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Sample records for 1-octanol-water partition coefficients

  1. Salting-out phenomenon and 1-octanol/water partition coefficient of metalaxyl pesticide.

    PubMed

    Saab, J; Bassil, G; Abou Naccoul, R; Stephan, J; Mokbel, I; Jose, J

    2011-02-01

    In this paper, we present the effect of inorganic cations such as Na+, K+, Ca2+, Mg2+ on the salting-out phenomenon of metalaxyl from pure water to aqueous salt solutions. Moreover the 1-octanol/water partition coefficient in pure water is presented. To accomplish this, aqueous solubility of metalaxyl was determined in pure water, in different salt solution (NaCl, KCl, CaCl2 and MgCl2), and at different concentration level ranging from 0.01 to 1.5 M. The 1-octanol/water partition coefficient was determined using the static shake-flask method. Solubility was determined using dynamic saturation method for pure water in the range of 298.15-325.15 K and at 298.15 K for different salt solutions. The solubility value in pure water for studied interval was found constant (m=3.118×10(-2) mol kg(-1)). Solubility values were used to calculate the standard molar Gibbs free energy of dissolution (ΔsolG°) and transfer (ΔtrG°) at 298.15 K. The values of ΔtrG° from pure to all studied aqueous salt solutions did not exceed 2 kJ mol(-1), the value of ΔsolG° of dissolution is 18.5 ±0.72 kJ mol(-1). The 1-octanol/water partition coefficient in pure water log Ko/w is equal to 1.69. The obtained results confirm the classification of the neutral metalaxyl as a slightly hydrophobic molecule. PMID:21094973

  2. Aqueous solubilities, vapor pressures, and 1-octanol-water partition coefficients for C9-C14 linear alkylbenzenes

    USGS Publications Warehouse

    Sherblom, P.M.; Gschwend, P.M.; Eganhouse, R.P.

    1992-01-01

    Measurements and estimates of aqueous solubilities, 1-octanol-water partition coefficients (Kow), and vapor pressures were made for 29 linear alkylbenzenes having alkyl chain lengths of 9-14 carbons. The ranges of values observed were vapor pressures from 0.002 to 0.418 Pa, log Kow, from 6.83 to 9.95, and aqueous solubilities from 4 to 38 nmol??L-1. Measured values exhibited a relationship to both the alkyl chain length and the position of phenyl substitution on the alkyl chain. Measurement of the aqueous concentrations resulting from equilibration of a mixture of alkylbenzenes yielded higher than expected values, indicating cosolute or other interactive effects caused enhanced aqueous concentrations of these compounds. ?? 1992 American Chemical Society.

  3. Bile acid structure-activity relationship: evaluation of bile acid lipophilicity using 1-octanol/water partition coefficient and reverse phase HPLC.

    PubMed

    Roda, A; Minutello, A; Angellotti, M A; Fini, A

    1990-08-01

    Two independent methods have been developed and compared to determine the lipophilicity of a representative series of naturally occurring bile acids (BA) in relation to their structure. The BA included cholic acid (CA), chenodeoxycholic acid (CDCA), ursodeoxycholic acid (UDCA), deoxycholic acid (DCA), hyodeoxycholic acid (HDCA), ursocholic acid (UCA), hyocholic acid (HCA), as well as their glycine and taurine amidates. Lipophilicity was determined using a 1-octanol/water shake-flask procedure and the experiments were performed at different pH and ionic strengths and at initial BA concentrations below their critical micellar concentrations (CMC) and the water solubility of the protonated form. The experimental data show that both the protonated (HA) and ionized (A-) forms of BA can distribute in 1-octanol, and consequently a partition coefficient for HA (logP' HA) and for A- (logP' A-) must be defined. An equation to predict a weighted apparent distribution coefficient (D) value as a function of pH and pKa has been developed and fits well with the experimental data. Differences between logP for protonated and ionized species for unconjugated BA were in the order of 1 log unit, which increased to 2 for glycine-amidate BA. The partition coefficient of the A- form increased with Na+ concentration and total ionic strength, suggesting an ion-pair mechanism for its partition into 1-octanol. Lipophilicity was also assessed using reverse phase chromatography (C-18-HPLC), and a capacity factor (K') for ionized species was determined. Despite a broad correlation with the logP data, some BA behaved differently. The logP values showed that the order of lipophilicity was DCA greater than CDCA greater than UDCA greater than HDCA greater than HCA greater than CA greater than UCA for both the protonated and ionized unconjugated and glycine-amidate BA, while the K' data showed an inversion for some BA, i.e., DCA greater than CDCA greater than CA greater than HCA greater than UDCA

  4. Enhancement of the 1-Octanol/Water Partition Coefficient of the Anti-Inflammatory Indomethacin in the Presence of Lidocaine and Other Local Anesthetics.

    PubMed

    Tateuchi, Ryo; Sagawa, Naoki; Shimada, Yohsuke; Goto, Satoru

    2015-07-30

    Side effects and excessive potentiation of drug efficacy caused by polypharmacy are becoming important social issues. The apparent partition coefficient of indomethacin (log P'IND) increases in the presence of lidocaine, and this is used as a physicochemical model for investigating polypharmacy. We examined the changes in log P'IND caused by clinically used local anesthetics-lidocaine, tetracaine, mepivacaine, bupivacaine, and dibucaine-and by structurally similar basic drugs-procainamide, imipramine, and diltiazem. The quantitative structure-activity relationship study of log P'IND showed that the partition coefficient values (log PLA) and the structural entropic terms (ΔSobs, log f) of the additives affect log P'IND. These results indicate that the local anesthetics and structurally similar drugs function as phase-transfer catalysts, increasing the membrane permeability of indomethacin via heterogeneous intermolecular association. Therefore, we expect that the potency of indomethacin, an acidic nonsteroidal anti-inflammatory drug, will be increased by concurrent administration of the other drugs. PMID:26121007

  5. Application of ALOGPS to predict 1-octanol/water distribution coefficients, logP, and logD, of AstraZeneca in-house database.

    PubMed

    Tetko, Igor V; Bruneau, Pierre

    2004-12-01

    The ALOGPS 2.1 was developed to predict 1-octanol/water partition coefficients, logP, and aqueous solubility of neutral compounds. An exclusive feature of this program is its ability to incorporate new user-provided data by means of self-learning properties of Associative Neural Networks. Using this feature, it calculated a similar performance, RMSE = 0.7 and mean average error 0.5, for 2569 neutral logP, and 8122 pH-dependent logD(7.4), distribution coefficients from the AstraZeneca "in-house" database. The high performance of the program for the logD(7.4) prediction looks surprising, because this property also depends on ionization constants pKa. Therefore, logD(7.4) is considered to be more difficult to predict than its neutral analog. We explain and illustrate this result and, moreover, discuss a possible application of the approach to calculate other pharmacokinetic and biological activities of chemicals important for drug development. PMID:15514985

  6. Partition coefficients of three new anticonvulsants.

    PubMed

    Hernandez-Gallegos, Z; Lehmann, P A

    1990-11-01

    The partition coefficients of three homologous anticonvulsant phenylalkylamides [racemic alpha-hydroxy-alpha-ethyl-alpha-phenylacetamide (HEPA); beta-hydroxy-beta-ethyl-beta-phenylpropionamide (HEPP); and gamma-hydroxy-gamma-ethyl-gamma-phenylbutyramide (HEPB)] were determined by reversed-phase high-performance liquid chromatography (RP-HPLC). The system was calibrated with a series of simple amines and amides, using their published log P values. The log kw values (methanol:water, extrapolated to 100% water) were 1.260 for HEPA, 1.670 for HEPP, and 1.852 for HEPB. From these results, the partition coefficients (log P) were calculated by regression as 1.20, 1.83, and 2.11, respectively. The log P values were essentially equal to those calculated by the Leo-Hansch fragmental method. Since the potency of the three anticonvulsants is approximately the same in a variety of tests, no dependence on lipophilicity could be established. PMID:2292764

  7. Partition Coefficients at High Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    Righter, K.; Drake, M. J.

    2003-12-01

    Differentiation of terrestrial planets includes separation of a metallic core and possible later fractionation of mineral phases within either a solid or molten mantle (Figure 1). Lithophile and siderophile elements can be used to understand these two different physical processes, and ascertain whether they operated in the early Earth. The distribution of elements in planets can be understood by measuring the partition coefficient, D (ratio of concentrations of an element in different phases (minerals, metals, or melts)). (14K)Figure 1. Schematic cross-section through the Earth, showing: (a) an early magma ocean stage and (b) a later cool and differentiated stage. The siderophile elements (iron-loving) encompass over 30 elements and are defined as those elements for which D(metal/silicate)>1, and are useful for deciphering the details of core formation. This group of elements is commonly broken up into several subclasses, including the slightly siderophile elements (1104). Because these three groups encompass a wide range of partition coefficient values, they can be very useful in trying to determine the conditions under which metal may have equilibrated with the mantle (or a magma ocean). Because metal and silicate may equilibrate by several different mechanisms, such as at the base of a deep magma ocean, or as metal droplets descend through a molten mantle, partition coefficients can potentially shed light on which mechanism may be most important, thus linking the physics and chemistry of core formation. In this chapter, we summarize metal/silicate partitioning of siderophile elements and show how they may be used to understand planetary core formation.Once a planet is differentiated into core and mantle, a mantle will cool during convection, and can start in either a molten or solid state, depending upon the initial thermal conditions. If hot enough, minerals will

  8. REE and Strontium Partition Coefficients for Nakhla Pyroxenes

    NASA Technical Reports Server (NTRS)

    Oe, K.; McKay, G.; Le, L.

    2001-01-01

    We present new partition coefficients for REE and Sr determined using a synthetic melt that crystallizes pyroxenes very similar in composition to Nakhla pyroxene cores. We believe these are the most appropriate partition coefficients to use in studying Nakhla Additional information is contained in the original extended abstract..

  9. Correlation of octanol/water solubility ratios and partition coefficients

    SciTech Connect

    Pinsuwan, S.; Li, A.; Yalkowsky, S.H.

    1995-05-01

    The partition coefficient between octanol and water in an important physicochemical parameter for characterizing the lipophilicity or hydrophobicity of a compound and it is used in many fields, especially in the environmental and pharmaceutical sciences. The octanol/water solubility ratio (S{sub o}/S{sub W}) was found to be highly correlated with the octanol/water partition coefficient (K{sub ow}) of 82 pharmaceutically and environmentally relevant compounds. The solubility ratio gives comparable estimates to that of the group contribution (log P(calcd)) method for estimating the partition coefficient of the compounds used in this study.

  10. Mapping Pesticide Partition Coefficients By Electromagnetic Induction

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A potential method for reducing pesticide leaching is to base application rates on the leaching potential of a specific chemical and soil combination. However, leaching is determined in part by the partitioning of the chemical between the soil and soil solution, which varies across a field. Standard...

  11. PARTITION COEFFICIENTS FOR METALS IN SURFACE WATER, SOIL, AND WASTE

    EPA Science Inventory

    This report presents metal partition coefficients for the surface water pathway and for the source model used in the Multimedia, Multi-pathway, Multi-receptor Exposure and Risk Assessment (3MRA) technology under development by the U.S. Environmental Protection Agency. Partition ...

  12. Orientation and velocity dependence of the nonequilibrium partition coefficient

    NASA Technical Reports Server (NTRS)

    Beatty, K. M.; Jackson, K. A.

    1995-01-01

    Monte Carlo simulations based on a Spin-1 Ising Model for binary alloys have been used to investigate the non-equilibrium partition coefficient (k(sub neq)) as a function of solid-liquid interface velocity and orientation. In simulations of Si with a second component k(sub neq) is greater in the [111] direction than the [100] direction in agreement with experimental results reported by Azlz et al. The simulated partition coefficient scales with the square of the step velocity divided by the diffusion coefficient of the secondary component in the liquid.

  13. Estimation of octanol/water partition coefficients using LSER parameters

    USGS Publications Warehouse

    Luehrs, Dean C.; Hickey, James P.; Godbole, Kalpana A.; Rogers, Tony N.

    1998-01-01

    The logarithms of octanol/water partition coefficients, logKow, were regressed against the linear solvation energy relationship (LSER) parameters for a training set of 981 diverse organic chemicals. The standard deviation for logKow was 0.49. The regression equation was then used to estimate logKow for a test of 146 chemicals which included pesticides and other diverse polyfunctional compounds. Thus the octanol/water partition coefficient may be estimated by LSER parameters without elaborate software but only moderate accuracy should be expected.

  14. Effect of electrolytes on the partition coefficient of irbesartan.

    PubMed

    Mbah, C J

    2005-05-01

    The effect of various electrolytes namely monovalent, divalent and trivalent on the partition coefficient of irbesartan between n-octanol and water systems was investigated at room temperature. It was found that all the electrolytes increase the partition coefficient of irbesartan. The uptake of irbesartan by the organic phase from the aqueous phase is increased with increasing salt concentration except for potassium iodide and aluminum chloride. The effect was found to depend on the size and charge of the ions present in solution. PMID:15918582

  15. Estimation of high temperature metal-silicate partition coefficients

    NASA Technical Reports Server (NTRS)

    Jones, John H.; Capobianco, Christopher J.; Drake, Michael J.

    1992-01-01

    It has been known for some time that abundances of siderophile elements in the upper mantle of the Earth are far in excess of those expected from equilibrium between metal and silicate at low pressures and temperatures. Murthy (1991) has re-examined this excess of siderophile element problem by estimating liquid metal/liquid silicate partition coefficients reduces from their measured values at a lower temperature, implying that siderophile elements become much less siderophilic at high temperatures. Murthy then draws the important conclusion that metal/silicate equilibrium at high temperatures can account for the abundances of siderophile elements in the Earth's mantle. Of course, his conclusion is critically dependent on the small values of the partition coefficients he calculates. Because the numerical values of most experimentally-determined partition coefficients increase with increasing temperature at both constant oxygen fugacity and at constant redox buffer, we think it is important to try an alternative extrapolation for comparison. We have computed high temperature metal/silicate partition coefficients under a different set of assumptions and show that such long temperature extrapolations yield values which are critically dependent upon the presumed chemical behavior of the siderophile elements in the system.

  16. METHOD FOR MEASURING AIR-IMMISCIBLE LIQUID PARTITION COEFFICIENTS

    EPA Science Inventory

    The principal objective of this work was to measure nonaqueous phase liquid-air partition coefficients for various gas tracer compounds. Known amounts of trichloroethene (TCE) and tracer, as neat compounds, were introduced into glass vials and allowed to equilibrate. The TCE and ...

  17. n-Alcohol/Water Partition Coefficients for Decachlorobiphenyl (PCB 209)

    EPA Science Inventory

    Measurements of n-octanol/water partition coefficients (Kow) for highly hydrophobic chemicals are extremely difficult and are rarely made, in part due to the large volumes of water typically needed to quantify these compounds in the aqueous phase. An extrapolation approach using ...

  18. Partition coefficients of Hf, Zr, and REE between zircon, apatite, and liquid

    USGS Publications Warehouse

    Fujimaki, H.

    1986-01-01

    Concentration ratios of Hf, Zr, and REE between zircon, apatite, and liquid were determined for three igneous compositions: two andesites and a diorite. The concentration ratios of these elements between zircon and corresponding liquid can approximate the partition coefficient. Although the concentration ratios between apatite and andesite groundmass can be considered as partition coefficients, those for the apatite in the diorite may deviate from the partition coefficients. The HREE partition coefficients between zircon and liquid are very large (100 for Er to 500 for Lu), and the Hf partition coefficient is even larger. The REE partition coefficients between apatite and liquid are convex upward, and large (D=10-100), whereas the Hf and Zr partition coefficients are less than 1. The large differences between partition coefficients of Lu and Hf for zircon-liquid and for apatite-liquid are confirmed. These partition coefficients are useful for petrogenetic models involving zircon and apatite. ?? 1986 Springer-Verlag.

