mass yields with no wall-loss correction applied are comparable to previous experiments. In the mixtures containing myrcene a higher yield than expected was produced. We attribute this to an increased condensation sink, arising from myrcene producing a significantly higher number of nucleation particles compared to the other precursors. Isoprene did not produce much mass in single VOC experiments but contributed to the mass of the mixtures. The effect of high concentrations of isoprene on the OH exposure was found to be small, even at OH reactivities that previously have been reported to significantly suppress OH exposures in oxidation flow reactors. Furthermore, isoprene shifted the particle size distribution of mixtures towards larger sizes, which could be due to a change in oxidant dynamics inside the reactor.

  17. 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.

  18. Strategies for Transferring Mixtures of Organic Contaminants from Aquatic Environments into Bioassays.

    PubMed

    Jahnke, Annika; Mayer, Philipp; Schäfer, Sabine; Witt, Gesine; Haase, Nora; Escher, Beate I

    2016-06-07

    Mixtures of organic contaminants are ubiquitous in the environment. Depending on their persistence and physicochemical properties, individual chemicals that make up the mixture partition and distribute within the environment and might then jointly elicit toxicological effects. For the assessment and monitoring of such mixtures, a variety of cell-based in vitro and low-complexity in vivo bioassays based on algae, daphnids or fish embryos are available. A very important and sometimes unrecognized challenge is how to combine sampling, extraction and dosing to transfer the mixtures from the environment into bioassays, while conserving (or re-establishing) their chemical composition at adjustable levels for concentration-effect assessment. This article outlines various strategies for quantifiable transfer from environmental samples including water, sediment, and biota into bioassays using total extraction or polymer-based passive sampling combined with either solvent spiking or passive dosing.

  19. Liquid-liquid phase separation in atmospheric aerosol particles: dependence on organic functionalities and mixture complexity

    NASA Astrophysics Data System (ADS)

    Song, M.; Marcolli, C.; Krieger, U. K.; Zuend, A.; Peter, T.

    2012-04-01

    In the troposphere, aerosol particles undergo phase transitions such as deliquescence and efflorescence during humidity cycles (Marcolli and Krieger, 2006). In addition, interactions between organic and inorganic compounds lead to liquid-liquid phase separation (LLPS) (Ciobanu et al., 2009). Recent studies on a limited number of model systems have shown that oxygen-to-carbon ratios (O:C) of the organic aerosol fraction might be a good predictor for LLPS in mixed organic/ammonium sulfate (AS) particles (Bertram et al., 2011; Song et al., 2011). However, in order to corroborate this hypothesis experiments with an organic fraction that consists of a higher number of components with different O:C ratios and functional groups are needed. In order to determine the influence of O:C ratio, the specific organic functionalities and the mixture complexity on LLPS, we subjected organic/AS particles deposited on a hydrophobically coated substrate to relative humidity (RH) cycles and observed phase changes using optical microscopy and micro-Raman spectroscopy. To determine the influence of mixture complexity, we mixed together up to 10 organic compounds. We also prepared mixtures that were rich in different types of functional groups like polyols, aromatics and dicarboxylic acids which were identified from field measurements. We screened for a miscibility gap by varying the organic-to-inorganic ratio from 2:1 to 1:6. AS in the investigated single particles effloresced at 27 - 50 %RH and deliquesced at 72 - 79 %RH during humidity cycles. The occurrence of LLPS is determined to a high degree by the O:C of the organics: there was no LLPS for mixtures with O:C > 0.8 and there was always LLPS for mixtures with O:C < 0.57. In the range in between, we observed a dependence on the specific functional groups: a high share of aromatic functionalities shifts the range of O:C for which LLPS occurs to lower values. A correlation was also found for the onset RH of LLPS as a function of O

  20. Exposure of humans to a volatile organic mixture. 1. Behavioral assessment

    SciTech Connect

    Otto, D.A.; Hudnell, H.K.; House, D.E.; Moelhave, L.; Counts, W.

    1991-01-01

    Exposure to a low-level mixture of volatile organic compounds, typical of those found in new buildings, has been reported to impair neurobehavioral function in persons who have experienced sick building syndrome (SBS). Sixty-six healthy young males who had no history of chemical sensitivity were exposed for 2.75 h to a complex mixture of volatile organic compounds at 0 and 25 mg/cu m. Even though subjects reported more fatigue and more mental confusion following exposure to volatile organic compounds than to clean air, performance on 13 neurobehavioral tests was not affected. Practice or learning effects were observed if administration of many behavioral tests were repeated. Further studies are needed to clarify the relationship of exposure to volatile organic chemicals, neurobehavioral performance, and subject characteristics, e.g., age, gender, and chemical sensitivity.

  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. 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.

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

    USDA-ARS?s Scientific Manuscript database

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

  4. 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

  5. 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.

  6. 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.

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

    PubMed

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

    2016-07-01

    The hygroscopic behaviors of atmospherically relevant multicomponent water soluble organic compounds (WSOCs) and their effects on ammonium sulfate (AS) and sodium chloride were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA) in the relative humidity (RH) range of 5%-90%. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model (E-AIM) and Zdanovskii-Stokes-Robinson (ZSR) method. The equal mass multicomponent WSOCs mixture containing levoglucosan, succinic acid, phthalic acid and humic acid showed gradual water uptake without obvious phase change over the whole RH range. It was found that the organic content played an important role in the water uptake of mixed particles. When organic content was dominant in the mixture (75%), the measured hygroscopic growth was higher than predictions from the E-AIM or ZSR relation, especially under high RH conditions. For mass fractions of organics not larger than 50%, the hygroscopic growth of mixtures was in good agreement with model predictions. The influence of interactions between inorganic and organic components on the hygroscopicity of mixed particles was related to the salt type and organic content. These results could contribute to understanding of the hygroscopic behaviors of multicomponent aerosol particles. Copyright © 2016. Published by Elsevier B.V.

  8. Thermodynamic aspects of phase equilibrium in binary water-organic solvent mixtures

    NASA Astrophysics Data System (ADS)

    Mizerovskii, L. N.

    2017-02-01

    It is shown that the boundary curves of liquid equilibria in binary systems characterize the temperature-concentration boundary of the existence of homogeneous mixtures whose formation is not accompanied by changes in the Gibbs energy of the system and are a combination of two branches that do not convert into each other but intersect at the temperature of homogenization of a mixture of critical composition. The phase diagrams of a number of water-organic solvent systems are analyzed to determine the thermodynamic particularities of the latter.

  9. 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

  10. 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.

  11. 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

  12. Comparison of activity coefficient models for atmospheric aerosols containing mixtures of electrolytes, organics, and water

    NASA Astrophysics Data System (ADS)

    Tong, Chinghang; Clegg, Simon L.; Seinfeld, John H.

    Atmospheric aerosols generally comprise a mixture of electrolytes, organic compounds, and water. Determining the gas-particle distribution of volatile compounds, including water, requires equilibrium or mass transfer calculations, at the heart of which are models for the activity coefficients of the particle-phase components. We evaluate here the performance of four recent activity coefficient models developed for electrolyte/organic/water mixtures typical of atmospheric aerosols. Two of the models, the CSB model [Clegg, S.L., Seinfeld, J.H., Brimblecombe, P., 2001. Thermodynamic modelling of aqueous aerosols containing electrolytes and dissolved organic compounds. Journal of Aerosol Science 32, 713-738] and the aerosol diameter dependent equilibrium model (ADDEM) [Topping, D.O., McFiggans, G.B., Coe, H., 2005. A curved multi-component aerosol hygroscopicity model framework: part 2—including organic compounds. Atmospheric Chemistry and Physics 5, 1223-1242] treat ion-water and organic-water interactions but do not include ion-organic interactions; these can be referred to as "decoupled" models. The other two models, reparameterized Ming and Russell model 2005 [Raatikainen, T., Laaksonen, A., 2005. Application of several activity coefficient models to water-organic-electrolyte aerosols of atmospheric interest. Atmospheric Chemistry and Physics 5, 2475-2495] and X-UNIFAC.3 [Erdakos, G.B., Change, E.I., Pandow, J.F., Seinfeld, J.H., 2006. Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water—Part 3: Organic compounds, water, and ionic constituents by consideration of short-, mid-, and long-range effects using X-UNIFAC.3. Atmospheric Environment 40, 6437-6452], include ion-organic interactions; these are referred to as "coupled" models. We address the question—Does the inclusion of a treatment of ion-organic interactions substantially improve the performance of the coupled models over

  13. Global phase behavior of supercritical water - environmentally significant organic chemicals mixtures

    NASA Astrophysics Data System (ADS)

    Artemenko, S. V.; Mazur, V. A.

    Recent developments of the global phase equilibria studies of binary mixtures provide some basic ideas of how the required methods can be developed based on global phase diagrams for visualization of the phase behavior of mixtures. The mapping of the global equilibrium surface in the parameter space of the equation of state (EoS) model provides the most comprehensive system of criteria for predicting binary mixture phase behavior. The main types of phase behavior for environmentally significant organic chemicals in aqueous environments are considered using structure-property correlations for the critical parameters of substances. Analytic expressions for azeotropy prediction for cubic EoS are derived. A local mapping concept is introduced to describe thermodynamically consistently the saturation curve of water.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  17. 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.

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

    PubMed

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

    2016-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Jahangir, Ifat; Koley, Goutam

    2016-07-01

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

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

    PubMed Central

    Jahangir, Ifat; Koley, Goutam

    2016-01-01

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

  1. 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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-08-01

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

  4. 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.

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

    PubMed

    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(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.

  6. Desolventizing of Jatropha curcas oil from azeotropes of solvents using ceramic membranes.

    PubMed

    Carniel, Naira; Zabot, Giovani L; Paliga, Marshall; Mignoni, Marcelo L; Mazutti, Marcio A; Priamo, Wagner L; Oliveira, J V; Di Luccio, Marco; Tres, Marcus V

    2017-02-03

    The separation of Jatropha curcas oil from azeotropes of ethyl alcohol-n-hexane and isopropyl alcohol-n-hexane using ceramic membranes with different cutoffs (5, 10 and 20 kDa) is presented. The mass ratios of oil:azeotropes (O:S) studied were 1:3 for feeding pressures of 0.1, 0.2 and 0.3 MPa, and 1:1 for the feeding pressure of 0.1 MPa. Isopropyl alcohol was the best solvent for the membranes conditioning to permeate n-hexane (240 kg/m(2 )h). In the separation of J. curcas oil and azeotropes of solvents, both membranes showed oil retention and total flux decreases with time. Overall, the lowest decrease in the retentions was reached in the 5 kDa membrane, while the lowest decrease in the total flux was reached in the 20 kDa. In the separation of oil and ethyl alcohol-n-hexane azeotrope, the best retention at 60 min of the process was equal to 17.3 wt% in the 20 kDa membrane at 0.3 MPa and O:S ratio equalled to 1:3. In this condition, the total permeate flux was 17.5 kg/m(2) h. Different retentions and permeabilities are provided when changing the O:S ratio, the feeding pressure and the molecular weight cutoff of membranes.

  7. 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.

  8. 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

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  11. A non-ideal model for predicting the effect of dissolved salt on the flash point of solvent mixtures.

    PubMed

    Liaw, Horng-Jang; Wang, Tzu-Ai

    2007-03-06

    Flash point is one of the major quantities used to characterize the fire and explosion hazard of liquids. Herein, a liquid with dissolved salt is presented in a salt-distillation process for separating close-boiling or azeotropic systems. The addition of salts to a liquid may reduce fire and explosion hazard. In this study, we have modified a previously proposed model for predicting the flash point of miscible mixtures to extend its application to solvent/salt mixtures. This modified model was verified by comparison with the experimental data for organic solvent/salt and aqueous-organic solvent/salt mixtures to confirm its efficacy in terms of prediction of the flash points of these mixtures. The experimental results confirm marked increases in liquid flash point increment with addition of inorganic salts relative to supplementation with equivalent quantities of water. Based on this evidence, it appears reasonable to suggest potential application for the model in assessment of the fire and explosion hazard for solvent/salt mixtures and, further, that addition of inorganic salts may prove useful for hazard reduction in flammable liquids.

  12. 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

  13. 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.

  14. Elimination of the azeotropic point of acetone and methanol by 1,3-dimethylimidazolium dimethylphosphate: an ab initio calculation study.

    PubMed

    Yu, Guangren; Liu, Xiaomin; Zhang, Xiaochun; Chen, Xiaochun; Liu, Zhiping; Abdeltawab, Ahmed A

    2017-03-01

    1,3-Dimethylimidazolium dimethylphosphate ([C1mim][DMP]) was observed experimentally to be able to eliminate the atmospheric azeotropic point of acetone and methanol, which is an important azeotrope generally encountered in furfural production and the Fischer-Tropsch process. Here, we employed ab initio calculation to understand the underlying mechanism of [C1mim][DMP] in eliminating the azeotropic point of acetone and methanol. Structure, energy and interaction in binary-, ternary- and quaternary-clusters composed of methanol, acetone, [C1mim](+) or/and [DMP]‾ were calculated. The σ-hole, AIM and NBO analyses were performed to understand intermolecular interaction with electron density, electron occupancy, charge transfer and molecular orbital interaction. Hydrogen bond interaction plays a key role in azeotropic point elimination; due to the much stronger hydrogen bond interaction between methanol and [C1mim][DMP] than that between acetone and [C1mim][DMP], [C1mim][DMP] prefers to interact with methanol rather than acetone, and the original interaction between methanol and acetone is separated by [C1mim][DMP]. The hydrogen bond is from the orbital interaction between O lone-pair-electron orbitals of the hydrogen bond acceptor and σ * (C-H) or σ * (O-H) anti-bonding orbitals of the hydrogen bond donor, where remarkable electron or charge transfer occurs. These theoretical calculation results are in agreement with the experimental observation that [C1mim][DMP] eliminates the azeotropic point of methanol and acetone. This work shows that ab initio calculation may be employed to rationalize the design or synthesis of ionic liquids for separating azeotropes. Graphical Abstract Elimination of azeotropic point of acetone and methanol by [C1mim][DMP].

  15. Evaluating the aquatic toxicity of complex organic chemical mixtures: lessons learned from polycyclic aromatic hydrocarbon and petroleum hydrocarbon case studies.

    PubMed

    Landrum, Peter F; Chapman, Peter M; Neff, Jerry; Page, David S

    2012-04-01

    Experimental designs for evaluating complex mixture toxicity in aquatic environments can be highly variable and, if not appropriate, can produce and have produced data that are difficult or impossible to interpret accurately. We build on and synthesize recent critical reviews of mixture toxicity using lessons learned from 4 case studies, ranging from binary to more complex mixtures of primarily polycyclic aromatic hydrocarbons and petroleum hydrocarbons, to provide guidance for evaluating the aquatic toxicity of complex mixtures of organic chemicals. Two fundamental requirements include establishing a dose-response relationship and determining the causative agent (or agents) of any observed toxicity. Meeting these 2 requirements involves ensuring appropriate exposure conditions and measurement endpoints, considering modifying factors (e.g., test conditions, test organism life stages and feeding behavior, chemical transformations, mixture dilutions, sorbing phases), and correctly interpreting dose-response relationships. Specific recommendations are provided. Copyright © 2011 SETAC.

  16. 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

  17. Personal exposure to mixtures of volatile organic compounds: modeling and further analysis of the RIOPA data.

    PubMed

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

    2014-06-01

    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

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  19. Modeling sorption of neutral organic compound mixtures to simulated aquifer sorbents with pseudocompounds.

    PubMed

    Joo, Jin Chul; Shackelford, Charles D; Reardon, Kenneth F

    2013-01-01

    The feasibility of the ideal adsorbed solution theory (IAST) in reducing the complexity associated with predicting the sorption behaviors of 12 neutral organic compounds (NOCs) contained in complex mixtures as a fewer number (four to six) of pseudocompounds (groups of compounds) to simulated aquifer sorbents was investigated. All sorption isotherms from individual- and multiple-pseudocompound systems were fit reasonably well ( ≥ 0.953) by the Freundlich sorption model over the range of aqueous concentrations evaluated (i.e., ≤200 μmol L). The presence and magnitude of mutual competition among pseudocompounds varied depending on the composition of the mixtures (i.e., concentrations and polarities of pseudocompounds) and the properties of sorbents (i.e., the fraction of organic carbon and the availability of hydrophilic specific sorption sites). Finally, comparisons between the IAST-based predictions with individual-pseudocompound sorption parameters and experimentally measured data revealed that the accuracy in predicting the sorption behaviors of several NOCs in terms of a fewer number of pseudocompounds decreased with increasing deviations from the assumption of equal and ideal competition in the IAST (i.e., differential availability of sorption sites and nonideal competitions among pseudocompounds).

  20. Phase behavior of skin lipid mixtures: the effect of cholesterol on lipid organization.

    PubMed

    Mojumdar, E H; Gooris, G S; Bouwstra, J A

    2015-06-07

    The lipid matrix in the stratum corneum (SC), the upper layer of the skin, plays a critical role in the skin barrier. The matrix consists of ceramides (CERs), cholesterol (CHOL) and free fatty acids (FFAs). In human SC, these lipids form two coexisting crystalline lamellar phases with periodicities of approximately 6 and 13 nm. In the studies reported here, we investigated the effect of CHOL on lipid organization in each of these lamellar phases separately. For this purpose, we used lipid model mixtures. Our studies revealed that CHOL is imperative for the formation of each of the lamellar phases. At low CHOL levels, the formation of the lamellar phases was dramatically changed: a minimum 0.2 CHOL level in the CER/CHOL/FFA (1 : 0.2 : 1) mixture is required for the formation of each of the lamellar phases. Furthermore, CHOL enhances the formation of the highly dense orthorhombic lateral packing. The gradual increment of CHOL increases the fraction of lipids forming the very dense orthorhombic lateral packing. Therefore, these studies demonstrate that CHOL is an indispensable component of the SC lipid matrix and is of fundamental importance for appropriate dense lipid organization and thus important for the skin barrier function.

  1. 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.

  2. 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.

  3. The design of an environmentally relevant mixture of persistent organic pollutants for use in in vivo and in vitro studies.

    PubMed

    Berntsen, Hanne Friis; Berg, Vidar; Thomsen, Cathrine; Ropstad, Erik; Zimmer, Karin Elisabeth

    2017-08-30

    Amongst the substances listed as persistent organic pollutants (POP) under the Stockholm Convention on Persistent Organic Pollutants (SCPOP) are chlorinated, brominated, and fluorinated compounds. Most experimental studies investigating effects of POP employ single compounds. Studies focusing on effects of POP mixtures are limited, and often conducted using extracts from collected specimens. Confounding effects of unmeasured substances in such extracts may bias the estimates of presumed causal relationships being examined. The aim of this investigation was to design a model of an environmentally relevant mixture of POP for use in experimental studies, containing 29 different chlorinated, brominated, and perfluorinated compounds. POP listed under the SCPOP and reported to occur at the highest levels in Scandinavian food, blood, or breast milk prior to 2012 were selected, and two different mixtures representing varying exposure scenarios constructed. The in vivo mixture contained POP concentrations based upon human estimated daily intakes (EDIs), whereas the in vitro mixture was based upon levels in human blood. In addition to total in vitro mixture, 6 submixtures containing the same concentration of chlorinated + brominated, chlorinated + perfluorinated, brominated + perfluorinated, or chlorinated, brominated or perfluorinated compounds only were constructed. Using submixtures enables investigating the effect of adding or removing one or more chemical groups. Concentrations of compounds included in feed and in vitro mixtures were verified by chemical analysis. It is suggested that this method may be utilized to construct realistic mixtures of environmental contaminants for toxicity studies based upon the relative levels of POP to which individuals are exposed.

  4. Single- and mixture toxicity of three organic UV-filters, ethylhexyl methoxycinnamate, octocrylene, and avobenzone on Daphnia magna.

    PubMed

    Park, Chang-Beom; Jang, Jiyi; Kim, Sanghun; Kim, Young Jun

    2017-03-01

    In freshwater environments, aquatic organisms are generally exposed to mixtures of various chemical substances. In this study, we tested the toxicity of three organic UV-filters (ethylhexyl methoxycinnamate, octocrylene, and avobenzone) to Daphnia magna in order to evaluate the combined toxicity of these substances when in they occur in a mixture. The values of effective concentrations (ECx) for each UV-filter were calculated by concentration-response curves; concentration-combinations of three different UV-filters in a mixture were determined by the fraction of components based on EC25 values predicted by concentration addition (CA) model. The interaction between the UV-filters were also assessed by model deviation ratio (MDR) using observed and predicted toxicity values obtained from mixture-exposure tests and CA model. The results from this study indicated that observed ECxmix (e.g., EC10mix, EC25mix, or EC50mix) values obtained from mixture-exposure tests were higher than predicted ECxmix (e.g., EC10mix, EC25mix, or EC50mix) values calculated by CA model. MDR values were also less than a factor of 1.0 in a mixtures of three different UV-filters. Based on these results, we suggest for the first time a reduction of toxic effects in the mixtures of three UV-filters, caused by antagonistic action of the components. Our findings from this study will provide important information for hazard or risk assessment of organic UV-filters, when they existed together in the aquatic environment. To better understand the mixture toxicity and the interaction of components in a mixture, further studies for various combinations of mixture components are also required.

  5. 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

  6. Long-term stability measurements of low concentration Volatile Organic Compound gas mixtures

    NASA Astrophysics Data System (ADS)

    Allen, Nick; Amico di Meane, Elena; Brewer, Paul; Ferracci, Valerio; Corbel, Marivon; Worton, David

    2017-04-01

    VOCs (Volatile Organic Compounds) are a class of compounds with significant influence on the atmosphere due to their large anthropogenic and biogenic emission sources. VOC emissions have a significant impact on the atmospheric hydroxyl budget and nitrogen reservoir species, while also contributing indirectly to the production of tropospheric ozone and secondary organic aerosol. However, the global budget of many of these species are poorly constrained. Moreover, the World Meteorological Organization's (WMO) Global Atmosphere Watch (GAW) have set challenging data quality objectives for atmospheric monitoring programmes for these classes of traceable VOCs, despite the lack of available stable gas standards. The Key-VOCs Joint Research Project is an ongoing three-year collaboration with the aim of improving the measurement infrastructure of important atmospheric VOCs by providing traceable and comparable reference gas standards and by validating new measurement systems in support of the air monitoring networks. It focuses on VOC compounds that are regulated by European legislation, that are relevant for indoor air monitoring and for air quality and climate monitoring programmes like the VOC programme established by the WMO GAW and the European Monitoring and Evaluation Programme (EMEP). These VOCs include formaldehyde, oxy[genated]-VOCs (acetone, ethanol and methanol) and terpenes (a-pinene, 1,8-cineole, δ-3-carene and R-limonene). Here we present the results of a novel long term stability study for low concentration formaldehyde, oxy-VOC and terpenes gas mixtures produced by the Key-VOCs consortium with discussion regarding the implementation of improved preparation techniques and the use of novel cylinder passivation chemistries to guarantee mixture stability.

  7. 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.

  8. 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. © 2014 SETAC.

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

    PubMed

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

    2015-03-17

    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.

  10. Fundamental measure density functional theory studies on the freezing of binary hard-sphere and Lennard-Jones mixtures

    SciTech Connect

    Warshavsky, Vadim B.; Song, Xueyu

    2008-07-18

    Free energies and correlation functions of liquid and solid hard-sphere (HS) mixtures are calculated using the fundamental measure density functional theory. Using the thermodynamic perturbation theory the free energies of solid and liquid Lennard-Jones (LJ) mixtures are obtained from correlation functions of HS systems within a single theoretical approach. The resulting azeotrope- and spindle-type solid-liquid phase diagrams of HS and LJ binary mixtures are in good agreement with the corresponding ones from computer simulations.

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

    PubMed

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

    1978-01-01

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

  12. Decrease in the abundance and viability of oceanic phytoplankton due to trace levels of complex mixtures of organic pollutants.

    PubMed

    Echeveste, Pedro; Dachs, Jordi; Berrojalbiz, Naiara; Agustí, Susana

    2010-09-01

    Long range atmospheric transport and deposition is a significant introduction pathway of organic pollutants to remote oceanic regions, leading to their subsequent accumulation in marine organisms. Persistent organic pollutants (POPs) bioconcentrate in planktonic food webs and these exert a biogeochemical control on the regional and global cycling of POPs. Therefore, an important issue is to determine whether the anthropogenic chemical perturbation of the biosphere introduced by the myriad of organic pollutants present in seawater influences phytoplankton abundance and productivity. The results reported here from five sets of experiments performed in the NE Atlantic Ocean show that there is a toxic effect induced by trace levels of complex mixtures of organic pollutants on phytoplankton oceanic communities. The levels of single pollutant, such as phenanthrene and pyrene, at which lethality of phytoplankton is observed are high in comparison to field levels. Complex mixtures of organic pollutants, however, have an important toxic effect on phytoplankton abundances, viability and concentrations of Chlorophyll a at pollutant concentrations 20-40 folds those found in the open ocean. The toxicity of these complex mixtures of organic pollutants exceeds by 10(3) times the toxicity expected for a single pollutant. Therefore, our results point out the need for a systematic investigation of the influence of complex mixtures of organic hydrophobic pollutants to oceanic phytoplankton communities, a perturbation not accounted for on previous assessments of anthropogenic pressures in the marine environment.

  13. Molecular dynamics simulation studies on ethane and acetylene mixture in CuBTC metal organic framework

    NASA Astrophysics Data System (ADS)

    Prabhudesai, S. A.; Sharma, V. K.; Mitra, S.; Mukhopadhyay, R.

    2014-04-01

    Molecular Dynamics (MD) simulation studies have been carried out on the mixture containing ethane and acetylene molecules in 1:1 ratio at various concentrations of each species in CuBTC metal organic framework (MOF). MOFs are important class of materials which are tremendously useful for applications such as gas storage and separation. They have complex structure consisting of pore and pockets connected by windows. Results obtained from MD simulation showed that the self diffusivity of the ethane increases with the concentration while it decreases in case of acetylene. Correlation effects are responsible for this kind of phenomena. Pair distribution function showed the strong peaks at higher correlation length indicating the complex crystalline structure of the host matrix. We have also obtained the velocity auto correlation function (VACF) and velocity cross correlation functions (VCCF) at each studied concentration and found that the contribution from VCCF is almost negligible at lower concentration. Since the transport properties of mixture also depend on the mutual diffusivity and distinct diffusivity besides the self diffusivity, attempt has been made to quantify both the diffusivities. In the present system, at lower concentration, contribution to the mutual diffusivity comes from self diffusivities of species alone and distinct diffusivity contributes only at higher concentration.

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

    PubMed

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

    2000-08-01

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

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

    PubMed

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

    2015-12-15

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

  16. Evidence for Anisotropic Electronic Coupling of Charge Transfer States in Weakly Interacting Organic Semiconductor Mixtures.

    PubMed

    Belova, Valentina; Beyer, Paul; Meister, Eduard; Linderl, Theresa; Halbich, Marc-Uwe; Gerhard, Marina; Schmidt, Stefan; Zechel, Thomas; Meisel, Tino; Generalov, Alexander V; Anselmo, Ana Sofia; Scholz, Reinhard; Konovalov, Oleg; Gerlach, Alexander; Koch, Martin; Hinderhofer, Alexander; Opitz, Andreas; Brütting, Wolfgang; Schreiber, Frank

    2017-06-28

    We present a comprehensive investigation of the charge-transfer (CT) effect in weakly interacting organic semiconductor mixtures. The donor-acceptor pair diindenoperylene (DIP) and N,N'-bis(2-ethylhexyl)-1,7-dicyanoperylene-3,4/9,10-bis(dicarboxyimide) (PDIR-CN2) has been chosen as a model system. A wide range of experimental methods was used in order to characterize the structural, optical, electronic, and device properties of the intermolecular interactions. By detailed analysis, we demonstrate that the partial CT in this weakly interacting mixture does not have a strong effect on the ground state and does not generate a hybrid orbital. We also find a strong CT transition in light absorption as well as in photo- and electroluminescence. By using different layer sequences and compositions, we are able to distinguish electronic coupling in-plane vs out-of-plane and, thus, characterize the anisotropy of the CT state. Finally, we discuss the impact of CT exciton generation on charge-carrier transport and on the efficiency of photovoltaic devices.