  19. Fluid/Melt Partition Coefficients Of Halogens In Basaltic Melt

    NASA Astrophysics Data System (ADS)

    Alletti, M.; Baker, D.; Scaillet, B.; Aiuppa, A.; Moretti, R.; Ottolini, L.

    2007-12-01

    Despite the importance of halogens (F, Cl) in volcanic degassing, solubility and fluid/melt partitioning of these elements have not been comprehensively studied in natural basaltic melts. Experimental determinations of halogen solubility in Mount Etna melts are lacking, despite this volcano being one of the most active and intensively monitored on Earth with an estimated output of thousands tonnes of halogens per day. In order to better understand halogen degassing, we present the results of a series of halogen partitioning experiments performed at different pressures (1-200 MPa), redox conditions (from Δ NNO = + 2 to Δ NNO = - 0.3) and fluid compositions. Experiments used a hawaiitic, glassy, alkaline basalt with Mg# = 0.59, sampled during the July 2001 eruption of Mount Etna. A series of experiments were conducted using H2O-NaCl or H2O-NaF solutions. The effect of CO2 in multi-component fluid H2O-CO2-NaCl or H2O-CO2-NaF was also investigated. The experimental run products were mostly glasses, but a few run products contained less than 10% crystals. The concentration of halogens in the fluid phase after the experiment was calculated from mass balance, and the partition coefficients for both Cl and F at the studied conditions determined. Using these measurements and thermodynamical models, the dependence of these partition coefficients on the fugacities of various gaseous species was investigated.

  20. Origins of Linear Partitioning in Binary Solutions: the Exchange Coefficient

    NASA Astrophysics Data System (ADS)

    Morse, S. A.

    2006-05-01

    Linear partitioning occurs when, as often in petrologic systems and perhaps always in azeotropes, a straight- line relationship occurs when the partition coefficient D = X1S/X1L is plotted against the solid composition X2S and runs from an intercept value KD at pure (2) to 1.0 at pure (1). The equation is then D = KD*X2S + X1S (Morse 1997, JGeol 105:471; 2000 GCA, 64:2309). The notation KD was taken from its long-standing familiarity in binary solutions (Roeder & Emslie 1970, CMP 29:275) and described as the exchange coefficient (Beattie et al. 1993 GCA 57:1605). But the binary loop is not in itself an exchange equilibrium; it is a transfer equilibrium marching to a different drummer, and that causes a problem (Kretz 2005, CanMin 43:1349). In at least three ways, the binary loop qualifies as an exchange reaction and justifies calling the intercept KD. To the experimentalist this issue never arises. In a perfect liquidus experiment, an infinitesimal mass of liquid is indeed transferred to the crystal. A second bulk composition is then made, and at the new liquidus a second mass transfer occurs. The ensemble of all such perfect partitioning experiments in sufficient number then completely delineates the binary loop without any continuous transfer at changing T having taken place. The partitionings are therefore truly independent of the path. Moreover, each equilibrium pair defines a common tangent in G-X space whose intercept at pure (2) unarguably gives the value of the common chemical potential, a partial Gibbs energy. But where is the exchange reaction? The real experimentalist makes no perfect experiments, and neither does nature. In reality, the barrier to nucleation (particularly formidable in the case of plagioclase) dictates that the crystals nucleate only at some supercooling. They therefore have some composition between the initial solidus and the liquid lying at the bulk composition (BC). Over time the two phases may drift apart by diffusion, the crystal

  1. Clinopyroxene and perovskite partition coefficients in kamafugitic rocks

    NASA Astrophysics Data System (ADS)

    D Amelio, F.; Ruberti, E.; Gomes, C. B.; Lustrino, M.; Melluso, L.; Morbidelli, L.; Morra, V.

    2003-04-01

    A LAM-ICP-MS study has been carried out on clinopyroxene and perovskite in kamafugitic rocks of the Alto Paranaíba Igneous Province (Brazil) in order to determine partition coefficients of 22 trace elements. Clinopyroxene ranges from diopside to salite; few Na-richer samples plot between diopside and augite fields. The phenocrysts are zoned with cores richer in Fe2+ (> 0.1 a.p.f.u.) and poorer in Ti (< 0.02 a.p.f.u.), compared to rims richer in Ca (> 0.9 a.p.f.u.), Mg (> 0.8 a.p.f.u.) and Ti (0.025-0.8 a.p.f.u.). Groundmass clinopyroxene is chemically similar to phenocrysts rims. Trace elements contents allow to distinguish two types of clinopyroxene: the first type (Mg#=0.44-0.74) is rich in Y (av. Y=83 ppm), HREE (av. La/Yb=4) and poor in Sr (av. Sr=280 ppm) and Ti (av. Ti=4000 ppm) showing Eu negative anomaly. The second type (Mg#=0.83-0.88) is rich in Sr (av. Sr=740 ppm) and in LREE (av. La/Yb=28). Due to the absence of glass in groundmass, mass-balance calculations have been performed in order to determine the trace elements composition of melts in equilibrium with the phases. Average calculated clinopyroxene/melt partition coefficients (DZr=0.167; DHf=0.222; DSr=0.169; DNb=0.009; DTa=0.005; DTi=0.200; DY=0.690; DLa=0.060; DCe=0.120; DNd=0.205; DSm=0.358; DYb=0.994) agree well with results from previous studies on similar rocks. Perovskite shows an ideal molecular formula CaTiO3 (93-96 wt%), with variable Ce2O3 (0.21-2.74 wt%), Nb2O5 (0.17-0.40 wt%), Na2O (0.40-0.95 wt%) and SrO (0.25-0.95 wt%). Perovskites are zoned, with cores richer in REE and poorer in CaO and SrO than the rims (average contents for cores: La=0.86 wt%, Ce=2.34 wt%, CaO=36 wt%, SrO=0.30 wt%; rims: La=0.37 wt%, Ce=0.82 wt%, CaO=40 wt%, SrO=0.50 wt%). Perovskite/melt partition coefficients have been determined on potassic ultramafic rocks for the first time. Zr, Hf, and Sr are incompatible or slightly compatible (DZr=0.31-1.16; DHf=0.39-2.10; DSr=1.12-1.94); Nb, Ta, Ti, Y and REE are highly

  2. ESTIMATION OF WATER SOLUBILITY AND OCTANOL/WATER PARTITION COEFFICIENT OF HYDROPHOBIC DYES - PART I. RELATIONSHIP BETWEEN SOLUBILITY AND PARTITION COEFFICIENT

    EPA Science Inventory

    Three regression approaches are examined for use in estimating water solubilities and octanol/water partition coefficients, two fundamental equilibrium constants that are widely used predicting the fate of organic chemicals in aquatic systems. pproaches examined are regression of...

  3. Determination of partition coefficients of refrigerants by gas liquid chromatographic headspace analysis.

    PubMed

    Abraham, Michael H; Gil-Lostes, Javier; Corr, Stuart; Acree, William E

    2012-11-23

    Gas-water partition coefficients, K(w), and gas-solvent partition coefficients, K(s), have been determined for chlorodifluoromethane and for 1,1,1,3,3,3-hexafluoropropane by headspace analysis, using a very simple experimental procedure. These partition coefficients then yield water-solvent partition coefficients, P(s). Where comparisons can be made there is excellent agreement with literature values for K(w) and P(s). The obtained values of K(s) and P(s) can be used to obtain physicochemical properties, or descriptors, for the refrigerants. Combination of these descriptors with previous equations we have developed enables partition coefficients to be obtained for a host of systems. PMID:23089519

  4. Experimental Method Development for Estimating Solid-phase Diffusion Coefficients and Material/Air Partition Coefficients of SVOCs

    EPA Science Inventory

    The solid-phase diffusion coefficient (Dm) and material-air partition coefficient (Kma) are key parameters for characterizing the sources and transport of semivolatile organic compounds (SVOCs) in the indoor environment. In this work, a new experimental method was developed to es...

  5. Partition coefficients of organic compounds in lipid-water systems and correlations with fish bioconcentration factors

    USGS Publications Warehouse

    Chiou, C.T.

    1985-01-01

    Triolein-water partition coefficients (KtW) have been determined for 38 slightly water-soluble organic compounds, and their magnitudes have been compared with the corresponding octanol-water partition coefficients (KOW). In the absence of major solvent-solute interaction effects in the organic solvent phase, the conventional treatment (based on Raoult's law) predicts sharply lower partition coefficients for most of the solutes in triolein because of its considerably higher molecular weight, whereas the Flory-Huggins treatment predicts higher partition coefficients with triolein. The data are in much better agreement with the Flory-Huggins model. As expected from the similarity in the partition coefficients, the water solubility (which was previously found to be the major determinant of the KOW) is also the major determinant for the Ktw. When the published BCF values (bioconcentration factors) of organic compounds in fish are based on the lipid content rather than on total mass, they are approximately equal to the Ktw, which suggests at least near equilibrium for solute partitioning between water and fish lipid. The close correlation between Ktw and Kow suggests that Kow is also a good predictor for lipid-water partition coefficients and bioconcentration factors.

  6. Partition coefficients of Hf, Zr, and REE between phenocrysts and groundmasses

    NASA Technical Reports Server (NTRS)

    Fujimaki, H.; Tatsumoto, M.; Aoki, K.-I.

    1984-01-01

    Partition coefficients of Hf, Zr, and REE between olivine, orthopyroxene, clinopyroxene, plagioclase, garnet, amphibole, ilmenite, phlogopite, and liquid are presented. Samples consist of megacrysts in kimberlite, phenocrysts in alkaline basalts, tholeiitic basalts and andesitic to dacitic rocks, and synthetic garnet and clinopyroxene in Hawaiian tholeiites. The Hf-Lu and Zr-Lu elemental fractionations are as large as the Lu-Sm or Lu-Nd fractionation. The Hf and Zr partition coefficients between mafic phenocrysts and liquids are smaller than the Lu partition coefficients, but are similar to the Nd or Sm partition coefficients. The Hf and Zr partition coefficients between ilmenite, phlogopite, and liquid are larger than the Lu partition coefficients for these minerals and their corresponding liquids. The Hf-Zr elemental fractionation does not occur except for extreme fractionation involving Zr-minerals and extremely low fO2. These data have an important bearing on chronological and petrogenetic tracer studies involving the Lu-Hf isotopic system.

  7. Garnet/high-silica rhyolite trace element partition coefficients measured by ion microprobe

    USGS Publications Warehouse

    Sisson, T.W.; Bacon, C.R.

    1992-01-01

    Garnet/liquid trace element partition coefficients have been measured in situ by ion microprobe in a rhyolite from Monache Mountain, California. Partition coefficients are reported for La, Ce, Nd, Sm, Dy, Er, Yb, Sc, Ti, V, Cr, Sr, Y, and Zr. The in situ analyses avoid the problem of contamination of the garnet phase by trace element-rich accessory minerals encountered in traditional bulk phenocryst/matrix partitioning studies. The partitioning pattern for the rare earth elements (REEs, excluding Eu) is smooth and rises steeply from the light to the heavy REEs with no sharp kinks or changes in slope, unlike patterns for garnet /silicic liquid REE partitioning determined by bulk methods. This difference suggests that the previous determinations by bulk methods are in error, having suffered from contamination of the phenocryst separates. ?? 1992.

  8. Prediction of Partition Coefficients of Organic Compounds between SPME/PDMS and Aqueous Solution

    PubMed Central

    Chao, Keh-Ping; Lu, Yu-Ting; Yang, Hsiu-Wen

    2014-01-01

    Polydimethylsiloxane (PDMS) is commonly used as the coated polymer in the solid phase microextraction (SPME) technique. In this study, the partition coefficients of organic compounds between SPME/PDMS and the aqueous solution were compiled from the literature sources. The correlation analysis for partition coefficients was conducted to interpret the effect of their physicochemical properties and descriptors on the partitioning process. The PDMS-water partition coefficients were significantly correlated to the polarizability of organic compounds (r = 0.977, p < 0.05). An empirical model, consisting of the polarizability, the molecular connectivity index, and an indicator variable, was developed to appropriately predict the partition coefficients of 61 organic compounds for the training set. The predictive ability of the empirical model was demonstrated by using it on a test set of 26 chemicals not included in the training set. The empirical model, applying the straightforward calculated molecular descriptors, for estimating the PDMS-water partition coefficient will contribute to the practical applications of the SPME technique. PMID:24534804

  9. Prediction of partition coefficients of organic compounds between SPME/PDMS and aqueous solution.

    PubMed

    Chao, Keh-Ping; Lu, Yu-Ting; Yang, Hsiu-Wen

    2014-01-01

    Polydimethylsiloxane (PDMS) is commonly used as the coated polymer in the solid phase microextraction (SPME) technique. In this study, the partition coefficients of organic compounds between SPME/PDMS and the aqueous solution were compiled from the literature sources. The correlation analysis for partition coefficients was conducted to interpret the effect of their physicochemical properties and descriptors on the partitioning process. The PDMS-water partition coefficients were significantly correlated to the polarizability of organic compounds (r = 0.977, p < 0.05). An empirical model, consisting of the polarizability, the molecular connectivity index, and an indicator variable, was developed to appropriately predict the partition coefficients of 61 organic compounds for the training set. The predictive ability of the empirical model was demonstrated by using it on a test set of 26 chemicals not included in the training set. The empirical model, applying the straightforward calculated molecular descriptors, for estimating the PDMS-water partition coefficient will contribute to the practical applications of the SPME technique. PMID:24534804

  10. Predicting solute partitioning in lipid bilayers: Free energies and partition coefficients from molecular dynamics simulations and COSMOmic

    NASA Astrophysics Data System (ADS)

    Jakobtorweihen, S.; Zuniga, A. Chaides; Ingram, T.; Gerlach, T.; Keil, F. J.; Smirnova, I.

    2014-07-01

    Quantitative predictions of biomembrane/water partition coefficients are important, as they are a key property in pharmaceutical applications and toxicological studies. Molecular dynamics (MD) simulations are used to calculate free energy profiles for different solutes in lipid bilayers. How to calculate partition coefficients from these profiles is discussed in detail and different definitions of partition coefficients are compared. Importantly, it is shown that the calculated coefficients are in quantitative agreement with experimental results. Furthermore, we compare free energy profiles from MD simulations to profiles obtained by the recent method COSMOmic, which is an extension of the conductor-like screening model for realistic solvation to micelles and biomembranes. The free energy profiles from these molecular methods are in good agreement. Additionally, solute orientations calculated with MD and COSMOmic are compared and again a good agreement is found. Four different solutes are investigated in detail: 4-ethylphenol, propanol, 5-phenylvaleric acid, and dibenz[a,h]anthracene, whereby the latter belongs to the class of polycyclic aromatic hydrocarbons. The convergence of the free energy profiles from biased MD simulations is discussed and the results are shown to be comparable to equilibrium MD simulations. For 5-phenylvaleric acid the influence of the carboxyl group dihedral angle on free energy profiles is analyzed with MD simulations.

  11. Predicting solute partitioning in lipid bilayers: Free energies and partition coefficients from molecular dynamics simulations and COSMOmic

    SciTech Connect

    Jakobtorweihen, S. Ingram, T.; Gerlach, T.; Smirnova, I.; Zuniga, A. Chaides; Keil, F. J.