  17. Dew point fast measurement in organic vapor mixtures using quartz resonant sensor

    NASA Astrophysics Data System (ADS)

    Nie, Jing; Liu, Jia; Meng, Xiaofeng

    2017-01-01

    A fast dew point sensor has been developed for organic vapor mixtures by using the quartz crystal with sensitive circuits. The sensor consists of the quartz crystal and a cooler device. Proactive approach is taken to produce condensation on the surface of the quartz crystal, and it will lead to a change in electrical features of the quartz crystal. The cessation of oscillation was measured because this phenomenon is caused by dew condensation. Such a phenomenon can be used to detect the dew point. This method exploits the high sensitivity of the quartz crystal but without frequency measurement and also retains the stability of the resonant circuit. It is strongly anti-interfered. Its performance was evaluated with acetone-methanol mixtures under different pressures. The results were compared with the dew points predicted from the universal quasi-chemical equation to evaluate the performance of the proposed sensor. Though the maximum deviations of the sensor are less than 1.1 °C, it still has a fast response time with a recovery time of less than 10 s, providing an excellent dehumidifying performance.

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

    PubMed

    Gobrogge, Eric A; Walker, Robert A

    2014-08-07

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

  19. 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.

  20. 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.

  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

    2007-08-06

    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.

  2. Molecular dynamics simulation of nanostructural organization in ionic liquid/water mixtures.

    PubMed

    Jiang, Wei; Wang, Yanting; Voth, Gregory A

    2007-05-10

    Molecular dynamics simulations have been carried out to investigate nanostructural organization in mixtures of 1-octyl-3-methylimidazolium nitrate ionic liquid and water at multiple water concentrations. Evolution of the polar network, water network, and micelle structures is visualized and analyzed via partial radial distribution functions. The calculated static partial structure factors show that within the range of water contents examined, polar networks, water networks, and micelles possess an approximately invariant characteristic length at around 20 A. Furthermore, the above calculations point out that, as the amount of water increases, the polar network is continuously broken up (screened) by the intruding water, while the structural organization of the water network and the micelle exhibits a turnover. At the turnover point, the most ordered micelle (cation-cation) structure and water (water-anion-water) network are formed. Thereafter, the structural organization abates drastically, and only loose micelle structure exists due to the dominant water-water interactions. The simulated turnover of structural organization agrees with the sharpest peak in the experimentally obtained structure factor in aqueous solutions of similar ionic liquids; the simulated water structure reveals that water can form liquidlike associated aggregates due to the planar symmetry and strong basicity of NO(3)-, in agreement with experiment. The turnover of structural organization of micelles results from the persistent competition between the hydrophobic interactions of the nonpolar groups and the breakup of the charged polar network with increasing water content, whereas the turnover of the water network results from the competition between the water-water and water-anion interactions.

  3. 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

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

    PubMed

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

    2003-09-15

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

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

    NASA Astrophysics Data System (ADS)

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

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

  6. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. 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.

  8. 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.

  9. 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.

  10. Phase behaviour of deionized binary mixtures of charged colloidal spheres.

    PubMed

    Lorenz, Nina J; Schöpe, Hans Joachim; Reiber, Holger; Palberg, Thomas; Wette, Patrick; Klassen, Ina; Holland-Moritz, Dirk; Herlach, Dieter; Okubo, Tsuneo

    2009-11-18

    We review recent work on the phase behaviour of binary charged sphere mixtures as a function of particle concentration and composition. Both size ratios Γ and charge ratios Λ are varied over a wide range. Unlike the case for hard spheres, the long-ranged Coulomb interaction stabilizes the crystal phase at low particle concentrations and shifts the occurrence of amorphous solids to particle concentrations considerably larger than the freezing concentration. Depending on Γ and Λ, we observe upper azeotrope, spindle, lower azeotrope and eutectic types of phase diagrams, all known well from metal systems. Most solids are of body centred cubic structure. Occasionally stoichiometric compounds are formed at large particle concentrations. For very low Γ, entropic effects dominate and induce a fluid-fluid phase separation. Since for charged spheres the charge ratio Λ is also decisive for the type of phase diagram, future experiments with charge variable silica spheres are suggested.

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

    PubMed

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

    2016-01-01

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

  12. Analysis of variants of separation of acetone-methanol-ethanol-waterbutyl acetate mixture

    SciTech Connect

    Polyakova, L.V.; Garber, Y.N.; Inyutin, S.M.; Komarova, L.F.

    1986-01-10

    A separation flowchart (SFC) is presented which may be based on comparison of the operating parameters of the principal elements of the designed flowcharts. The SFC was intented to study the SFC according to which the original mixture is separated into two fractions: binary (acetone (1)-methanol (2) azeotrope), and three-component (ethanol (3)-water (4)-butyl acetate (5)) with recycling of acetone. An analysis of the phase-equilibrium data suggest that the system may be separated analogously to variant III, but without recycling of acetone, i.e., obtaining a 1-2 mixture differing in composition from the azeotrope as the distillate. Estimation of the performace parameters of the principal elements of the SFC studied with respect to the mixtures indicated in the tables, with the data of Frolkova et al. on energy consumption for the separation taken into account, shows that preference should be given to variant I.

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

    PubMed Central

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

    2005-01-01

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

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

    USGS Publications Warehouse

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

    2013-01-01

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

  15. Removal of Selenium and Nitrate in Groundwater Using Organic Carbon-Based Reactive Mixtures

    NASA Astrophysics Data System (ADS)

    An, Hyeonsil; Jeen, Sung-Wook

    2016-04-01

    Treatment of selenium and nitrate in groundwater was evaluated through column experiments. Four columns consisting of reactive mixtures, either organic carbon-limestone (OC-LS) or organic carbon-zero valent iron (OC-ZVI), were used to determine the removal efficiency of selenium with different concentrations of nitrate. The source waters were collected from a mine site in Korea or were prepared artificially based on the mine drainage water or deionized water, followed by spiking of elevated concentrations of Se (40 mg/L) and nitrate (100 or 10 mg/L as NO3-N). The results for the aqueous chemistry showed that selenium and nitrate were effectively removed both in the mine drainage water and deionized water-based artificial input solution. However, the removal of selenium was delayed when selenium and nitrate coexisted in the OC-LS columns. The removal of selenium was not significant when the influent nitrate concentration was 100 mg/L as NO3-N, while most of nitrate was gradually removed within the columns. In contrast, 94% of selenium was removed when the influent nitrate concentration was reduced to 10 mg/L as NO3-N. In the OC-ZVI column, selenium and nitrate was removed almost simultaneously and completely even with the high nitrate concentration; however, a high concentration of ammonia was produced as a by-product of abiotic reaction between ZVI and nitrate. The elemental analysis for the solid samples after the termination of the experiments showed that selenium was accumulated in the reactive materials where removal of aqueous-phase selenium mostly occurred. The X-ray absorption near-edge structure (XANES) study indicated that selenium existed in the forms of SeS2 and Se(0) in the OC-LS column, while selenium was present in the forms of FeSe, SeS2 and absorbed Se(IV) in the OC-ZVI column. This study shows that OC-based reactive mixtures have an ability to remove selenium and nitrate in groundwater. However, the removal of selenium was influenced by the high

  16. Lipid organization in human and porcine stratum corneum differs widely, while lipid mixtures with porcine ceramides model human stratum corneum lipid organization very closely.

    PubMed

    Caussin, Julia; Gooris, Gert S; Janssens, Michelle; Bouwstra, Joke A

    2008-06-01

    The conformational disordering and lateral packing of lipids in porcine and human isolated stratum corneum (SC) was compared using Fourier transform infrared spectroscopy (FTIR). It was shown that SC of both species differ markedly, porcine SC lipids being arranged predominantly in a hexagonal lattice while lipids in human SC are predominantly packed in the denser orthorhombic lattice. However, the lipid organization of equimolar ceramide:cholesterol:free fatty acid (CER:CHOL:FFA) mixtures prepared with isolated porcine CER or human CER is very similar, only the transition temperatures differed being slightly lower in mixtures with porcine CER. Therefore, the difference in lateral packing between human and porcine stratum corneum is not due to the difference in CER composition. Furthermore, it is possible to use more readily available porcine CER in model lipid mixtures to mimic lipid organization in human SC. As the equimolar porcine CER:CHOL:FFA mixtures closely mimic the lipid organization in human SC, both human SC and this mixture were selected to examine the effect of glycerol on the lipid phase behaviour. It was found that high concentrations of glycerol change the lamellar organization slightly, while domains with an orthorhombic lateral packing are still observed.

  17. 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...

  18. 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...

  19. 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...

  20. 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...

  1. 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.

  2. 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

    2014-05-06

    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.

  3. 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.

  4. Toxicity of organic compounds from unresolved complex mixtures (UCMs) to primary fish hepatocytes.

    PubMed

    Petersen, Karina; Hultman, Maria T; Rowland, Steven J; Tollefsen, Knut Erik

    2017-09-01

    Many environmental matrices contaminated with organic pollutants derived from crude oil or degraded petroleum contain mixtures so complex that they are typically unresolved by conventional analytical techniques such as gas chromatography. The resulting chromatographic features have become known as 'humps' or unresolved complex mixtures (UCMs). These UCMs often dominate the organic contaminants of polluted environmental samples: for example, in oil sands produced water up to 150mgL(-1) of 'naphthenic acids' appear as UCMs when examined by gas chromatography as the esters. In oil-contaminated mussels, aromatic hydrocarbon UCMs may comprise almost all of the total toxic hydrocarbons, with over 7000μgg(-1) dry weight reported in some samples. Over the last 25 years, efforts to resolve and thus identify, or at least to produce average structures, for some UCM components, have proved fruitful. Numerous non-polar UCM hydrocarbons and more polar UCM acids have been identified, then synthesised or purchased from commercial suppliers. As UCMs have been proposed to represent a risk to aquatic organisms, the need for assessment of the ecotoxicological effects and characterisation of the mode of action (MoA) of these environmental pollutants has arisen. In the present study, several chemicals with structures typical of those found in some UCMs, were assessed for their potential to disrupt membrane integrity, inhibit metabolic activity, activate the aryl hydrocarbon receptor (AhR), and activate the estrogen receptor (ER) in primary rainbow trout hepatocytes (Oncorhynchus mykiss). These endpoints were determined in order to screen for common toxic modes of action (MoA) in this diverse group of chemicals. The results from the in vitro screening indicated that of the endpoints tested, the predominant toxic MoA was cytotoxicity. EC50 values for cytotoxicity were obtained for 16 compounds and ranged from 77μM-24mM, whereof aliphatic monocyclic acids, monoaromatic acids, polycyclic

  5. Ozone and secondary organic aerosol production by interaction between and organophosphorous pesticide and biogenic VOCs mixture

    NASA Astrophysics Data System (ADS)

    Borrás, Esther; Ródenas, Mila; Vera, Teresa; Muñoz, Amalia

    2017-04-01

    Pesticides are the chemical compounds most widely used worldwide, and their toxicological characteristics can have harmful effects on human health. The entry into the atmosphere of pesticides occurs during application or subsequent processes. Once they are emitted, they can be distributed in the gas phase or particulate phase. However, most of them are in both phases, since they are semi-volatile compounds. As with other organic compounds, pesticides' removal in the atmosphere can be mainly accomplished by wet or dry deposition, by photolysis or by reaction with hydroxyl radicals (OH), nitrate radicals (NO3) and ozone (O3) [1]. All these processes give rise to the formation of other products, which could become more harmful than the starting compounds. It is therefore necessary to know all these processes to estimate the impact of pesticides in the atmosphere. In addition, it is important to study how the pesticides interact with organic compounds naturally emitted by crops and their possible impact on the formation of secondary organic aerosols, ozone and other compounds. In this work, the gas phase atmospheric degradation of an organothiophosphate insecticide has been investigated at the large outdoor European Photoreactor (EUPHORE) in the presence of a biogenic compound mixture typical from orange trees emissions. Its photolysis has been studied under sunlight conditions, in the presence of different concentration ratios of chlorpyrifos and biogenic VOCs mixture and in the absence of initial inorganic seeds. Reaction with ozone has also been studied. Gaseous phase compounds were determined by a Fourier Transform Infrared Spectrometer (FTIR), Proton Transfer Reaction - Mass Spectrometry (PTRMS), Solid Phase Microextraction (SPME) coupled to gas chromatography-mass spectrometry (GCMS) and NOx, O3 and SO2 monitors. Aerosol mass concentration was measured using a scanning mobility particle sizer (SMPS) and a tapered element oscillating monitor (TEOM). Chemical

  6. Crystallization of binary ionic mixtures in dense stellar plasmas

    NASA Astrophysics Data System (ADS)

    Segretain, L.; Chabrier, G.

    1993-04-01

    The crystallization diagrams of arbitrary dense binary ionic mixtures are examined within the framework of the density-functional theory of freezing. The behaviour of the phase diagram is shown to depend strongly on the charge ratio in the mixture. As the charge ratio Z1/Z2 is lowered, the phase diagram evolves from a spindle shape into an azeotropic phase diagram and finally into a eutectic phase diagram. This has import ant consequences on the crystallization of trace elements in White Dwarfs, and on the subsequent gravitational energy release, leading to a substantial modification of the cooling history of these stars.

  7. Toxicity to Eisenia andrei and Folsomia candida of a metal mixture applied to soil directly or via an organic matrix.

    PubMed

    Natal-da-Luz, T; Ojeda, G; Pratas, J; Van Gestel, C A M; Sousa, J P

    2011-09-01

    Regulatory limits for chemicals and ecological risk assessment are usually based on the effects of single compounds, not taking into account mixture effects. The ecotoxicity of metal-contaminated sludge may, however, not only be due to its metal content. Both the sludge matrix and the presence of other toxicants may mitigate or promote metal toxicity. To test this assumption, the toxicity of soils recently amended with an industrial sludge predominantly contaminated with chromium, copper, nickel, and zinc and soils freshly spiked with the same mixture of metals was evaluated through earthworm (Eisenia andrei) and collembolan (Folsomia candida) reproduction tests. The sludge was less toxic than the spiked metal mixture for E. andrei but more toxic for F. candida. Results obtained for the earthworms suggest a decrease in metal bioavailability promoted by the high organic matter content of the sludge. The higher toxicity of the sludge for F. candida was probably due to the additive toxic effect of other pollutants.

  8. Unprecedentedly high selective adsorption of gas mixtures in rho zeolite-like metal-organic framework: a molecular simulation study.

    PubMed

    Babarao, Ravichandar; Jiang, Jianwen

    2009-08-19

    We report a molecular simulation study for the separation of industrially important gas mixtures (CO(2)/H(2), CO(2)/CH(4), and CO(2)/N(2)) in rho zeolite-like metal-organic framework (rho-ZMOF). Rho-ZMOF contains a wide-open anionic framework and charge-balancing extraframework Na(+) ions. Two types of binding sites for Na(+) ions are identified in the framework. Site I is in the single eight-membered ring, whereas site II is in the alpha-cage. Na(+) ions at site I have a stronger affinity for the framework and thus a smaller mobility. The binding sites in rho-ZMOF resemble those in its inorganic counterpart rho-zeolite. CO(2) is adsorbed predominantly over other gases because of its strong electrostatic interactions with the charged framework and the presence of Na(+) ions acting as additional adsorption sites. At ambient temperature and pressure, the CO(2) selectivities are 1800 for the CO(2)/H(2) mixture, 80 for the CO(2)/CH(4) mixture, and 500 for the CO(2)/N(2) mixture. Compared with other MOFs and nanoporous materials reported to date, rho-ZMOF exhibits unprecedentedly high selective adsorption for these gas mixtures. This work represents the first simulation study to characterize extraframework ions and examine gas separation in a charged ZMOF. The simulation results reveal that rho-ZMOF is a promising candidate for the separation of syngas, natural gas, and flue gas.

  9. Soil surface colonization by phototrophic indigenous organisms, in two contrasted soils treated by formulated maize herbicide mixtures.

    PubMed

    Joly, Pierre; Misson, Benjamin; Perrière, Fanny; Bonnemoy, Frédérique; Joly, Muriel; Donnadieu-Bernard, Florence; Aguer, Jean-Pierre; Bohatier, Jacques; Mallet, Clarisse

    2014-11-01

    Soil phototrophic microorganisms, contributors to soil health and food webs, share their particular metabolism with plants. Current agricultural practices employ mixtures of pesticides to ensure the crops yields and can potentially impair these non-target organisms. However despite this environmental reality, studies dealing the susceptibility of phototrophic microorganisms to pesticide mixtures are scarce. We designed a 3 months microcosm study to assess the ecotoxicity of realistic herbicide mixtures of formulated S-metolachlor (Dual Gold Safeneur(®)), mesotrione (Callisto(®)) and nicosulfuron (Milagro(®)) on phototrophic communities of two soils (Limagne vertisol and Versailles luvisol). The soils presented different colonizing communities, with diatoms and chlorophyceae dominating communities in Limagne soil and cyanobacteria and bryophyta communities in Versailles soil. The results highlighted the strong impairment of Dual Gold Safeneur(®) treated microcosms on the biomass and the composition of both soil phototrophic communities, with no resilience after a delay of 3 months. This study also excluded any significant mixture effect on these organisms for Callisto(®) and Milagro(®) herbicides. We strongly recommend carrying on extensive soil studies on S-metolachlor and its commercial formulations, in order to reconsider its use from an ecotoxicological point of view.

  10. Identification and quantification of individual volatile organic compounds in a binary mixture by SAW multisensor array and pattern recognition analysis

    NASA Astrophysics Data System (ADS)

    Penza, M.; Cassano, G.; Tortorella, F.

    2002-06-01

    We have developed a surface acoustic wave (SAW) multisensor array with five acoustic sensing elements configured as two-port resonator 433.92 MHz oscillators and a reference SAW element to recognize different individual components and determine their concentrations in a binary mixture of volatile organic compounds (VOCs) such as methanol and acetone, in the ranges 15-130 and 50-250 ppm, respectively. The SAW sensors have been specifically coated by various sensing thin films such as arachidic acid, carbowax, behenic acid, triethanolamine or acrylated polysiloxane, operating at room temperature. By using the relative frequency change as the output signal of the SAW multisensor array with an artificial neural network (ANN), a recognition system has been realized for the identification and quantification of tested VOCs. The features of the SAW multisensor array exposed to a binary component organic mixture of methanol and acetone have been extracted from the output signals of five SAW sensors by pattern recognition (PARC) techniques, such as principal component analysis (PCA). An organic vapour pattern classifier has been implemented by using a multilayer neural network with a backpropagation learning algorithm. The normalized responses of a reduced set of SAW sensors or selected principal components scores have been used as inputs for a feed-forward multilayer perceptron (MLP), resulting in a 70% correct recognition rate with the normalized responses of the four SAW sensors and in an enhanced 80% correct recognition rate with the first two principal components of the original data consisting of the normalized responses of the four SAW sensors. The prediction of the individual vapour concentrations has been tackled with PCA for features extraction and by using the first two principal components scores as inputs to a feed-forward MLP consisting of a gating network, which decides which of three specific subnets should be used to determine the output concentration: the

  11. Combining polar organic chemical integrative samplers (POCIS) with toxicity testing to evaluate pesticide mixture effects on natural phototrophic biofilms.

    PubMed

    Pesce, Stéphane; Morin, Soizic; Lissalde, Sophie; Montuelle, Bernard; Mazzella, Nicolas

    2011-03-01

    Polar organic chemical integrative samplers (POCIS) are valuable tools in passive sampling methods for monitoring polar organic pesticides in freshwaters. Pesticides extracted from the environment using such methods can be used to toxicity tests. This study evaluated the acute effects of POCIS extracts on natural phototrophic biofilm communities. Our results demonstrate an effect of POCIS pesticide mixtures on chlorophyll a fluorescence, photosynthetic efficiency and community structure. Nevertheless, the range of biofilm responses differs according to origin of the biofilms tested, revealing spatial variations in the sensitivity of natural communities in the studied stream. Combining passive sampler extracts with community-level toxicity tests offers promising perspectives for ecological risk assessment.

  12. 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 CO₂ capture and H₂ 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 τ{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 τ{sub break} are dictated both by selectivity and by capacity metrics .By performing transient adsorber calculations for separation of CO₂/H₂, CO₂/CH₄, CH₄/H₂, and CO₂/CH₄/H₂ mixtures, we compare the values of τbreak 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.

  13. 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...

  14. 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 ...

  15. 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 ...

  16. 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...

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

    PubMed

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

    2015-10-22

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

  18. Surface excess isotherms of organic solvent mixtures in a system made of liquid carbon dioxide and a silicagel surface.

    PubMed

    Vajda, Péter; Guiochon, Georges

    2013-09-20

    The surface excess isotherms of methanol, ethanol, 2-propanol and acetonitrile from liquid carbon dioxide on a silica adsorbent were measured, using the minor disturbance method. The minor disturbance peaks - or system peaks - of each organic modifier were recorded using UV-detection in the whole composition range of the organic/liquid carbon dioxide mixtures, the whole composition range was completed by injecting the modifiers into pure liquid carbon dioxide as well. The excess isotherms were calculated based on the retention of the organic solvent signals. Our results show an enrichment of the organic modifier at the adsorbent surface. The alcohols show multilayer adsorption with an extremely high retention on the silica surface while acetonitrile shows weaker interactions and only a slight trend toward the formation of a multilayer above the surface.

  19. 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.

  20. Comparison of biochar, zeolite and their mixture amendment for aiding organic matter transformation and nitrogen conservation during pig manure composting.

    PubMed

    Wang, Quan; Awasthi, Mukesh Kumar; Ren, Xiuna; Zhao, Junchao; Li, Ronghua; Wang, Zhen; Chen, Hongyu; Wang, Meijing; Zhang, Zengqiang

    2017-08-30

    The aim of this work was to compare the impact of biochar, zeolite and their mixture on nitrogen conservation and organic matter transformation during pig manure (PM) composting. Four treatments were set-up from PM mixed with wheat straw and then applied 10% biochar (B), 10% zeolite (Z) and 10% biochar+10% zeolite (B+Z) into composting mixtures (dry weight basis), while treatment without additives applied used as control. Results indicated that adding B, Z and B+Z could obviously (p<0.05) improve the organic matter degradation and decrease the nitrogen loss. And combined addition of B and Z further promoted the organic matter humification and reduced the heavy metals mobility. Meanwhile the highest mitigation of ammonia (63.40%) and nitrogen dioxide (78.13%) emissions was observed in B+Z added treatment. Comparison of organic matter transformation, nitrogen conservation and compost quality indicated that the combined use of biochar and zeolite could be more useful for PM composting. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2010-11-01

    A complex mixture analysis by one- and two-dimensional nuclear magnetic resonance (NMR) spectroscopy was carried out for the first time for the identification and quantification of organic compounds in green coffee bean extract (GCBE). A combination of (1)H-(1)H DQF-COSY, (1)H-(13)C HSQC, and (1)H-(13)C CT-HMBC two-dimensional sequences was used, and 16 compounds were identified. In particular, three isomers of caffeoylquinic acid were identified in the complex mixture without any separation. In addition, GCBE components were quantified by the integration of carbon signals by use of a relaxation reagent and an inverse-gated decoupling method without a nuclear Overhauser effect. This NMR methodology provides detailed information about the kinds and amounts of GCBE components, and in our study, the chemical makeup of GCBE was clarified by the NMR results. 2010 John Wiley & Sons, Ltd.

  2. 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.

  3. 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

  4. 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.

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

    SciTech Connect

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

    1986-07-01

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

  6. Hygroscopic properties of potassium chloride and its internal mixtures with organic compounds relevant to biomass burning aerosol particles

    NASA Astrophysics Data System (ADS)

    Jing, Bo; Peng, Chao; Wang, Yidan; Liu, Qifan; Tong, Shengrui; Zhang, Yunhong; Ge, Maofa

    2017-02-01

    While water uptake of aerosols exerts considerable impacts on climate, the effects of aerosol composition and potential interactions between species on hygroscopicity of atmospheric particles have not been fully characterized. The water uptake behaviors of potassium chloride and its internal mixtures with water soluble organic compounds (WSOCs) related to biomass burning aerosols including oxalic acid, levoglucosan and humic acid at different mass ratios were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA). Deliquescence points of KCl/organic mixtures were observed to occur at lower RH values and over a broader RH range eventually disappearing at high organic mass fractions. This leads to substantial under-prediction of water uptake at intermediate RH. Large discrepancies for water content between model predictions and measurements were observed for KCl aerosols with 75 wt% oxalic acid content, which is likely due to the formation of less hygroscopic potassium oxalate from interactions between KCl and oxalic acid without taken into account in the model methods. Our results also indicate strong influence of levoglucosan on hygroscopic behaviors of multicomponent mixed particles. These findings are important in further understanding the role of interactions between WSOCs and inorganic salt on hygroscopic behaviors and environmental effects of atmospheric particles.

  7. Hygroscopic properties of potassium chloride and its internal mixtures with organic compounds relevant to biomass burning aerosol particles.

    PubMed

    Jing, Bo; Peng, Chao; Wang, Yidan; Liu, Qifan; Tong, Shengrui; Zhang, Yunhong; Ge, Maofa

    2017-02-27

    While water uptake of aerosols exerts considerable impacts on climate, the effects of aerosol composition and potential interactions between species on hygroscopicity of atmospheric particles have not been fully characterized. The water uptake behaviors of potassium chloride and its internal mixtures with water soluble organic compounds (WSOCs) related to biomass burning aerosols including oxalic acid, levoglucosan and humic acid at different mass ratios were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA). Deliquescence points of KCl/organic mixtures were observed to occur at lower RH values and over a broader RH range eventually disappearing at high organic mass fractions. This leads to substantial under-prediction of water uptake at intermediate RH. Large discrepancies for water content between model predictions and measurements were observed for KCl aerosols with 75 wt% oxalic acid content, which is likely due to the formation of less hygroscopic potassium oxalate from interactions between KCl and oxalic acid without taken into account in the model methods. Our results also indicate strong influence of levoglucosan on hygroscopic behaviors of multicomponent mixed particles. These findings are important in further understanding the role of interactions between WSOCs and inorganic salt on hygroscopic behaviors and environmental effects of atmospheric particles.

  8. Effect of Sodium Sulfate, Ammonium Chloride, Ammonium Nitrate, and Salt Mixtures on Aqueous Phase Partitioning of Organic Compounds.

    PubMed

    Wang, Chen; Lei, Ying Duan; Wania, Frank

    2016-12-06

    Dissolved inorganic salts influence the partitioning of organic compounds into the aqueous phase. This influence is especially significant in atmospheric aerosol, which usually contains large amounts of ions, including sodium, ammonium, chloride, sulfate, and nitrate. However, empirical data on this salt effect are very sparse. Here, the partitioning of numerous organic compounds into solutions of Na2SO4, NH4Cl, and NH4NO3 was measured and compared with existing data for NaCl and (NH4)2SO4. Salt mixtures were also tested to establish whether the salt effect is additive. In general, the salt effect showed a decreasing trend of Na2SO4 > (NH)2SO4 > NaCl > NH4Cl > NH4NO3 for the studied organic compounds, implying the following relative strength of the salt effect of individual anions: SO4(2-) > Cl(-) > NO3(-) and of cations: Na(+) > NH4(+). The salt effect of different salts is moderately correlated. Predictive models for the salt effect were developed based on the experimental data. The experimental data indicate that the salt effect of mixtures may not be entirely additive. However, the deviation from additivity, if it exists, is small. Data of very high quality are required to establish whether the effect of constituent ions or salts is additive or not.

  9. Hygroscopic properties of potassium chloride and its internal mixtures with organic compounds relevant to biomass burning aerosol particles

    PubMed Central

    Jing, Bo; Peng, Chao; Wang, Yidan; Liu, Qifan; Tong, Shengrui; Zhang, Yunhong; Ge, Maofa

    2017-01-01

    While water uptake of aerosols exerts considerable impacts on climate, the effects of aerosol composition and potential interactions between species on hygroscopicity of atmospheric particles have not been fully characterized. The water uptake behaviors of potassium chloride and its internal mixtures with water soluble organic compounds (WSOCs) related to biomass burning aerosols including oxalic acid, levoglucosan and humic acid at different mass ratios were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA). Deliquescence points of KCl/organic mixtures were observed to occur at lower RH values and over a broader RH range eventually disappearing at high organic mass fractions. This leads to substantial under-prediction of water uptake at intermediate RH. Large discrepancies for water content between model predictions and measurements were observed for KCl aerosols with 75 wt% oxalic acid content, which is likely due to the formation of less hygroscopic potassium oxalate from interactions between KCl and oxalic acid without taken into account in the model methods. Our results also indicate strong influence of levoglucosan on hygroscopic behaviors of multicomponent mixed particles. These findings are important in further understanding the role of interactions between WSOCs and inorganic salt on hygroscopic behaviors and environmental effects of atmospheric particles. PMID:28240258

  10. 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...

  11. 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...

  12. Menstrual disturbances and hormonal changes in women workers exposed to a mixture of organic solvents in a pharmaceutical company

    PubMed Central

    Hassani, Somayeh; Namvar, Mohamad; Ghoreishvandi, Maryam; Attarchi, Mirsaeed; Golabadi, Majid; Seyedmehdi, Seyed Mohammad; Khodarahmian, Mahshad

    2014-01-01

    Background: Chemicals are among risk factors that can affect women's reproductive system. This study is aimed to investigate the association of occupational exposure to a mixture of organic solvents with menstruation disturbances and hormonal changes among female workers. Methods: Female workers of a pharmaceutical company were divided into three groups of non-exposed, lowexposed and highly-exposed to a mixture of organic solvents (formaldehyde, phenol, N-hexane, and chloroform) based on workplace measurements. Menstrual disturbances (in terms of short cycles, long cycles, irregular cycles, and bleeding or spotting between periods) and mean of hormone levels (including follicle stimulating hormone, luteinizing hormone, thyroid stimulating hormone, prolactin, estrogen and progesterone levels) were compared between these three groups. For investigating associations, logistic regression was performed. Results: Our study showed that mean length of cycles, duration of bleeding, and amount of flow and also prevalence of long cycles, irregular cycles, and bleeding or spotting between periods were higher in exposed groups (p≤0.05). Odds ratio for prevalence of menstrual disturbances in the low exposure group and high exposure group were 9.69 (p=0.001) and 3.40 (p=0.002) respectively compared to the reference group. Estrogen and progesterone levels were not affected (p> 0.05), but other hormones levels were significantly disturbed in the exposed groups compared with the non-exposed group (p=0.001). Conclusion: Occupational exposure to the mixture of organic solvents may be associated with the increase of menstrual disorders and hormonal changes in female workers. Based on our findings, periodic evaluation of reproductive system of female workers in pharmaceutical companies is recommended. PMID:25695014

  13. 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.

  14. 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.

  15. 'Quasi-Mixture' Descriptors for QSPR Analysis of Molecular Macroscopic Properties. The Critical Properties of Organic Compounds.

    PubMed

    Mokshyna, E; Nedostup, V I; Polishchuk, P G; Kuzmin, V E

    2014-10-01

    Rational approach towards the QSAR/QSPR modeling requires the descriptors to be computationally efficient, yet physically and chemically meaningful. On the basis of existing simplex representation of molecular structure (SiRMS) the novel 'quasi-mixture' descriptors were developed in order to accomplish the goal of characterization molecules on 2D level (i.e. without explicit generation of 3D structure and exhaustive conformational search) with account for potential intermolecular interactions. The critical properties of organic compounds were chosen as target properties for the estimation of descriptors' efficacy because of their well-known physical nature, rigorously estimated experimental errors and large quantity of experimental data. Among described properties are critical temperature, pressure and volume. Obtained models have high statistical characteristics, therefore showing the efficacy of suggested 'quasi-mixture' approach. Moreover, 'quasi-mixture' approach, as a branch of the SiRMS, allows to interpret results in terms of simple basic molecular properties. The obtained picture of influences corresponds to the accepted theoretical views.

  16. 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.

  17. 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. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  18. 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

  19. 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.

  20. Transport properties of the binary mixtures of the three organic liquids toluene, methanol, and cyclohexane

    NASA Astrophysics Data System (ADS)

    Lapeira, E.; Gebhardt, M.; Triller, T.; Mialdun, A.; Köhler, W.; Shevtsova, V.; Bou-Ali, M. M.

    2017-03-01

    We report on the measurements of diffusion (D), thermodiffusion (DT), and Soret (ST) coefficients in binary pairs of the ternary system toluene-methanol-cyclohexane using different instrumental techniques: microgravity measurements (SODI/DCMIX2) on the International Space Station, thermogravitational column in combination with sliding symmetric tubes, optical beam deflection, optical digital interferometry, and counter flow cell. The binary systems have large regions where the mixtures are either not miscible or the Soret coefficient is negative. All the coefficients have been measured over a wide composition range with the exception of a miscibility gap. Results from different instruments and literature data are in favorable agreement over a broad composition range. Additionally, we have carefully measured the physical properties and the optical contrast factors (∂n/∂c ) p ,T and (∂n/∂T ) p ,c. The latter ones were also calculated using the Looyenga equation. The measurements in methanol-cyclohexane mixture revealed a decay of the diffusion coefficient when approaching the miscibility gap. We have interpreted this in the spirit of the pseudospinodal concept.

  1. 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.

  2. Single Molecule Lateral Mobility and Membrane Organization in DMPC/Cholesterol Mixtures at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Shaikh, Saame; Stillwell, William; Naumann, Christoph

    2002-03-01

    To better understand the lipid heterogeneity of biological membranes, we have studied the lateral mobility and membrane organization of DMPC and cholesterol (Chol) mixtures at the air-water interface using single molecule fluorescence imaging and epifluorescence microscopy. The single molecule imaging technique was used to track the lateral diffusion of single molecules of TRITC-DPPE or cholesteryl Bodipy. In the absence of Chol, mean square displacement histograms obtained from single molecule tracking of TRITC-DPPE show unobstructed diffusion. Including Chol at low levels of Chol (<10 moldiffusion at intermediate levels ( 30 molof Chol (>40 molmacroscopic phase separations. Data obtained from tracking experiments of cholesteryl-Bodipy also show complementary changes in diffusion. Our results indicate that our techniques provide insight into the micro and macro organization of lipid domains at the air-water interface.

  3. 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.

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

    DOEpatents

    Pekala, Richard W.

    1996-01-01

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

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

    DOEpatents

    Pekala, Richard W.

    1998-04-28

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

  6. 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.

  7. 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.

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

    DOEpatents

    Pekala, Richard W.

    1995-01-01

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

  9. Self-organized Gels in DNA/F-Actin mixtures without Crosslinkers

    NASA Astrophysics Data System (ADS)

    Butler, John; Hwee Lai, Ghee; Zribi, Olena; Smalyukh, Ivan; Angelini, Thomas; Purdy, Kirstin; Golestanian, Ramin; Wong, Gerard C. L.

    2009-03-01

    Interactions between flexible chains and rigid rods govern a broad range of soft matter systems. As a model system of like-charged rigid rods and flexible chains, we examine mixtures of DNA and filamentous actin (F-actin). Confocal microscopy reveals the formation of elongated nematic F-actin domains reticulated via defect-free vertices into a network embedded in a mesh of random DNA. Synchrotron small-angle x-ray scattering (SAXS) indicates that the DNA mesh squeezes the F-actin domains into a nematic state with an inter-actin spacing that decreases with increasing DNA concentration. Salt strongly influences the domain sizes and transitions the system from a counterion-controlled regime to a depletion-controlled regime, both mechanisms of which are entropic in origin.

  10. Enthalpy characteristics of L-proline dissolution in certain water-organic mixtures at 298.15 K

    NASA Astrophysics Data System (ADS)

    Badelin, V. G.; Smirnov, V. I.

    2017-01-01

    A thermochemical study of the processes of L-proline dissolution in aqueous solutions of acetonitrile, 1,4-dioxane, acetone, dimethyl sulfoxide, nitromethane and tetrahydrofuran at T = 298.15 K in the range of organic solvent concentrations x2 = 0-0.25 mole fractions is performed. Standard values of the enthalpies of solution and transfer of L-proline from water to mixed solvent, and the enthalpy coefficients of pairwise interactions between L-proline and molecules of organic solvents, are calculated. The effect the composition of a water-organic mixture and the structure of organic solvents have on the enthalpy characteristics of L-proline dissolution and transfer is examined. The effect the energy properties of intermolecular interactions between components of a mixed solvent has on the intermolecular interactions between L-proline and molecules of cosolvent is estimated. The correlation between the enthalpy characteristics of L-proline dissolution and electron-donor properties of organic cosolvent in aqueous solutions is determined.

  11. Thermodynamics of Multicomponent PAH Mixtures and Development of Tar-Like Behavior

    PubMed Central

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

    2011-01-01

    This study explores the solid/liquid phase behavior of mixtures of polycyclic aromatic hydrocarbons (PAHs), exploring the transition from non-ideal solid mixtures to a relatively ideal liquid behavior characteristic of “tars”. PAH mixtures have been studied using differential scanning calorimetry, melting point analysis and Knudsen effusion. Mixtures of anthracene, pyrene and fluoranthene show behavior that is consistent with other binary PAH mixtures; that is, the initially solid mixture exhibits a significant melting point depression, relative to the pure components, and in a certain range of composition, solid azeotrope behavior on vaporization. As the number of distinct PAH species is increased (by adding in benzo[a]pyrene, phenanthrene, fluorene and chrysene) this behavior gradually gives way to liquid phase character at even room temperature, and the vaporization behavior approaches that crudely predictable from ideal mixture theory. PMID:21442010

  12. Non-Porous Organic Solids Capable of Dynamically Resolving Mixtures of Diiodoperfluoroalkanes (Preprint)

    DTIC Science & Technology

    2008-12-11

    equipped with UATR unit. Melting points were determined with a Reichert instrument by observing the melting and crystallizing process through an...Journal Article 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Non -Porous Organic Solids Capable of Dynamically...14. ABSTRACT A well-known class of organic non -porous compounds, polymethylene bismethonium iodides, undergoes selective capture and release of

  13. 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.

  14. Enhancing rock phosphate integration rate for fast bio-transformation of cow-dung waste-paper mixtures to organic fertilizer.

    PubMed

    Unuofin, F O; Siswana, M; Cishe, E N

    2016-01-01

    Rock phosphate (RP) addition in cow-dung waste-paper mixtures at rates above 2% P has been reported to increase the rate of bio-transformation and humification of organic waste mixtures during vermicomposting to produce organic fertilizer for organic farming. However, the optimization of RP for vermicomposting was not established. The objective of this study was to determine the optimal amount of RP integration rates for effective bio-transformation of cow-dung waste-paper mixtures. Arrays of RP integration degrees (0, 0.5, 1, 1.5, 2, and 4% P as RP) were thoroughly mixed with cow- dung waste-paper mixtures to achieve an optimized C:N ratio of 30 and allowed to vermidegrade following the introduction of earthworms at a stocking mass of 12.5 g-worms kg(-1). The bio-transformation of the waste mixtures was examined by measuring C:N ratios and humification index (HI) and per cent ash and volatile solids. Application of 1% P as RP resulted in fast bio-transformation and maturation of cow-dung waste-paper mixtures. A scanning electron microscopy (SEM) was used to evaluate the morphological properties of the different vermicomposts affected by rates of RP showing the degree of degradation of initial compacted aggregates of cellulose and protein fibres in the mixtures at maturity. A germination test was used to further determine phytotoxicity of the final composts and microbial biomass assessment. The final vermicompost (organic fertilizer) had a C:N ratio of 7, MBC of 900 mg kg(-1) and HI of 27.1%. The RP incorporation rate of 1% P of RP investigated is therefore, recommended for efficient vermidegradation and humification of cow-dung waste-paper mixtures. However, higher rates of RP incorporation should be considered where greater P enrichment of the final vermicompost (organic fertilizer) is desired.

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

    PubMed

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

    2016-06-16

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

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

    NASA Astrophysics Data System (ADS)

    Francisca, Franco M.; Montoro, Marcos A.

    2012-05-01

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

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

    PubMed Central

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

    2016-01-01

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

  18. 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...

  19. 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.

  20. 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...

  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. 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...

  3. Nanostructural organization in carbon disulfide/ionic liquid mixtures: Molecular dynamics simulations and optical Kerr effect spectroscopy

    NASA Astrophysics Data System (ADS)

    Yang, Peng; Voth, Gregory A.; Xiao, Dong; Hines, Larry G.; Bartsch, Richard A.; Quitevis, Edward L.

    2011-07-01

    In this paper, the nanostructural organization and subpicosecond intermolecular dynamics in the mixtures of CS2 and the room temperature ionic liquid (IL) 1-pentyl-3-methylimidazolium bis{(trifluoromethane)sulfonyl}amide ([C5mim][NTf2]) were studied as a function of concentration using molecular dynamics (MD) simulations and optical heterodyne-detected Raman-induced Kerr effect spectroscopy. At low CS2 concentrations (<10 mol.% CS2/IL), the MD simulations indicate that the CS2 molecules are localized in the nonpolar domains. In contrast, at higher concentrations (≥10 mol.% CS2/IL), the MD simulations show aggregation of the CS2 molecules. The optical Kerr effect (OKE) spectra of the mixtures are interpreted in terms of an additivity model with the components arising from the subpicosecond dynamics of CS2 and the IL. Comparison of the CS2-component with the OKE spectra of CS2 in alkane solvents is consistent with CS2 mainly being localized in the nonpolar domains, even at high CS2 concentrations, and the local CS2 concentration being higher than the bulk CS2 concentration.

  4. High performance liquid chromatography study of complex oxygenated alkane mixtures from organic aerosols

    NASA Astrophysics Data System (ADS)

    Kalafut-Pettibone, Alicia J.; Klems, Joseph P.; McGivern, W. Sean

    2013-05-01

    The composition of secondary organic aerosol particles is of primary importance both in identifying particle sources and in determining physical parameters, such as cloud condensation nucleus propensity. Further, measurements of composition are valuable in determining the chemistry of formation and aging. In this work, we describe the application of a recently-developed derivatization technique to a complex synthetic organic aerosol derived from the photolysis of 1-iodooctane. The technique utilizes high-performance liquid chromatography (HPLC) coupled to both ultravioletvisible (UV/VIS) spectroscopy and tandem mass spectrometry (MS-MS) to determine the overall distribution of hydroxyl (OH), non-acid carbonyl (C=O), and carboxylic acid (COOH) moieties as well as the specific identities of chromatographically separated products. This composition data will then be used to constrain models of the particle formation mechanisms.

  5. 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.

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

    PubMed

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

    2006-01-31

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

  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. Extraction of lignins from aqueous-ionic liquid mixtures by organic solvents.

    PubMed

    Xin, Qin; Pfeiffer, Katie; Prausnitz, John M; Clark, Douglas S; Blanch, Harvey W

    2012-02-01

    The commercial development of ionic liquids (ILs) to pretreat lignocellulose by dissolution of whole biomass and cellulose precipitation by addition of water is hindered by the absence of an effective technique to recover the lignin content of the biomass from the IL. Three organic solvents [ethyl acetate, 1,4-dioxane, and tetrahydrofuran (THF)] were studied for their ability to form a two-liquid-phase system with water and 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]), and for partitioning model lignins and lignin monomers between the two liquid phases. Ternary diagrams were obtained for three [C(2)mim][OAc]/organic solvent/water systems at 22°C. Partition coefficients were measured for several types of lignin in these three systems. Partition coefficients increase with rising water content in the IL phase, and depend strongly on the type of lignin and on the organic solvent. Partition coefficients rise as the pH of the ionic-liquid-rich phase falls. Small molecule model lignin monomer compounds (guaiacol, syringaldehyde) are also readily extracted from the IL/water system by THF. Copyright © 2011 Wiley Periodicals, Inc.

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

    PubMed

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

    2011-01-01

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

  10. Sorption of ionic and nonionic organic solutes onto giant Miscanthus-derived biochar from methanol-water mixtures.

    PubMed

    Kim, Juhee; Hyun, Seunghun

    2017-10-06

    The sorption of naphthalene (NAP) and 1-naphthoic acid (1-NAPA) onto giant Miscanthus-derived biochar was investigated in methanol volume fractions (fc) of 0-0.6 as a function of ionic composition (5mM CaCl2 and 10mM KCl) and liquid pH (2 and 7). The sorption onto biochar was nonlinear with 0.42≤N≤0.95; thus, a concentration-specific sorption constant (Km) was compared. The Km log linearly decreased with increasing fc, except for 1-NAPA from a CaCl2 mixture at pH7. Isotherm data was fitted with a cosolvency sorption model through which the slope (ασ) of the inverse log linear Km-fc plot and empirical constant (α) were obtained. NAP sorption was well described by the cosolvency model with the α value being 0.41-0.53, indicating a methanol-biochar interaction favoring more sorption than the cosolvency based prediction. In particular, the slope (ασ) of 1-NAPA was lower than that of NAP, indicating less reduction of 1-NAPA sorption (i.e., lower α value) by methanol. In comparison with other sorbents, the α value was approximately intermediate between a humic substance and kaolinite clay. An analysis of FT-IR spectra suggested the transformation of O-containing functional groups by methanol, which will subsequently boost the π-π interaction between an organic solute and biochar. Moreover, Ca(2+)-induced sorption between anionic 1-NAPA and a negatively charged biochar surface was also fortified in the methanol mixture. The results revealed unexplored cosolvent effects on organic solute sorption onto biochar and identified the hydrophobic and hydrophilic sorption moieties of biochar as affected by the cosolvent. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Sorption of acidic organic solute onto kaolinitic soils from methanol-water mixtures.

    PubMed

    Kim, Juhee; Kim, Minhee; Hyun, Seunghun; Kim, Jeong-Gyu; Ok, Yong Sik

    2012-01-01

    The fate of the acidic organic solute from the soil-water-solvent system is not well-understood. In this study, the effect of the acidic functional group of organic solute in the sorption from cosolvent system was evaluated. The sorption of naphthalene (NAP) and 1-naphthoic acid (1-NAPA) by three kaolinitic soils and two model sorbents (kaolinite and humic acid) were measured as functions of the methanol volume fractions (f (c) ≤ 0.4) and ionic compositions (CaCl(2) and KCl). The solubility of 1-NAPA was also measured in various ionic compositions. The sorption data were interpreted using the cosolvency-induced sorption model. The K (m) values (= the linear sorption coefficient) of NAP with kaolinitic soil for both ionic compositions was log linearly decreased with f (c). However, the K (m) values of 1-NAPA with both ionic compositions remained relatively constant over the f (c) range. For the model sorbent, the K (m) values of 1-NAPA with kaolinite for the KCl system and with humic acid for both ionic compositions decreased with f (c), while the sorption of 1-NAPA with kaolinite for the CaCl(2) system was increased with f (c). From the solubility data of 1-NAPA with f (c), no significant difference was observed with the different ionic compositions, indicating an insignificant change in the aqueous activity of the liquid phase. In conclusion, the enhanced 1-NAPA sorption, greater than that predicted from the cosolvency-induced model, was due to an untraceable interaction between the carboxylate and hydrophilic soil domain in the methanol-water system. Therefore, in order to accurately predict the environmental fate of acidic pesticides and organic solutes, an effort to quantitatively incorporate the enhanced hydrophilic sorption into the current cosolvency-induced sorption model is required.

  12. 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.

  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. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  16. A traceable reference for direct comparative assessment of total naphthenic acid concentrations in commercial and acid extractable organic mixtures derived from oil sands process water.

    PubMed

    Brunswick, Pamela; Hewitt, L Mark; Frank, Richard A; Kim, Marcus; van Aggelen, Graham; Shang, Dayue

    2017-02-23

    The advantage of using naphthenic acid (NA) mixtures for the determination of total NA lies in their chemical characteristics and identification of retention times distinct from isobaric interferences. However, the differing homolog profiles and unknown chemical structures of NA mixtures do not allow them to be considered a traceable reference material. The current study provides a new tool for the comparative assessment of different NA mixtures by direct reference to a single, well-defined and traceable compound, decanoic-d19 acid. The method employed an established liquid chromatography time-of-flight mass spectrometry (LC/QToF) procedure that was applicable both to the classic O2 NA species dominating commercial mixtures and additionally to the O4 species known to be present in acid extractable organics (AEOs) derived from oil sands process water (OSPW). Four different commercial NA mixtures and one OSPW-derived AEOs mixture were comparatively assessed. Results showed significant difference among Merichem Technical, Aldrich, Acros, and Kodak commercial NA mixtures with respect to "equivalent to decanoic-d19 acid" concentration ratios to nominal. Furthermore, different lot numbers of single commercial NA mixtures were found to be inconsistent with respect to their homolog content by percent response. Differences in the observed homolog content varied significantly, particularly at the lower (n = 9-14) and higher (n = 20-23) carbon number ranges. Results highlighted the problem between using NA mixtures from different sources and different lot numbers but offered a solution to the problem from a concentration perspective. It is anticipated that this tool may be utilized in review of historical data in addition to future studies, such as the study of OSPW derived acid extractable organics (AEOs) and fractions employed during toxicological studies.

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

    PubMed

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

    2012-10-11

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

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

    PubMed

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

    2015-10-01

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

  19. In vitro steroidogenic effects of mixtures of persistent organic pollutants (POPs) extracted from burbot (Lota lota) caught in two Norwegian lakes.

    PubMed

    Zimmer, Karin E; Montaño, Mauricio; Olsaker, Ingrid; Dahl, Ellen; Berg, Vidar; Karlsson, Camilla; Murk, Albertinka J; Skaare, Janneche U; Ropstad, Erik; Verhaegen, Steven

    2011-05-01

    This study investigated the effects of two mixtures of persistent organic pollutants (POPs) on steroidogenesis in the H295R cell line. The two mixtures were obtained from the livers of burbot (Lota lota) caught in two Norwegian lakes (Mjøsa and Losna) with different contaminant profiles. Steroid hormone levels in the cell culture medium and mRNA levels of 16 genes involved in steroidogenesis were investigated. The crude Lake Mjøsa extract had to be diluted ten times more than the Lake Losna extract in order to prevent cytotoxicity. The ten times diluted Lake Mjøsa mixture had higher levels of DDT and derivates (∑DDTs, 1.7 times) and brominated flame retardants (∑BDEs and HBCD, 15-25 times) than the Lake Losna mixture, which, on the other hand, had higher concentrations of ∑PCBs (1.5 times higher) and also of HCB, ∑HCH isomers and ∑chlordane isomers (5-20 times higher). In the cell culture media, only cortisol levels were increased at the highest exposure concentration to the Lake Mjøsa mixture, while both cortisol and estradiol levels were increased following exposure to the two highest Lake Losna mixture exposure concentrations. Testosterone levels decreased only at the highest exposure concentration of the Lake Losna mixture. Multivariate models suggested that ∑PCBs, and to a lesser extent ∑DDTs, were responsible for the cortisol responses, while estradiol and testosterone alterations were best explained by HCB and ∑PCBs, respectively. Exposure to the mixtures generally increased mRNA levels, with smaller effects exerted by the Lake Mjøsa mixture than the Lake Losna mixture. It was concluded that both mixtures affected steroidogenesis in the H295R cells. Small differences in mixture composition, rather than the high content of brominated flame retardants in the Lake Mjøsa mixture, were suggested to be the most probable reason for the apparent differences in potencies of the two mixtures.

  20. Picosecond dynamics of proton transfer of a 7-hydroxyflavylium salt in aqueous-organic solvent mixtures.

    PubMed

    Freitas, Adilson A; Quina, Frank H; Maçanita, António A L

    2011-10-13

    The intermediacy of the geminate base-proton pair (A*···H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH(+)* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base-proton pair A*···H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*···H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec), of A*···H(+)) from the diffusion controlled rates (dissociation, k(diss), and formation, k(diff)[H(+)], of A*···H(+)), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)).

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

    PubMed

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

    2005-10-01

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

  2. Kinetics of organic molecules in pulsed plasmas of nitrogen or N2/O2 mixtures at near atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Pasquiers, S.; Blin-Simiand, N.; Magne, L.

    2013-12-01

    In plasmas of atmospheric gases, the kinetics of some aliphatic organic molecules belonging to the hydrocarbons (propene, propane), aldehydes (acetaldehyde) and ketones (acetone) families were studied using a photo-triggered discharge (homogeneous plasma). It was shown that quenchings of N2 metastable states, A\\,^{3}\\Sigma_{u}^{+} and the group of singlets a'\\,^{1}\\Sigma_{u}^{-} , a 1Πg and w 1Δu, are important processes for the decomposition of such molecules. It plays a fundamental role in the nitrogen plasma, but it is also present in air. At low temperature, the oxidation reactions by the oxygen atom or by the hydroxyl radical are not always sufficiently effective to induce an increase of the molecule decomposition when oxygen is added to the nitrogen/organic mixture. For most cases, quenching processes appear purely dissociative. However, recent results obtained for propene lead to the conclusion that a non-dissociative exit route could exist. The quenching of the singlet states induces a break of the double bound C = O for the acetaldehyde and acetone molecules. Some kinetic analogies appear between filamentary and homogeneous plasmas, which could be very useful to get a comprehensive understanding of the physico-chemical processes in dielectric barriers or corona discharges used for various applications.

  3. 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.

  4. Modeling and interpreting bioavailability of organic contaminant mixtures in subsurface environments

    NASA Astrophysics Data System (ADS)

    Haws, Nathan W.; Ball, William P.; Bouwer, Edward J.

    2006-01-01

    Bioavailability often controls the fate of organic contaminants in surface and subsurface aquatic environments. Bioavailability can be limited by sorption, mass transfer, and intrinsic biodegradation potential and can be further altered by the presence of other compounds. This paper reviews current perspectives on the processes influencing subsurface contaminant bioavailability, how these processes are modeled, and how the relative role of the various processes can be assessed through bioavailability indices. Although these processes are increasingly well understood, the use of sophisticated models and indices often are precluded by an inability to estimate the many parameters that are associated with complex models. Nonetheless, the proper representation of sorption, mass transfer, biodegradation, and co-solute effects can be critical in predicting bio-attenuation. The influence of these processes on contaminant fate is illustrated with numerical simulations for the simultaneous degradation of toluene (growth substrate) and trichloroethylene (nongrowth cometabolite) in hypothetical, aerobic, solid-water systems. The results show how the relative impacts on contaminant fate of the model's various component processes depends upon system conditions, including co-solute concentrations. Slow biodegradation rates increase the inhibition effects of a cometabolite and suppress the rate enhancement effects of a growth substrate. Irrespective of co-solute effects, contaminant fate is less sensitive to biodegradation processes in systems with strong sorption and slow desorption rates. Bioavailability indices can be used to relate these findings and to help identify appropriate modeling simplifications. In general, however, there remains a need to redefine such indices in order that bioavailability concepts can be better incorporated into site characterization, remediation design, and regulatory oversight.

  5. Accumulation of soil organic C and N in planted forests fostered by tree species mixture

    NASA Astrophysics Data System (ADS)

    Liu, Yan; Lei, Pifeng; Xiang, Wenhua; Yan, Wende; Chen, Xiaoyong

    2017-09-01

    With the increasing trend of converting monocultures into mixed forests, more and more studies have been carried out to investigate the admixing effects on tree growth and aboveground carbon storage. However, few studies have considered the impact of mixed forests on belowground carbon sequestration, particularly changes in soil carbon and nitrogen stocks as a forest grows. In this study, paired pure Pinus massoniana plantations, Cinnamomum camphora plantations and mixed Pinus massoniana-Cinnamomum camphora plantations at ages of 10, 24 and 45 years were selected to test whether the mixed plantations sequestrate more organic carbon (OC) and nitrogen (N) in soils and whether this admixing effect becomes more pronounced with stand ages. The results showed that tree species identification, composition and stand age significantly affected soil OC and N stocks. The soil OC and N stocks were the highest in mixed Pinus-Cinnamomum stands compared to those in counterpart monocultures with the same age in the whole soil profile or specific soil depth layers (0-10, 10-20 and 20-30 cm) for most cases, followed by Cinnamomum stands and Pinus stands with the lowest. These positive admixing effects were mostly nonadditive. Along the chronosequence, the soil OC stock peaked in the 24-year-old stand and was maintained as relatively stable thereafter. The admixing effects were also the highest at this stage. However, in the topsoil layer, the admixing effects increased with stand ages in terms of soil OC stocks. When comparing mixed Pinus-Cinnamomum plantations with corresponding monocultures within the same age, the soil N stock in mixed stands was 8.30, 11.17 and 31.45 % higher than the predicted mean value estimated from counterpart pure species plantations in 10-, 24- and 45-year-old stands, respectively. This suggests that these admixing effects were more pronounced along the chronosequence.