    2014-07-28

    Quantitative predictions of biomembrane/water partition coefficients are important, as they are a key property in pharmaceutical applications and toxicological studies. Molecular dynamics (MD) simulations are used to calculate free energy profiles for different solutes in lipid bilayers. How to calculate partition coefficients from these profiles is discussed in detail and different definitions of partition coefficients are compared. Importantly, it is shown that the calculated coefficients are in quantitative agreement with experimental results. Furthermore, we compare free energy profiles from MD simulations to profiles obtained by the recent method COSMOmic, which is an extension of the conductor-like screening model for realistic solvation to micelles and biomembranes. The free energy profiles from these molecular methods are in good agreement. Additionally, solute orientations calculated with MD and COSMOmic are compared and again a good agreement is found. Four different solutes are investigated in detail: 4-ethylphenol, propanol, 5-phenylvaleric acid, and dibenz[a,h]anthracene, whereby the latter belongs to the class of polycyclic aromatic hydrocarbons. The convergence of the free energy profiles from biased MD simulations is discussed and the results are shown to be comparable to equilibrium MD simulations. For 5-phenylvaleric acid the influence of the carboxyl group dihedral angle on free energy profiles is analyzed with MD simulations.

  12. Predicting solute partitioning in lipid bilayers: Free energies and partition coefficients from molecular dynamics simulations and COSMOmic.

    PubMed

    Jakobtorweihen, S; Zuniga, A Chaides; Ingram, T; Gerlach, T; Keil, F J; Smirnova, I

    2014-07-28

    Quantitative predictions of biomembrane/water partition coefficients are important, as they are a key property in pharmaceutical applications and toxicological studies. Molecular dynamics (MD) simulations are used to calculate free energy profiles for different solutes in lipid bilayers. How to calculate partition coefficients from these profiles is discussed in detail and different definitions of partition coefficients are compared. Importantly, it is shown that the calculated coefficients are in quantitative agreement with experimental results. Furthermore, we compare free energy profiles from MD simulations to profiles obtained by the recent method COSMOmic, which is an extension of the conductor-like screening model for realistic solvation to micelles and biomembranes. The free energy profiles from these molecular methods are in good agreement. Additionally, solute orientations calculated with MD and COSMOmic are compared and again a good agreement is found. Four different solutes are investigated in detail: 4-ethylphenol, propanol, 5-phenylvaleric acid, and dibenz[a,h]anthracene, whereby the latter belongs to the class of polycyclic aromatic hydrocarbons. The convergence of the free energy profiles from biased MD simulations is discussed and the results are shown to be comparable to equilibrium MD simulations. For 5-phenylvaleric acid the influence of the carboxyl group dihedral angle on free energy profiles is analyzed with MD simulations. PMID:25084963

  13. Large partition coefficients for trace elements in high-silica rhyolites

    USGS Publications Warehouse

    Mahood, G.; Hildreth, W.

    1983-01-01

    The partitioning of 25 trace elements between high-silica rhyolitic glass and unzoned phenocrysts of potassic and sodic sanidine, biotite, augite, ferrohedenbergite, hypersthene, fayalite, titanomagnetite, ilmenite, zircon, and allanite has been determined by INAA on suites of samples from the mildly peralkaline lavas and tuff of the Sierra La Primavera, Mexico, and the metaluminous, compo. sitionally zoned, Bishop Tuff, California. The partition coefficients are much larger than published values for less silicic compositions; the range of values among Primavera samples that differ only slightly in temperature or bulk composition approaches that previously reported from basalts to rhyodacites. Intrinsic temperature dependence of the crystal/liquid partitioning is apparently small. The high values of partition coefficients reflect principally the strongly polymerized nature of the alkali-aluminosilicate liquid, whereas the marked variability of values for partition coefficients is attributed to differences in the concentrations of complexing ligands and/or different degrees of melt polymerization. Great variation in the values of partition coefficients that are potentially applicable to early stages in the partial melting of crustal rocks complicates assessment of 1. (1) source regions for granitic melts and 2. (2) contributions by crustal-melt increments to andesites. ?? 1983.

  14. Calculating Partition Coefficients of Small Molecules in Octanol/Water and Cyclohexane/Water.

    PubMed

    Bannan, Caitlin C; Calabró, Gaetano; Kyu, Daisy Y; Mobley, David L

    2016-08-01

    Partition coefficients describe how a solute is distributed between two immiscible solvents. They are used in drug design as a measure of a solute's hydrophobicity and a proxy for its membrane permeability. We calculate partition coefficients from transfer free energies using molecular dynamics simulations in explicit solvent. Setup is done by our new Solvation Toolkit which automates the process of creating input files for any combination of solutes and solvents for many popular molecular dynamics software packages. We calculate partition coefficients between octanol/water and cyclohexane/water with the Generalized AMBER Force Field (GAFF) and the Dielectric Corrected GAFF (GAFF-DC). With similar methods in the past we found a root-mean-squared error (RMSE) of 6.3 kJ/mol in hydration free energies which would correspond to an error of around 1.6 log units in partition coefficients if solvation free energies in both solvents were estimated with comparable accuracy. Here we find an overall RMSE of about 1.2 log units with both force fields. Results from GAFF and GAFF-DC seem to exhibit systematic biases in opposite directions for calculated cyclohexane/water partition coefficients. PMID:27434695

  15. Multiphase Oscillatory Flow Strategy for in Situ Measurement and Screening of Partition Coefficients.

    PubMed

    Abolhasani, Milad; Coley, Connor W; Jensen, Klavs F

    2015-11-01

    Taking advantage of the difference between the surface energies of aqueous and organic solvents on a Teflon substrate, a fully automated small-scale strategy is developed on the basis of gas-driven oscillatory motion of a biphasic slug for high-throughput in situ measurement and screening of partition coefficients of organic substances between aqueous and organic phases. The developed oscillatory flow strategy enables single partition coefficient data point measurement within 8 min (including the sample preparation time) which is 360 times faster than the conventional "shake-flask" method, while using less than a 30 μL volume of the two phases and 9 nmol of the target organic substance. The developed multiphase strategy is validated using a conventional shake-flask technique. Finally, the developed strategy is extended to include automated screening of partition coefficients at physiological temperature. PMID:26436292

  16. The dependence of the lipid bilayer membrane: buffer partition coefficient of pentobarbitone on pH and lipid composition.

    PubMed Central

    Miller, K W; Yu, S C

    1977-01-01

    1 The membrane/buffer partition coefficient of [14C]-pentobarbitone has been determined as a function of the lipid composition of bilayer membranes. 2 A new technique based on ultrafiltration gave comparable results to conventional techniques but required less time for equilbration. 3 The membrane/buffer coefficient was independent of pentobarbitone concentration in the range studies. 4 The apparent partition coefficient varied with pH and was a linear function of the degree of dissociation of pentobarbition. 5 Both the charged and uncharged forms of pentobarbitone partitioned into the membrane, the latter to a much greater extent than the former. 6 At low pH the highest partition coefficient observed was in egg phosphatidylcholine bilayer membranes. 7 Incorporation of cholesterol or phosphatidic acid into phosphatidylcholine membranes greatly reduced the partition coefficient. 8 High pressures do not greatly change these partition coefficients. PMID:21013

  17. Partition coefficients for Al, Ca, Ti, Cr, and Ni in olivine obtained by melting experiment on an LL6 chondrite

    NASA Technical Reports Server (NTRS)

    Miyamoto, M.; Mikouchi, T.; Mckay, G. A.

    1994-01-01

    We report the partition coefficients for Ca, Al, Ti, Cr, and Ni in olivine obtained through a series of melting experiments on an LL6 chondrite under varying conditions of temperature and oxygen fugacity. It is necessary to examine the variation of partition coefficients up to extremely reducing conditions in order to study meteoritic olivines. For Ca, Al, and Cr, the partition coefficients tend to decrease as temperature increases, but do not change even under extremely reducing conditions.

  18. Trophic Magnification of PCBs and Its Relationship to the Octanol−Water Partition Coefficient

    EPA Science Inventory

    We investigated polychlorinated biphenyl (PCB) bioaccumulation relative to octanol-water partition coefficient (KOW) and organism trophic position (TP) at the Lake Hartwell Superfund (South Carolina, USA). We measured PCBs (127 congeners) and stable isotopes (δ15...

  19. Local cerebral blood flow and partition coefficients measured in cerebral astrocytomas of different grades of malignancy

    SciTech Connect

    Tachibana, H.; Meyer, J.S.; Rose, J.E.; Kandula, P.

    1984-02-01

    Local cerebral blood flow and local partition coefficients were measured in patients with different grades of malignant cerebral astrocytomas (n . 5) who inhaled 35% stable xenon during computed tomography scanning. Results were compared with those in age-matched normal subjects (n . 5. Mean values for local cerebral blood flow in the gray matter in patients with astrocytomas were decreased throughout the tumor mass and surrounding brain that was apparently free of tumor. Patients with highly malignant glioblastoma multiforme (astrocytoma grade IV; n . 2) showed more variable values for local cerebral blood flow and local partition coefficients compared to those with astrocytomas of lower grades (grades I-II; n . 3). Local partition coefficients in gray matter invaded by grade IV astrocytoma were significantly higher than those in gray matter invaded by grade I-III astrocytomas. Local cerebral blood flow and local partition coefficients in the brain tissue surrounding grade IV astrocytomas were reduced to a greater extent than those in more benign tumors.

  20. Carbon Tetrachloride and Chloroform Partition Coefficients Derived from Aqueous Desorption of Contaminated Hanford Sediments

    SciTech Connect

    Riley, Robert G.; Sklarew, Debbie S.; Brown, Christopher F.; Gent, Philip M.; Szecsody, Jim E.; Mitroshkov, Alexandre V.; Thompson, Christopher J.

    2005-07-08

    Researchers at PNNL determined CCl4 and CHCl3 groundwater/sediment partition coefficients (Kd values) for contaminated aquifer sediments collected from borehole C3246 (299-W15-46) located in the 200 West Area adjacent to the Z-9 trench. Having realistic values for this parameter is critical to predict future movement of CCl4 in groundwater from the 200 West Area.

  1. CALCULATION OF SOIL-WATER AND BENTHIC SEDIMENT PARTITION COEFFICIENTS FOR MERCURY

    EPA Science Inventory

    To accurately model mercury transport to water bodies, an assessment of this pollutant's behavior in the watershed is critical. Partition coefficients, defined as an estimate of the ratio of the pollutant concentration sorbed onto soil/sediment particles to the pollutant concentr...

  2. PREDICTION OF OCTANOL/WATER PARTITION COEFFICIENT (KOW) WITH ALGORITHMICALLY DERIVED VARIABLES

    EPA Science Inventory

    A statistical model was developed with algorithmically derived independent variables based on chemical structure for prediction of octanol/water partition coefficients (Kow) measured for more than 4,000 chemicals. he procedure first classified the chemicals into 14 groups based o...

  3. Measurement and analysis of the mannitol partition coefficient in sucrose crystallization under simulated industrial conditions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Mannitol is a major deterioration product of Leuconstoc mesenteroides bacterial deterioration of both sugarcane and sugar beet. The effect of crystallization conditions on the mannitol partition coefficient (Keff) between impure sucrose syrup and crystal has been investigated in a batch laboratory c...

  4. Influence of colloids on sediment-water partition coefficients of polychlorobiphenyl congeners in natural waters

    SciTech Connect

    Baker, J.E.; Capel, P.D.; Eisenreich, S.J.

    1986-11-01

    Measurements of sediment-water partitioning of polychlorobiphenyl (PCB) congeners in Lake Superior provide some of the first field evidence demonstrating the importance of colloids to the fates of highly hydrophobic organic pollutants. Laboratory-derived correlations between sediment-water distribution coefficients and properties of both the contaminant (octanol-water partition coefficient) and the suspended solids (organic carbon content, concentration) do not accurately predict PCB speciation in Lake Superior. This failure can be explained by the presence of colloidal matter with which contaminants may associate and the very low solids concentrations in oligotrophic surface waters. A surprising consequence of such colloid associations is that the observed sediment-water distribution coefficients are independent of properties of highly hydrophobic compounds. A three-phase model including nonfilterable microparticles and macromolecular organic matter shows that colloidal-associated contaminants may be the dominant species in most surface waters. Colloidal associations are therefore likely to significantly impact the geochemistry of hydrophobic pollutants.

  5. Partition coefficients of organic compounds between water and imidazolium-, pyridinium-, and phosphonium-based ionic liquids.

    PubMed

    Padró, Juan M; Pellegrino Vidal, Rocío B; Reta, Mario

    2014-12-01

    The partition coefficients, P IL/w, of several compounds, some of them of biological and pharmacological interest, between water and room-temperature ionic liquids based on the imidazolium, pyridinium, and phosphonium cations, namely 1-octyl-3-methylimidazolium hexafluorophosphate, N-octylpyridinium tetrafluorophosphate, trihexyl(tetradecyl)phosphonium chloride, trihexyl(tetradecyl)phosphonium bromide, trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide, and trihexyl(tetradecyl)phosphonium dicyanamide, were accurately measured. In this way, we extended our database of partition coefficients in room-temperature ionic liquids previously reported. We employed the solvation parameter model with different probe molecules (the training set) to elucidate the chemical interactions involved in the partition process and discussed the most relevant differences among the three types of ionic liquids. The multiparametric equations obtained with the aforementioned model were used to predict the partition coefficients for compounds (the test set) not present in the training set, most being of biological and pharmacological interest. An excellent agreement between calculated and experimental log P IL/w values was obtained. Thus, the obtained equations can be used to predict, a priori, the extraction efficiency for any compound using these ionic liquids as extraction solvents in liquid-liquid extractions. PMID:25326892

  6. Experimental method development for estimating solid-phase diffusion coefficients and material/air partition coefficients of SVOCs

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoyu; Guo, Zhishi; Roache, Nancy F.

    2014-06-01

    The solid-phase diffusion coefficient (Dm) and material/air partition coefficient (Kma) are key parameters for characterizing the sources and transport of semivolatile organic compounds (SVOCs) in the indoor environment. In this work, a new experimental method was developed to estimate parameters Dm and Kma. The SVOCs chosen for study were polychlorinated biphenyl (PCB) congeners, including PCB-52, PCB-66, PCB-101, PCB-110, and PCB-118. The test materials included polypropylene, high density polyethylene, low density polyethylene, polytetrafluoroethylene, polyether ether ketone, glass, stainless steel and concrete. Two 53-L environmental chambers were connected in series, with the relatively stable SVOCs source in the source chamber and the test materials, made as small “buttons”, in the test chamber. Prior to loading the test chamber with the test materials, the test chamber had been dosed with SVOCs for 12 days to “coat” the chamber walls. During the tests, the material buttons were removed from the test chamber at different exposure times to determine the amount of SVOC absorbed by the buttons. SVOC concentrations at the inlet and outlet of the test chamber were also monitored. The data were used to estimate the partition and diffusion coefficients by fitting a sink model to the experimental data. The parameters obtained were employed to predict the accumulation of SVOCs in the sink materials using an existing mass transfer model. The model prediction agreed reasonably well with the experimental data.