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

    PubMed

    Pratik, Saied Md; Datta, Ayan

    2016-08-04

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

  7. 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

  8. 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.

  9. 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.

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

    PubMed Central

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

    2011-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  12. A COSMO-RS based guide to analyze/quantify the polarity of ionic liquids and their mixtures with organic cosolvents.

    PubMed

    Palomar, José; Torrecilla, José S; Lemus, Jesús; Ferro, Víctor R; Rodríguez, Francisco

    2010-02-28

    A COSMO-RS descriptor (S(sigma-profile)) has been used in quantitative structure-property relationship (QSPR) studies by a neural network (NN) for the prediction of empirical solvent polarity E(T)(N) scale of neat ionic liquids (ILs) and their mixtures with organic solvents. S(sigma-profile) is a two-dimensional quantum chemical parameter which quantifies the polar electronic charge of chemical structures on the polarity (sigma) scale. Firstly, a radial basis neural network exact fit (RBNN) is successfully optimized for the prediction of E(T)(N), the solvatochromic parameter of a wide variety of neat organic solvents and ILs, including imidazolium, pyridinium, ammonium, phosphonium and pyrrolidinium families, solely using the S(sigma-profile) of individual molecules and ions. Subsequently, a quantitative structure-activity map (QSAM), a new concept recently developed, is proposed as a valuable tool for the molecular understanding of IL polarity, by relating the E(T)(N) polarity parameter to the electronic structure of cations and anions given by quantum-chemical COSMO-RS calculations. Finally, based on the additive character of the S(sigma-profile) descriptor, we propose to simulate the mixture of IL-organic solvents by the estimation of the S(sigma-profile)(Mixture) descriptor, defined as the weighted mean of the S(sigma-profile) values of the components. Then, the E(T)(N) parameters for binary solvent mixtures, including ILs, are accurately predicted using the S(sigma-profile)(Mixture) values from the RBNN model previously developed for pure solvents. As result, we obtain a unique neural network tool to simulate, with similar reliability, the E(T)(N) polarity of a wide variety of pure ILs as well as their mixtures with organic solvents, which exhibit significant positive and negative deviations from ideality.

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

    EPA Science Inventory

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

  14. 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/...

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2015-11-01

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

  17. Effects of mixtures of persistent organic pollutants (POPs) derived from cod liver oil on H295R steroidogenesis.

    PubMed

    Montaño, M; Zimmer, K E; Dahl, E; Berg, V; Olsaker, I; Skaare, J U; Murk, A J; Ropstad, E; Verhaegen, S

    2011-09-01

    Crude cod liver oil and liver oil supplements are consumed as a source of vitamin A, D and polyunsaturated fatty acids; during winter and early pregnancy. Crude cod liver oil however constitutes a considerable source of persistent organic pollutants (POPs). This paper aimed at characterizing and quantifying the influence of POP mixtures extracted from three different steps in the cod liver oil industrial process on hormone production and the expression of steroidogenesis-related genes in H295R cells. Exposure to extracts from crude cod liver oil and from its industrial waste increased progesterone (P4), cortisol (Cort), testosterone (T) and estradiol (E2) production; and among others, the expression of MC2R, CYP11B1 and HSD3B2 genes. Observed effects after exposure to pharmaceutical cod liver oil extract were considerably lower. The type of effects on gene expression and hormone production were similar to those induced by forskolin and PCBs, the latter being the major contaminants within the extracts. Additional research is required to further unveil the mechanisms behind the observed steroidogenic effects and to assess whether the potential risk might outweigh the potential benefits of crude and processed cod liver oil consumption. Copyright © 2011 Elsevier Ltd. All rights reserved.

  18. 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.

  19. A Mixture of Persistent Organic Pollutants and Perfluorooctanesulfonic Acid Induces Similar Behavioural Responses, but Different Gene Expression Profiles in Zebrafish Larvae

    PubMed Central

    Khezri, Abdolrahman; Fraser, Thomas W. K.; Nourizadeh-Lillabadi, Rasoul; Kamstra, Jorke H.; Berg, Vidar; Zimmer, Karin E.; Ropstad, Erik

    2017-01-01

    Persistent organic pollutants (POPs) are widespread in the environment and some may be neurotoxic. As we are exposed to complex mixtures of POPs, we aimed to investigate how a POP mixture based on Scandinavian human blood data affects behaviour and neurodevelopment during early life in zebrafish. Embryos/larvae were exposed to a series of sub-lethal doses and behaviour was examined at 96 h post fertilization (hpf). In order to determine the sensitivity window to the POP mixture, exposure models of 6 to 48 and 48 to 96 hpf were used. The expression of genes related to neurological development was also assessed. Results indicate that the POP mixture increases the swimming speed of larval zebrafish following exposure between 48 to 96 hpf. This behavioural effect was associated with the perfluorinated compounds, and more specifically with perfluorooctanesulfonic acid (PFOS). The expression of genes related to the stress response, GABAergic, dopaminergic, histaminergic, serotoninergic, cholinergic systems and neuronal maintenance, were altered. However, there was little overlap in those genes that were significantly altered by the POP mixture and PFOS. Our findings show that the POP mixture and PFOS can have a similar effect on behaviour, yet alter the expression of genes relevant to neurological development differently. PMID:28146072

  20. Testing the accuracy of correlations for multicomponent mass transport of adsorbed gases in metal-organic frameworks: diffusion of H2/CH4 mixtures in CuBTC.

    PubMed

    Keskin, Seda; Liu, Jinchen; Johnson, J Karl; Sholl, David S

    2008-08-05

    Mass transport of chemical mixtures in nanoporous materials is important in applications such as membrane separations, but measuring diffusion of mixtures experimentally is challenging. Methods that can predict multicomponent diffusion coefficients from single-component data can be extremely useful if these methods are known to be accurate. We present the first test of a method of this kind for molecules adsorbed in a metal-organic framework (MOF). Specifically, we examine the method proposed by Skoulidas, Sholl, and Krishna (SSK) ( Langmuir, 2003, 19, 7977) by comparing predictions made with this method to molecular simulations of mixture transport of H 2/CH 4 mixtures in CuBTC. These calculations provide the first direct information on mixture transport of any species in a MOF. The predictions of the SSK approach are in good agreement with our direct simulations of binary diffusion, suggesting that this approach may be a powerful one for examining multicomponent diffusion in MOFs. We also use our molecular simulation data to test the ideal adsorbed solution theory method for predicting binary adsorption isotherms and a method for predicting mixture self-diffusion coefficients.

  1. A Mixture of Persistent Organic Pollutants and Perfluorooctanesulfonic Acid Induces Similar Behavioural Responses, but Different Gene Expression Profiles in Zebrafish Larvae.

    PubMed

    Khezri, Abdolrahman; Fraser, Thomas W K; Nourizadeh-Lillabadi, Rasoul; Kamstra, Jorke H; Berg, Vidar; Zimmer, Karin E; Ropstad, Erik

    2017-01-29

    Persistent organic pollutants (POPs) are widespread in the environment and some may be neurotoxic. As we are exposed to complex mixtures of POPs, we aimed to investigate how a POP mixture based on Scandinavian human blood data affects behaviour and neurodevelopment during early life in zebrafish. Embryos/larvae were exposed to a series of sub-lethal doses and behaviour was examined at 96 h post fertilization (hpf). In order to determine the sensitivity window to the POP mixture, exposure models of 6 to 48 and 48 to 96 hpf were used. The expression of genes related to neurological development was also assessed. Results indicate that the POP mixture increases the swimming speed of larval zebrafish following exposure between 48 to 96 hpf. This behavioural effect was associated with the perfluorinated compounds, and more specifically with perfluorooctanesulfonic acid (PFOS). The expression of genes related to the stress response, GABAergic, dopaminergic, histaminergic, serotoninergic, cholinergic systems and neuronal maintenance, were altered. However, there was little overlap in those genes that were significantly altered by the POP mixture and PFOS. Our findings show that the POP mixture and PFOS can have a similar effect on behaviour, yet alter the expression of genes relevant to neurological development differently.

  2. 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.

  3. Chronic toxicity of an environmentally relevant mixture of pharmaceuticals to three aquatic organisms (alga, daphnid, and fish).

    PubMed

    Watanabe, Haruna; Tamura, Ikumi; Abe, Ryoko; Takanobu, Hitomi; Nakamura, Ataru; Suzuki, Toshinari; Hirose, Akihiko; Nishimura, Tetsuji; Tatarazako, Norihisa

    2016-04-01

    Principles of concentration addition and independent action have been used as effective tools to predict mixture toxicity based on individual component toxicity. The authors investigated the toxicity of a pharmaceutical mixture composed of the top 10 detected active pharmaceutical ingredients (APIs) in the Tama River (Tokyo, Japan) in a relevant concentration ratio. Both individual and mixture toxicities of the 10 APIs were evaluated by 3 short-term chronic toxicity tests using the alga Pseudokirchneriella subcapitata, the daphnid Ceriodaphnia dubia, and the zebrafish Danio rerio. With the exception of clarithromycin toxicity to alga, the no-observed-effect concentration of individual APIs for each test species was dramatically higher than the highest concentration of APIs found in the environment. The mixture of 10 APIs resulted in toxicity to alga, daphnid, and fish at 6.25 times, 100 times, and 15,000 times higher concentrations, respectively, than the environmental concentrations of individual APIs. Predictions by concentration addition and independent action were nearly identical for alga, as clarithromycin was the predominant toxicant in the mixture. Both predictions described the observed mixture toxicity to alga fairly well, whereas they slightly underestimated the observed mixture toxicity in the daphnid test. In the fish embryo test, the observed toxicity fell between the predicted toxicity by concentration addition and independent action. These results suggested that the toxicity of environmentally relevant pharmaceutical mixtures could be predicted by individual toxicity using either concentration addition or independent action. © 2015 SETAC.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Tube radial distribution phenomenon with a two-phase separation solution of a fluorocarbon and hydrocarbon organic solvent mixture in a capillary tube and metal compounds separation.

    PubMed

    Kitaguchi, Koichi; Hanamura, Naoya; Murata, Masaharu; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

    2014-01-01

    A fluorocarbon and hydrocarbon organic solvent mixture is known as a temperature-induced phase-separation solution. When a mixed solution of tetradecafluorohexane as a fluorocarbon organic solvent and hexane as a hydrocarbon organic solvent (e.g., 71:29 volume ratio) was delivered in a capillary tube that was controlled at 10°C, the tube radial distribution phenomenon (TRDP) of the solvents was clearly observed through fluorescence images of the dye, perylene, dissolved in the mixed solution. The homogeneous mixed solution (single phase) changed to a heterogeneous solution (two phases) with inner tetradecafluorohexane and outer hexane phases in the tube under laminar flow conditions, generating the dynamic liquid-liquid interface. We also tried to apply TRDP to a separation technique for metal compounds. A model analyte mixture, copper(II) and hematin, was separated through the capillary tube, and detected with a chemiluminescence detector in this order within 4 min.

  9. Pyrolysis experiment of simulated exogenous complex organics synthesized from the gas mixtures of CO, NH3, and H2O by 3 MeV proton irradiation.

    PubMed

    Takano, Yoshinori; Tsuboi, Taiki; Tohnishi, Hisako; Kaneko, Takeo; Kobayashi, Kensei; Hashimoto, Hirofumi; Marumo, Katsumi

    2003-10-01

    High molecular weight organic matter synthesized from mixtures of carbon monoxide, ammonia and water gases similar to those found in the interstellar medium were irradiated with a 3 MeV proton beam and analyzed by Curie point pyrolysis with detection by gas chromatograph and mass spectrometer (Pyr-GC-MS). A wide variety of organic compounds, not only a number of amide compounds, but also heterocyclic and polycyclic aromatic hydrocarbons (PAHs), were detected among the products of the pyrolysis. The present data shows that primary and primitive organic matter serving as precursors to bioorganic compounds such as amino acids, nucleic acid bases and sugar might have been formed in a gaseous mixture of similar composition to that of the interstellar dust environment.

  10. Rotational Diffusion of Charged and Nondipolar Solutes in Ionic Liquid-Organic Solvent Mixtures: Evidence for Stronger Specific Solute-Solvent Interactions in Presence of Organic Solvent.

    PubMed

    Prabhu, Sugosh R; Dutt, G B

    2015-08-20

    Rotational diffusion of a charged solute, rhodamine 110 (R110), and a nondipolar solute, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP), has been investigated in ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N]) and 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([BMIM][FAP]), with 0.8 mole fraction of dibenzyl ether (DBE). This study has been undertaken to find out how specific interactions between the solute and the ionic liquid are affected upon dilution with a nondipolar solvent. It has been observed that at a given viscosity (η) and temperature (T), the reorientation times of R110 increase by 40-60% in the ionic liquid-organic solvent mixtures compared to ones in the corresponding neat ionic liquids. In the case of DMDPP, the influence of DBE is less pronounced, and its reorientation times increase by 25-50% at a given η/T. The addition of DBE weakens the numerous interactions prevailing between the cations and the anions of the ionic liquids, which results in stronger specific interactions between the solutes and the constituent ions, consequently leading to slower rotation of the solutes.

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

    PubMed

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

    2015-01-01

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

  12. Nitrogen transformation during organic waste composting by the Rutgers system and its effects on pH, EC and maturity of the composting mixtures.

    PubMed

    Sánchez-Monedero, M A; Roig, A; Paredes, C; Bernal, M P

    2001-07-01

    The evolution of the different forms of nitrogen during the composting of several wastes was studied, as well as its relation to the pH, electrical conductivity and parameters of maturity of the composts obtained. Four mixtures were prepared from different organic materials: sewage sludge, municipal solid waste, brewery sludge, sorghum bagasse, cotton waste and pine bark. The evolution of the different forms of nitrogen during composting depended on the material which supplied the nitrogen to the mixtures and the organic matter (OM) degradation rate during composting. The greatest concentration of ammonium was observed during the first weeks of composting, coinciding with the most intense period of OM degradation, and ammonium then decreased gradually to reach final values of below 0.04%. The use of urea as a nitrogen source in the mixtures led to high ammonium levels during the first weeks as a result of its rapid hydrolysis. The nitrification process began only when the temperature of the mixtures had dropped below 40 degrees C and its intensity depended on the quantity of ammonium present when the process began. The highest concentrations of NO3-N were always produced at the end of maturation, reaching values of 0.52%, 0.53%, 0.12% and 0.20% in the four mixtures studied. Nitrogen losses during composting depended on the materials used and on the pH values of the mixtures. Mixtures with the highest lignocellulose content showed the lowest losses (below 25%), while those containing municipal solid waste lost more than 40% of the initial content. Statistically significant correlations at a high probability level were found between the NO3-N concentration and pH and electrical conductivity. confirming that nitrification was responsible for the falling pH values and increasing electrical conductivity. The ratio of NH4-N and NO3-N concentrations was shown to be a clear indicator of the maturity of the mixtures during composting, the final values of 0.08, 0.04, 0

  13. 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

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

    PubMed

    Squillace, Paul J; Moran, Michael J

    2007-04-01

    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-trimethyl-benzene, and perchloroethene were some of the frequently detected VOCs. Concentrations generally were less than 1 microg/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

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

    PubMed

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

    2016-01-01

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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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...

  1. 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...

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

    PubMed

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

    2015-10-01

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

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

    PubMed

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

    2016-01-01

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

  4. Maternal exposure to a mixture of persistent organic pollutants (POPs) affects testis histology, epididymal sperm count and induces sperm DNA fragmentation in mice.

    PubMed

    Khezri, Abdolrahman; Lindeman, Birgitte; Krogenæs, Anette K; Berntsen, Hanne F; Zimmer, Karin E; Ropstad, Erik

    2017-08-15

    Persistent organic pollutants (POPs) are widespread throughout the environment and some are suspected to induce reproductive toxicity. As animals and humans are exposed to complex mixtures of POPs, it is reasonable to assess how such mixtures could interact with the reproductive system. Our aim is to investigate how maternal exposure to a mixture of 29 different persistent organic pollutants, formulated to mimic the relative POP levels in the food basket of the Scandinavian population, could alter reproductive endpoints. Female mice were exposed via feed from weaning, during pregnancy and lactation in 3 exposure groups (control (C), low (L) and high (H)). Testicular morphometric endpoints, epididymal sperm concentration and sperm DNA integrity were assessed in adult male offspring. We found that the number of tubules, proportion of tubule compartments and epididymal sperm concentration significantly decreased in both POP exposed groups. Epididymal sperm from both POP exposed groups showed increased DNA fragmentation. It is concluded that maternal exposure to a defined POP mixture relevant to human exposure can affect testicular development, sperm production and sperm chromatin integrity. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Understanding the Effect of Solvent Structure on Organic Reaction Outcomes When Using Ionic Liquid/Acetonitrile Mixtures.

    PubMed

    Keaveney, Sinead T; Greaves, Tamar L; Kennedy, Danielle F; Harper, Jason B

    2016-12-15

    The rate constant for the reaction between hexan-1-amine and 4-methoxybenzaldehyde was determined in ionic liquids containing an imidazolium cation. The effect on the rate constant of increasing the length of the alkyl substituent on the cation was examined in a number of ionic liquid/acetonitrile mixtures. In general it was found that there was no significant effect of changing the alkyl substituent on the rate constant of this process, suggesting that any nanodomains in these mixtures do not have a significant effect on the outcome of this process. A series of small-angle X-ray scattering and wide-angle X-ray scattering experiments were performed on mixtures of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim][N(CF3SO2)2]) and acetonitrile; this work indicated that the main structural changes in the mixtures occur by about a 0.2 mole fraction of ionic liquid in the mixture (χIL). This region at which the main changes in the solvent structuring occurs corresponds to the region at which the main changes in the rate constant and activation parameters occur for SN2 and condensation reactions examined previously; this is the first time that such a correlation has been observed. To examine the ordering of the solvent about the nucleophile hexan-1-amine, WAXS experiments were performed on a number of [Bmim][N(CF3SO2)2]/acetonitrile/hexan-1-amine mixtures, where it was found that some of the patterns featured asymmetric peaks as well as additional peaks not observed in the [Bmim][N(CF3SO2)2]/acetonitrile mixtures; this suggests that the addition of hexan-1-amine to the mixture affects the bulk structure of the liquid. The SAXS/WAXS patterns of mixtures of 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ([Bm2im][N(CF3SO2)2]) and acetonitrile were also determined, with the results suggesting that [Bm2im][N(CF3SO2)2] is more ordered than [Bmim][N(CF3SO2)2] due to an enhancement in the short-range interactions.

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

    PubMed

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

    2016-10-01

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

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

    PubMed

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

    2012-07-01

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

  8. Natural mixtures of persistent organic pollutants (POP) increase weight gain, advance puberty, and induce changes in gene expression associated with steroid hormones and obesity in female zebrafish.

    PubMed

    Lyche, Jan L; Nourizadeh-Lillabadi, Rasoul; Almaas, Camilla; Stavik, Benedicte; Berg, Vidar; Skåre, Janneche Utne; Alestrøm, Peter; Ropstad, Erik

    2010-01-01

    In the present study, developmental and reproductive effects of lifelong exposure to environmental relevant concentrations of two natural mixtures of persistent organic pollutants (POP) were investigated using classical and molecular methods in a controlled zebrafish model. The mixtures used were extracted from burbot (Lota lota) liver originating from freshwater systems in Norway: one mixture with high levels and one mixture with background levels of polybrominated diphenyl ethers (PBDE), polychlorinated biphenyls (PCB), and dichlorodiphenyltrichloroethane metabolites (DDT). The concentration of POP measured in the zebrafish ranged from levels detected in wild fish from Lake Mjøsa to concentrations reported in human and wildlife populations, indicating that the experimental fish were exposed to concentrations comparable with wild fish. Phenotypic effects observed in both exposure groups included earlier onset of puberty, increased male/female sex ratio, and differences in body weight at 5 mo of age. Interestingly, genome-wide transcription profiling showed changes in regulation of genes involved in endocrine signaling and growth. The transcriptomics changes include key regulator genes for steroid hormone functions (ncoa3), and growth (c/ebp, ncoa3). The effects observed in the experimental zebrafish model raise the question whether chemical pollution represents a risk to reproductive health of wild fish inhabitating the freshwater system.

  9. 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.

  10. Correlating solubility parameters and solvatochromic parameters with the self-assembly of poly(3-hexylthiophene) in mixtures of organic solvents

    NASA Astrophysics Data System (ADS)

    Gordon, Madeleine; Boucher, David

    2015-03-01

    We have studied the assembly and crystallinity of poly(3-hexylthiophene) (P3HT) (Mn ~ 28.2 kDa, regioregularity > 96 %, PDI ~ 1.3) in >100 binary solvent mixtures using UV-Vis absorption spectroscopy, and it is clear that the identity of the poor solvent used to drive aggregation has a significant impact on the structural order and crystallinity of the P3HT aggregates in solution. Here we report our findings using Hansen solubility parameters (HSPs), specifically the solubility distance vector, Ra, and the Kamlet-Taft solvatochromic parameters of the solvent mixtures to better understand the dominant solvent forces driving the self assembly of P3HT. We find that the directionality of the Ra vector provides a better measure of the crystallinity of the P3HT assemblies formed in the solvent mixtures than does the magnitude of the Ra vector. Our analysis of the Kamlet-Taft (α, β, π*) and ET(30) solvatochromic parameters reveals that the β parameter correlates best with the crystallinity of P3HT and that, in general, assemblies having higher structural order are formed in solvent mixtures with lower values of β.

  11. Molecular dynamics study of nanoscale organization and hydrogen bonding in binary mixtures of butylammonium nitrate ionic liquid and primary alcohols.

    PubMed

    Shrivastav, Gourav; Gupta, Aditya; Rastogi, Aman; Dhabal, Debdas; Kashyap, Hemant K

    2017-02-14

    Molecular dynamics simulations are utilized here to explore the nanoscale morphology and the nature of hydrogen bonding in the equimolar mixtures of butylammonium nitrate protic ionic liquid with ethanol, propanol, and butanol. The X-ray scattering experimental study of Greaves et al. [Phys. Chem. Chem. Phys. 13, 13 501 (2011)] has evidenced that alkylammonium nitrate plus alcohol mixtures possess nanoscale structural order which becomes more pronounced as the chain length of the alcohol increases. Our analysis carried out using simulated total and partial X-ray scattering structure functions quantifies the basis of these observations. The partial structure functions highlight the off-phase density correlations of alcohol with both cation and anion in the low-q region. We demonstrate that the chain lengthening of alcohols offers significant variation in the structuring of the polar and apolar moieties in the mixtures. The inspection based on radial distribution functions manifests the non-linear hydrogen bonds of cations with nitrate anions as well as alcohol molecules. The alcohol's hydroxyl group prefers to form linear hydrogen bonds with anions and with other alcohol molecules. Incremented chain length of alcohol improves the extent of hydrogen bonding but does not alter their geometry. Spatial distribution functions delineate similar preferences. It shows stronger directional preferences of the hydroxyl group of alcohols than cation in the vicinity of an anion. Enhanced pair correlations associated with the terminal methyl carbons suggest aggregation of butanol chains in apolar domains. Triplet correlation functions (TCFs) are also used to evaluate the orientational preferences of the present polar moieties in the mixtures. Information based on TCFs for distribution of polar head group of cations and anions unveils the dominance of equilateral configurations over the less frequent isosceles configurations in all the three mixtures.

  12. Molecular dynamics study of nanoscale organization and hydrogen bonding in binary mixtures of butylammonium nitrate ionic liquid and primary alcohols

    NASA Astrophysics Data System (ADS)

    Shrivastav, Gourav; Gupta, Aditya; Rastogi, Aman; Dhabal, Debdas; Kashyap, Hemant K.

    2017-02-01

    Molecular dynamics simulations are utilized here to explore the nanoscale morphology and the nature of hydrogen bonding in the equimolar mixtures of butylammonium nitrate protic ionic liquid with ethanol, propanol, and butanol. The X-ray scattering experimental study of Greaves et al. [Phys. Chem. Chem. Phys. 13, 13 501 (2011)] has evidenced that alkylammonium nitrate plus alcohol mixtures possess nanoscale structural order which becomes more pronounced as the chain length of the alcohol increases. Our analysis carried out using simulated total and partial X-ray scattering structure functions quantifies the basis of these observations. The partial structure functions highlight the off-phase density correlations of alcohol with both cation and anion in the low-q region. We demonstrate that the chain lengthening of alcohols offers significant variation in the structuring of the polar and apolar moieties in the mixtures. The inspection based on radial distribution functions manifests the non-linear hydrogen bonds of cations with nitrate anions as well as alcohol molecules. The alcohol's hydroxyl group prefers to form linear hydrogen bonds with anions and with other alcohol molecules. Incremented chain length of alcohol improves the extent of hydrogen bonding but does not alter their geometry. Spatial distribution functions delineate similar preferences. It shows stronger directional preferences of the hydroxyl group of alcohols than cation in the vicinity of an anion. Enhanced pair correlations associated with the terminal methyl carbons suggest aggregation of butanol chains in apolar domains. Triplet correlation functions (TCFs) are also used to evaluate the orientational preferences of the present polar moieties in the mixtures. Information based on TCFs for distribution of polar head group of cations and anions unveils the dominance of equilateral configurations over the less frequent isosceles configurations in all the three mixtures.

  13. 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.

  14. 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.

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

    PubMed Central

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Hayes, Robert

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

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

    NASA Astrophysics Data System (ADS)

    Hayes, Robert

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

  18. Bubble and droplet motion in binary mixtures: Evaporation-condensation mechanism and Marangoni effect.

    PubMed

    Onuki, Akira

    2009-04-01

    Bubble and droplet motion in binary mixtures is studied in weak heat and diffusion fluxes and in gravity by solving the linearized hydrodynamic equations supplemented with appropriate surface boundary conditions. Without gravity, the velocity field is induced by evaporation and condensation at the interface and by the Marangoni effect due to a surface-tension gradient. In pure fluids, the latter nearly vanishes since the interface temperature tends to the coexistence temperature T_{cx}(p) even in heat flow. In binary mixtures, the velocity field can be much enhanced by the Marangoni effect above a crossover concentration c;{ *} inversely proportional to the radius R of the bubble or droplet. Here c;{ *} is usually very small for large R for non-azeotropic mixtures. The temperature and concentration deviations are also calculated.

  19. 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.

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

    PubMed

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

    2013-06-15

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

  1. 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.

  2. Features of non-congruent phase transition in modified Coulomb model of the binary ionic mixture

    NASA Astrophysics Data System (ADS)

    Stroev, N. E.; Iosilevskiy, I. L.

    2016-11-01

    Non-congruent gas-liquid phase transition (NCPT) have been studied previously in modified Coulomb model of a binary ionic mixture C(+6) + O(+8) on a uniformly compressible ideal electronic background /BIM(∼)/. The features of NCPT in improved version of the BIM(∼) model for the same mixture on background of non-ideal electronic Fermi-gas and comparison it with the previous calculations are the subject of present study. Analytical fits for Coulomb corrections to equation of state of electronic and ionic subsystems were used in present calculations within the Gibbs-Guggenheim conditions of non-congruent phase equilibrium. Parameters of critical point-line were calculated on the entire range of proportions of mixed ions 0 < X < 1. Strong “distillation” effect was found for NCPT in the present BIM(∼) model. Just similar distillation was obtained in the variant of NCPT in dense nuslear matter. The absence of azeotropic compositions was revealed in studied variants of BIM(∼) in contrast to an explicit existence of the azeotropic compositions for the NCPT in chemically reacting plasmas and in astrophysical applications.

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

    PubMed

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

    2016-01-01

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

  4. Spectrophotometric determination of acidity constants of 2-(2-Thiazolylazo)-Cresol in various water-organic solvent media mixtures using chemometrics methods.