  7. Partition coefficients of organic compounds in new imidazolium based ionic liquids using inverse gas chromatography.

    PubMed

    Revelli, Anne-Laure; Mutelet, Fabrice; Jaubert, Jean-Noël

    2009-06-01

    Partition coefficients of organic compounds in four ionic liquids: 1-ethanol-3-methylimidazolium tetrafluoroborate, 1-ethanol-3-methylimidazolium hexafluorophosphate, 1,3-dimethylimidazolium dimethylphosphate and 1-ethyl-3-methylimidazolium diethylphosphate were measured using inverse gas chromatography from 303.3 to 332.55K. The influence of gas-liquid and gas-solid interfacial adsorption of different solutes on ionic liquids was also studied. Most of the polar solutes were retained largely by partition while light hydrocarbons were retained predominantly by interfacial adsorption on the ionic liquids studied in this work. The solvation characteristics of the ionic liquids were evaluated using the Abraham solvation parameter model. PMID:19414174

  8. The effect of glycerol, propylene glycol and polyethylene glycol 400 on the partition coefficient of benzophenone-3 (oxybenzone).

    PubMed

    Mbah, C J

    2007-01-01

    Sunscreen products are widely used to protect the skin from sun-related deleterious effects. The objective of the study was to investigate the potential effect of glycerol, propylene glycol and polyethylene glycol 400 on dermal absorption of oxybenzone by studying their effects on its partition coefficient. The partition coefficient was evaluated in a chloroform-water system at room temperature. It was found that glycerol and propylene glycol decreased the partition coefficient of oxybenzone, while an increase in partition coefficient was observed with polyethylene glycol 400. The findings suggest that polyethylene glycol 400 in contrast to glycerol and propylene glycol has the potential of increasing the vehicle-skin partition coefficient of oxybenzone when cosmetic products containing such an UV absorber are topically applied to the skin. PMID:17294811

  9. Protein partition coefficients can be estimated efficiently by hybrid shortcut calculations.

    PubMed

    Kress, Christian; Sadowski, Gabriele; Brandenbusch, Christoph

    2016-09-10

    The extraction of therapeutic proteins like monoclonal antibodies in aqueous two-phase systems (ATPS) is a suitable alternative to common cost intensive chromatographic purification steps within the downstream processing. Thereby the protein partitioning can be selectively changed using a displacement agent (additional salt) in order to allow for a successful purification of the target protein. Within this work a new shortcut strategy for the calculation of protein partition coefficients in polymer-salt ATPS is presented. The required protein-solute (phase-forming component, displacement agent) interactions are covered by the cross virial coefficient B23 measured by composition gradient multi-angle light scattering (CG-MALS). Using this shortcut calculation allows for an efficient determination of the partition coefficients of the target protein immunoglobulin G (IgG) and the impurity human serum albumin (HSA) within PEG-citrate and PEG-phosphate ATPS independently on the protein concentration. We demonstrate that the selection of a suitable displacement agent allowing for a selective purification of IgG from HSA is accessible by B23. Based on the determination of the protein-protein interactions via CG-MALS covered by the second osmotic virial coefficient B22 a further optimization of ATPS preventing protein precipitation is enabled. The results show that our approach contributes to an efficient downstream processing development. PMID:27388598

  10. Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

    NASA Technical Reports Server (NTRS)

    King, C.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

    2010-01-01

    Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

  11. Determining Partition Coefficient (Log P), Distribution Coefficient (Log D) and Ionization Constant (pKa) in Early Drug Discovery.

    PubMed

    Bharate, Sonali S; Kumar, Vikas; Vishwakarma, Ram A

    2016-01-01

    An early prediction of physicochemical properties is highly desirable during drug discovery to find out a viable lead candidate. Although there are several methods available to determine partition coefficient (log P), distribution coefficient (log D) and ionization constant (pKa), none of them involves simple and fixed, miniaturized protocols for diverse set of compounds. Therefore, it is necessary to establish simple, uniform and medium-throughput protocols requiring small sample quantities for the determination of these physicochemical properties. Log P and log D were determined by shake flask method, wherein, the compound was partitioned between presaturated noctanol and water phase (water/PBS pH 7.4) and the concentration of compound in each phase was determined by HPLC. The pKa determination made use of UV spectrophotometric analysis in a 96-well microtiter plate containing a series of aqueous buffers ranging from pH 1.0 to 13.0. The medium-throughput miniaturized protocols described herein, for determination of log P, log D and pKa, are straightforward to set up and require very small quantities of sample (< 5 mg for all three properties). All established protocols were validated using diverse set of compounds. PMID:27137915

  12. Descriptors for the Prediction of Partition Coefficients and Solubilities of Organophosphorus Compounds

    PubMed Central

    Acree, William E.

    2013-01-01

    From literature data on partition coefficients and in some cases solubilities in nonaqueous solvents we have been able to determine Abraham descriptors for several series of organophosphorus compounds including the dialkyl- and diaryl-phosphates (dialkylphosphoric acids), trialkyl- and triphenyl-phosphates, dialkylphosphinic acids and diphenylphosphinic acid, trialkyl- and triaryl-phosphine oxides, and dialkylphosphites and triarylphosphines. Other organophosphorus compounds studied were dimethyl methylphosphonate and the flame retardant PBMP. For all these compounds, knowledge of the Abraham descriptors enables partition coefficients to be predicted for transfer from water to over 40 (wet) solvents. If the solubility of a given compound in just one dry solvent (out of a list of 47 dry solvents) is available, then the solubility in all the other listed dry solvents can be predicted through very simple equations. PMID:25170182

  13. Ionization constants by curve fitting: application to the determination of partition coefficients.

    PubMed

    Clarke, F H

    1984-02-01

    A multiparametric curve-fitting technique for pKa calculation has been adapted for use with a programmable calculator or microcomputer. This method provides for the convenient and accurate determination of the ionization constant in aqueous solution and of the apparent ionization constant in the presence of octanol. From these parameters, partition coefficients and apparent partition coefficients are easily calculated and agree with data reported using the shaker technique or HPLC. The curve-fitting method has been applied to the differential titration technique in which the solvent curve is subtracted from the solution curve before calculations are begun. This method has been applied to the potentiometric titration of aqueous solutions of the salts of bases with a very low solubility in water. PMID:6707889

  14. Hf, Zr, and REE partition coefficients between ilmenite and liquid - Implications for lunar petrogenesis

    NASA Technical Reports Server (NTRS)

    Nakamura, Y.; Fujimaki, H.; Nakamura, N.; Tatsumoto, M.; Mckay, G. A.

    1986-01-01

    Partition coefficients (D) between ilmenite and coexisting liquid were determined under near-lunar conditions for Hf, Zr, and REE. Through isotope dilution analysis, ilmenite D values of 0.41 and 0.33 were obtained for Hf and Zr respectively, values significantly lower than those of ilmenite from a kimberlite megacryst. Partition coefficients of REE for the synthesized ilmenite are slightly smaller than those of ilmenite from the kimberlite megacryst, and the lunar (Lu) partition coefficient is 0.056. These results suggest that ilmenite was significant in the lunar-Hf evolution of lunar mare basalts. Using lunar and Hf D values for ilmenite, the Lu-Hf evolution of lunar cumulates and the coexisting magma was examined for various crystallization sequences. The Lu-Hf variation trend of most high-Ti mare basalts is explained by a small degree of partial cumulate melting, though a higher degree is required to explain the variation of very low-Ti basalts, green glass, and Apollo 12 low-Ti basalts. Apollo 15 low-Ti basalts may require chromite crystallization as well.

  15. Measurement of octanol-air partition coefficients for polycyclic aromatic hydrocarbons and polychlorinated naphthalenes

    SciTech Connect

    Harner, T.; Bidleman, T.F. |

    1998-01-01

    Measurements of the octanol-air partition coefficient, K{sub OA}, are reported for 4 polycyclic aromatic hydrocarbons (PAHs) and 24 polychlorinated naphthalenes (PCNs) as a function of temperature over the range (0 to 50) C. Results for PAHs are within a factor of 1.5 to 2 of values calculated as the ratio of the octanol-water and air-water partition coefficients. The enthalpies of transfer from octanol to air, {Delta}{sub O}{sup A}H, for fluorene, phananthrene and pyrene are (82.9, 75.5, and 76.3) kJ/mol, respectively. Except for fluorene, these are within the range of reported values of the enthalpy of vaporization, {Delta}{sub vap}H. There is also good agreement between {Delta}{sub O}{sup A}H and the temperature coefficient for vegetation-atmosphere partitioning (Q{sub D}). Correlations of log K{sub OA} against log vapor pressure (p{sup 0}) are compared with previous results for polychlorinated biphenyls (PCBs). Values of log K{sub OA} for PCNs show a stepwise change and increase by more than 3 orders of magnitude from the 2-Cl to 6-Cl homologue groups.

  16. Partition coefficient of cadmium between organic soils and bean and oat plants

    SciTech Connect

    Siddqui, M.F.R.; Courchesne, F.; Kennedy, G.; Zayed, J.

    1995-12-31

    Environmental fate models require the partition coefficient data of contaminants among two or more environmental compartments. The bioaccumulation of cadmium (Cd) by bean and oat plants grown on organic soils in a controlled growth chamber was investigated to validate the plant/soil partition coefficient. Total Cd was measured in the soils and in the different parts of the plants. The mean total Cd concentrations for soil cultivated with beans and oats were 0.86 and 0.69 {micro}g/g, respectively. Selective extractants (BaCl{sub 2}, Na-pyrophosphate and HNO{sub 3}-hydroxy) were used to evaluate solid phase Cd species in the soil. In the soil cultivated with bean, BaCl{sub 2} exchangeable, Na-pyrophosphate extractable and HNO{sub 3}-NH{sub 2}OH extractable Cd represented 1.2, 1.6 and 50.9% of total soil Cd, respectively. For the soil cultivated with oats, the same extractants gave values of 1.1, 1.8 and 61.9%. Cd concentration levels in bean plants followed the sequence roots > fruits = stems > leaves (p < 0.01) while the following sequence was observed for oat plants: roots > fruits > stems > leaves (p < 0.05). The partition coefficient for total Cd (Cd{sub Plant tissue}/Cd{sub Soil}) was in the range of 0.28--0.55 for bean plants and 1.03--1.86 for oat plants.

  17. Lipid-water partition coefficients and correlations with uptakes by algae of organic compounds.

    PubMed

    Hung, Wei-Nung; Chiou, Cary T; Lin, Tsair-Fuh

    2014-08-30

    In view of the scarcity of the lipid-water partition coefficients (Ktw) for organic compounds, the logKtw values for many environmental contaminants were measured using ultra-pure triolein as the model lipid. Classes of compounds studied include alkyl benzenes, halogenated benzenes, short-chain chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides. In addition to logKtw determination, the uptakes of these compounds from water by a dry algal species were measured to evaluate the lipid effect on the algal uptake. The measured logKtw are closely related to their respective logKow (octanol-water), with logKow=1.9 to 6.5. A significant difference is observed between the present and early measured logKtw for compounds with logKow>∼5, which is attributed to the presence and absence of a triolein microemulsion in water affecting the solute partitioning. The observed lipid-normalized algae-water distribution coefficients (logKaw/lipid) are virtually identical to the respective logKtw values, which manifests the dominant lipid-partition effect of the compounds with algae. PMID:25064256

  18. Ambient gas/particle partitioning. 3. Estimating partition coefficients of apolar, polar, and ionizable organic compounds by their molecular structure.

    PubMed

    Arp, Hans Peter H; Gosses, Kai-Uwe

    2009-03-15

    Equilibrium gas/particle partitioning coefficients of terrestrial aerosols, Kip, are dependent on various intermolecular interactions that can be quantified by experimentally determined compound-specific descriptors. For many compounds of environmental interest, such as emerging contaminants and atmospheric phototransformation products, these compound-specific descriptors are unknown or immeasurable. Often, only the molecular structure is known. Here we present the ability of two computer programs to predict equilibrium partitioning to terrestrial aerosols solely on the basis of molecular structure: COSMOtherm and SPARC. The greatest hurdle with designing such an approach is to identify suitable molecular surrogates to represent the dominating sorbing phases, which for ambient terrestrial aerosols are the water insoluble organic matter (WIOM) phase and the mixed-aqueous phase. For the WI0M phase, hypothetical urban secondary organic aerosol structural units from Kalberer et al. Science 2004, 303, 1659-1662 were investigated as input surrogates, and for the mixed-aqueous phase mildly acidic water was used as a surrogate. Using a validation data set of more than 1400 experimentally determined Kip values for polar, apolar, and ionic compounds ranging over 9 orders of magnitude (including semivolatile compounds such as PCDD/Fs, pesticides, and PBDEs), SPARC and COSMOtherm were generally able to predict Kip values well within an order of magnitude over an ambient range of temperature and relative humidity. This is remarkable as these two models were not fitted or calibrated to any experimental data. As these models can be used for potentially any organic molecule, they are particularly recommended for environmental screening purposes and for use when experimental compound descriptor data are not available. PMID:19368193

  19. Determination of partition coefficient of spin probe between different lipid membrane phases.

    PubMed

    Arsov, Zoran; Strancar, Janez

    2005-01-01

    Model lipid membranes made from binary mixtures of dimyristoylphosphatidylcholine/dipalmitoylphosphatidylcholine (DMPC/DPPC) and dimyristoylphosphatidylcholine/cholesterol (DMPC/Chol) exhibit coexistence of diverse lipid phases at appropriate temperature and composition. Since lipids in different phases show different structural and motional properties, it is expected that the corresponding spin probe electron paramagnetic resonance (EPR) spectra will be superposition of several spectral components. From comparison of proportions of spectral components of the EPR spectrum with the fractions of the corresponding lipid phases obtained from known phase diagrams the partition coefficient of spin probe methyl ester of 5-doxyl palmitate between different lipid phases was determined. The results indicate that the used spin probe partitions approximately equally between different phases. PMID:16309270

  20. Octanol-water partition coefficient of benzo(a)pyrene: measurement, calculation, and environmental implications

    SciTech Connect

    Mallon, B.J.; Harrison, F.L.

    1984-03-01

    Benzo(a)pyrene (BaP) is a potent carcinogen produced in significant quantities during pyrolysis of such substances as coal, wood, and cigarettes. Several researchers have shown that the lipophilic storage and soil sediment accumulation of many organic solutes is proportional to the partitioning between octanol-1 and water. The octanol-water partition coefficient (P) is defined as P = C/sub o//C/sub w/, where C/sub o/ and C/sub w/ are the concentration of the solute in n-octanol and water. Considerable data are available demonstrating that P values measured in the laboratory can be used to predict the environmental behavior of organic pollutants. Literature searches reveal that calculated, but not measured, log P values are reported for BaP. This laboratory study was initiated to define better the log P of BaP.

  1. Rare Earth Element Partition Coefficients from Enstatite/Melt Synthesis Experiments

    NASA Technical Reports Server (NTRS)

    Schwandt, Craig S.; McKay, Gordon A.

    1997-01-01

    Enstatite (En(80)Fs(19)Wo(01)) was synthesized from a hypersthene normative basaltic melt doped at the same time with La, Ce, Nd, Sm, Eu, Dy, Er, Yb and Lu. The rare earth element concentrations were measured in both the basaltic glass and the enstatite. Rare earth element concentrations in the glass were determined by electron microprobe analysis with uncertainties less than two percent relative. Rare earth element concentrations in enstatite were determined by secondary ion mass spectrometry with uncertainties less than five percent relative. The resulting rare earth element partition signature for enstatite is similar to previous calculated and composite low-Ca pigeonite signatures, but is better defined and differs in several details. The partition coefficients are consistent with crystal structural constraints.

  2. UNDERSTANDING VARIATION IN PARTITION COEFFICIENT KD, VALUES, VOLUME III: AMERICIUM, ARSENIC, CURIUM, IODINE, NEPTUNIUM, RADIUM, AND TECHNETIUM

    EPA Science Inventory

    This report describes the conceptualization, measurement, and use of the partition (or distribution) coefficient, Kd, parameter, and the geochemical aqueous solution and sorbent properties that are most important in controlling adsorption/retardation behavior of selected contamin...