    PubMed

    Momeni-Isfahani, Tahereh; Niazi, Ali

    2014-01-01

    The combination of soft- and hard-modeling was used to the spectrophotometric studies of the acidity constants of 2-(2-Thiazolylazo)-Cresol (TAC) at 25°C and at ionic strength 0.1 mol L(-1) in pure water as well as in aqueous media containing variable percentages (10-50%) of organic solvents. The organic solvents used were methanol, ethanol, dimethyl formamide (DMF) and 1,4-dioxane. The acidity constants of all related equilibria are estimated using the whole spectral fitting of the collected data to an established factor analysis model. DATAN program was applied for determining acidity constants and pure spectra of different form of TAC. Results show that the acidity constants of TAC are influenced as the percentages of solvents added to the solution. The corresponding pKa values in solvent-water mixtures were determined. There are linear relationships between acidity constants and the mole fraction of organic solvents in the solvent mixtures. The effects of various solvents on absorption properties and acidity constants of each component are also discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Aspects of High-Resolution Gas Chromatography as Applied to the Analysis of Hydrocarbon Fuels and Other Complex Organic Mixtures. Volume 2. Survey of Sample Insertion Techniques.

    DTIC Science & Technology

    1985-06-01

    AD-A158 772 ASPECTS OF HIGH-RESOL.UTION GAS CHROMATOGRAPHY S 1ll APPLIED0 TO THE ANALYSIS 0..(U)1 DAYTON UNIV ON RESEARCH INST W A RUSEY ET AL. JUN...RESOLUTION GAS CHROMATOGRAPHY AS APPLIED TO THE ANALYSIS OF HYDROCARBON FUELS AND OTHER COMPLEX ORGANIC MIXTURES Volume II - Survey of Sample Insertion...NO. NO. 45433-6563 62203F 3048 05 91 11. TITLE (Include Security Classification) (cont’ d on reverse) ASPECTS OF HIGH-RESOLUTION GAS CHROMATOGRAPHY T

  6. The combined effect of persistent organic pollutants in the serum POP mixture in Greenlandic Inuit: xenoestrogenic, xenoandrogenic and dioxin-like transactivities.

    PubMed

    Krüger, Tanja; Long, Manhai; Ghisari, Mandana; Bonefeld-Jørgensen, Eva C

    2012-12-01

    Greenlandic Inuit have high body burden of persistent organic pollutants (POPs). We analyzed the combined effect of the actual lipophilic serum POP mixture on estrogen-, androgen- and aryl hydrocarbon-receptor functions as effect biomarkers, and the associations between the effect biomarkers and serum POPs, and lifestyle characteristics. The serum POPs were extracted from 232 Inuit from Ittoqqortoormiit, Narsaq and Qeqertarsuaq. The POP-related receptor transactivities correlated negatively to the POP levels and were associated to the lifestyle characteristics. The POP-related receptor transactivities can be used as effect biomarkers. The serum POPs have hormone disruptive potentials.

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

    SciTech Connect

    LaVerne, Jay A.

    2004-12-01

    Scope. The radiation chemistry of aqueous systems containing chlorinated hydrocarbons is investigated using a multi-pronged approach employing 60Co gamma ray and alpha particle irradiation experiments in conjunction with diffusion-kinetic modeling incorporating track structure simulations. The goal is to determine 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 information obtained is of a fundamental nature, but the radiation chemical systems studied are found throughout the DOE portfolio and are important in radioactive waste remediation and management. Program Highlights. Radiation-induced production of H2 and HCl from chlorinated hydrocarbons. 60Co gamma-radiolysis experiments and stochastic kinetic modeling have been used to investigated the radiation-induced yield of H2 and Cl- from aqueous solutions of 1,2-dichloroethane (1,2-DCE) and 1,1-dichloroethane (1,1-DCE) over the concentration range 1-80 mM. In deoxygenated solution, the yield of H2 from both 1,2-DCE and 1,1-DCE solutions decreases as the concentration of DCE is increased. The decrease in the H2 yield shows that the reaction of H atom with DCE does not lead to the production of H2. This observation is unexpected and reflects the reverse of the effect seen in the gas phase, where the reaction of H atom with 1,2-DCE and 1,1-DCE leads to the production of H2. The yield of Cl- from 1,2-DCE and 1,1-DCE solutions increases slightly from 2.8 ions/100eV to 3.6 over the concentration range 10-50 mM, demonstrating the increased competition of the DCE with intra-track processes. Comparison of the measured yields of Cl- with the predictions of stochastic kinetic modeling shows that the reactions of eaq- with 1,2-DCE and with 1,1-DCE are quantitative, and that the reaction of H atom with both DCEs leads to the production of Cl- (and Haq+). In aerated solution, the yield of Cl

  8. 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. Published by Elsevier B.V.

  9. 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...

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

    EPA Science Inventory

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

  11. Distillation of binary mixtures with capillary porous plates

    SciTech Connect

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

    1998-07-01

    Distillation of liquid mixtures using capillary porous plates is a new process which depends upon the use of the intermolecular interactions between solids and liquids to alter the normal vapor-liquid equilibrium of a given mixture. Distillation of different binary mixtures, namely ethanol-water, ethanol-benzene, and acetone-ethanol systems, of different compositions was experimentally studied in a continuous distillation column equipped with four, five, or six porous sintered stainless steel fractionating plates of 13.5 {micro}m pore diameter as well as six normal sieve plates. The results showed that the main factors affecting the separation efficiency in a given porous plate are the polarization of the pure liquids and the polarization difference between the mixture components. For the ethanol-water system, the results showed that while no separation was achieved in a distillation column with conventional stages, the zeotropic point of this system was broken in the distillation column with porous plates. A distillate of about 94 mol% ethanol was obtained for a feed of the zeotropic composition, i.e., 89.7 mol% ethanol. For the ethanol-benzene system, the azeotropic point was shifted from 40 mol% ethanol to about 30 mol% ethanol. For the acetone-ethanol system, there was no significant difference between the results obtained with normal stages and those with the porous plates. These results are in agreement with the developed theory.

  12. Phase Behavior and Thermodynamic Model Parameters in Simulations of Extractive Distillation for Azeotrope Separation.

    PubMed

    Li, Min; Xu, Xicai; Li, Xin; Ma, Kang; Qin, Bin; Zhu, Zhaoyou; Wang, Yinglong

    2017-08-25

    Extractive distillation (ED) processes for separating ternary mixtures of benzene-cyclohexane-toluene with dimethyl formamide (DMF) and N-methyl-2-pyrrolidone (NMP) were studied using Aspen Plus and PRO/II simulators. The Aspen Plus built-in binary interaction parameters for the toluene-DMF, benzene-NMP and cyclohexane-NMP systems resulted in inaccurate phase behavior calculations. The vapor-liquid equilibrium (VLE) for the three binary systems was regressed to illustrate the importance of using accurate model parameters. The obtained binary interaction parameters described the phase behavior more accurately compared with the built-in binary interaction parameters in Aspen Plus. In this study, the effects of the regressed and built-in binary interaction parameters on the ED process design are presented. The total annual cost (TAC) was calculated to further illustrate the importance of the regressed binary interaction parameters. The results show that phase behavior and thermodynamic model parameters should receive more attention during the research and development of ED processes.

  13. Self-Organized Gels in DNA/F-Actin Mixtures without Crosslinkers: Networks of Induced Nematic Domains with Tunable Density

    NASA Astrophysics Data System (ADS)

    Lai, Ghee Hwee; Butler, John C.; Zribi, Olena V.; Smalyukh, Ivan I.; Angelini, Thomas E.; Purdy, Kirstin R.; Golestanian, Ramin; Wong, Gerard C. L.

    2008-11-01

    We examine mixtures of DNA and filamentous actin (F-actin) as a model system of like-charged rigid rods and flexible chains. Confocal microscopy reveals the formation of elongated nematic F-actin domains reticulated via defect-free vertices into a network embedded in a mesh of random DNA. Synchrotron x-ray scattering results indicate that the DNA mesh squeezes the F-actin domains into a nematic state with an interactin spacing that decreases with increasing DNA concentration as dactin∝ρDNA-1/2. Interestingly, the system changes from a counterion-controlled regime to a depletion-controlled regime with added salt, with drastic consequences for the osmotic pressure induced phase behavior.

  14. Influence of organic solvent on the separation of an ionic liquid from a lignin-ionic liquid mixture.

    PubMed

    Weerachanchai, Piyarat; Lim, Kok Hwa; Lee, Jong-Min

    2014-03-01

    Sixteen solvents added in lignin-ionic liquid mixture provide four types of solubility characteristics. The distinct characteristics can be classified by considering solubility parameters including ET Scale, Kamlet-Taft parameters and solubility parameters. Group 1 solvent shows promising solvents for lignin-ionic liquid separation, contributing full dissolution of ionic liquid with lignin precipitation. Isopropanol, the most potential solvent has solubility properties as following normalized molar electronic transition energies (ET(N))=0.57, hydrogen-bond acidity (α)=0.76 and Hildebrand solubility parameter (δT)=23.58. This study examines potential solvents for ionic recovery, provides simple method of separation and leads to the feasibility of using ionic liquids in industrial applications.

  15. Self-organized gels in DNA/F-actin mixtures without crosslinkers: networks of induced nematic domains with tunable density.

    PubMed

    Lai, Ghee Hwee; Butler, John C; Zribi, Olena V; Smalyukh, Ivan I; Angelini, Thomas E; Purdy, Kirstin R; Golestanian, Ramin; Wong, Gerard C L

    2008-11-21

    We examine mixtures of DNA and filamentous actin (F-actin) as a model system of like-charged rigid rods and flexible chains. Confocal microscopy reveals the formation of elongated nematic F-actin domains reticulated via defect-free vertices into a network embedded in a mesh of random DNA. Synchrotron x-ray scattering results indicate that the DNA mesh squeezes the F-actin domains into a nematic state with an interactin spacing that decreases with increasing DNA concentration as d(actin) proportional, variantrho(DNA)(-1/2). Interestingly, the system changes from a counterion-controlled regime to a depletion-controlled regime with added salt, with drastic consequences for the osmotic pressure induced phase behavior.

  16. Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures

    PubMed Central

    Liu, Shurong; Berns, Anne E.; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

    2017-01-01

    Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH2OH) to nitrous oxide (N2O) is a possible mechanism of N2O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO2) and organic matter (OM) content of soil as well as soil pH are important control variables of N2O formation in the soil. But until now, their combined effect on abiotic N2O formation from NH2OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO2 and OM, respectively, and quantified the interactive effects of the three variables on the NH2OH-to-N2O conversion ratio (RNH2OH-to-N2O). Furthermore, the effect of OM quality on RNH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO2 and OM on RNH2OH-to-N2O. In general, increasing MnO2 and decreasing pH increased RNH2OH-to-N2O, while increasing OM content was associated with a decrease in RNH2OH-to-N2O. Organic matter quality also affected RNH2OH-to-N2O. However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials. PMID:28145407

  17. Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures

    NASA Astrophysics Data System (ADS)

    Liu, Shurong; Berns, Anne E.; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

    2017-02-01

    Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH2OH) to nitrous oxide (N2O) is a possible mechanism of N2O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO2) and organic matter (OM) content of soil as well as soil pH are important control variables of N2O formation in the soil. But until now, their combined effect on abiotic N2O formation from NH2OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO2 and OM, respectively, and quantified the interactive effects of the three variables on the NH2OH-to-N2O conversion ratio (RNH2OH-to-N2O). Furthermore, the effect of OM quality on RNH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO2 and OM on RNH2OH-to-N2O. In general, increasing MnO2 and decreasing pH increased RNH2OH-to-N2O, while increasing OM content was associated with a decrease in RNH2OH-to-N2O. Organic matter quality also affected RNH2OH-to-N2O. However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials.

  18. Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures.

    PubMed

    Liu, Shurong; Berns, Anne E; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

    2017-02-01

    Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH2OH) to nitrous oxide (N2O) is a possible mechanism of N2O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO2) and organic matter (OM) content of soil as well as soil pH are important control variables of N2O formation in the soil. But until now, their combined effect on abiotic N2O formation from NH2OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO2 and OM, respectively, and quantified the interactive effects of the three variables on the NH2OH-to-N2O conversion ratio (RNH2OH-to-N2O). Furthermore, the effect of OM quality on RNH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO2 and OM on RNH2OH-to-N2O. In general, increasing MnO2 and decreasing pH increased RNH2OH-to-N2O, while increasing OM content was associated with a decrease in RNH2OH-to-N2O. Organic matter quality also affected RNH2OH-to-N2O. However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials.

  19. Chiral mixtures

    NASA Astrophysics Data System (ADS)

    Petitjean, Michel

    2002-08-01

    An index evaluating the amount of chirality of a mixture of colored random variables is defined. Properties are established. Extreme chiral mixtures are characterized and examples are given. Connections between chirality, Wasserstein distances, and least squares Procrustes methods are pointed out.

  20. Solvation of deoxynucleosides in aqueous mixtures of organic solvents probed through their intrinsic fluorescence: Implications for open base pair states in DNA

    NASA Astrophysics Data System (ADS)

    Ababneh, Anas Mohammad

    Because of the importance of solvation in the function of DNA, there is considerable interest in understanding the solvation network of its constituent components. This is of particular importance in connection with the closing of base pairs that have been disrupted as a result of structural fluctuations. Following the opening of a base pair, the open base is exposed to a heterogeneous environment which involves polar as well as nonpolar interactions. Toward the goal of understanding how the open bases interact with such a heterogeneous environment, we have studied the intrinsic fluorescence properties of the purine and pyrimidine nucleosides (dG, dA, dT, and dC) in organic solvents in the presence of small amounts of water. Exposure of the nucleoside to water was done by preparing solutions in three different ways: (i) "premixed" solution in which the nucleoside is dissolved in a water-organic solvent mixture, (ii) "carry its own water" solution in which the nucleoside is first dissolved in water and then diluted in the organic solvent, and (iii) "injected" solution in which water is added to a solution of the nucleoside in the organic solvent. The organic solvents used in the present study were: n-butanol, acetonitrile, methanol, n-propanol, isopropanol, and isobutanol. We find that for n-butanol and acetonitrile, which have a high degree of amphiphilicity and weak hydrogen bonding ability, respectively, the fluorescence spectral properties of the purines are found to depend on the sequence of the steps in which the aqueous mixture was formed. By contrast, no such dependence was observed in the other organic solvents. On the other hand, no such dependence was observed for the pyrimidines in any of the organic solvents used in the present study. These findings suggest that the final solvation network around the purines is dependent on the nature of the environment to which they were initially exposed. This would tend to present an impediment to the closing of

  1. Study of the feasibility of controlling the length scale of the phase separation of organic molecular mixtures on Si(111) substrates

    NASA Astrophysics Data System (ADS)

    Cezza, Miriam

    We present investigations on the arrangements of phase separating small organic molecules in mixtures subsequent to deposition from liquid solution. This phenomenon may have technological applications in efficient organic solar cells. The spontaneous formation of a morphology during phase separation from a solvent-based, bimolecular solution onto a substrate depends on several parameters, including relative molecular concentrations, individual molecules/solvent/substrate interactions, solvent evaporation rate, and annealing conditions. Our molecular mixtures consist of tetranitro zinc-phthalocyanine (tn-ZnPc) and [6,6]-phenyl-C 61-butyric acid methyl ester (PCBM) in chloroform, deposited on native oxide-covered Si(111) substrates. We investigate the role that solvent evaporation rate during deposition, solvent vapor annealing (SVA) and thermal annealing play on the morphology formation of molecular domains. We find that slow enough rates of solvent evaporation, along with SVA action, lead to ordered PCBM structures. Most of tn-ZnPc molecules aggregate in rod-shaped clusters of size ~ 100 nm while in liquid solution, even at diluted concentrations, but some remain solvated, and form a wetting layer on the Si(111) surfaces, affecting the morphology of PCBM deposited through mixture solutions. We find that PCBM aggregates vertically diffuse upon heating in spin-coated samples, while tn-ZnPc clusters and wetting layer are not affected. Investigations of different relative concentrations of individual molecules in mixtures show that the concentration of tn-ZnPc strongly affects the crystallization process of PCBM: for a 1:1 ratio PCBM crystallization is suppressed, while changing the amount of tn-ZnPc, PCBM crystals form. While PCBM domains display several different morphologies, tn-ZnPc cluster morphology is not affected by changes in the deposition conditions or by post-deposition treatments. Overall we find that, under the conditions studied here, PCBM molecules

  2. 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

  3. Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene.

    PubMed

    Tong, Haijie; Lakey, Pascale S J; Arangio, Andrea M; Socorro, Joanna; Kampf, Christopher J; Berkemeier, Thomas; Brune, William H; Pöschl, Ulrich; Shiraiwa, Manabu

    2017-08-24

    Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (<3) conditions. ROS formation can be explained by the decomposition of organic hydroperoxides, which are a prominent fraction of SOA, through interactions with water and Fenton-like reactions with dissolved transition metal ions. Our findings imply that the chemical reactivity and aging of SOA particles can be enhanced upon interaction with mineral dust in deliquesced particles or cloud/fog droplets. SOA decomposition could be comparably important to the classical Fenton reaction of H2O2 with Fe(2+) and that SOA can be the main source of OH radicals in aqueous droplets at low concentrations of H2O2 and Fe(2+). In the human respiratory tract, the inhalation and deposition of SOA and mineral dust can also lead to the release of ROS, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols in the Anthropocene.

  4. New insights into self-organization of a model lipid mixture and quantification of its adsorption on spherical polymer particles.

    PubMed

    Troutier, Anne-Lise; Véron, Laurent; Delair, Thierry; Pichot, Christian; Ladavière, Catherine

    2005-10-25

    The adsorption of lipids onto spherical polymer colloids led to original assemblies presenting structural characteristics adjustable with the lipid formulation. The model system selected for this work involved sulfate-charged poly(styrene) submicrometer particles and zwitterionic/cationic lipid mixtures composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-3-trimethylammonium-propane (DPTAP). According to the theoretical packing parameter calculations and whatever the DPPC/DPTAP ratio, the two lipids self-assembled in aqueous media to spontaneously form vesicles. A phase transition investigation of these DPPC/DPTAP vesicles using differential scanning calorimetry revealed particular thermotropic behaviors, especially for the equimolar formulation where very strong interactions occurred between DPPC and DPTAP. Furthermore, the coating of the lipids around particles was monitored versus DPPC/DPTAP ratio by means of numerous appropriate techniques. First, a thermogravimetric analysis, providing decomposition profiles of lipid/polymer particle assemblies with temperature, was atypically carried out for such nanostructures. Then, 1H NMR spectroscopy enabled the exact DPPC/DPTAP molar ratios adsorbed on particles to be determined by differentiating both lipids. Subsequently, it also pointed out the major role of electrostatic interactions as driving forces in the assembly elaboration process. In addition to these findings, quantitative information has been collected and correlated with chemical lipid assays and permitted the statement of a lipid bilayer coverage for the assemblies prepared in water, in agreement with quasi-elastic light scattering data.

  5. Anion exchange of organic carboxylate by soils responsible for positive Km-fc relationship from methanol mixture.

    PubMed

    Kim, Minhee; Han, Junho; Hyun, Seunghun

    2013-09-01

    The cosolvency model was not applicable for predicting the sorption of organic carboxylic acids. The reason of inapplicability was investigated by analyzing the solubility (Sm) and sorption (Km) of benzoic acid, 2,4-dichlorophenoxyacetic acid (2,4-D), and 2,4,6-trichlorophenol (2,4,6-TCP). The Sm and Km by two iron-rich soils was measured as a function of methanol volume fraction (fc), electrolyte compositions, and pH(app). For 2,4,6-TCP, the Km of both neutral and anion species was well-explainable by the cosolvency model, exemplifying the knowledge of cosolvency power (σ) being sufficient to describe its sorption. However, for benzoic acid and 2,4-D, the Km of organic anions increased with fc, illustrating the organic carboxylate to be responsible for the deviation. The Sm of organic anions was not affected by the ionic valence (Ca(2+) vs. K(+)) of liquid phase. Among hydrophilic quantities of the 2,4-D sorption, the fraction of anion exchange increased with fc while the fraction of Ca-bridge decreased in the same range. Adding solvent in soil-water system is likely to render soil surface charge more positive, fortifying the anion exchange, but opposing the formation of Ca-bridging. Therefore, it can be concluded that the positive Km-fc relationship is due to the anion exchange of organic carboxylate with positively charged soil surface, whose contribution is >50% of overall sorption at solvent-free system and becomes greater with fc up to 82%.

  6. 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.

  7. Photosynthetic based algal-bacterial combined treatment of mixtures of organic pollutants and CO2 mitigation in a continuous photobioreactor.

    PubMed

    Essam, Tamer; ElRakaiby, Marwa; Hashem, Abdelgawad

    2013-06-01

    An algal-bacterial microcosm was synthetically constructed of Chlorella vulgaris MMl and Pseudomonas MTl. This microcosm was able to treat simulated wastewater supplemented with mixtures of phenol and pyridine up to 4.6 and 4.4 mM, respectively, in a continuous stirred tank bioreactor (CSTR) using photosynthetic oxygenation. Complete pollutant removal and detoxification and 82 % removal of introduced chemical oxygen demand (COD) were achieved at a hydraulic retention time (HRT) of 2.7 days. Increasing the influent load to 5.3 and 6.3 mM reduced the removal of phenol, pyridine and COD to 78, 21 and 59 %, respectively. Fertilization of the photobioreactor with 24 mM NaHCO3 restored the treatment and detoxification efficiencies. The system was able to additionally mitigate up to 72 mM NaHCO3 at the same HRT. Although the fertilization increased the system treatment efficiency, the settleability of the algal-bacterial microcosm was significantly reduced. When the photobioreactor was operated at HRT of 2.7 days in a 12/12 h of dark/light cycle, complete removal of 4.7 mM phenol was recorded but only 11 % of 5.7 mM pyridine was removed. The COD removal efficiency and CO2 mitigation were also reduced to 65 and 86 %, respectively, and the effluent retained significant toxicity where 73 % inhibition was recorded. Elongation of the illumination time to 48 h (HRT of 4 days at 12/12 h dark/light cycle) restored the treatment and detoxification efficiencies.

  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.

  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. Copyright © 2011 Elsevier B.V. All rights reserved.

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

    SciTech Connect

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

    2011-01-01

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

  11. 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

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

    PubMed

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

    2016-11-01

    Surface mining extraction of bitumen from oil sand in Alberta, Canada results in the accumulation of oil sands process-affected water (OSPW). In attempts to maximize water recycling, and because its constituents are recognized as being toxic, OSPW is retained in settling basins. Consequently, research efforts are currently focused on developing remediation strategies capable of detoxifying OSPW to allow for eventual release. One potential bioremediation strategy proposes to utilize phytoplankton native to the Alberta oil sand region to sequester, break down, or modify the complex oil sands acid extractable organic (AEO) mixtures in OSPW. Preliminary attempts to quantify changes in total oil sands AEO concentration in test solutions by ESI-MS following a 14-day algal remediation period revealed the presence of unknown organic acids in control samples, likely released by the phytoplankton strains and often of the same atomic mass range as the oil sands AEO under investigation. To address the presence of these "biogenic" organic acids in test samples, ESI-MS in MRM mode was utilized to identify oil sands AEO "marker ions" that were a) present within the tested oil sands AEO extract and b) unique to the oil sands AEO extract only (e.g. atomic masses different from biogenic organic acids). Using this approach, one of the 21 tested algal strains, Stichococcus sp. 1, proved capable of significantly reducing the AEO marker ion concentration at test concentrations of 10, 30, and 100mgL(-1). This result, along with the accelerated growth rate and recalcitrance of this algal strain with exposure to oil sands AEO, suggests the strong potential for the use of the isolated Stichococcus sp. 1 as a candidate for bioremediation strategies. Copyright © 2016 Elsevier Inc. All rights reserved.

  14. Thermodynamic parameters monitoring the equilibrium shift of enzyme-catalyzed hydrolysis/synthesis reactions in favor of synthesis in mixtures of water and organic solvent.

    PubMed

    Deschrevel, Brigitte; Vincent, Jean-Claude; Ripoll, Camille; Thellier, Michel

    2003-01-20

    The main strategy developed to shift the equilibrium state of a hydrolase-catalyzed hydrolysis/synthesis reaction consists in reducing water activity by addition of organic solvents in the reaction medium. We have used several mixtures of water and 1,4-butanediol, ranging from pure water to pure 1,4-butanediol, to study the hydrolysis/synthesis reaction of the N-Cbz-L-tryptophanyl-glycineamide dipeptide, catalyzed by alpha-chymotrypsin. In the presence of 1,4-butanediol, alpha-chymotrypsin also catalyzed the esterification reaction between this diol and N-Cbz-L-tryptophan; this ester hydrolysis/synthesis reaction has thus also been examined. The dipeptide and ester equilibrium concentrations increase when the water content of the reaction medium is decreased. Using our experimental data, we have determined the equilibrium constants of the hydrolysis/synthesis equilibria involving the nonionized forms of the protected amino acids, the estimated values of which are Ksp = 8 10(5) for the dipeptide and Kse = 78 for the ester respectively. They are true thermodynamic equilibrium constants, each related to a single, well-defined reaction equilibrium and with water activity being taken into account. If an organic solvent is added to the reaction medium these equilibria can be shifted towards synthesis by decreasing the water activity but also by modifying the ionization/neutralization equilibrium constant of the ionizable groups. These two effects depend both on the water content and on the nature of the organic solvent used, and, in particular, on its dielectric constant. Because of the importance of this parameter in our study, we discuss using it as an indicator to select an appropriate organic solvent to perform an enzyme-catalyzed synthesis.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  16. Complex organic pollutant mixtures originating from industrial and municipal emissions in surface waters of the megacity Jakarta-an example of a water pollution problem in emerging economies.

    PubMed

    Dsikowitzky, Larissa; Hagemann, Lukas; Dwiyitno; Ariyani, Farida; Irianto, Hari Eko; Schwarzbauer, Jan

    2017-09-19

    During the last decades, the global industrial production partly shifted from industrialized nations to emerging and developing countries. In these upcoming economies, the newly developed industrial centers are generally located in densely populated areas, resulting in the discharge of often only partially treated industrial and municipal wastewaters into the surface waters. There is a huge gap of knowledge about the composition of the complex organic pollutant mixtures occurring in such heavily impacted areas. Therefore, we applied a non-target screening to comprehensively assess river pollution in a large industrial area located in the megacity Jakarta. More than 100 structurally diverse organic contaminants were identified, some of which were reported here for the first time as environmental contaminants. The concentrations of paper manufacturing chemicals in river water-for example, of the endocrine-disrupting compound bisphenol A (50-8000 ng L(-1))-were as high as in pure untreated paper industry wastewaters. The non-target screening approach is the adequate tool for the identification of water contaminants in the new global centers of industrial manufacturing-as the first crucial step towards the evaluation of as yet unrecognized environmental risks.

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

    PubMed

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

    2016-07-19

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

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

    PubMed

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

    2013-03-05

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

  19. Molecular simulations for adsorptive separation of CO2/CH4 mixture in metal-exposed, catenated, and charged metal-organic frameworks.

    PubMed

    Babarao, Ravichandar; Jiang, Jianwen; Sandler, Stanley I

    2009-05-05

    The adsorption and separation of CO2/CH4 mixture are studied using molecular simulations in a series of metal-organic frameworks (MOFs) with unique characteristics such as exposed metals (Cu-BTC, PCN-6' and PCN-6), catenation (IRMOF-13 and PCN-6), and extraframework ions (soc-MOF). Because of the strong affinity with the framework, CO2 is preferentially adsorbed over CH4 in all MOFs. Framework catenation leads to constricted pores and additional adsorption sites and enhances the interaction with the adsorbate. Therefore, catenated IRMOF-13 and PCN-6 exhibit a greater extent of adsorption, particularly for CO2, at low pressures than IRMOF-14 and PCN-6'; however, the opposite is true at high pressures. CO2/CH4 selectivity in IRMOF-1 and IRMOF-14 is almost constant at low pressures and increases with increasing pressure. As a result of a counterbalance between energetic and entropic effects, the selectivity in IRMOF-13 initially decreases at low pressures and then increases with pressure and finally approaches a constant value. Catenated MOFs have a higher selectivity than their non-catenated counterparts. The presence of electrostatic interaction between CO2 and the framework leads to an increase in CO2 adsorption and a corresponding decrease in CH4 adsorption and consequently enhanced selectivity. In charged soc-MOF, the extraframework NO3- ions are identified to be equally distributed from the nearest metal atoms and vibrate around the favorable sites. The selectivity in soc-MOF is substantially higher than in the other IRMOFs and PCNs and is the highest among various MOFs reported to date. The simulation results reveal that the selectivity of CO2 over CH4 in MOFs is enhanced slightly by exposed metals, catenation, and significantly by extraframework ions and that charged MOFs are promising candidates for the separation of CO2/CH4 mixture.

  20. Monte Carlo simulations of mixtures involving ketones and aldehydes by a direct bubble pressure calculation.

    PubMed

    Ferrando, Nicolas; Lachet, Véronique; Boutin, Anne

    2010-07-08

    Ketone and aldehyde molecules are involved in a large variety of industrial applications. Because they are mainly present mixed with other compounds, the prediction of phase equilibrium of mixtures involving these classes of molecules is of first interest particularly to design and optimize separation processes. The main goal of this work is to propose a transferable force field for ketones and aldehydes that allows accurate molecular simulations of not only pure compounds but also complex mixtures. The proposed force field is based on the anisotropic united-atoms AUA4 potential developed for hydrocarbons, and it introduces only one new atom, the carbonyl oxygen. The Lennard-Jones parameters of this oxygen atom have been adjusted on saturated thermodynamic properties of both acetone and acetaldehyde. To simulate mixtures, Monte Carlo simulations are carried out in a specific pseudoensemble which allows a direct calculation of the bubble pressure. For polar mixtures involved in this study, we show that this approach is an interesting alternative to classical calculations in the isothermal-isobaric Gibbs ensemble. The pressure-composition diagrams of polar + polar and polar + nonpolar binary mixtures are well reproduced. Mutual solubilities as well as azeotrope location, if present, are accurately predicted without any empirical binary interaction parameters or readjustment. Such result highlights the transferability of the proposed force field, which is an essential feature toward the simulation of complex oxygenated mixtures of industrial interest.

  1. An acellular assay to assess the genotoxicity of complex mixtures of organic pollutants bound on size segregated aerosol. Part I: DNA adducts.

    PubMed

    Topinka, Jan; Hovorka, Jan; Milcova, Alena; Schmuczerova, Jana; Krouzek, Jiri; Rossner, Pavel; Sram, Radim J

    2010-10-20

    An acellular assay consisting of calf thymus DNA with/without rat liver microsomal S9 fraction was used to study the genotoxicity of complex mixtures of organic air pollutants bound to size segregated aerosols by means of DNA adduct analysis. We compared the genotoxicity of the organic extracts (EOMs) from three size fractions of aerosol ranging from 0.17μm to 10μm that were collected by high volume cascade impactors in four localities of the Czech Republic differing in the extent of the environmental pollution: (1) small village in proximity of a strip mine, (2) highway, (3) city center of Prague and (4) background station. The total DNA adduct levels induced by 100μg/ml of EOMs were analyzed by (32)P-postlabelling analysis with a nuclease P1 method for adduct enrichment. The main finding of the study was most of the observed genotoxicity was connected with a fine particulate matter fraction (<1μm). The concentrations of carcinogenic polycyclic aromatic hydrocarbons (c-PAHs) in EOMs indicate that fine fractions (0.5-1μm) bound the highest amount of c-PAHs in all aerosol sampling sites, which might be related to the higher specific surface of this fraction as compared with a course fraction (1-10μm) and higher mass as compared with a condensational fraction (0.17-0.5μm). As for aerosol mass, both fine and condensational fractions are effective carriers of c-PAHs. Similarly, the DNA adduct levels per m(3) of air were highest for the fine fraction, while the condensational fraction (strip mine site and city center) revealed the highest DNA adduct levels in cases where aerosol mass is taken into consideration. A strong correlation was found between the c-PAHs and DNA adduct levels induced by EOMs in all the localities and for various size fractions (R(2)=0.98, p<0.001). It may be concluded that the analysis of total DNA adducts induced in an acellular assay with/without metabolic activation represents a relatively simple method to assess the genotoxic potential

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

    PubMed

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

    2012-02-18

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

  3. 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.

  4. Inorganic and organic concentration data collected from 38 streams in the United States, 2012-2014, with supporting data, as part of the Chemical Mixtures and Environmental Effects Pilot Study.

    USGS Publications Warehouse

    Romanok, Kristin M.; Bradley, Paul M.; Journey, Celeste

    2017-01-01

    This USGS data release contains station and laboratory method information and geospatial information, as well as concentration results for inorganic and organic compounds and bioluminescent yeast estrogen screen and transgenic zebrafish embryo estrogren bioassay, analyzed at 38 sites in 25 states as part of the Chemical Mixtures and Environmental Effects Pilot Study, 2012-2014.

  5. Reduction of lead oxide (PbO2) and release of Pb(II) in mixtures of natural organic matter, free chlorine and monochloramine.

    PubMed

    Lin, Yi-Pin; Valentine, Richard L

    2009-05-15

    The primary focus of this paper is to elucidate the influence of mixtures of natural organic matter (NOM) and free chlorine and NOM and monochloramine on the reduction of PbO2 in drinking water. Parallel experiments using PbO2 particles of two different sizes (approximately 20 and approximately 200 nm) were conducted to explore the effects of particle size on this process. In the absence of NOM, reduction of PbO2 was observed in monochloramine solutions but not in free chlorine solutions. In the presence of NOM, significant Pb(II) formation was observed in disinfectant-free solutions. The release of Pb(II) was suppressed by the additional presence of free chlorine until the point in time when free chlorine was exhausted. Monochloramine also repressed Pb(II) formation in the presence of NOM but not as significantly as free chlorine. The presence of NOM and monochloramine does not necessarily act additively or synergistically due to complex interactions including reduction of PbO2 by NOM, monochloramine mediated reduction of PbO2, and oxidation of NOM by monochloramine. Higher surface area-normalized Pb(ll) formation was found in experiments using larger PbO2 particles. The high reactivity generally associated with nanoparticles was not observed in our study.

  6. Order of photocatalytic degradation as ranked by critical photonic times (CPTs) indicates the composition of organic dye mixtures: selectivity of hydroxyl radicals.

    PubMed

    Shigwedha, Nditange; Hua, Zhaozhe; Chen, Jian

    2006-01-01

    A simple critical photonic time (CPT) ranking method for the simultaneous determination of known organic dyes in the industrial wastewater of different concentrations was developed. A kinetic-measure, CPT theory, was developed to discriminate between the dyes in the textile effluent solution. The CPTs were calculated and ranked 1-4 from the smallest to the largest. The ranks indicate the order in which the individual dyes in the effluents were photocatalytically degraded. The described procedure allowed us to monitor the decolorization kinetics of the dyes in mixtures of different concentrations, when subjected to immobilized TiO2 photocatalysis in the presence of H2O2 from the start (H2O2FS). The outcome of hydroxyl radical (HO*) attack was consistently specific and regioselective for the individual dyes in the textile effluent. To explain the effect of HO*, the order of degradation of Acid Orange 52 < Acid Yellow 36 < Acid Red 17 < Acid Blue 45 < polyvinyl alcohol (PVA) was inferred.

  7. 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.

  8. Vapor-liquid equilibria of binary and ternary mixtures of cyclohexane, 3-methyl-2-butanone, and octane at 101.3 kPa

    SciTech Connect

    Chen, C.C.; Tang, M.; Chen, Y.P.

    1996-05-01

    Vapor-liquid equilibria were measured at 101.3 kPa for the three binary and one ternary mixtures of cyclohexane, 3-methyl-2-butanone, and octane. The isobaric T-x-y data were reported, including an azeotropic point for the binary mixture cyclohexane + 3-methyl-2-butanone. The virial equation of state truncated after the second coefficient was used to calculate the vapor-phase fugacity coefficients. The Tsonopoulos correlation equation was applied to determine the second virial coefficients. Various activity coefficient models of the Wilson, the NRTL, and the UNIQUAC equations were used to correlate the binary experimental vapor-liquid equilibrium results. Optimally-fitted binary parameters of the activity coefficient models were obtained and those parameters of the NRTL model were employed to predict the ternary vapor-liquid equilibria. Satisfactory results were presented for the correlation and prediction of the vapor-liquid equilibrium data on binary and ternary mixtures.

  9. Adsorption, Mobility and Organization Molecules at Clay Surfaces Probed by Photophysics and Photochemistry

    DTIC Science & Technology

    1988-06-15

    silica) was added to 500 cm 3 1-propanol (P.A.-grade, Janscen Chimica) The water was removed by azeotropic destillation of the propanol- water mixtuie (79...added to remove the polymer from the surface. Once the polymer is detached, it will go to the organic phase,due to its insolubility in water . The...very well shielded from the surrounding medium, which in our case is water . A possible explanation would be that the aqueous surrounding induces, at a

  10. Pulse-echo overlap technique of signal processing and ultrasonic velocity measurements of Cu(I) and some tetra-alkylammonium salts in binary organic mixtures to study various structural effects

    NASA Astrophysics Data System (ADS)

    Singh, Parvinder; Kansal, Deepika; Singh, Gurdev

    2001-08-01

    AIM OF THE PRESENT WORK Copper (I) salts are unstable in many orgnic solvents. Previous investigations of copper(I) salts are limited only to acetonitrile and its binary mixtures with some organic solvents. Benzonitrile like acetonitrile has also -C -N group attached to the benzene ring system. This solvent like acetonitrile also stabilize copper (I) salts strongly. Moreover, the solubility of copper(I) salts in benzonitrile and its binary mixtures with other organic solvents is much higher as compared to that in acetonitrile. In spite of very favourable properties of benzonitrile, studies of copper salts have never been made in benzonitrile and its binaru mixtures with other organic solvents. The binary mixtures of benzonitrile with acetonitrile and pyridine has a wide range of dielectric constant and viscosity. these solvent systems are very interesting solvent systems for the study of copper(I) salts. Cu+ and Na+ ions have almost some ionic radii (Cu+ = 0.90 A and Na+ = 0.95 A). These ions are expected to have some type of solvation behaviour in many solvents. It has been found that in nitrile solvents and pyridine Cu+ is solvated by a special type of interaction while Na+ is solvated by the normal electrostatic ion-dipole interaction.

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

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

  13. 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

    2014-08-05

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

  14. Pervaporation study for the dehydration of tetrahydrofuran-water mixtures by polymeric and ceramic membranes.

    PubMed

    McGinness, Colleen A; Slater, C Stewart; Savelski, Mariano J

    2008-12-01

    Pervaporation technology can effectively separate a tetrahydrofuran (THF) solvent-water waste stream at an azeotropic concentration. The performance of a Sulzer 2210 polyvinyl alcohol (PVA) membrane and a Pervatech BV silica membrane were studied, as the operating variables feed temperature and permeate pressure, were varied. The silica membrane was found to exhibit a flux of almost double that of the PVA membrane, but both membranes had comparable separation ability in purifying the solvent-water mixture. At benchmark feed conditions of 96 wt% THF and 4 wt% water, 50 degrees C and 10 torr permeate pressure, the silica membrane flux was 0.276 kg/m(2)hr and selectivity was 365. For both membranes, flux was found to increase at an exponential rate as the feed temperature increased from 20 to 60 degrees C. The flux through the silica membrane increases at a 6% faster rate than the PVA membrane. Flux decreased as permeate pressure was increased from 5 to 25 torr for both membranes. The amount of water in the permeate decreased exponentially as the permeate pressure was increased, but increased linearly with increasing temperature. Optimum conditions for flux and selectivity are at low permeate pressure and high feed temperature. When a small amount of salt is added to the feed solution, an increase in flux is observed. Overall models for flux and permeate concentration were created from the experimental data. The models were used to predict scale-up performance in separating an azeotropic feed waste to produce dehydrated THF solvent for reuse and a permeate stream with a dilute THF concentration.

  15. Adsorptive separation of xenon/krypton mixtures using a zirconium-based metal-organic framework with high hydrothermal and radioactive stabilities.

    PubMed

    Lee, Seung-Joon; Yoon, Tae-Ung; Kim, Ah-Reum; Kim, Seo-Yul; Cho, Kyung-Ho; Hwang, Young Kyu; Yeon, Jei-Won; Bae, Youn-Sang

    2016-12-15

    The separation of xenon/krypton mixtures is important for both environmental and industrial purposes. The potential of three hydrothermally stable MOFs (MIL-100(Fe), MIL-101(Cr), and UiO-66(Zr)) for use in Xe/Kr separation has been experimentally investigated. From the observed single-component Xe and Kr isotherms, isosteric heat of adsorption (Qst(o)), and IAST-predicted Xe/Kr selectivities, we observed that UiO-66(Zr) has the most potential as an adsorbent among the three candidate MOFs. We performed dynamic breakthrough experiments with an adsorption bed filled with UiO-66(Zr) to evaluate further the potential of UiO-66(Zr) for Xe/Kr separation under mixture flow conditions. Remarkably, the experimental breakthrough curves show that UiO-66(Zr) can efficiently separate the Xe/Kr mixture. Furthermore, UiO-66(Zr) maintains most of its Xe and Kr uptake capacity, as well as its crystallinity and internal surface area, even after exposure to gamma radiation (2kGy) for 7h and aging for 16 months under ambient conditions. This result indicates that UiO-66(Zr) can be considered to be a potential adsorbent for Xe/Kr mixtures under both ambient and radioactive conditions.

  16. 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.

  17. Activation of the aryl hydrocarbon receptor is the major toxic mode of action of an organic extract of a reference urban dust particulate matter mixture: the role of polycyclic aromatic hydrocarbons.

    PubMed

    Andrysík, Zdeněk; Vondráček, Jan; Marvanová, Soňa; Ciganek, Miroslav; Neča, Jiří; Pěnčíková, Kateřina; Mahadevan, Brinda; Topinka, Jan; Baird, William M; Kozubík, Alois; Machala, Miroslav

    2011-09-01

    Many of the toxic and carcinogenic effects of urban air pollution have been linked to polycyclic aromatic hydrocarbons (PAHs) adsorbed to airborne particulate matter (PM). The carcinogenic properties of PAHs in complex organic mixtures derived from PM have been chiefly attributed to their mutagenicity. Nevertheless, PAHs are also potent activators of the aryl hydrocarbon receptor (AhR), which may contribute to their nongenotoxic effects, including tumor promotion. As the genotoxicity of carcinogenic PAHs in complex mixtures derived from urban PM is often inhibited by other mixture constituents, the AhR-mediated activity of urban PM extracts might significantly contribute to the carcinogenic activity of such mixtures. In the present study, we used an organic extract of the urban dust standard reference material, SRM1649a, as a model mixture to study a range of toxic effects related to DNA damage and AhR activation. Both the organic extract and its neutral aromatic fraction formed a low number of DNA adducts per nucleotide in the liver epithelial WB-F344 cells model, without inducing DNA damage response, such as tumor suppressor p53 activation and apoptosis. In contrast, we found that this extract, as well as its neutral and polar fractions, were potent inducers of a range of AhR-mediated responses, including induction of the AhR-mediated transcription, such as cytochrome P450 1A1/1B1 expression, and the AhR-dependent cell proliferation. Importantly, these toxic events occurred at doses one order of magnitude lower than DNA damage. The AhR-mediated activity of the neutral fraction was linked to PAHs and their derivatives, as polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls were only minor contributors to the overall AhR-mediated activity. Taken together, our data suggest that more attention should be paid to the AhR-dependent nongenotoxic events elicited by urban PM constituents, especially PAHs and their derivatives. Copyright © 2011 Elsevier B.V. All

  18. 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

  19. Two- and three-dimensional van krevelen diagrams: a graphical analysis complementary to the kendrick mass plot for sorting elemental compositions of complex organic mixtures based on ultrahigh-resolution broadband fourier transform ion cyclotron resonance mass measurements.

    PubMed

    Wu, Zhigang; Rodgers, Ryan P; Marshall, Alan G

    2004-05-01

    Ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry has resolved and identified the elemental compositions of over 10000 organic constituents of coal and petroleum crude oil. A plot of Kendrick mass defect versus Kendrick nominal mass sorts compounds into homologous series according to compound class (i.e., numbers of N, O, and S heteroatoms), type (number of rings plus double bonds), and degree of alkylation (number of CH(2) groups), to yield unique elemental assignments from ultrahigh-resolution mass measurements in the 200-900 Da range. Interpretation of such a vast compilation requires a simple (preferably graphical) means to differentiate between complex organic mixtures of different origin or processing. In an extension of the recently revived van Krevelen plot, each elemental composition is projected onto two or three axes according to its H/C, O/C, and/or N/C atomic ratios. The H/C ratio separates compounds according to degree of saturation, whereas O/C or N/C ratios separate according to O and N classes. We show that the three-dimensional van Krevelen diagram can completely separate different classes in pyridine-extracted coal or petroleum samples and can also graphically distinguish fossil fuels according to their nature (coal vs petroleum), maturation (coals of different rank), and processing (the same coal at two stages of liquefaction). The van Krevelen diagram thus appears well suited to amplifying and exposing compositional differences within and between complex organic mixtures.

  20. 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).

  1. 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.

  2. 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.

  3. 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.

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

    PubMed

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

    2015-09-01

    Individuals, typically, are exposed to mixtures of environmental xenobiotics affecting multiple organs and acting through different xenosensors and pathways in species and cell-type specific manners. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and α-endosulfan are Persistent Organic Pollutants (POPs) and endocrine disruptors which act through different xenosensors and accumulate in the liver. Our objective in this HEALS study was to investigate the effects of the mixture of these POPs on gene expression in a human-derived hepatocyte cell line, HepaRG. We found that, in spite of having largely uncorrelated effects, TCDD and α-endosulfan, when mixed, alter the expression of genes. The combined effects of the mixture of the POPs significantly altered the expression of 100 genes (42 up- and 58 down-regulated) whereas the same concentration of either POP alone did not alter significantly the expression of these genes. For 32 other genes, selective inhibitory crosstalk between TCDD and α-endosulfan was observed. One of the POPs inhibited the effect, on gene expression, of the other in the mixture although, when used alone, that POP did not affect expression. The expression of another 82 genes was significantly altered (up- or down-regulated) by a single POP. The addition of the second POP either increased, in the same direction, the effect on gene expression or had no further effect. At low concentrations (0.2 nM TCDD and 1 μM α-endosulfan), the POPs still had significant effects and the levels of expression of the corresponding proteins were found to be affected for some genes. Particularly striking was the 80-90% inhibition, by the mixture, of the expression of a number of genes of several hepatic intermediary metabolic pathways (glycerolipid metabolism, FXR/RXR activation, glycolysis/gluconeogenesis, retinoid and bile acid biosynthesis), whereas each pollutant alone had only a moderate effect. Copyright © 2015 Elsevier B.V. and Société Française de Biochimie

  5. Contributions of toluene and alpha-pinene to SOA formed in an irradiated toluene/alpha-pinene/NO(x)/ air mixture: comparison of results using 14C content and SOA organic tracer methods.

    PubMed

    Offenberg, John H; Lewis, Charles W; Lewandowski, Michael; Jaoui, Mohammed; Kleindienst, Tadeusz E; Edney, Edward O

    2007-06-01

    An organic tracer method, recently proposed for estimating individual contributions of toluene and alpha-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydrocarbon, toluene, and the biogenic monoterpene, alpha-pinene, was irradiated in air in the presence of NO(x) to form SOA. The contributions of toluene and alpha-pinene to the total SOA concentration, calculated using the organic tracer method, were compared with those obtained with a more direct 14C content method. In the study, SOA to SOC ratios of 2.07 +/- 0.08 and 1.41 +/- 0.04 were measured for toluene and (alpha-pinene SOA, respectively. The individual tracer-based SOA contributions of 156 microg m(-3) for toluene and 198 microg m(-)3 for alpha-pinene, which together accounted for 82% of the gravimetrically determined total SOA concentration, compared well with the 14C values of 182 and 230 microg m(-3) measured for the respective SOA precursors. While there are uncertainties associated with the organic tracer method, largely due to the chemical complexity of SOA forming chemical mechanisms, the results of this study suggest the organic tracer method may serve as a useful tool for determining whether a precursor hydrocarbon is a major SOA contributor.

  6. 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...

  7. Crystallization using reverse micelles and water-in-oil microemulsion systems: the highly selective tool for the purification of organic compounds from complex mixtures.

    PubMed

    Kljajic, Alen; Bester-Rogac, Marija; Klobcar, Andrej; Zupet, Rok; Pejovnik, Stane

    2013-02-01

    The active pharmaceutical ingredient orlistat is usually manufactured using a semi-synthetic procedure, producing crude product and complex mixtures of highly related impurities with minimal side-chain structure variability. It is therefore crucial for the overall success of industrial/pharmaceutical application to develop an effective purification process. In this communication, we present the newly developed water-in-oil reversed micelles and microemulsion system-based crystallization process. Physiochemical properties of the presented crystallization media were varied through surfactants and water composition, and the impact on efficiency was measured through final variation of these two parameters. Using precisely defined properties of the dispersed water phase in crystallization media, a highly efficient separation process in terms of selectivity and yield was developed. Small-angle X-ray scattering, high-performance liquid chromatography, mass spectrometry, and scanning electron microscopy were used to monitor and analyze the separation processes and orlistat products obtained. Typical process characteristics, especially selectivity and yield in regard to reference examples, were compared and discussed. Copyright © 2012 Wiley Periodicals, Inc.

  8. 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...

  9. 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...

  10. Mixtures research at NIEHS: an evolving program.

    PubMed

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

    2013-11-16

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

  11. 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

  12. Two-phase spray cooling with water/2-propanol binary mixtures for high heat flux focal source

    NASA Astrophysics Data System (ADS)

    Obuladinne, Sai Sujith

    with a plain, smooth surface. A cylindrical copper block, with a matching size square protrusion attached onto the back side of the test section, generates heat using cartridge heaters and simulates high heat flux source. Embedded thermocouples are used to determine the spray surface temperature. The working fluid, water/alcohol mixture, has various concentration levels of 2-propanol by mass fraction 0.0 (pure water), 0.25, 0.50, 0.879 (azeotrope) and 1.0 (pure alcohol)), representing both non-azeotropic and azeotropic cases. Spray cooling tests are performed with a constant flow rate of 5.6 ml/cm2.s at subcooled temperatures ( 20°C) and atmospheric pressure. Experimental procedure involves controlling the heat flux in increasing steps, and recording the corresponding steady-state temperatures to obtain cooling curves in the form of surface superheat vs. heat flux. The second part of the study investigates an advanced heat spreader design for thermal management of a high heat flux focal source. The heat spreader comprises of three layers: a copper layer that interfaces with the heat source, a high and directional thermal conductivity material (such as CVD diamond and Pyrolytic graphite) layer, and another copper layer that is exposed to two-phase spray cooling. The analysis applies various heat fluxes on the heat source side and the experimentally obtained heat transfer coefficients on the spray side of the spreader design to determine the temperature and heat flux distributions, and examine the potential capabilities of this configuration.

  13. 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

  14. 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.

  15. A comparison of four porewater sampling methods for metal mixtures and dissolved organic carbon and the implications for sediment toxicity evaluations.

    PubMed

    Cleveland, Danielle; Brumbaugh, William G; MacDonald, Donald D

    2017-06-09

    Evaluations of sediment quality conditions are commonly conducted using whole-sediment chemistry analyses but can be enhanced by evaluating multiple lines of evidence, including measures of the bioavailable forms of contaminants. In particular, porewater chemistry data provide information that is directly relevant for interpreting sediment toxicity data. Various methods for sampling porewater for trace metals and dissolved organic carbon (DOC), which is an important moderator of metal bioavailability, have been employed. The present study compares the peeper, push point, centrifugation, and diffusive gradients in thin films (DGT) methods for the quantification of 6 metals and DOC. The methods were evaluated at low and high concentrations of metals in 3 sediments having different concentrations of total organic carbon and acid volatile sulfide and different particle-size distributions. At low metal concentrations, centrifugation and push point sampling resulted in up to 100 times higher concentrations of metals and DOC in porewater compared with peepers and DGTs. At elevated metal levels, the measured concentrations were in better agreement among the 4 sampling techniques. The results indicate that there can be marked differences among operationally different porewater sampling methods, and it is unclear if there is a definitive best method for sampling metals and DOC in porewater. Environ Toxicol Chem 2017;9999:1-10. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America. Published 2017 Wiley Periodicals Inc., on behalf of SETAC.

  16. Isolation of polychlorinated dibenzodioxins and polychlorinated dibenzofurans from a complex organic mixture by two-step liquid chromatographic fractionation for quantitative analysis

    SciTech Connect

    Tong, H.Y.; Shore, D.L.; Karasek, F.W.

    1984-11-01

    Polychlorinated dibenzodioxins (PCDD) and polychlorinated dibenzofurans (PCDF) are present with several hundred organic compounds in raw fly ash extract. A first-step normal-phase semipreparative high-pressure liquid chromatography (HPLC) fractionation with a three-solvent gradient elution program separates PCDD and PCDF into a single fraction with about 100 other components. The PCDD and PCDF in this fraction are further isolated from the accompanying compounds by a second-step HPLC fractionation using a reverse-phase semipreparative column and a two-solvent gradient elution program. The distribution of PCDD and PCDF into five subfractions facilitates isomer identification and their quantitation. The separation of PCDD and PCDF by this procedure shows high recovery and good reproducibility.

  17. Neurotoxicity of Metal Mixtures.

    PubMed

    Andrade, V M; Aschner, M; Marreilha Dos Santos, A P

    2017-01-01

    Metals are the oldest toxins known to humans. Metals differ from other toxic substances in that they are neither created nor destroyed by humans (Casarett and Doull's, Toxicology: the basic science of poisons, 8th edn. McGraw-Hill, London, 2013). Metals are of great importance in our daily life and their frequent use makes their omnipresence and a constant source of human exposure. Metals such as arsenic [As], lead [Pb], mercury [Hg], aluminum [Al] and cadmium [Cd] do not have any specific role in an organism and can be toxic even at low levels. The Substance Priority List of Agency for Toxic Substances and Disease Registry (ATSDR) ranked substances based on a combination of their frequency, toxicity, and potential for human exposure. In this list, As, Pb, Hg, and Cd occupy the first, second, third, and seventh positions, respectively (ATSDR, Priority list of hazardous substances. U.S. Department of Health and Human Services, Public Health Service, Atlanta, 2016). Besides existing individually, these metals are also (or mainly) found as mixtures in various parts of the ecosystem (Cobbina SJ, Chen Y, Zhou Z, Wub X, Feng W, Wang W, Mao G, Xu H, Zhang Z, Wua X, Yang L, Chemosphere 132:79-86, 2015). Interactions among components of a mixture may change toxicokinetics and toxicodynamics (Spurgeon DJ, Jones OAH, Dorne J-L, Svendsen C, Swain S, Stürzenbaum SR, Sci Total Environ 408:3725-3734, 2010) and may result in greater (synergistic) toxicity (Lister LJ, Svendsen C, Wright J, Hooper HL, Spurgeon DJ, Environ Int 37:663-670, 2011). This is particularly worrisome when the components of the mixture individually attack the same organs. On the other hand, metals such as manganese [Mn], iron [Fe], copper [Cu], and zinc [Zn] are essential metals, and their presence in the body below or above homeostatic levels can also lead to disease states (Annangi B, Bonassi S, Marcos R, Hernández A, Mutat Res 770(Pt A):140-161, 2016). Pb, As, Cd, and Hg can induce Fe, Cu, and Zn

  18. 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.

  19. Toxicity of individual pharmaceuticals and their mixtures to Aliivibrio fischeri: Experimental results for single compounds and considerations of their mechanisms of action and potential acute effects on aquatic organisms.

    PubMed

    Di Nica, Valeria; Villa, Sara; Finizio, Antonio

    2017-03-01

    In the first part of a broader study on the effects of individual and multicomponent mixtures of pharmaceutical active compounds, the authors used the Microtox(®) test system to analyze in detail the effects of 10 widely used human and veterinary pharmaceutical active compounds toward the bioluminescent bacterium Aliivibrio fischeri. The experimental results indicated moderate toxicity for the majority of the tested compounds. Comparison between experimental 50% inhibitory concentrations and those predicted from the quantitative structure-activity relationship models indicated that most of the tested pharmaceutical active compounds behave as polar narcotic compounds toward A. fischeri (only the antibiotic chlortetracycline seemed to have a specific mechanism of action). A comparison between the experimental results and a collection of acute toxicity data on other nontarget organisms indicated that in general A. fischeri has a comparable sensitivity to other aquatic species. However, according to the Globally Harmonized System of Classification and Labelling of Chemicals, the majority of the investigated chemicals can be classified as harmful or nontoxic for aquatic ecosystems. Finally, based on comparisons among the 95th percentile of measured environmental concentrations found in European Union water bodies and acute toxicity data on various aquatic organisms, no risk to aquatic life exists when the tested pharmaceutical active compounds are assessed as individual chemicals. Environ Toxicol Chem 2017;36:807-814. © 2016 SETAC.