  3. Determination of partition and diffusion coefficients of formaldehyde in selected building materials and impact of relative humidity (journal)

    EPA Science Inventory

    The partition and effective diffusion coefficients of formaldehyde were measured for three materials (conventional gypsum wallboard, "green" gypsum wallboard, and "green" carpet) under three relative humidity (RH) conditions (20%, 50% and 70% RH). A dynamic dual-chamber test meth...

  4. Determination of partition and diffusion coefficient of formaldehyde in selected building materials and impact of relative humidity

    EPA Science Inventory

    The partition and effective diffusion coefficients of formaldehyde were measured for three materials (conventional gypsum wallboard, "green" gypsum wallboard, and "green" carpet) under three relative humidity (RH) conditions (20%, 50% and 70% RH). A dynamic dual-chamber test meth...

  5. Aqueous solubilities and octanol-water partition coefficients of cymenes and chlorocymenes

    SciTech Connect

    Lun, R.; Varhanickova, D.; Shiu, W.Y.; Mackay, D.

    1997-09-01

    Aqueous discharges to the environment from pulp mill bleach plants of dissolved wood degradation products and products of reactions between bleaching chemicals and the pulp are a continuing source of pollution. The aqueous solubilities and octanol-water partition coefficients of o-cymene, m-cymene, p-cymene, 2,3-dichloro-p-cymene 2,5-dichloro-p-cymene, 2,3,6-trichloro-p-cymene and tetrachloro-p-cymene, were determined at 25 C using GC and HPLC methods. These properties correlate well with additive LeBas molar volumes.

  6. Analysis of algorithms predicting blood:air and tissue:blood partition coefficients from solvent partition coefficients for prevalent components of JP-8 jet fuel.

    PubMed

    Sterner, Teresa R; Goodyear, Charles D; Robinson, Peter J; Mattie, David R; Burton, G Allen

    2006-08-01

    Algorithms predicting tissue and blood partition coefficients (PCs) from solvent properties were compared to assess their usefulness in a petroleum mixture physiologically based pharmacokinetic/pharmacodynamic model. Measured blood:air and tissue:blood PCs for rat and human tissues were sought from literature resources for 14 prevalent jet fuel (JP-8) components. Average experimental PCs were compared with predicted PCs calculated using algorithms from 9 published sources. Algorithms chosen used solvent PCs (octanol:water, saline or water:air, oil:air coefficients) due to the relative accessibility of these parameters. Tissue:blood PCs were calculated from ratios of predicted tissue:air and experimental blood:air values (PCEB). Of the 231 calculated values, 27% performed within +/- 20% of the experimental PC values. Physiologically based equations (based on water and lipid components of a tissue type) did not perform as well as empirical equations (derived from linear regression of experimental PC data) and hybrid equations (physiological parameters and empirical factors combined) for the jet fuel components. The major limitation encountered in this analysis was the lack of experimental data for the selected JP-8 constituents. PCEB values were compared with tissue:blood PCs calculated from ratios of predicted tissue:air and predicted blood:air values (PCPB). Overall, 68% of PCEB values had smaller absolute % errors than PCPB values. If calculated PC values must be used in models, a comparison of experimental and predicted PCs for chemically similar compounds would estimate the expected error level in calculated values. PMID:16766479

  7. Improved estimation of solubility and partitioning through correction of UNIFAC-derived activity coefficients

    SciTech Connect

    Banerjee, S.; Howard, P.H.

    1988-07-01

    Octanol-water partition coefficients (K/sub ow/) of 75 compounds ranging over 9 orders of magnitude are correlated by log K/sub ow/ = -0.40 + 0.73 log (..gamma../sub W/)/sub U/ -0.39 log (..gamma../sub 0/)/sub U/ (r = 0.98), where (..gamma..//sub W/)/sub U/ and (..gamma../sub 0/)/sub U/ are UNIFAC-derived activity coefficients in water and octanol, respectively. The constants 0.73 and -0.39 are obtained empirically and are intended to compensate for group nonadditivity. Correction factors of similar magnitude are obtained in independent correlations of water solubility with (..gamma../sub W/)/sub U/ and of octanol solubility with (..gamma../sub 0/)/sub U/, thereby confirming the validity of the approach.

  8. Rare Earth Element Partition Coefficients During High-Grade Metamorphism: Experiments, Realities, And Large Datasets

    NASA Astrophysics Data System (ADS)

    Taylor, R.; Clark, C.; Kylander-Clark, A. R.; Hacker, B. R.

    2015-12-01

    For 15 years rare earth element (REE) partitioning between zircon and garnet has facilitated the coupling of U-Pb ages to metamorphism, particularly in the granulite facies. The combination of in situ analysis and rapid data acquisition, particularly through combined techniques such as laser ablation split stream (LASS), means that complex terranes can be interrogated with increasing detail. However this detail provided by large datasets must also be combined with an understanding of the processes involved, for example the relative mobility of the REE, Ti, U and Pb within zircon grains that have withstood intense P-T conditions to varying degrees. Care must also be taken in identifying open system conditions, for example the presence or passage of partial melts that result in non-equilibrium, or very localised equilibrium, between the phases of interest. Visualisation of REE partition coefficients (DREE) becomes more complex with large datasets particularly when dealing with variably recrystallised zircon grains or multiple generations of garnet. Simple methods of visualising the important partitioning parameters identify temperature trends in experimental datasets [1, 2]. These trends can be used as clear indicators of zircon growing or recrystallizing in the presence of stable garnet and may be used as thermometers for zircon growth and for the identification of thermal peaks. Investigation of zircon-garnet DREE values in both long-lived high grade terranes (e.g. S. India), and complex polymetamorphic terranes (e.g. Enderby Land, E. Antarctica) provides insight into how partitioning information can be carefully interrogated, by looking at systematic or erratic variations from experimental data, even when dealing with issues such as variably recrystallised zircon and melt migration. Rubatto and Hermann, (2007). Chemical Geology. Taylor et al., (2015). Journal Metamorphic Geology.

  9. Solid-phase microextraction to determine micropollutant-macromolecule partition coefficients.

    PubMed

    Bridle, Helen L; Heringa, Minne B; Schäfer, Andrea I

    2016-08-01

    Aqueous micropollutants such as estradiol can have a large environmental impact-even at low concentrations. Part of understanding this impact involves determining the extent to which the micropollutants interact with macromolecules in water. In environmental samples, relevant macromolecules to which micropollutants bind are referred to as dissolved organic matter, and the most common examples of these in freshwater and coastal seawater are fulvic and humic acids. In living organisms, the most common macromolecules that affect bioavailability of a drug (or toxin) are proteins such as albumin. Using [2, 4, 6, 7 - (3)H]estradiol as an example compound, this protocol uses solid-phase microextraction and scintillation detection as analytical tools to quantify the amount of radiolabeled micropollutant available in solution. The measured free concentration after exposure to various concentrations of macromolecule (dissolved organic matter or protein) or micropollutant is used to determine the partition coefficient in the case of micropollutant-macromolecule interactions. The calibration and preparatory studies take at least 8 d, and the steps to determine the partition coefficient can be completed within 3 d. The protocol could be modified such that nonlabeled compounds are studied; instead of detection of activity by a liquid scintillation counter (LSC), the compounds can be quantified using gas chromatography-mass spectrometry (GC-MS) or liquid chromatography (LC)-MS(/MS). PMID:27362336

  10. Comparison of prediction methods for octanol-air partition coefficients of diverse organic compounds.

    PubMed

    Fu, Zhiqiang; Chen, Jingwen; Li, Xuehua; Wang, Ya'nan; Yu, Haiying

    2016-04-01

    The octanol-air partition coefficient (KOA) is needed for assessing multimedia transport and bioaccumulability of organic chemicals in the environment. As experimental determination of KOA for various chemicals is costly and laborious, development of KOA estimation methods is necessary. We investigated three methods for KOA prediction, conventional quantitative structure-activity relationship (QSAR) models based on molecular structural descriptors, group contribution models based on atom-centered fragments, and a novel model that predicts KOA via solvation free energy from air to octanol phase (ΔGO(0)), with a collection of 939 experimental KOA values for 379 compounds at different temperatures (263.15-323.15 K) as validation or training sets. The developed models were evaluated with the OECD guidelines on QSAR models validation and applicability domain (AD) description. Results showed that although the ΔGO(0) model is theoretically sound and has a broad AD, the prediction accuracy of the model is the poorest. The QSAR models perform better than the group contribution models, and have similar predictability and accuracy with the conventional method that estimates KOA from the octanol-water partition coefficient and Henry's law constant. One QSAR model, which can predict KOA at different temperatures, was recommended for application as to assess the long-range transport potential of chemicals. PMID:26802270

  11. Local Partition Coefficients Govern Solute Permeability of Cholesterol-Containing Membranes

    PubMed Central

    Zocher, Florian; van der Spoel, David; Pohl, Peter; Hub, Jochen S.

    2013-01-01

    The permeability of lipid membranes for metabolic molecules or drugs is routinely estimated from the solute’s oil/water partition coefficient. However, the molecular determinants that modulate the permeability in different lipid compositions have remained unclear. Here, we combine scanning electrochemical microscopy and molecular-dynamics simulations to study the effect of cholesterol on membrane permeability, because cholesterol is abundant in all animal membranes. The permeability of membranes from natural lipid mixtures to both hydrophilic and hydrophobic solutes monotonously decreases with cholesterol concentration [Chol]. The same is true for hydrophilic solutes and planar bilayers composed of dioleoyl-phosphatidylcholine or dioleoyl-phosphatidyl-ethanolamine. However, these synthetic lipids give rise to a bell-shaped dependence of membrane permeability on [Chol] for very hydrophobic solutes. The simulations indicate that cholesterol does not affect the diffusion constant inside the membrane. Instead, local partition coefficients at the lipid headgroups and at the lipid tails are modulated oppositely by cholesterol, explaining the experimental findings. Structurally, these modulations are induced by looser packing at the lipid headgroups and tighter packing at the tails upon the addition of cholesterol. PMID:24359748

  12. Development of a full automation solid phase microextraction method for investigating the partition coefficient of organic pollutant in complex sample.

    PubMed

    Jiang, Ruifen; Lin, Wei; Wen, Sijia; Zhu, Fang; Luan, Tiangang; Ouyang, Gangfeng

    2015-08-01

    A fully automated solid phase microextraction (SPME) depletion method was developed to study the partition coefficient of organic compound between complex matrix and water sample. The SPME depletion process was conducted by pre-loading the fiber with a specific amount of organic compounds from a proposed standard gas generation vial, and then desorbing the fiber into the targeted samples. Based on the proposed method, the partition coefficients (Kmatrix) of 4 polyaromatic hydrocarbons (PAHs) between humic acid (HA)/hydroxypropyl-β-cyclodextrin (β-HPCD) and aqueous sample were determined. The results showed that the logKmatrix of 4 PAHs with HA and β-HPCD ranged from 3.19 to 4.08, and 2.45 to 3.15, respectively. In addition, the logKmatrix values decreased about 0.12-0.27 log units for different PAHs for every 10°C increase in temperature. The effect of temperature on the partition coefficient followed van't Hoff plot, and the partition coefficient at any temperature can be predicted based on the plot. Furthermore, the proposed method was applied for the real biological fluid analysis. The partition coefficients of 6 PAHs between the complex matrices in the fetal bovine serum and water were determined, and compared to ones obtained from SPME extraction method. The result demonstrated that the proposed method can be applied to determine the sorption coefficients of hydrophobic compounds between complex matrix and water in a variety of samples. PMID:26118804

  13. Determination of partition and diffusion coefficients of formaldehyde in selected building materials and impact of relative humidity.

    PubMed

    Xu, Jing; Zhang, Jianshun S; Liu, Xiaoyu; Gao, Zhi

    2012-06-01

    The partition and effective diffusion coefficients of formaldehyde were measured for three materials (conventional gypsum wallboard, "green" gypsum wallboard, and "green" carpet) under three relative humidity (RH) conditions (20%, 50%, and 70% RH). The "green" materials contained recycled materials and were friendly to environment. A dynamic dual-chamber test method was used. Results showed that a higher relative humidity led to a larger effective diffusion coefficient for two kinds of wallboards and carpet. The carpet was also found to be very permeable resulting in an effective diffusion coefficient at the same order of magnitude with the formaldehyde diffusion coefficient in air. The partition coefficient (K(ma)) of formaldehyde in conventional wallboard was 1.52 times larger at 50% RH than at 20% RH, whereas it decreased slightly from 50% to 70% RH, presumably due to the combined effects of water solubility of formaldehyde and micro-pore blocking by condensed moisture at the high RH level. The partition coefficient of formaldehyde increased slightly with the increase of relative humidity in "green" wallboard and "green" carpet. At the same relative humidity level, the "green" wallboard had larger partition coefficient and effective diffusion coefficient than the conventional wallboard, presumably due to the micro-pore structure differences between the two materials. The data generated could be used to assess the sorption effects of formaldehyde on building materials and to evaluate its impact on the formaldehyde concentration in buildings. PMID:22788105

  14. Experimental determination of solvent-water partition coefficients and Abraham parameters for munition constituents.

    PubMed

    Liang, Yuzhen; Kuo, Dave T F; Allen, Herbert E; Di Toro, Dominic M

    2016-10-01

    There is concern about the environmental fate and effects of munition constituents (MCs). Polyparameter linear free energy relationships (pp-LFERs) that employ Abraham solute parameters can aid in evaluating the risk of MCs to the environment. However, poor predictions using pp-LFERs and ABSOLV estimated Abraham solute parameters are found for some key physico-chemical properties. In this work, the Abraham solute parameters are determined using experimental partition coefficients in various solvent-water systems. The compounds investigated include hexahydro-1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX), hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX), hexahydro-1,3-dinitroso-5- nitro-1,3,5-triazine (DNX), 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitrobenzene (TNB), and 4-nitroanisole. The solvents in the solvent-water systems are hexane, dichloromethane, trichloromethane, octanol, and toluene. The only available reported solvent-water partition coefficients are for octanol-water for some of the investigated compounds and they are in good agreement with the experimental measurements from this study. Solvent-water partition coefficients fitted using experimentally derived solute parameters from this study have significantly smaller root mean square errors (RMSE = 0.38) than predictions using ABSOLV estimated solute parameters (RMSE = 3.56) for the investigated compounds. Additionally, the predictions for various physico-chemical properties using the experimentally derived solute parameters agree with available literature reported values with prediction errors within 0.79 log units except for water solubility of RDX and HMX with errors of 1.48 and 2.16 log units respectively. However, predictions using ABSOLV estimated solute parameters have larger prediction errors of up to 7.68 log units. This large discrepancy is probably due to the missing R2NNO2

  15. A NON-LINEAR STRUCTURE-PROPERTY MODEL FOR OCTANOL-WATER PARTITION COEFFICIENT

    PubMed Central

    Yerramsetty, Krishna M.; Neely, Brian J.; Gasem, Khaled A. M.