  20. 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)

  1. Organizers.

    ERIC Educational Resources Information Center

    Callison, Daniel

    2000-01-01

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

  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. Organizers.

    ERIC Educational Resources Information Center

    Callison, Daniel

    2000-01-01

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

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. Plasma etchant mixture

    SciTech Connect

    Zafiropoulo, A.W.; Mayer, J.A. Jr.

    1984-09-25

    Method and apparatus for masked etching of a polysilicon surface layer or film to expose a dielectric underlying layer or film on a semiconductor material using ion bombardment from an ionized mixture of a fluorine based gas with a chlorine or bromine containing gas. A particularly useful gas is a mixture of sulfur hexafluoride and Freon 115 gases (C/sub 2/C1F/sub 5/). The mixture of gases achieves the result of highly selective etching through the polysilicon film without significantly attacking the underlying dielectric film and without significant undercutting in the polysilicon film or etching of the masking layer.

  9. SEPARATION OF FLUID MIXTURES

    DOEpatents

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

    1958-10-28

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

  10. Carbonaceous materials water mixtures

    SciTech Connect

    Papalos, J.G.; Sinka, J.V.

    1985-04-30

    Particulate carbonaceous materials water mixtures are prepared by adding a condensate which is a condensation product of an aldehyde having from about 1 to about 7 carbon atoms, a benzene derivative such as benzene sulfonic acid, an alkyl benzene sulfonic acid having at least one alkyl group of from about 1 to about 20 carbon atoms and mixtures thereof, and optionally, and a naphthalene derivative such as naphthalene sulfonic acid, an alkyl naphthalene sulfonic acid having at least one alkyl group of from about 1 to about 12 carbon atoms and mixtures thereof. The condensate is added in an amount sufficient to reduce viscosity of the water mixture of carbonaceous materials, to stabilize carbonaceous materials in the water network and to improve pumpability. An acid form of the condensate or a salt may be added.

  11. Condensate Mixtures and Tunneling

    SciTech Connect

    Timmermans, E.

    1998-09-14

    The experimental study of condensate mixtures is a particularly exciting application of the recently developed atomic-trap Bose-Einstein condensate (BEC) technology: such multiple condensates represent the first laboratory systems of distinguishable boson superfluid mixtures. In addition, as the authors point out in this paper, the possibility of inter-condensate tunneling greatly enhances the richness of the condensate mixture physics. Not only does tunneling give rise to the oscillating particle currents between condensates of different chemical potentials, such as those studied extensively in the condensed matter Josephson junction experiments, it also affects the near-equilibrium dynamics and stability of the condensate mixtures. In particular, the stabilizing influence of tunneling with respect to spatial separation (phase separation) could be of considerable practical importance to the atomic trap systems. Furthermore, the creation of mixtures of atomic and molecular condensates could introduce a novel type of tunneling process, involving the conversion of a pair of atomic condensate bosons into a single molecular condensate boson. The static description of condensate mixtures with such type of pair tunneling suggests the possibility of observing dilute condensates with the liquid-like property of a self-determined density.

  12. Physical properties of fluorinated propane and butane derivatives and the vapor pressure of R-245ca/338mccq mixtures as R-11 alternatives

    SciTech Connect

    Beyerlein, A.L.; DesMarteau, D.D.; Xie, Y.; Naik, K.N.

    1996-11-01

    Two new fluorinated propane derivatives, six new fluorinated butane derivatives,and the R-245ca(HCF{sub 2}CF{sub 2}CH{sub 2}F)/338mccq(CF{sub 3}CF{sub 2}CH{sub 2}CH{sub 2}F) mixtures are investigated as R-11 alternatives. The investigations on the pure chemicals included measurements of the melting point, boiling point, vapor pressure below the boiling point, heat of vaporization at the boiling point, saturated liquid density, and critical properties (temperature and density). Four of the butane derivatives--R-338mcfm, R-356mffm, R-356mecs, and R-356mms--have boiling points comparable to that of R-11 and have potential as far-term R-11 alternatives. The vapor pressures of the R-245ca/338mccq mixtures were measured over the entire concentration range for temperatures ranging from 25 C (77 F) to 135 C (275 F). The mixtures form an azeotrope at 0.64 R-245ca mole fraction with a normal boiling point of 22.6 C (72.7 F).

  13. 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

    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.

  14. Characterization of the thermotropic behavior and lateral organization of lipid-peptide mixtures by a combined experimental and theoretical approach: effects of hydrophobic mismatch and role of flanking residues.

    PubMed Central

    Morein, Sven; Killian, J Antoinette; Sperotto, Maria Maddalena

    2002-01-01

    A combined experimental and theoretical study was performed on a series of mixtures of dipalmitoylphosphatidylcholine (DPPC) and synthetic peptides to investigate their thermotropic behavior and lateral organization. The experimental study was based on differential scanning calorimetry (DSC) and phosphorous nuclear magnetic resonance ((31)P-NMR) techniques; the theoretical study was based on calculations on a microscopic molecular interaction model, where the lipid-peptide interaction is built on the hydrophobic matching principle. The chosen peptides, WALP and KALP, consist of a hydrophobic stretch, of variable length, of alternating leucine and alanine residues, flanked on both ends with tryptophan and lysine residues, respectively. By systematically varying the peptide hydrophobic length it was thus possible to explore different matching conditions between the peptide's hydrophobic length and the lipid bilayer hydrophobic thickness, and to investigate the potential role of flanking residues. The results show that both the WALP and the KALP peptides tend to favor the liquid-crystalline (or fluid) phase of the system; i.e., they tend to depress the main-transition temperature, T(m), of pure DPPC. However, the detailed effects of both peptides on the lateral phase behavior of the lipid-peptide system are dependent on the peptide length and the type of flanking residues. The results suggest that below T(m), the shortest among the WALP and KALP peptides induce gel-fluid phase separation in the system within an extensive temperature-composition region. The longer the hydrophobic length of the peptides is, the more narrow this region appears to become. PMID:11867456

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

    NASA Astrophysics Data System (ADS)

    Kim, Namil

    mixtures underwent phase separation. As the crystalline and nematic ordering of monomeric unit was frozen, LMWLC was dispersed in the continuum of isotropic or anisotropic networks. Phase diagram exhibited the broad immiscible regions. The phase diagram of annealed hyperbranched polymer/LMWLC mixtures was an upper azeotrope, exhibiting the coexistence of nematic + isotropic phase above the clearing temperature of neat LMWLC. With decreasing temperature a focal-conic fan shaped texture developed in the composition range of 63~93 wt %, suggestive of induced smectic phase in the mixture.

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

    NASA Astrophysics Data System (ADS)

    Brouet, Yann; Levasseur-Regourd, Anny-Chantal; Sabouroux, Pierre; Neves, Luisa; Encrenaz, Pierre; Poch, Olivier; Pommerol, Antoine; Thomas, Nicolas; Kofman, Wlodek; Le Gall, Alice; Ciarletti, Valérie; Hérique, Alain; Lethuillier, Anthony

    2016-10-01

    The CONSERT bistatic radar on Rosetta and Philae sounded the interior of the small lobe of 67P/C-G at 90 MHz and determined the average of the real part of the complex permittivity (hereafter ɛ') to be equal to 1.27±0.05 [1,2]. The permittivity probe (PP) of the SESAME package sounded the near-surface in the 400-800 Hz range and derived a lower limit of ɛ' equal to 2.45±0.20 [3,4]. At the time of the measurements, the temperature was found to be below 150 K at Philae's location and expected to be close or below 100 K inside the nucleus [4-6].The complex permittivity depends of the frequency, the composition, the porosity and the temperature of the material [7,8,9]. These parameters have to be taken into account to interpret the permittivity values. The non-dispersive behavior of ɛ' below 150 K [9], allows us to compare the CONSERT and SESAME-PP results and to interpret their difference in terms of porosity and/or composition. For this purpose we use a semi-empirical formula obtained from reproducible permittivity measurements performed in the laboratory at 243 K on water ice particles and ice-basaltic dust mixtures [10], with a controlled porosity in the 26-91% range and dust-to-ice volumetric ratios in the 0.1-2.8 range. The influence of the presence of organic materials on ɛ' is also discussed based on new measurements of analogues of complex extraterrestrial organic matter [11]. Our results suggest an increase of the porosity of the small lobe of 67P with depth [11], in agreement Lethuillier et al. [4]'s conclusion using a different method.[1]Kofman et al., 1998. Adv. Space Res., 21, 1589.[2]Ciarletti et al., 2015. A&A, 583, A40.[3]Seidensticker et al., 2007. Space Sci. Rev., 128, 301.[4]Lethuillier et al., 2016. A&A, 591, A32.[5]Spohn et al., 2015. Science, 349, aab0464.[6]Festou et al. (Eds.), Comets II. Univ. of Arizona Press.[7]Campbell and Ulrichs, 1969. J. Geophys. Res., 74, 5867.[8]Brouet et al., 2015. A&A, 583, A39.[9]Mattei et al., 2014. Icarus

  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

  18. The influence of white and blue silica gels as adsorbents in adsorptive-distillation of ethanol-water mixture

    NASA Astrophysics Data System (ADS)

    Megawati, Jannah, Reni Ainun; Rahayuningtiyas, Indi

    2017-01-01

    This research studied the difference of white and blue silica gels when used as an adsorbent for ethanol purification that is processed via Adsorptive-Distillation (AD) at 1 atm pressure. The effect of process duration to purification process is also recorded and studied to evaluate the performance of designed AD equipment. The experiment was conducted using boiling flask covered with a heating mantle and the temperature was maintained at 78°C. The vapour flowed into the adsorbent column and was condensed using water as a cooling medium. The initial ethanol concentration was 90.8% v/v and volume was 300 mL. Experiment shows that designed AD equipment could be used to purify ethanol. The average vapour velocity was about 39.29 and 45.91 m/s for white and blue silica gels, respectively, which is considered very high. Therefore the saturated adsorption could not be obtained. Highest ethanol concentration achieved using white silica gel is about 96.671% v/v after 50 minutes. Thus AD with white silica gel showed good performance and passed azeotropic point. But AD with blue silica gel showed a different result, the adsorption of blue silica gel failed to break the azeotropic point. The outlet average water concentration for white and blue silica gels is 3.54 and 3.42 mole/L. Based on the weight ratio of adsorbed water per adsorbent, at 55th minutes of time; this ratio of blue silica gel is about 0.053 gwater/gads. The time required by the blue silica to achieve 0.5 wwater-adsorbed/wwater-initial is 45 minutes, and the average outlet water concentration is 3.42 mole/L. Meanwhile, the time required by a white silica to complete 0.5 wwater-adsorbed/wwater-initial is 35 minutes, and the average outlet water level is 3.54 mole/L. Based on the results, the blue silica as an adsorbent for AD of ethanol-water mixture is better than white silica gel.

  19. Transport in superfluid mixtures

    NASA Astrophysics Data System (ADS)

    Geracie, Michael

    2017-04-01

    We present a general method for constructing effective field theories for nonrelativistic superfluids, generalizing the previous approaches of Greiter, Witten, and Wilczek, and Son and Wingate to the case of several superfluids in solution. We investigate transport in mixtures with broken parity and find a parity-odd "Hall drag" in the presence of independent motion as well as a pinning of mass, charge, and energy to sites of nonzero relative velocity. Both effects have a simple geometric interpretation in terms of the signed volumes and directed areas of various subcomplexes of a "velocity polyhedron": the convex hull formed by the end points of the velocity vectors of a superfluid mixture. We also provide a simple quasi-one-dimensional model that exhibits nonzero Hall drag.

  20. Critical dynamics in mixtures

    NASA Astrophysics Data System (ADS)

    Folk, R.; Moser, G.

    1998-11-01

    We derive the nonasymptotic expressions for the frequency- and temperature-dependent sound velocity and sound absorption near a critical point in a mixture within renormalization group theory in one-loop order. The dynamic model considered is an extension of the corresponding model for pure fluids including concentration fluctuations. The theoretical result for the complex sound velocity is the same as at consolute points and gas-liquid critical points reflecting universality. Differences observed in the experiments at the two critical points mentioned are due to the different behavior of the sound velocity at Tc, which is finite in mixtures and zero in pure fluids, as well as due to nonasymptotic effects. Near the consolute point we compare our result with the phenomenological theory of Ferrell and Bhattacharjee [Phys. Rev. B 24, 4095 (1981); Phys. Rev. A 31, 1788 (1985)] and near the gas-liquid critical point with experiments in the 3He-4He mixture. A genuine dynamic parameter not considered so far and related to the critical enhancement of the thermal conductivity appears in the nonasymptotic expressions of the transport coefficients and the complex sound velocity. All nonuniversal background parameters of the complex sound velocity are fixed by a comparison of the corresponding theoretical expressions for the transport coefficients with experiments.

  1. Toxicology of complex mixtures of indoor air pollutants

    SciTech Connect

    Lewtas, J.

    1989-01-01

    This review focuses on strategies for assessing the toxicology of indoor air pollutant mixtures. These strategies are illustrated by reviewing the current problems and approaches to the toxicology of indoor air pollutants from three indoor source categories that make a major contribution to human exposure: environmental tobacco smoke, combustion emissions, and volatile organic compound (VOC) mixtures from materials and products. The strategies include assessment of: exposure and dosimetry, toxic effects of mixtures, causative agents in mixtures, and the predictability of toxicology from one mixture to another. Case studies from indoor air pollution are used to illustrate these strategies. Environmental tobacco smoke research on exposure and dosimetry illustrates new methods using biological markers. Unvented combustion sources such as kerosene heaters emit genotoxic incomplete combustion products and recent research is focused on identifying the genotoxic (causative) agents in these mixtures.

  2. Prevalence Incidence Mixture Models

    Cancer.gov

    The R package and webtool fits Prevalence Incidence Mixture models to left-censored and irregularly interval-censored time to event data that is commonly found in screening cohorts assembled from electronic health records. Absolute and relative risk can be estimated for simple random sampling, and stratified sampling (the two approaches of superpopulation and a finite population are supported for target populations). Non-parametric (absolute risks only), semi-parametric, weakly-parametric (using B-splines), and some fully parametric (such as the logistic-Weibull) models are supported.

  3. 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.

  4. 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.

  5. Effect of stirring on the safety of flammable liquid mixtures.

    PubMed

    Liaw, Horng-Jang; Gerbaud, Vincent; Chen, Chan-Cheng; Shu, Chi-Min

    2010-05-15

    Flash point is the most important variable employed to characterize fire and explosion hazard of liquids. The models developed for predicting the flash point of partially miscible mixtures in the literature to date are all based on the assumption of liquid-liquid equilibrium. In real-world environments, however, the liquid-liquid equilibrium assumption does not always hold, such as the collection or accumulation of waste solvents without stirring, where complete stirring for a period of time is usually used to ensure the liquid phases being in equilibrium. This study investigated the effect of stirring on the flash-point behavior of binary partially miscible mixtures. Two series of partially miscible binary mixtures were employed to elucidate the effect of stirring. The first series was aqueous-organic mixtures, including water+1-butanol, water+2-butanol, water+isobutanol, water+1-pentanol, and water+octane; the second series was the mixtures of two flammable solvents, which included methanol+decane, methanol+2,2,4-trimethylpentane, and methanol+octane. Results reveal that for binary aqueous-organic solutions the flash-point values of unstirred mixtures were located between those of the completely stirred mixtures and those of the flammable component. Therefore, risk assessment could be done based on the flammable component flash-point value. However, for the assurance of safety, it is suggested to completely stir those mixtures before handling to reduce the risk. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  6. 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.

  7. Detection of heteroquality taste mixtures.

    PubMed

    Stevens, J C

    1995-01-01

    Detection thresholds were measured for sweet (sucrose), salty (sodium chloride), sour (citric acid), and bitter (quinine hydrochloride) and for the 11 possible mixtures of these four substances. These 11 mixtures (6 binary, 4 ternary, and 1 quaternary) all turned out to be stimulus additive, in the sense that a person could reliably detect mixtures whose individual components are weaker than their unmixed thresholds. Tastants too weak to be perceived alone can thus make impact when in mixtures. The threshold concentration for a given compound was reduced in approximate proportion to the number of compounds added to it. This liberal heteroquality additivity contests the widespread belief that heteroquality mixtures (different chemicals evoking different qualities) are non-additive and homoquality mixtures (different chemicals evoking the same quality) are additive. Heteroquality additivity emerges on appropriate definition of the subject's task by forced choice (unavailable to earlier investigators), in order to skirt methodological pitfalls. Operating together, homo- and heteroquality additivity may concomitantly enable a person to sense natural mixtures of hosts of weak constituents, such as drinking water. In this regard, gustatory mixtures may function much as do mixtures of frequencies in audition and mixtures of gaseous compounds in olfaction.

  8. 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

  9. Mixtures and Mineral Reactions

    NASA Astrophysics Data System (ADS)

    Rumble, D.

    The monograph Mixtures and Mineral Reactions contains a large amount of information of value to mineralogists, petrologists, and geochemists. The first four chapters are a succinct account of the thermodynamic description of crystalline solutions. In these early chapters a comparison is made between different mathematical treatments of activitycomposition models, there is a discussion of the unmixing by exsolution of a single solution into two phases, and methods of computing phase equilibria in assemblages of different minerals are given. If the reader is perplexed by the discussion of standard states (cf. Figure 1.3), not to worry. That is a normal condition for anyone forced to choose between equivalent reference frames yet knowing, somewhere down the line, that the choice will ultimately make one's computational life more or less difficult.

  10. 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.

    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.

  11. 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.

  12. 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

  13. 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

  14. 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...

  15. 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...

  16. Performance of Granite Asphalt Mixture Modified by Silane Coupling Agent

    NASA Astrophysics Data System (ADS)

    Liu, Zhihang; Li, Xia; Wang, Li; Kang, Rongling

    2017-06-01

    In order to improve pavement performance of granite asphalt mixture, the surface of granite mineral powder was organic modified by silane coupling agent. The water stability and high temperature stability of the asphalt mixture were analyzed by Marshall tests, immersion Marshall test, freeze-thaw splitting test and rutting test. The results show that the mixing amount of silane coupling agent in the range from 0.5% to 2.5% can significantly improve the high temperature stability and water stability of the asphalt mixture. Taking into account the performance and economic factors, 2.0% silane coupling agent on the surface of granite filler was recommended.

  17. Continuous dielectrophoretic separation of cell mixtures.

    PubMed

    Pohl, H A; Kaler, K

    1979-03-01

    Use of stream-centered dielectrophoresis (1-4) produced continuous separations on three cell mixtures (1) Chorella vulgaris with Netrium digitus, (2) Ankistrodesmus falcatus with Staurastrum gracile, and (3) Saccharomyces cerevisiae with Netrium digitus. Maximal separations were obtained for these mixtures of live cells at 100 kHz, 600 kHz, and 2.0 MHz, respectively. The technique was restricted to a frequency range of 0.01-32 MHz, and to suspensions of low conductivity in which microorganisms such as these algae and yeast are tolerant. Extension, however, to cellular organisms requiring higher osmolarity is readily feasible through the use of nonionic solutes such as sucrose, mannose, glycine, etc.

  18. 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...

  19. 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.

  20. TEST REPORT #33: Compressor Calorimeter Test of R-410A Alternative: R-32/R-134a Mixture Using a Scroll Compressor

    SciTech Connect

    Shrestha, Som; Sharma, Vishaldeep; Abdelaziz, Omar

    2014-02-18

    This report investigates the tested performance of lower - GWP candidate refrigerant, 94.07 wt% R - 32 + 5.93 wt % R - 134 a mixture (hereafter referred to as R - 32/134a), as an alternative to baseline refrigerant R - 410 A using a 36,000 Btu/hr compressor calorimeter located at the Heat Exchanger Advanced Testing Facility at Oak Ridge National Laboratory . These tests were conducted during May and August 2013. R - 410A is a near - azeotropic blend of R - 32 and R - 125 with 0.5/0.5 mass fraction and has a GWP 100 of 2100. R - 32 and R - 134a are pure refrigerants and have GWP 100 of 716 and 1370 1, respectively. Based on the GWP 100 values of pure refrigerants and their mass fraction in the blend, GWP 100 of R - 32/134a, which is under development by National Refrigerant, is 755. This report compares various performance parameters, such as cooling capacity, compressor power, refrigerant mass flow rate, EER, isentropic efficiency and discharge temperature of the alternative refrigerant to that of R - 410 A.

  1. Nonlinearity of bituminous mixtures

    NASA Astrophysics Data System (ADS)

    Mangiafico, S.; Babadopulos, L. F. A. L.; Sauzéat, C.; Di Benedetto, H.

    2017-07-01

    This paper presents an experimental characterization of the strain dependency of the complex modulus of bituminous mixtures for strain amplitude levels lower than about 110 μm/m. A series of strain amplitude sweep tests are performed at different temperatures (8, 10, 12 and 14°C) and frequencies (0.3, 1, 3 and 10 Hz), during which complex modulus is monitored. For each combination of temperature and frequency, four maximum strain amplitudes are targeted (50, 75, 100 and 110 μm/m). For each of them, two series of 50 loading cycles are applied, respectively at decreasing and increasing strain amplitudes. Before each decreasing strain sweep and after each increasing strain sweep, 5 cycles are performed at constant maximum targeted strain amplitude. Experimental results show that the behavior of the studied material is strain dependent. The norm of the complex modulus decreases and phase angle increases with strain amplitude. Results are presented in Black and Cole-Cole plots, where characteristic directions of nonlinearity can be identified. Both the effects of nonlinearity in terms of the complex modulus variation and of the direction of nonlinearity in Black space seem to validate the time-temperature superposition principle with the same shift factors as for linear viscoelasticity. The comparison between results obtained during increasing and decreasing strain sweeps suggests the existence of another phenomenon occurring during cyclic loading, which appears to systematically induce a decrease of the norm of the complex modulus and an increase of the phase angle, regardless of the type of the strain sweep (increasing or decreasing).

  2. Kimberlites: Magmas or mixtures?

    NASA Astrophysics Data System (ADS)

    Patterson, Michael; Francis, Don; McCandless, Tom

    2009-11-01

    Although the presence of xenocrystic olivine is widely recognized in kimberlite, there is little consensus about its contribution to the existing estimates for the composition of kimberlite magma. Whole rock geochemistry is critical to the debate regarding the composition of kimberlite magma, however, it has received little attention as an indicator of diamond grade due to conventional thought that diamonds are xenocrysts unrelated to their host kimberlite. The Foxtrot kimberlite Field in Northern Québec is comprised of at least three distinct kimberlite intrusions exhibiting variation in both diamond grade and geochemistry making it an ideal suite with which to test a possible correlation between diamond grade and whole rock composition. Olivine is ubiquitous (30 to 70%) in the Foxtrot kimberlites and exhibits a restricted composition that overlaps that of olivine in harzburgite xenoliths suggesting that the majority of olivine is xenocrystic. Carbonate is also abundant (8 to 35%) in the Foxtrot kimberlites and exhibits magmatic textures requiring that carbon be considered in any petrogenetic model for the Foxtrot kimberlites. Pearce element ratio analysis assuming P as a conserved element indicates that much of the major element variation in the Foxtrot kimberlites can be explained by variable amounts of olivine and orthopyroxene in proportions (~ 80/20), similar to that of cratonic mantle xenoliths. The xenocrystic nature of olivine requires that the contribution of mantle harzburgite must be removed to constrain the composition of the magma. The calculated magma composition that results from the mathematical removal of olivine and orthopyroxene (80/20) from the whole rock compositions is significantly poorer in MgO (15 wt.%) and silica (~ 24 wt.%), but CO 2 rich (~ 17 wt.%) compared to previous estimates for kimberlite magma. The Foxtrot kimberlites are best modelled as mixtures of harzburgite mantle and a relatively carbonate-rich magma. According to this

  3. Some results on Gaussian mixtures

    NASA Astrophysics Data System (ADS)

    Felgueiras, Miguel; Santos, Rui; Martins, João Paulo

    2014-10-01

    We investigate Gaussian mixtures with independent components, whose parameters are numerically estimated. A decomposition of a Gaussian mixture is presented when the components have a common variance. We introduce a shifted and scaled t-Student distribution as an approximation for the distribution of Gaussian mixtures when their components have a common mean and develop a hypothesis test for testing the equality of the components means. Finally, we analyse the fitness of the approximate model to the logarithmic daily returns of the Portuguese stock index PSI-20.

  4. 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.

  5. Bridging environmental mixtures and toxic effects

    PubMed Central

    Allan, Sarah E.; Smith, Brian W.; Tanguay, Robert L.; Anderson, Kim A.

    2012-01-01

    BRIDGES is a bioanalytical tool that combines passive sampling with the embryonic zebrafish developmental toxicity bioassay to provide a quantitative measure of the toxicity of bioavailable complex mixtures. Passive sampling devices (PSDs), which sequester and concentrate bioavailable organic contaminants from the environment, were deployed in the Willamette and Columbia Rivers within and outside of the Portland Harbor Superfund site in Portland, Oregon. Six sampling events were conducted in the summer and fall of 2009 and 2010. PSD extracts were analyzed for polycyclic aromatic hydrocarbon (PAH) compounds and screened for 1201 chemicals of concern using deconvolution reporting software. The developmental toxicity of the extracts was analyzed using the embryonic zebrafish bioassay. BRIDGES provided site-specific, temporally resolved information about environmental contaminant mixtures and their toxicity. Multivariate modeling approaches were applied to paired chemical and toxic effects data sets to help unravel chemistry-toxicity associations. Modeling demonstrated a significant correlation between PAH concentrations and the toxicity of the samples and identified a subset of PAH analytes that were the most highly correlated with observed toxicity. Although this research highlights the complexity of discerning specific bioactive compounds in complex mixtures, it demonstrates methods for associating toxic effects with chemical characteristics of environmental samples. PMID:23001962

  6. Critical sound propagation in mixtures

    NASA Astrophysics Data System (ADS)

    Folk, R.; Moser, G.

    1998-01-01

    We calculate critical effects in the sound propagation in mixtures near consolute or plait points within a non-asymptotic renormalization group theory and derive general expressions for the frequency-dependent sound velocity and sound attenuation. The critical non-asymptotic time scale in the sound mode in mixtures is set by an effective order parameter Onsager coefficient containing a dynamical parameter related to the enhancement of the thermal conductivity in the mixture, not considered so far. The differences in the critical behavior near the consolute and plait point are due to the different non-asymptotic behavior of the zero-frequency sound velocity. We compare our predictions for the sound velocity and sound absorption near the plait point in 3He-4He mixtures.

  7. Risk assessment of complex mixtures: Polynuclear aromatic hydrocarbons

    SciTech Connect

    Chaloupka, K.; Harper, N.; Steinberg, M.; Safe, S.; Rodriguez, L.V.; Goldstein, L.S.

    1994-12-31

    Complex mixtures of polynuclear aromatic hydrocarbons (PAHs) are organic combustion products and are components of creosote and oily wastes which have been identified in a large number of hazardous chemical waste sites. Risk assessment of PAH mixtures must take into account the toxicity or carcinogenicity of the individual compounds and their possible additive or nonadditive interactive effects. A reconstituted PAH mixture which resembled manufactured gas plant PAH residues was prepared using 16 different compounds and the immunotoxicity and monooxygenase induction activity of the 2-ring, 3-ring and {ge} 4-ring PAHs were compared to that observed for the reconstituted mixtures in B6C3F1 mice. The results showed that the reconstituted mixture inhibited the splenic plaque-forming cell response to T-cell dependent and independent antigens and induced hepatic microsomal ethoxyresorufin O-deethylase activity and Cyp1a-1 mRNA levels. The relative potencies of the reconstituted mixture and its components indicated that most of the activity was associated with {ge} 4-ring PAHs and the interactive effects of the individual PAHs in the reconstituted PAH mixture were essentially additive.

  8. Experimental study on the adsorptive-distillation for dehydration of ethanol-water mixture using natural and synthetic zeolites

    NASA Astrophysics Data System (ADS)

    Megawati, Wicaksono, D.; Abdullah, M. S.