    2012-01-01

    Octanol-water partition coefficient (Kow) is an important thermodynamic property used to characterize the partitioning of solutes between an aqueous and organic phase and has importance in such areas as pharmacology, pharmacokinetics, pharmacodynamics, chemical production and environmental toxicology. We present a non-linear quantitative structure-property relationship model for determining Kow values of new molecules in silico. A total of 823 descriptors were generated for 11,308 molecules whose Kow values are reported in the PhysProp dataset by Syracuse Research. Optimum network architecture and its associated inputs were identified using a wrapper-based feature selection algorithm that combines differential evolution and artificial neural networks. A network architecture of 50-33-35-1 resulted in the least root-mean squared error (RMSE) in the training set. Further, to improve on single-network predictions, a neural network ensemble was developed by combining five networks that have the same architecture and inputs but differ in layer weights. The ensemble predicted the Kow values with RMSE of 0.28 and 0.38 for the training set and internal validation set, respectively. The ensemble performed reasonably well on an external dataset when compared with other popular Kow models in the literature. PMID:23185102

  16. Mg-perovskite/silicate melt and magnesiowuestite/silicate melt partition coefficients for KLB-1 at 250 Kbars

    NASA Technical Reports Server (NTRS)

    Drake, Michael J.; Rubie, David C.; Mcfarlane, Elisabeth A.

    1992-01-01

    The partitioning of elements amongst lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements was reported previously, and these results as well as interpretations based on them have generated controversy. Here we report what are to our knowledge only the second set of directly measured trace element partition coefficients for a natural system (KLB-1).

  17. Partition coefficients of substrates and products and solvent selection for biocatalysis under nearly anhydrous conditions

    SciTech Connect

    Yang, Zhen; Robb, D.A. . Dept. of Bioscience and Biotechnology)

    1994-03-05

    The effect of solvent on the activity of mushroom tyrosinase toward three substrates was studied at a constant water activity of either 0.74 or 0.86. No simple correlation was observed between enzyme activity and log P, but partition coefficients of substrate (P[sub s]) and product (P[sub p]) gave systematic relations with enzyme activity. When initial reaction rates were considered, there was a bell-shaped relationship between enzyme and P[sub s] with an optimal P[sub s] for each substrate. This can be explained by assuming that the solvent affected the enzyme activity primarily by affecting the substrate concentration in the aqueous layer around the catalyst where the enzymic reaction occurs. When long-term reaction rates were considered, a high P[sub p]/P[sub s] ratio was consistent with preservation of enzyme activity.

  18. Experimental determination and prediction of the gas-liquid n-hexadecane partition coefficients.

    PubMed

    Mutelet, F; Rogalski, M

    2001-07-20

    Experimental methods based on gas-phase chromatography were tested with a view to determine the gas-liquid n-hexadecane partition coefficients, log L16 of non-volatile compounds at 298.2 K. It was demonstrated that reliable values of log L16 of compounds more volatile than n-docosane can be obtained using either capillary, or packed columns. The main limitation of both methods is the column stability at high temperatures. Here we propose a new method based on the temperature gradient mode, to obtain log L16 of high-boiling compounds. A group contribution model is also presented in view to predicting log L16 values of non-volatile compounds. PMID:11510537

  19. Structural Determinants of Drug Partitioning in n-Hexadecane/Water System

    PubMed Central

    Natesan, Senthil; Wang, Zhanbin; Lukacova, Viera; Peng, Ming; Subramaniam, Rajesh; Lynch, Sandra; Balaz, Stefan

    2013-01-01

    Surrogate phases have been widely used as correlates for modeling transport and partitioning of drugs in biological systems, taking advantage of chemical similarity between the surrogate and the phospholipid bilayer as the elementary unit of biological phases, which is responsible for most of transport and partitioning. Solvation in strata of the phospholipid bilayer is an important drug characteristics because it affects the rates of absorption and distribution, as well as the interactions with the membrane proteins having the binding sites located inside the bilayer. The bilayer core can be emulated by n-hexadecane (C16), and the headgroup stratum is often considered a hydrophilic phase because of the high water content. Therefore, we tested the hypothesis that the C16/water partition coefficients (P) can predict the bilayer locations of drugs and other small molecules better than other surrogate systems. Altogether 514 PC16/W values for nonionizable (458) and completely ionized (56) compounds were collected from the literature or measured, when necessary. With the intent to create a fragment-based prediction system, the PC16/W values were factorized into the fragment solvation parameters (f) and correction factors based on the ClogP fragmentation scheme. A script for the PC16/W prediction using the ClogP output is provided. To further expand the prediction system and reveal solvation differences, the fC16/W values were correlated with their more widely available counterparts for the 1-octanol/water system (O/W) using solvatochromic parameters. The analysis for 50 compounds with known bilayer location shows that the available and predicted PC16/W and PO/W values alone or the PC16/O values representing their ratio do not satisfactorily predict the preference for drug accumulation in bilayer strata. These observations indicate that the headgroups stratum, albeit well hydrated, does not have solvation characteristics similar to water and is also poorly described by

  20. Accretion and core formation: The effects of sulfur on metal-silicate partition coefficients

    NASA Astrophysics Data System (ADS)

    Wood, Bernard J.; Kiseeva, Ekaterina S.; Mirolo, Francesca J.

    2014-11-01

    addition of S in the latter stages of accretion, the Mo/W ratio of silicate Earth would be several times larger than that observed. Addition of ∼2% S accompanied by small amounts of carbon in the last 15% of accretion, however, enables us to match the observed concentrations of these elements in silicate Earth. This confirms an earlier conclusion that the Mo/W ratio of silicate Earth requires late sulfide addition to the core (Wade et al., 2012). Further support for late sulfide addition to the core comes from the depletion factors of volatile chalcophile elements Cu, Ga, Sb, Ag, Zn, Pb, Cd, In and Tl in silicate Earth relative to lithophile elements of similar volatility. We find that depletions of these elements are well correlated with their partition coefficients into sulfide (FeS) liquids at 1.5 GPa and temperatures of 1460-1650 °C. In contrast there is essentially no correlation between their depletion factors and sulfur-free liquid Fe-silicate partition coefficients.

  1. Measuring partition and diffusion coefficients for volatile organic compounds in vinyl flooring

    NASA Astrophysics Data System (ADS)

    Cox, Steven S.; Zhao, Dongye; Little, John C.

    Interactions between volatile organic compounds (VOCs) and vinyl flooring (VF), a relatively homogenous, diffusion-controlled building material, were characterized. The sorption/desorption behavior of VF was investigated using single-component and binary systems of seven common VOCs ranging in molecular weight from n-butanol to n-pentadecane. The simultaneous sorption of VOCs and water vapor by VF was also investigated. Rapid determination of the material/air partition coefficient ( K) and the material-phase diffusion coefficient ( D) for each VOC was achieved by placing thin VF slabs in a dynamic microbalance and subjecting them to controlled sorption/desorption cycles. K and D are shown to be independent of concentration for all of the VOCs and water vapor. For the four alkane VOCs studied, K correlates well with vapor pressure and D correlates well with molecular weight, providing a means to estimate these parameters for other alkane VOCs. While the simultaneous sorption of a binary mixture of VOCs is non-competitive, the presence of water vapor increases the uptake of VOCs by VF. This approach can be applied to other diffusion-controlled materials and should facilitate the prediction of their source/sink behavior using physically-based models.

  2. Experimental Solubility Approach to Determine PDMS-Water Partition Constants and PDMS Activity Coefficients.

    PubMed

    Grant, Sharon; Schacht, Veronika J; Escher, Beate I; Hawker, Darryl W; Gaus, Caroline

    2016-03-15

    Freely dissolved aqueous concentration and chemical activity are important determinants of contaminant transport, fate, and toxic potential. Both parameters are commonly quantified using Solid Phase Micro-Extraction (SPME) based on a sorptive polymer such as polydimethylsiloxane (PDMS). This method requires the PDMS-water partition constants, KPDMSw, or activity coefficient to be known. For superhydrophobic contaminants (log KOW >6), application of existing methods to measure these parameters is challenging, and independent measures to validate KPDMSw values would be beneficial. We developed a simple, rapid method to directly measure PDMS solubilities of solid contaminants, SPDMS(S), which together with literature thermodynamic properties was then used to estimate KPDMSw and activity coefficients in PDMS. PDMS solubility for the test compounds (log KOW 7.2-8.3) ranged over 3 orders of magnitude (4.1-5700 μM), and was dependent on compound class. For polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins (PCDDs), solubility-derived KPDMSw increased linearly with hydrophobicity, consistent with trends previously reported for less chlorinated congeners. In contrast, subcooled liquid PDMS solubilities, SPDMS(L), were approximately constant within a compound class. SPDMS(S) and KPDMSw can therefore be predicted for a compound class with reasonable robustness based solely on the class-specific SPDMS(L) and a particular congener's entropy of fusion, melting point, and aqueous solubility. PMID:26881312

  3. Accumulation kinetics and equilibrium partitioning coefficients for semivolatile organic pollutants in forest litter.

    PubMed

    Nizzetto, Luca; Liu, Xiang; Zhang, Gan; Komprdova, Klara; Komprda, Jiri

    2014-01-01

    Soils are important stores of environmentally cycling semivolatile organic contaminants (SVOCs) and represent relevant atmospheric secondary sources whenever environmental conditions favor re-emission. The exchange between air and soil is controlled by resistances posed by interfacial matrices such as the ubiquitously distributed vegetation litter. For the first time, this study focused on the experimental characterization of accumulation parameters for SVOCs in litter under real field conditions. The logarithm of the litter-air equilibrium partitioning coefficient ranged 6.8-8.9 and had a similar dependence on logKOA as that of plant foliage and soil data. Uptake and release rates were also KOA dependent with values (relevant for real environmental conditions) ranging 30,000-150,000 d(-1) and 0.0004-0.0134 d(-1), respectively. The overall mass transfer coefficient v controlling litter-air exchange (0.03-1.4 cm s(-1)) was consistent with previously reported data of v for foliage in forest canopies after normalization on leaf area index. Obtained data suggest that litter holds the potential for influencing atmospheric fugacity in proximity to soil, likely affecting overall exchange of SVOCs between the soil reservoir and the atmosphere. PMID:24320106

  4. Predicting passive and active tissue:plasma partition coefficients: interindividual and interspecies variability.

    PubMed

    Ruark, Christopher D; Hack, C Eric; Robinson, Peter J; Mahle, Deirdre A; Gearhart, Jeffery M

    2014-07-01

    A mechanistic tissue composition model incorporating passive and active transport for the prediction of steady-state tissue:plasma partition coefficients (K(t:pl)) of chemicals in multiple mammalian species was used to assess interindividual and interspecies variability. This approach predicts K(t:pl) using chemical lipophilicity, pKa, phospholipid membrane binding, and the unbound plasma fraction, together with tissue fractions of water, neutral lipids, neutral and acidic phospholipids, proteins, and pH. Active transport K(t:pl) is predicted using Michaelis-Menten transport parameters. Species-specific biological properties were identified from 126 peer reviewed journal articles, listed in the Supporting Information, for mouse, rat, guinea pig, rabbit, beagle dog, pig, monkey, and human species. Means and coefficients of variation for biological properties were used in a Monte Carlo analysis to assess variability. The results show K(t:pl) interspecies variability for the brain, fat, heart, kidney, liver, lung, muscle, red blood cell, skin, and spleen, but uncertainty in the estimates obscured some differences. Compounds undergoing active transport are shown to have concentration-dependent K(t:pl). This tissue composition-based mechanistic model can be used to predict K(t:pl) for organic chemicals across eight species and 10 tissues, and can be an important component in drug development when scaling K(t:pl) from animal models to humans. PMID:24832575

  5. Molecular Dynamics Simulations of Water/Mucus Partition Coefficients for Feeding Stimulants in Fish and the Implications for Olfaction

    PubMed Central

    Rygg, Alex D.; van Duin, Adri C. T.; Craven, Brent A.

    2013-01-01

    The odorant partition coefficient is a physicochemical property that has been shown to dramatically influence odorant deposition patterns in the mammalian nose, leading to a chromatographic separation of odorants along the sensory epithelium. It is unknown whether a similar phenomenon occurs in fish. Here we utilize molecular dynamics simulations, based on a simplified molecular model of olfactory mucus, to calculate water/mucus partition coefficients for amino acid odorants (alanine, glycine, cysteine, and valine) that are known to elicit feeding behavior in fish. Both fresh water and salt water environments are considered. In fresh water, all four amino acids prefer the olfactory mucus phase to water, and the partition coefficient is shown to correlate with amino acid hydrophobicity. In salt water, a reversal in odorant partitioning is found, where each of the feeding stimulants (except glycine) prefer the water phase to olfactory mucus. This is due to the interactions between the salt ions and the odorant molecules (in the water phase), and between the salt and simplified mucin (in the olfactory mucus phase). Thus, slightly different odorant deposition patterns may occur in the fish olfactory organ in fresh and salt water environments. However, in both underwater environments we found that the variation of the water/mucus odorant partition coefficient is approximately one order of magnitude, in stark contrast to air/mucus odorant partition coefficients that can span up to six orders of magnitude. We therefore anticipate relatively similar deposition patterns for most amino acid odorants in the fish olfactory chamber. Thus, in contrast to terrestrial species, living in an underwater environment may preclude appreciable chromatographic odorant separation that may be used for spatial coding of odor identity across the olfactory epithelium. This is consistent with the reported lack of spatial organization of olfactory receptor neurons in the fish olfactory

  6. PCDD/F and PCB water column partitioning examination using natural organic matter and black carbon partition coefficient models.

    PubMed

    Howell, Nathan L; Rifai, Hanadi S

    2016-04-01

    A 9-year water dataset from the Houston Ship Channel (HSC) was analyzed to understand partitioning in polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs). Total PCBs had more mass as dissolved (74%) whereas total PCDD/Fs did not (11%). Generally, the limited number of PCDD/Fs (only 2378 substituted) explained these differences though differences in chemical behavior beyond log K ow also likely influence partitioning. The particular fractionation seen in the HSC also seemed related to a wide variation in particulate organic carbon (POC)/dissolved organic carbon (DOC) ratio (0.42-180%). Published and unaltered linear free energy and linear solvation energy relationships for DOC, POC, and particulate black carbon (BC) resulted in predictions that were at best 27% (PCB) and 25% root-mean-square error (RMSE) (PCDD/F) partition fraction compared to observed (using estimated BC/POC fractions of 10 and 25%, respectively). These results show, at least in light of the uncertainties in this data (e.g., precise fraction of BC), that a 25% accuracy in model prediction of operationally dissolved or suspended fraction for any one PCB or PCDD/F congener is the best prediction that may be expected. It is therefore recommended that site-specific data be used to calibrate most any water column-partitioning model if it is to be expected to describe what actually occurs in field conditions. PMID:26614453

  7. Organic aerosol molecular composition and gas-particle partitioning coefficients at a Mediterranean site (Corsica).

    PubMed

    Rossignol, Stéphanie; Couvidat, Florian; Rio, Caroline; Fable, Sébastien; Grignion, Guillaume; Savelli; Pailly, Olivier; Leoz-Garziandia, Eva; Doussin, Jean-Francois; Chiappini, Laura

    2016-02-01

    Molecular speciation of atmospheric organic matter was investigated during a short summer field campaign performed in a citrus fruit field in northern Corsica (June 2011). Aimed at assessing the performance on the field of newly developed analytical protocols, this work focuses on the molecular composition of both gas and particulate phases and provides an insight into partitioning behavior of the semi-volatile oxygenated fraction. Limonene ozonolysis tracers were specifically searched for, according to gas chromatography-mass spectrometry (GC-MS) data previously recorded for smog chamber experiments. A screening of other oxygenated species present in the field atmosphere was also performed. About sixty polar molecules were positively or tentatively identified in gas and/or particle phases. These molecules comprise a wide range of branched and linear, mono and di-carbonyls (C3-C7), mono and di-carboxylic acids (C3-C18), and compounds bearing up to three functionalities. Among these compounds, some can be specifically attributed to limonene oxidation and others can be related to α- or β-pinene oxidation. This provides an original snapshot of the organic matter composition at a Mediterranean site in summer. Furthermore, for compounds identified and quantified in both gaseous and particulate phases, an experimental gas/particle partitioning coefficient was determined. Several volatile products, which are not expected in the particulate phase assuming thermodynamic equilibrium, were nonetheless present in significant concentrations. Hypotheses are proposed to explain these observations, such as the possible aerosol viscosity that could hinder the theoretical equilibrium to be rapidly reached. PMID:26969549

  8. Octanol/water partition coefficients of phthalate esters: A comparison of measured, estimated, and computed values

    SciTech Connect

    Ellington, J.; Floyd, T.

    1995-12-31

    Reliable octanol/water partition coefficients (K{sub ow}) of nine dialkyl phthalate esters are needed in an ongoing benthic organisms toxicity testing program. The equilibrium distribution of an organic chemical between water and octanol (K{sub ow}) is a physical constant that can be used to calculate both bioaccumulation factors (BAFs) and equilibrium constants for sediment-organic carbon partitioning (K{sub oc}). The log K{sub ow}s reported in the literature for a single chemical often span several orders of magnitude. For example, the reported log K{sub ow}s of bis(2-ethylehxyl) phthalate range from a low of 5.11 to a high of 9.61. The log K{sub ow}s of the dialkyl phthalate esters in this study were expected to range from < 2 (dimethyl) to > 8 (didecyl). The slow-stir method as described by de Bruijn has been shown to avoid emulsion formation and allow measure of K{sub ow}s of chemicals with log K{sub ow} > 6. In addition to measurement by the slow-stir method the K{sub ow}s were also determined by a high performance liquid chromatography (HPLC) estimation method and calculated by a computer based program that was designed to calculate physical/chemical properties (SPARC). The greatest difference between the slow-stir and SPARC K{sub ow} values was 0.19 with the other differences less than 0.1 log units. All the HPLC estimated values were at least 0.7 log units lower than the slow-stir value. For example, the log K{sub ow}s determined for dibutly phthalate by the slow-stir, SPARC, and HPLC methods were 4.50 {+-} 0.03, 4.61, and 4.00, respectively.

  9. Field estimates of polyurethane foam - air partition coefficients for hexachlorobenzene, alpha-hexachlorocyclohexane and bromoanisoles.

    PubMed

    Bidleman, Terry F; Nygren, Olle; Tysklind, Mats

    2016-09-01

    Partition coefficients of gaseous semivolatile organic compounds (SVOCs) between polyurethane foam (PUF) and air (KPA) are needed in the estimation of sampling rates for PUF disk passive air samplers. We determined KPA in field experiments by conducting long-term (24-48 h) air sampling to saturate PUF traps and shorter runs (2-4 h) to measure air concentrations. Sampling events were done at daily mean temperatures ranging from 1.9 to 17.5 °C. Target compounds were hexachlorobenzene (HCB), alpha-hexachlorocyclohexane (α-HCH), 2,4-dibromoanisole (2,4-DiBA) and 2,4,6-tribromoanisole (2,4,6-TriBA). KPA (mL g(-1)) was calculated from quantities on the PUF traps at saturation (ng g(-1)) divided by air concentrations (ng mL(-1)). Enthalpies of PUF-to-air transfer (ΔHPA, kJ mol(-1)) were determined from the slopes of log KPA/mL g(-1) versus 1/T(K) for HCB and the bromoanisoles, KPA of α-HCH was measured only at 14.3 to 17.5 °C and ΔHPA was not determined. Experimental log KPA/mL g(-1) at 15 °C were HCB = 7.37; α-HCH = 8.08; 2,4-DiBA = 7.26 and 2,4,6-TriBA = 7.26. Experimental log KPA/mL g(-1) were compared with predictions based on an octanol-air partition coefficient (log KOA) model (Shoeib and Harner, 2002a) and a polyparameter linear free relationship (pp-LFER) model (Kamprad and Goss, 2007) using different sets of solute parameters. Predicted KP values varied by factors of 3 to over 30, depending on the compound and the model. Such discrepancies provide incentive for experimental measurements of KPA for other SVOCs. PMID:27285381

  10. Re-analysis of narcotic critical body residue data using the equilibrium distribution concept and refined partition coefficients.

    PubMed

    Endo, Satoshi

    2016-08-10

    Narcosis occurs as a result of the accumulation of chemicals in the phospholipid membrane. The toxic threshold concentration in the membrane is thought to be relatively constant across different chemicals and species. Hence, estimating chemical concentrations in the membrane is expected to reduce the variability of narcotic critical body residue (CBR) data. In this study, a high quality CBR dataset for three aquatic species reported recently in the literature was evaluated with the internal equilibrium distribution concept. The raw wet-weight-based CBR values were converted to membrane-weight-based CBR values by assuming that the chemical is distributed in storage lipids, membranes, proteins, and water according to the respective equilibrium partition coefficients. Several sets of partition coefficients were compared for this analysis. The results were consistent with the notion that the use of a structural protein instead of serum albumin as a surrogate for the body protein fraction could reduce the variability of CBRs. Partition coefficients predicted by polyparameter linear free energy relationships (PP-LFERs) reduced the variability of CBRs as much as or even more than experimental partition coefficients did. It is suggested that CBR data for chemicals with larger structural diversity and biological species with more distinct compositions are needed to evaluate further the equilibrium distribution concept and the constant membrane threshold hypothesis. PMID:27136717

  11. Evaluation of alternative approaches for measuring n-octanol/water partition coefficients for methodologically challenging chemicals (MCCs)

    EPA Science Inventory

    Measurements of n-octanol/water partition coefficients (KOW) for highly hydrophobic chemicals, i.e., greater than 108, are extremely difficult and are rarely made, in part because the vanishingly small concentrations in the water phase require extraordinary analytical sensitivity...

  12. Estimation of octanol/water partition coefficient and aqueous solubility of environmental chemicals using molecular fingerprints and machine learning methods

    EPA Science Inventory

    Octanol/water partition coefficient (logP) and aqueous solubility (logS) are two important parameters in pharmacology and toxicology studies, and experimental measurements are usually time-consuming and expensive. In the present research, novel methods are presented for the estim...

  13. High-Throughput Determination of Octanol-Water Partition Coefficients by Ultrasound-Assisted Liquid-Phase Microextraction.

    PubMed

    Guo, Yugao; Ma, Shuo; Guan, Shan; Zhang, Yan; Pan, Jie

    2015-09-01

    A method of high-throughput determination, which is based on ultrasound-assisted liquid-phase microextraction, was developed to measure directly the partition coefficients of n-octanol-water. In ultrasound-assisted liquid-phase microextraction, ultrasonic energy can facilitate the mass transfer process of six or more microextractors simultaneously. Therefore, high-throughput determination of n-octanol-water partition coefficients can be performed favorably, and the equilibrium time of each microextractor can be decreased effectively. Several experimental parameters including ultrasonic power and frequency, centrifugation conditions, extractant volume and sample concentration were analyzed and optimized at 25°C. Under the optimum conditions, it only takes 2 min to reach extraction equilibrium, and the solutions of sample can be separated by centrifugation in 4 min. After centrifugation, the concentrations in n-octanol phases are analyzed with gas chromatography. The method was further evaluated with eight reference compounds and the findings demonstrated that this method is suitable to determine the partition coefficients of organic compounds accurately and quickly. Next, the method was exploited to measure the partition coefficients of n-octanol-water containing 20 organic compounds, which cover the [Formula: see text] values from 0.05 to 4.36, with comparatively low relative standard deviation (RSD) directly. The results of this study illustrated that the RSD (n = 6) was under 3%. PMID:25583971

  14. Solubilization of amphiphilic carboxylic acids in nonionic micelles: determination of partition coefficients from pKa measurements and NMR experiments.

    PubMed

    Dupont-Leclercq, Laurence; Giroux, Sébastien; Henry, Bernard; Rubini, Patrice

    2007-10-01

    The solubilization of octylamidotartaric acid (C8T) and octanoic acid (C8C) in Triton X-100 and Brij 58 nonionic micelles has been studied by pHmetric and 1H NMR self-diffusion experiments. As both C8C and C8T exhibit acid-base properties, a distinction between the partition of the neutral acidic form, in terms of the partition coefficient KPH, and the partition of the charged basic form, in terms of the partition coefficient KP-, has been made. The acidity constants, Ka, of C8T and C8C in the presence of micelles have been evaluated from pHmetric experiments. For both solutes, an increase in the pKa is observed in micellar media due to the difference in the partition of acidic and basic forms of the solutes. A model has been developed to determine KPH and KP- from the pKa shifts observed. The values obtained by this pKa shift modeling method and those from self-diffusion coefficient measurements are in good agreement. The acidic form of C8C is incorporated to a larger extent into the Brij 58 micelles than the acidic form of C8T, whereas the opposite trend is observed for the basic forms. Both the acidic and basic forms of C8T are more easily incorporated into Brij 58 micelles than into Triton X-100 micelles. The influence of the structure of the polar head on the solubilization properties is demonstrated. Moreover, evidence for the localization of the solutes in the micelles is obtained from the comparison of the partition coefficients and from 1H NMR data. PMID:17850105

  15. Trophic magnification of PCBs and its relationship to the octanol-water partition coefficient

    USGS Publications Warehouse

    Walters, D.M.; Mills, M.A.; Cade, B.S.; Burkard, L.P.

    2011-01-01

    We investigated polychlorinated biphenyl (PCB) bioaccumulation relative to octanol-water partition coefficient (KOW) and organism trophic position (TP) at the Lake Hartwell Superfund site (South Carolina). We measured PCBs (127 congeners) and stable isotopes (??15N) in sediment, organic matter, phytoplankton, zooplankton, macroinvertebrates, and fish. TP, as calculated from ??15N, was significantly, positively related to PCB concentrations, and food web trophic magnification factors (TMFs) ranged from 1.5-6.6 among congeners. TMFs of individual congeners increased strongly with log KOW, as did the predictive power (r2) of individual TP-PCB regression models used to calculate TMFs. We developed log KOW-TMF models for eight food webs with vastly different environments (freshwater, marine, arctic, temperate) and species composition (cold- vs warmblooded consumers). The effect of KOW on congener TMFs varied strongly across food webs (model slopes 0.0-15.0) because the range of TMFs among studies was also highly variable. We standardized TMFs within studies to mean = 0, standard deviation (SD) = 1 to normalize for scale differences and found a remarkably consistent KOW effect on TMFs (no difference in model slopes among food webs). Our findings underscore the importance of hydrophobicity (as characterized by KOW) in regulating bioaccumulation of recalcitrant compounds in aquatic systems, and demonstrate that relationships between chemical KOW and bioaccumulation from field studies are more generalized than previously recognized. ?? This article not subject to U.S. Copyright. Published 2011 by the American Chemical Society.

  16. Aqueous solubility and octan-1-ol to water partition coefficients of aliphatic hydrocarbons

    SciTech Connect

    Coates, M.; Connell, D.W.; Barron, D.M.

    1985-07-01

    The aqueous solubility (S) and octanol-water partition coefficients (P) of homologous series of n-, 2-methyl-, and 3-methylalkanes, as well as 1-alkenes, have been determined by extrapolation of known results, direct measurement, and high-pressure liquid chromatography (HP-LC). Long-term equilibration experiments, used to reduce aggregate formation, indicated that n-dodecane and n-tetradecane have S values in agreement with those obtained by extrapolation of the data on lower members. HPLC data from reverse-phase columns further validated the use of extrapolation. By use of published values for P and S for lower n-alkanes, the relationships between log P, log S, and N/sub c/ were obtained. Cochromatography of n-alkanes with members of the other series then allowed these relationships to be determined for the 2- and 3-methylalkanes and the 1-alkenes. The derived S values were in reasonable agreement with values from previous work and those obtained by extrapolation. The log P values have not been previously determined for these compounds.

  17. Prediction of octanol-water partition coefficients using a group contribution solvation model

    SciTech Connect

    Lin, S.T.; Sandler, S.I.

    1999-10-01

    Using the recently derived group contribution solvation (GCS) model, the authors have developed a predictive model for the octanol-water partition coefficient (K{sub OW}), the GCSKOW model. In this model K{sub OW} is calculated from two molecular structure parameters, which take into account the size and shape effects, and one energy parameter that determines the attractive interactions between the solute and the solvent. On the basis of quantum mechanical studies, the authors found that for organic solutes with a single strong functional group, all these parameters can be obtained in a group contribution manner. Consequently, the authors present a database here for various functional group contributions in this new, easy-to-use model. The root-mean-square deviation of the predicted log K{sub OW} from the GCSKOW model for 226 solutes is found to be 0.14 (which corresponds to 38% in K{sub OW}), which is considerably less than those from the methods of Hansch and Leo (0.18 in log K{sub OW} or 51%), KOW-UNIFAC (0.21 or 62%), and LSER (0.23 or 71%).

  18. Zone fluidics for measurement of octanol-water partition coefficient of drugs.

    PubMed

    Wattanasin, Panwadee; Saetear, Phoonthawee; Wilairat, Prapin; Nacapricha, Duangjai; Teerasong, Saowapak

    2015-02-20

    A novel zone fluidics (ZF) system for the determination of the octanol-water partition coefficient (Pow) of drugs was developed. The ZF system consisted of a syringe pump with a selection valve, a holding column, a silica capillary flow-cell and an in-line spectrophotometer. Exact microliter volumes of solvents (octanol and phosphate buffer saline) and a solution of the drug, sandwiched between air segments, were sequentially loaded into the vertically aligned holding column. Distribution of the drug between the aqueous and octanol phases occurred by the oscillation movement of the syringe pump piston. Phase separation occurred due to the difference in densities. The liquid zones were then pushed into the detection flow cell. In this method, absorbance measurements in only one of the phase (octanol or aqueous) were employed, which together with the volumes of the solvents and pure drug sample, allowed the calculation of the Pow. The developed system was applied to the determination of the Pow of some common drugs. The log (Pow) values agreed well with a batch method (R(2)=0.999) and literature (R(2)=0.997). Standard deviations for intra- and inter-day analyses were both less than 0.1log unit. This ZF system provides a robust and automated method for screening of Pow values in the drug discovery process. PMID:25682240

  19. Concentration-dependent apparent partition coefficients of ionic liquids possessing ethyl- and bi-sulphate anions.

    PubMed

    Jain, Preeti; Kumar, Anil

    2016-01-14

    This study deals with the concentration dependent apparent partition coefficients log P of the ethyl and bisulfate-based ionic liquids. It is observed that the bisulfate-based ionic liquids show different behaviour with respect to concentration as compared to ethyl sulphate-based ionic liquids. It is significant and useful analysis for the further implementation of alkyl sulfate based ionic liquids as solvents in extraction processes. The log P values of the ethyl sulphate-based ionic liquids were noted to vary linearly with the concentration of the ionic liquid, whereas a flip-flop trend with the concentration for the log P values of the bisulphate-based ionic liquids was observed due to the difference in hydrogen bond accepting basicity and possibility of aggregate formation of these anions. The π-π interactions between the imidazolium and pyridinium rings were seen to affect the log P values. The alkyl chain length of anions was also observed to influence the log P values. The hydrophobicity of ionic liquid changes with the alkyl chain in the anion in the order; [HSO4](-) < [EtSO4](-) < [BuSO4](-). PMID:26660452

  20. Lab-scale experimental strategy for determining micropollutant partition coefficient and biodegradation constants in activated sludge.