    2017-03-01

    This research studied adsorptive-distillation (AD) for dehydration of ethanol-water mixture using natural and synthetic zeolites as adsorbent for ethanol purification. Especially, the effect of purification time is recorded and studied to evaluate performance of designed AD equipment. This AD was performed in a batch condition using boiling flask covered with heating mantle and it was maintained at 78°C temperature and 1 atm pressure. The initial ethanol volume was 300 mL with 93.8% v/v concentration. The synthetic zeolite type used was zeolite 3A. The flowed vapour was condensed using water as a cooling medium. Every 5 minutes of time duration the samples were collected until the vapour could not be condensed in that condition and then be analyzed its concentration using Gas-Chromatography. Experiment shows that the designed AD equipment could increase ethanol concentration at first 5 minutes with highest ethanol concentration achieved using synthetic zeolite (97.47% v/v). However, ethanol concentration from AD process using natural zeolite only reached 96.5% v/v. Thus, synthetic zeolite as adsorbent could pass azeotropic point, but natural zeolite fail. The ratio of adsorbed water per adsorbent for natural and synthetic zeolites are about 0.023 and 0.056 gwater/gads, respectively, at 50 minutes of time. Finally, synthetic zeolite (at 55 minutes the value of C/C0 is about 0.85 and the average outlet water concentration is 4.70 mole/L) as adsorbent for AD of ethanol water is better than natural zeolite (at 55 minutes the value of C/C0 is about 0.63 and the average outlet water concentration is 6.43 mole/L).

  9. 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.

  10. 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...

  11. Predicting the toxicity of metal mixtures

    USGS Publications Warehouse

    Balistrieri, Laurie S.; Mebane, Christopher A.

    2013-01-01

    The toxicity of single and multiple metal (Cd, Cu, Pb, and Zn) solutions to trout is predicted using an approach that combines calculations of: (1) solution speciation; (2) competition and accumulation of cations (H, Ca, Mg, Na, Cd, Cu, Pb, and Zn) on low abundance, high affinity and high abundance, low affinity biotic ligand sites; (3) a toxicity function that accounts for accumulation and potency of individual toxicants; and (4) biological response. The approach is evaluated by examining water composition from single metal toxicity tests of trout at 50% mortality, results of theoretical calculations of metal accumulation on fish gills and associated mortality for single, binary, ternary, and quaternary metal solutions, and predictions for a field site impacted by acid rock drainage. These evaluations indicate that toxicity of metal mixtures depends on the relative affinity and potency of toxicants for a given aquatic organism, suites of metals in the mixture, dissolved metal concentrations and ratios, and background solution composition (temperature, pH, and concentrations of major ions and dissolved organic carbon). A composite function that incorporates solution composition, affinity and competition of cations for two types of biotic ligand sites, and potencies of hydrogen and individual metals is proposed as a tool to evaluate potential toxicity of environmental solutions to trout.

  12. 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

  13. 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

  14. 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)

  15. 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)

  16. Separation of copper from aqueous sulfate solutions by mixtures of Cyanex 301 and LIX 984N.

    PubMed

    Fouad, E A

    2009-07-30

    The extraction equilibria of copper(II) with Cyanex 301, LIX 984N, and their mixtures have been investigated. Extraction was studied as a function of organic phase composition, sulfuric acid concentration, pH, temperature, initial copper concentration, mixing speed, and aqueous/organic volume ratio. Considerable synergistic enhancement has been observed in the extraction of Cu(2+) with mixtures of Cyanex 301 and LIX 984N. The results demonstrate that copper ion is extracted as CuRL(2)H with synergistic mixture. The thermodynamic parameter, enthalpy change (Delta H) of Cyanex 301, LIX 984N, and their mixtures have been determined and the endothermic process has been found. The synergistic enhancement factor of copper(II) with mixtures is higher at more acidic solutions, which suggests that it is a promising synergistic extraction system for the separation of copper(II) from more acidic medium. HCl was found to be more efficient for copper stripping from loaded synergistic mixtures.

  17. Bayesian Kernel Mixtures for Counts.

    PubMed

    Canale, Antonio; Dunson, David B

    2011-12-01

    Although Bayesian nonparametric mixture models for continuous data are well developed, there is a limited literature on related approaches for count data. A common strategy is to use a mixture of Poissons, which unfortunately is quite restrictive in not accounting for distributions having variance less than the mean. Other approaches include mixing multinomials, which requires finite support, and using a Dirichlet process prior with a Poisson base measure, which does not allow smooth deviations from the Poisson. As a broad class of alternative models, we propose to use nonparametric mixtures of rounded continuous kernels. An efficient Gibbs sampler is developed for posterior computation, and a simulation study is performed to assess performance. Focusing on the rounded Gaussian case, we generalize the modeling framework to account for multivariate count data, joint modeling with continuous and categorical variables, and other complications. The methods are illustrated through applications to a developmental toxicity study and marketing data. This article has supplementary material online.

  18. 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.

  19. 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…

  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... 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...

  1. 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...

  2. 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”...

  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, 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”...

  5. 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”...

  6. 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...

  7. 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”...

  8. 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...

  9. 14 CFR 23.1147 - Mixture controls.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...

  10. Estimating proportions of materials using mixture models

    NASA Technical Reports Server (NTRS)

    Heydorn, R. P.; Basu, R.

    1983-01-01

    An approach to proportion estimation based on the notion of a mixture model, appropriate parametric forms for a mixture model that appears to fit observed remotely sensed data, methods for estimating the parameters in these models, methods for labelling proportion determination from the mixture model, and methods which use the mixture model estimates as auxiliary variable values in some proportion estimation schemes are addressed.

  11. 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

  12. Dipole oscillations in fermionic mixtures

    SciTech Connect

    Chiacchiera, S.; Macri, T.; Trombettoni, A.

    2010-03-15

    We study dipole oscillations in a general fermionic mixture. Starting from the Boltzmann equation, we classify the different solutions in the parameter space through the number of real eigenvalues of the small oscillations matrix. We discuss how this number can be computed using the Sturm algorithm and its relation with the properties of the Laplace transform of the experimental quantities. After considering two components in harmonic potentials having different trapping frequencies, we study dipole oscillations in three-component mixtures. Explicit computations are done for realistic experimental setups using the classical Boltzmann equation without intraspecies interactions. A brief discussion of the application of this classification to general collective oscillations is also presented.

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

    PubMed

    Krishna, Rajamani

    2015-01-07

    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.

  14. Mixture toxicity of flubendazole and fenbendazole to Daphnia magna.

    PubMed

    Puckowski, Alan; Stolte, Stefan; Wagil, Marta; Markiewicz, Marta; Łukaszewicz, Paulina; Stepnowski, Piotr; Białk-Bielińska, Anna

    2017-02-03

    Nowadays, residual amounts of many pharmaceuticals can be found in various environmental compartments including surface and ground waters, soils and sediments as well as biota. Even though they undergo degradability, their environmental discharge is relatively continuous, thus they may be regarded as quasi-persistent contaminants, and are also frequently regarded as emerging organic pollutants. Benzimidazoles, especially flubendazole (FLU) and fenbendazole (FEN), represent two anthelmintic drugs belonging to this group. Although their presence in environmental matrices has been reported, there is relatively little data concerning their (eco)toxicological impact. Furthermore, no data is available on their mixture toxicity. FLU and FEN have been found to have a strong impact on an environmentally important non-target organism - Daphnia magna. Moreover, these compounds are usually present in the environment as a part of pharmaceutical mixtures. Therefore, there is a need to evaluate their mixture toxicity, which was the main aim of this study. Single substance toxicity tests were carried out in parallel with mixture studies of FLU and FEN, with the application of two well established concepts of Concentration Addition (CA) and Independent Action (IA). As a result, both models (CA and IA) were found to underestimate the toxicity of mixtures, however CA yielded more accurate predictions.

  15. Influence factors of multicomponent mixtures containing reactive chemicals and their joint effects.

    PubMed

    Tian, Dayong; Lin, Zhifen; Yu, Jianqiao; Yin, Daqiang

    2012-08-01

    Organic chemicals usually coexist as a mixture in the environment, and the mixture toxicity of organic chemicals has received increased attention. However, research regarding the joint effects of reactive chemicals is lacking. In this study, we examined two kinds of reactive chemicals, cyanogenic toxicants and aldehydes and determined their joint effects on Photobacterium phosphoreum. Three factors were found to influence the joint effects of multicomponent mixtures containing reactive chemicals, including the number of components, the dominating components and the toxic ratios. With an increased number of components, the synergistic or antagonistic effects (interactions) will weaken to the additive effects (non-interactions) if the added component cannot yield a much stronger joint effect with an existing component. Contrarily, the joint effect of the mixture may become stronger instead of weaker if the added components can yield a much stronger joint effect than the existing joint effect of the multicomponent mixture. The components that yield the strongest interactions in their binary mixture can be considered the dominating components. These components contribute more to the interactions of multicomponent mixtures than other components. Moreover, the toxic ratios also influence the joint effects of the mixtures. This study provides an insight into what are the main factors and how they influence the joint effects of multicomponent mixtures containing reactive chemicals, and thus, the findings are beneficial to the study of mixture toxicology. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. 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.

  17. 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).

  18. Electrochemical signatures of multivitamin mixtures.

    PubMed

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

    2015-11-21

    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.

  19. Taylor dispersion analysis of mixtures.

    PubMed

    Cottet, Hervé; Biron, Jean-Philippe; Martin, Michel

    2007-12-01

    Taylor dispersion analysis (TDA) is a fast and simple method for determining hydrodynamic radii. In the case of sample mixtures, TDA, as the other nonseparative methods, leads to an average diffusion coefficient on the different molecules constituting the mixture. We set in this work the equations giving, on a consistent basis, the average values obtained by TDA with detectors with linear response functions. These equations confronted TDA experiments of sample mixtures containing different proportions of a small molecule and a polymer standard. Very good agreement between theory and experiment was obtained. In a second part of this work, on the basis of monomodal or bimodal molar mass distributions of polymers, the different average diffusion coefficients corresponding to TDA were compared to the z-average diffusion coefficient (D(z)) obtained from dynamic light scattering (DLS) experiments and to the weight average diffusion coefficient (D(w)). This latter value is sometimes considered as the most representative of the sample mixture. From these results, it appears that, for monomodal distribution and relatively low polydispersity (I = 1.15), the average diffusion coefficient generally derived from TDA is very close to Dw. However, for highly polydisperse samples (e.g., bimodal polydisperse distributions), important differences could be obtained (up to 35% between TDA and D(w)). In all the cases, the average diffusion coefficient obtained by TDA for a mass concentration detector was closer to the Dw value than the z-average obtained by DLS.

  20. 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

  1. 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)

  2. Marangoni convection in binary mixtures.

    PubMed

    Zhang, Jie; Behringer, Robert P; Oron, Alexander

    2007-07-01

    Marangoni instabilities in binary mixtures in the presence of the Soret effect and evaporation are different from those in pure liquids. In contrast to a large amount of experimental work on Marangoni convection in pure liquids, such experiments in binary mixtures are not available in the literature, to our knowledge. Using binary mixtures of NaCl/water in an open system, evaporation of water molecules at the liquid-vapor interface is inevitable. We have systematically investigated the pattern formation for a set of substrate temperatures and solute concentrations in an open system. The flow patterns evolve with time, driven by surface-tension fluctuations due to evaporation and the Soret effect, while the air-liquid interface does not deform. A shadow-graph method is used to follow the pattern formation in time. The patterns are mainly composed of polygons and rolls. The mean pattern size first decreases slightly, and then gradually increases during the evolution. Evaporation affects the pattern formation mainly at the early stages and the local evaporation rate tends to become spatially uniform at the film surface. The Soret effect becomes important at the later stages and affects the mixture for a large mean solute concentration where the Soret number is significantly above zero. The strength of convection increases with the initial solute concentration and the substrate temperature. Our findings differ from the theoretical predictions in which evaporation is neglected.

  3. Bioavailability of genotoxic mixtures in soil

    SciTech Connect

    Bordelon, N.; Washburn, K.; He, L.Y.; Donnelly, K.C.

    1996-12-31

    Contaminated media at Superfund sites typically consist of complex mixtures of organic and inorganic chemicals which are difficult to characterize, both analytically and toxicologically. The current EPA approach to risk assessment uses solvent extraction to remove chemicals from the soil as a basis for estimating risk to the human population. However, contaminants that can be recovered with a solvent extract may not represent the mixture of chemicals that are available for human exposure. A procedure using an aqueous extraction was investigated to provide a more realistic estimate of what chemicals are bioavailable. A study was conducted with two soil types: creosote-contaminated sandy soil and coal tar-contaminated clay soil spiked with benzo(a)pyrene [B(a)P], and trinitrotoluene (TNT). Samples were extracted with hexane:acetone and water titrated to pH2 and pH7. HPLC analysis demonstrated up to 35% and 29% recovery of contaminants using the aqueous extracts. The estimated cancer risk for the aqueous extract was one order of magnitude less than that for solvent extracts. Analysis using the Salmonella/microsome assay demonstrated that solvent extracts were genotoxic (133 revertants/mg) with metabolic activation while aqueous extracts of clay soil were not genotoxic. Sandy soil showed genotoxicity both with and without metabolic activation. These results suggest that solvent extraction techniques may overestimate the concentration of contaminants that are available for human exposure and, hence, the risk associated with the presence of the contaminants in soil.

  4. The long-term effect of initial pH control on the enrichment culture of phosphorus- and glycogen-accumulating organisms with a mixture of propionic and acetic acids as carbon sources.

    PubMed

    Zhang, Chao; Chen, Yinguang; Liu, Yan

    2007-11-01

    In most studies on phosphorus- and glycogen-accumulating organisms (PAO and GAO), pH was controlled constantly throughout the entire anaerobic and aerobic periods, and acetic acid was used as the carbon source. In this paper, the effect of long-term initial pH values on PAO and GAO was investigated with mixed propionic and acetic acids as carbon sources. It was observed that with pH increasing from 6.4 to 8.0, the anaerobic propionic acid uptake rate by PAO linearly increased but that by GAO proportionally decreased. At pH 6.70 and pH 7.51, PAO and GAO exhibited the same acetic and propionic acid uptake rates, respectively. The acetic acid uptake rate by PAO was greater than that by GAO at pH>6.70, and the propionic acid uptake rate by PAO was higher than that by GAO at pH>7.51, which indicated that PAO would take predominance over GAO at pH>7.51. Poly-3-hydroxybutyrate, poly-3-hydroxyvalerate and poly-3-hydroxy-2-methylvalerate shared 7%, 62% and 31%, respectively in the PAO system, and 11%, 44% and 45% respectively in the GAO system, and these fractions were observed independent of pH either in the PAO or in the GAO system. In the PAO system, with the increase of pH, the phosphorus removal efficiency was improved greatly, and a phosphorus removal efficiency of 100% was achieved at 8.0. Further investigation showed that the higher phosphorus removal efficiency at higher pH was mainly caused by a biological effect instead of chemical one.

  5. Profiling of odor components and their mixtures.

    PubMed

    Moskowitz, H R; Barbe, C D

    1977-05-01

    Observers evaluated five odors and their 26 mixtures (two, three, four, and five components) by magnitude estimation. Estimates revealed that in mixtures there is moderate suppression of perceived intensity; a vector model proposed by Berglund (Annals of the New York Academy of Sciences, 1974, 237, 35-51) provides a good prediction of the intensity of binary mixtures, but overpredicts the intensity of three, four, and five component mixtures. Hedonic tones of mixtures were difficult to predict from hedonic tones of components. Qualities of mixtures were difficult to predict from quality of components. Intermediacy, of quality and hedonic values, was often observed.

  6. Free Volume Theory of Hydrocarbon Mixture Transport in Nanoporous Materials.

    PubMed

    Obliger, Amaël; Pellenq, Roland; Ulm, Franz-Josef; Coasne, Benoit

    2016-10-06

    Despite recent focus on shale gas, hydrocarbon recovery from the ultraconfining and disordered porosity of organic matter in shales (kerogen) remains poorly understood. Key aspects such as the breakdown of hydrodynamics at the nanoscale and strong adsorption effects lead to unexplained non-Darcy behaviors. Here, molecular dynamics and statistical mechanics are used to elucidate hydrocarbon mixture transport through a realistic molecular model of kerogen [ Bousige, C.; et al. Nat. Mater. 2016 , 15 , 576 ]. Owing to strong adsorption effects, velocity cross-correlations between the mixture components and between molecules of the same species are shown to be negligible. This allows estimation of each component permeance from its self-diffusivity, which can be obtained from single-component data. These permeances are found to scale with the reciprocal of the alkane length and decrease with the number of adsorbed molecules following a simple free volume theory, therefore allowing mixture transport prediction as a function of the amount of trapped fluid.

  7. Generalized Beta Mixtures of Gaussians.

    PubMed

    Armagan, Artin; Dunson, David B; Clyde, Merlise

    2011-01-01

    In recent years, a rich variety of shrinkage priors have been proposed that have great promise in addressing massive regression problems. In general, these new priors can be expressed as scale mixtures of normals, but have more complex forms and better properties than traditional Cauchy and double exponential priors. We first propose a new class of normal scale mixtures through a novel generalized beta distribution that encompasses many interesting priors as special cases. This encompassing framework should prove useful in comparing competing priors, considering properties and revealing close connections. We then develop a class of variational Bayes approximations through the new hierarchy presented that will scale more efficiently to the types of truly massive data sets that are now encountered routinely.

  8. Local fluctuations in solution mixtures

    PubMed Central

    Ploetz, Elizabeth A.; Smith, Paul E.

    2011-01-01

    An extension of the traditional Kirkwood-Buff (KB) theory of solutions is outlined which provides additional fluctuating quantities that can be used to characterize and probe the behavior of solution mixtures. Particle-energy and energy-energy fluctuations for local regions of any multicomponent solution are expressed in terms of experimentally obtainable quantities, thereby supplementing the usual particle-particle fluctuations provided by the established KB inversion approach. The expressions are then used to analyze experimental data for pure water over a range of temperatures and pressures, a variety of pure liquids, and three binary solution mixtures – methanol and water, benzene and methanol, and aqueous sodium chloride. In addition to providing information on local properties of solutions it is argued that the particle-energy and energy-energy fluctuations can also be used to test and refine solute and solvent force fields for use in computer simulation studies. PMID:21806137

  9. MULTIVARIATE KERNEL PARTITION PROCESS MIXTURES

    PubMed Central

    Dunson, David B.

    2013-01-01

    Mixtures provide a useful approach for relaxing parametric assumptions. Discrete mixture models induce clusters, typically with the same cluster allocation for each parameter in multivariate cases. As a more flexible approach that facilitates sparse nonparametric modeling of multivariate random effects distributions, this article proposes a kernel partition process (KPP) in which the cluster allocation varies for different parameters. The KPP is shown to be the driving measure for a multivariate ordered Chinese restaurant process that induces a highly-flexible dependence structure in local clustering. This structure allows the relative locations of the random effects to inform the clustering process, with spatially-proximal random effects likely to be assigned the same cluster index. An exact block Gibbs sampler is developed for posterior computation, avoiding truncation of the infinite measure. The methods are applied to hormone curve data, and a dependent KPP is proposed for classification from functional predictors. PMID:24478563

  10. Gene Expression Responses in Male Fathead Minnows Exposed to Binary Mixtures of an Estrogen and Antiestrogen

    EPA Science Inventory

    Aquatic organisms are continuously exposed to complex mixtures of chemicals, many of which can interfere with their endocrine system, resulting in impaired reproduction, development or survival, among others. In order to analyze the effects and mechanisms of action of estrogen...

  11. 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...

  12. 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...

  13. 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-...

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

    DOEpatents

    Hupp, Joseph T.; Mulfort, Karen L.; Snurr, Randall Q.; Bae, Youn-Sang

    2011-01-04

    A method of separating a mixture of carbon dioxiode and hydrocarbon gas using a mixed-ligand, metal-organic framework (MOF) material having metal ions coordinated to carboxylate ligands and pyridyl ligands.

  15. International issues on human health effects of exposure to chemical mixtures.

    PubMed

    Feron, Victor J; Cassee, Flemming R; Groten, John P; van Vliet, Petronella W; van Zorge, Job A

    2002-12-01

    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

  16. 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

  17. A role of low dose chemical mixtures in adipose tissue in carcinogenesis.

    PubMed

    Lee, Duk-Hee; Jacobs, David R; Park, Ho Yong; Carpenter, David O

    2017-08-29

    The Halifax project recently hypothesized a composite carcinogenic potential of the mixture of low dose chemicals which are commonly encountered environmentally, yet which are not classified as human carcinogens. A long neglected but important fact is that adipose tissue is an important exposure source for chemical mixtures. In fact, findings from human studies based on several persistent organic pollutants in general populations with only background exposure should be interpreted from the viewpoint of chemical mixtures because serum concentrations of these chemicals can be seen as surrogates for chemical mixtures in adipose tissue. Furthermore, in conditions such as obesity with dysfunctional adipocytes or weight loss in which lipolysis is increased, the amount of the chemical mixture released from adipose tissue to circulation is increased. Thus, both obesity and weight loss can enhance the chance of chemical mixtures reaching critical organs, however paradoxical this idea may be when fat mass is the only factor considered. The complicated, interrelated dynamics of adipocytes and chemical mixtures can explain puzzling findings related to body weight among cancer patients, including the obesity paradox. The contamination of fat in human diet with chemical mixtures, occurring for reasons similar to contamination of human adipose tissue, may be a missing factor which affects the association between dietary fat intake and cancer. The presence of chemical mixtures in adipose tissue should be considered in future cancer research, including clinical trials on weight management among cancer survivors. Copyright © 2017. Published by Elsevier Ltd.

  18. Characterization and Coding of Behaviorally Significant Odor Mixtures

    PubMed Central

    Riffell, Jeffrey A.; Lei, Hong; Christensen, Thomas A.; Hildebrand, John G.

    2009-01-01

    Summary For animals to execute odor-driven behaviors, the olfactory system must process complex odor signals and maintain stimulus identity in the face of constantly changing odor intensities [1–5]. Surprisingly, how the olfactory system maintains identity of complex odors is unclear [6–10]. We took advantage of the plant-pollinator relationship between the Sacred Datura (Datura wrightii) and the moth Manduca sexta [11, 12] to determine how olfactory networks in this insect’s brain represent odor mixtures. We combined gas chromatography and neural-ensemble recording in the moth’s antennal lobe to examine population codes for the floral mixture and its fractionated components. Although the floral scent of D. wrightii comprises at least 60 compounds, only nine of those elicited robust neural responses. Behavioral experiments confirmed that these nine odorants mediate flower-foraging behaviors, but only as a mixture. Moreover, the mixture evoked equivalent foraging behaviors over a 1000-fold range in dilution, suggesting a singular percept across this concentration range. Furthermore, neural-ensemble recordings in the moth’s antennal lobe revealed that reliable encoding of the floral mixture is organized through synchronized activity distributed across a population of glomerular coding units, and this timing mechanism may bind the features of a complex stimulus into a coherent odor percept. PMID:19230669

  19. Consensus sediment quality guidelines for polycyclic aromatic hydrocarbon mixtures

    SciTech Connect

    Swartz, R.C.

    1999-04-01

    Sediment quality guidelines (SQGs) for polycyclic aromatic hydrocarbons (PAHs) have been derived from a variety of laboratory, field, and theoretical foundations. They include the screening level concentration, effects ranges-low and -median, equilibrium partitioning concentrations, apparent effects threshold, {Sigma}PAH model, and threshold and probable effects levels. The resolution of controversial differences among the PAH SQGs lies in an understanding of the effects of mixtures. Polycyclic aromatic hydrocarbons virtually always occur in field-collected sediment as a complex mixture of covarying compounds. When expressed as a mixture concentration, that is, total PAH (TPAH), the guidelines form three clusters that were intended in their original derivations to represent threshold (TEC = 290 {micro}g/g organic carbon [OC]), median (MEC = 1,800 {micro}g/g OC), and extreme (EEC = 10,000 {micro}g/g OC) effects concentrations. The TEC/MEC/EEC consensus guidelines provide a unifying synthesis of other SQGs, reflect causal rather than correlative effects, account for mixtures, and predict sediment toxicity and benthic community perturbations at sites of PAH contamination. The TEC offers the most useful SQG because PAH mixtures are unlikely to cause adverse effects on benthic ecosystems below the TEC.

  20. 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.

  1. Model Misspecification: Finite Mixture or Homogeneous?

    PubMed Central

    Tarpey, Thaddeus; Yun, Dong; Petkova, Eva

    2007-01-01

    A common problem in statistical modelling is to distinguish between finite mixture distribution and a homogeneous non-mixture distribution. Finite mixture models are widely used in practice and often mixtures of normal densities are indistinguishable from homogenous non-normal densities. This paper illustrates what happens when the EM algorithm for normal mixtures is applied to a distribution that is a homogeneous non-mixture distribution. In particular, a population-based EM algorithm for finite mixtures is introduced and applied directly to density functions instead of sample data. The population-based EM algorithm is used to find finite mixture approximations to common homogeneous distributions. An example regarding the nature of a placebo response in drug treated depressed subjects is used to illustrate ideas. PMID:18974843

  2. Medicines, shaken and stirred: a critical review on the ecotoxicology of pharmaceutical mixtures.

    PubMed

    Backhaus, Thomas

    2014-11-19

    Analytical monitoring surveys routinely confirm that organisms in the environment are exposed to complex multi-component pharmaceutical mixtures. We are hence tasked with the challenge to take this into consideration when investigating the ecotoxicology of pharmaceuticals. This review first provides a brief overview of the fundamental approaches for mixture toxicity assessment, which is then followed by a critical review on the empirical evidence that is currently at hand on the ecotoxicology of pharmaceutical mixtures. It is concluded that, while the classical concepts of concentration addition and independent action (response addition) provide a robust scientific footing, several knowledge gaps remain. This includes, in particular, the need for more and better empirical data on the effects of pharmaceutical mixtures on soil organisms as well as marine flora and fauna, and exploring the quantitative consequences of toxicokinetic, toxicodynamic and ecological interactions. Increased focus should be put on investigating the ecotoxicology of pharmaceutical mixtures in environmentally realistic settings.

  3. Experimental evaluation of drying characteristics of sewage sludge and hazelnut shell mixtures

    NASA Astrophysics Data System (ADS)

    Pehlivan, Hüseyin; Ateş, Asude; Özdemir, Mustafa

    2016-11-01

    In this study the drying behavior of organic and agricultural waste mixtures has been experimentally investigated. The usability of sewage sludge as an organic waste and hazelnut shell as an agricultural waste was assessed in different mixture range. The paper discusses the applicability of these mixtures as a recovery energy source. Moisture content of mixtures has been calculated in laboratory and plant conditions. Indoor and outdoor solar sludge drying plants were constructed in pilot scale for experimental purposes. Dry solids and climatic conditions were constantly measured. A total more than 140 samples including for drying has been carried out to build up results. Indoor and outdoor weather conditions are taken into consideration in winter and summer. The most effective drying capacity is obtained in mixture of 20 % hazelnut shell and 80 % sewage sludge.

  4. 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

  5. 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...

  6. 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...

  7. 14 CFR 27.1147 - Mixture controls.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Mixture controls. 27.1147 Section 27.1147... STANDARDS: NORMAL CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 27.1147 Mixture controls. If there are mixture controls, each engine must have a separate control and the controls must...

  8. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  9. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  10. 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...

  11. 14 CFR 29.1147 - Mixture controls.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Mixture controls. 29.1147 Section 29.1147... STANDARDS: TRANSPORT CATEGORY ROTORCRAFT Powerplant Powerplant Controls and Accessories § 29.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and the...

  12. 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...

  13. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  14. 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...

  15. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  16. 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...

  17. 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...

  18. 40 CFR 721.9540 - Polysulfide mixture.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Polysulfide mixture. 721.9540 Section... Substances § 721.9540 Polysulfide mixture. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polysulfide mixture (PMN P-93-1043)...

  19. 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...

  20. 21 CFR 82.6 - Certifiable mixtures.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Certifiable mixtures. 82.6 Section 82.6 Food and... PROVISIONALLY LISTED COLORS AND SPECIFICATIONS General Provisions § 82.6 Certifiable mixtures. (a) A batch of a mixture which contains no straight color listed in subpart C or D may be certified for use in food,...