    PubMed

    Pomiès, M; Choubert, J M; Wisniewski, C; Miège, C; Budzinski, H; Coquery, M

    2015-03-01

    The nitrifying/denitrifying activated sludge process removes several micropollutants from wastewater by sorption onto sludge and/or biodegradation. The objective of this paper is to propose and evaluate a lab-scale experimental strategy for the determination of partition coefficient and biodegradation constant for micropollutant with an objective of modelling their removal. Four pharmaceutical compounds (ibuprofen, atenolol, diclofenac and fluoxetine) covering a wide hydrophobicity range (log Kow from 0.16 to 4.51) were chosen. Dissolved and particulate concentrations were monitored for 4 days, inside two reactors working under aerobic and anoxic conditions, and under different substrate feed conditions (biodegradable carbon and nitrogen). We determined the mechanisms responsible for the removal of the target compounds: (i) ibuprofen was biodegraded, mainly under aerobic conditions by cometabolism with biodegradable carbon, whereas anoxic conditions suppressed biodegradation; (ii) atenolol was biodegraded under both aerobic and anoxic conditions (with a higher biodegradation rate under aerobic conditions), and cometabolism with biodegradable carbon was the main mechanism; (iii) diclofenac and fluoxetine were removed by sorption only. Finally, the abilities of our strategy were evaluated by testing the suitability of the parameters for simulating effluent concentrations and removal efficiency at a full-scale plant. PMID:25300180

  1. Uptake rate constants and partition coefficients for vapor phase organic chemicals using semipermeable membrane devices (SPMDs)

    USGS Publications Warehouse

    Cranor, W.L.; Alvarez, D.A.; Huckins, J.N.; Petty, J.D.

    2009-01-01

    To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants (kua) and no SPMD air partitioning coefficient (Ksa) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining kua and Ksa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The kuas were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07??m3??g-1??d-1. In cases where uptake was approaching equilibrium, Ksas were approximated. Ksa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean kua values (n??=??3) of anthracene and p,p???-DDE at 0.96 and 1.57??m3??g-1??d-1 with relative standard deviations of 8.4% and 8.6% respectively.

  2. Determination of polyoxymethylene (POM)--water partition coefficients for oxy-PAHs and PAHs.

    PubMed

    Josefsson, Sarah; Arp, Hans Peter H; Kleja, Dan Berggren; Enell, Anja; Lundstedt, Staffan

    2015-01-01

    Oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) are a class of ubiquitously occurring pollutants of which little is known. They can be co-emitted with PAHs or formed from PAHs in the environment. The environmental fate and risk of oxy-PAHs are difficult to assess due to a lack of methods to quantify their pore water concentrations. One sampler that can be used to determine freely dissolved concentrations of organic contaminants is polyoxymethylene (POM). In this study, POM - water partition coefficients (KPOM) were determined for 11 oxy-PAHs. KPOM values of 8 PAHs with similar hydrophobicities as the oxy-PAHs were determined for comparison. Results showed that logKPOM values ranged from 2.64 to 4.82 for the PAHs (2-4 rings), similar to previously determined values. LogKPOM values for investigated oxy-PAHs ranged from 0.96 to 5.36. The addition of carbonylic oxygen on a parent PAH generally lowered KPOM by 0.5 to 1.0 log units, which is attributable to the presence of carbonylic oxygens increasing water solubility. The KPOM values presented here will facilitate simultaneous assessments of freely dissolved water concentrations of oxy-PAHs and PAHs in environmental media. PMID:25460771

  3. High-throughput microplate assay for the determination of drug partition coefficients.

    PubMed

    Magalhães, Luís M; Nunes, Cláudia; Lúcio, Marlene; Segundo, Marcela A; Reis, Salette; Lima, José L F C

    2010-11-01

    Partition coefficients (K(p)) of drugs between the phospholipid bilayer and the aqueous phase provide useful information in quantitative structure-activity relationship studies. Hexadecylphosphocholine (HePC) micelles, composed of a zwitterionic hydrophilic surface and a hydrophobic core, mimic the biomembranes and have several advantages over other lipid structures to assess K(p) values. Their preparation is easy, fast and avoids the use of toxic organic solvents, and the output has fewer spectroscopic interferences. Here, we describe a high-throughput microplate protocol for assessing the K(p) of drugs using HePC micelles as membrane models and derivative spectrophotometry as the detection technique. Moreover, the time-consuming data treatment to assess K(p) values is easily performed by a dedicated Excel routine developed here and described in detail. The K(p) values of nonsteroidal anti-inflammatory drugs (acemetacin, clonixin, diclofenac and indomethacin) were determined to show the simplicity of the method and to validate this protocol, which provides K(p) values (n = 3) of two drugs in ∼ 2 h. PMID:21030957

  4. Uptake rate constants and partition coefficients for vapor phase organic chemicals using semipermeable membrane devices (SPMDs)

    NASA Astrophysics Data System (ADS)

    Cranor, Walter L.; Alvarez, David A.; Huckins, James N.; Petty, Jimmie D.

    To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants ( kua) and no SPMD air partitioning coefficient ( Ksa) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining kua and Ksa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The kuas were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07 m 3 g -1 d -1. In cases where uptake was approaching equilibrium, Ksas were approximated. Ksa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean kua values ( n = 3) of anthracene and p, p'-DDE at 0.96 and 1.57 m 3 g -1 d -1 with relative standard deviations of 8.4% and 8.6% respectively.

  5. Imidazolium ionic liquids as solvents of pharmaceuticals: influence on HSA binding and partition coefficient of nimesulide.

    PubMed

    Azevedo, Ana M O; Ribeiro, Diogo M G; Pinto, Paula C A G; Lúcio, Marlene; Reis, Salette; Saraiva, M Lúcia M F S

    2013-02-25

    In this work, the influence of imidazolium ionic liquids (ILs) on bio-chemical parameters that influence the in vivo behavior of nimesulide was evaluated. In this context, the binding of nimesulide to human serum albumin (HSA), in IL media, was studied. In parallel, the evaluation of the interaction of drug-IL systems, with micelles of hexadecylphosphocholine (HDPC), enabled the calculation of partition coefficients (K(p)). Both assays were performed in buffered media in the absence and in the presence of emim [BF(4)], emim [Ms] and emim [TfMs] 1%. Even though there was an increase of the dissociation constant (K(d)) in IL media, nimesulide still binds to HSA by means of strong interactions. The thermodynamic analysis indicates that the interaction is spontaneous for all the tested systems. Moreover, the studied systems exhibited properties that are favorable to the interaction of the drug with biological membranes, with K(p) values 2.5-3.5 higher than in aqueous environment. The studied nimesulide-IL systems presented promising characteristics regarding the absorption and distribution of the drug in vivo, so that the studied solvents seem to be good options for drug delivery. PMID:23287776

  6. Trophic magnification of PCBs and Its relationship to the octanol-water partition coefficient.

    PubMed

    Walters, David M; Mills, Marc A; Cade, Brian S; Burkard, Lawrence P

    2011-05-01

    We investigated polychlorinated biphenyl (PCB) bioaccumulation relative to octanol-water partition coefficient (K(OW)) and organism trophic position (TP) at the Lake Hartwell Superfund site (South Carolina). We measured PCBs (127 congeners) and stable isotopes (δ¹⁵N) in sediment, organic matter, phytoplankton, zooplankton, macroinvertebrates, and fish. TP, as calculated from δ¹⁵N, was significantly, positively related to PCB concentrations, and food web trophic magnification factors (TMFs) ranged from 1.5-6.6 among congeners. TMFs of individual congeners increased strongly with log K(OW), as did the predictive power (r²) of individual TP-PCB regression models used to calculate TMFs. We developed log K(OW)-TMF models for eight food webs with vastly different environments (freshwater, marine, arctic, temperate) and species composition (cold- vs warmblooded consumers). The effect of K(OW) on congener TMFs varied strongly across food webs (model slopes 0.0-15.0) because the range of TMFs among studies was also highly variable. We standardized TMFs within studies to mean = 0, standard deviation (SD) = 1 to normalize for scale differences and found a remarkably consistent K(OW) effect on TMFs (no difference in model slopes among food webs). Our findings underscore the importance of hydrophobicity (as characterized by K(OW)) in regulating bioaccumulation of recalcitrant compounds in aquatic systems, and demonstrate that relationships between chemical K(OW) and bioaccumulation from field studies are more generalized than previously recognized. PMID:21466215

  7. Measuring gas-liquid partition coefficients of aroma compounds by solid phase microextraction, sampling either headspace or liquid.

    PubMed

    Lloyd, Nathan W; Dungan, Stephanie R; Ebeler, Susan E

    2011-08-21

    Hydrophobic compounds are important odorants and nutrients in foods and beverages, as well as environmental contaminants and pharmaceuticals. Factors influencing their partitioning within multi-component systems and/or from the bulk liquid phase to the air are critical for understanding aroma quality and nutrient bioavailability. The equilibrium partitioning of hydrophobic analytes between air and water was analyzed using solid phase microextraction (SPME) in the headspace (HS-SPME) and via direct immersion in the liquid (DI-SPME). The compounds studied serve as models for hydrophobic aroma compounds covering a range of air-water partition coefficients that extends over four orders of magnitude. By varying the total amount of analyte as well as the ratio of vapor to liquid in the closed, static system, the partition coefficient, K(vl), can be determined without the need for an external calibration, eliminating many potential systematic errors. K(vl) determination using DI-SPME in this manner has not been demonstrated before. There was good agreement between results determined by DI-SPME and by HS-SPME over the wide range of partitioning behavior studied. This shows that these two methods are capable of providing accurate, complementary measurements. Precision in K(vl) determination depends strongly on K(vl) magnitude and the ratio of the air and liquid phases. PMID:21727981

  8. Experimental determination of trace element partition coefficients between spinel and silicate melt: the influence of chemical composition and oxygen fugacity

    NASA Astrophysics Data System (ADS)

    Wijbrans, C. H.; Klemme, S.; Berndt, J.; Vollmer, C.

    2015-04-01

    We present new experimentally determined trace element partition coefficients between spinel and silicate melt. The experiments were performed at atmospheric pressure and at temperatures between 1220 and 1450 °C. To study the effect of redox conditions on trace element partitioning, we performed experiments under different redox conditions, with fO2 ranging from log -12 to log -0.7. The effect of different spinel compositions is also investigated. Our results show that spinel of all compositions readily incorporates the transition metals Ni, Co and Ga and the corresponding partition coefficients are >1. D Ni,Co,Ga are not significantly affected by changing melt composition, crystal composition or redox conditions. However, the multivalent trace elements V and Mo show a strong effect of redox conditions on their partitioning behavior with D V and D Mo highest at very reducing conditions and considerably lower at more oxidizing conditions. Partition coefficients for the high field strength elements Ti, Zr, Hf, Nb, and Ta and the elements Sc and Lu strongly depend on crystal composition, with D Ti and D Sc >1 for very Fe3+- or Cr-rich (and Al-poor) spinels, but one to two orders of magnitude lower in systems with Al-rich spinels. We present some examples on how our data may be used to reconstruct redox conditions of spinel formation. We also present some results on the partitioning of Pt and Rh between spinel and melt. D Rh depends strongly on redox conditions, while D Pt is not significantly affected.

  9. Assessment of PDMS-water partition coefficients: implications for passive environmental sampling of hydrophobic organic compounds

    USGS Publications Warehouse

    DiFilippo, Erica L.; Eganhouse, Robert P.

    2010-01-01

    Solid-phase microextraction (SPME) has shown potential as an in situ passive-sampling technique in aquatic environments. The reliability of this method depends upon accurate determination of the partition coefficient between the fiber coating and water (Kf). For some hydrophobic organic compounds (HOCs), Kf values spanning 4 orders of magnitude have been reported for polydimethylsiloxane (PDMS) and water. However, 24% of the published data examined in this review did not pass the criterion for negligible depletion, resulting in questionable Kf values. The range in reported Kf is reduced to just over 2 orders of magnitude for some polychlorinated biphenyls (PCBs) when these questionable values are removed. Other factors that could account for the range in reported Kf, such as fiber-coating thickness and fiber manufacturer, were evaluated and found to be insignificant. In addition to accurate measurement of Kf, an understanding of the impact of environmental variables, such as temperature and ionic strength, on partitioning is essential for application of laboratory-measured Kf values to field samples. To date, few studies have measured Kf for HOCs at conditions other than at 20 degrees or 25 degrees C in distilled water. The available data indicate measurable variations in Kf at different temperatures and different ionic strengths. Therefore, if the appropriate environmental variables are not taken into account, significant error will be introduced into calculated aqueous concentrations using this passive sampling technique. A multiparameter linear solvation energy relationship (LSER) was developed to estimate log Kf in distilled water at 25 degrees C based on published physicochemical parameters. This method provided a good correlation (R2 = 0.94) between measured and predicted log Kf values for several compound classes. Thus, an LSER approach may offer a reliable means of predicting log Kf for HOCs whose experimental log Kf values are presently unavailable. Future

  10. Assessment of SPME Partitioning Coefficients: Implications for Passive Environmental Sampling of Hydrophobic Organic Compounds

    NASA Astrophysics Data System (ADS)

    Difilippo, E. L.; Eganhouse, R. P.

    2009-12-01

    Solid-phase microextraction (SPME) has shown potential as an in situ passive sampling technique in aqueous environments. The reliability of this method depends upon accurate determination of the partitioning coefficient between the fiber coating and water (Kf) for the compounds of interest. Kf values for poly(dimethylsiloxane) (PDMS) and water spanning 4 orders of magnitude have been reported for hydrophobic organic compounds (HOCs). However, most of the published data (86%) do not pass the criterion for negligible depletion (Vw > 100KfVf , where Vw is the sample volume [μl] and Vf is the fiber coating volume [μl]), resulting in erroneous Kf values. The range in reported Kf values is reduced to just over 2 orders of magnitude for some polychlorinated biphenyls (PCBs) when these erroneous values are removed. We conducted a two-tailed t-test comparing Kf values for the same compounds (polycyclic aromatic hydrocarbons (PAHs) and PCBs) measured with different fiber coating thicknesses and fiber manufacturers; the majority (85%) of these Kf values are not statistically different (p = 0.10). In addition to an accurate measurement of Kf, the impact of environmental factors on partitioning, such as temperature and ionic strength, are essential in applying laboratory-measured Kf values to field samples. To date, few studies have measured Kf at conditions other than at 25° C in distilled water. While the available data indicate slight differences in Kf at different temperatures and ionic strength, the data are too limited to make an accurate assessment of the impact of these factors on the accuracy of in situ concentration measurements. Because of the challenges in measuring Kf for HOCs, it may be useful to develop predictive models for calculating Kf using known or measured physico-chemical properties. A multi-parameter linear solvation energy relationship (LSER) was developed to estimate Kf in distilled water at 25° C for HOCs based on published physico

  11. Effects of environmental temperature and dietary energy on energy partitioning coefficients of female broiler breeders.

    PubMed

    Pishnamazi, A; Renema, R A; Paul, D C; Wenger, I I; Zuidhof, M J

    2015-10-01

    With increasing disparity between broiler breeder target weights and broiler growth potential, maintenance energy requirements have become a larger proportion of total broiler breeder energy intake. Because energy is partitioned to growth and egg production at a lower priority than maintenance, accurate prediction of maintenance energy requirements is important for practical broiler breeder feed allocation decisions. Environmental temperature affects the maintenance energy requirement by changing rate of heat loss to the environment. In the ME system, heat production (energy lost) is part of the maintenance requirement (ME). In the current study, a nonlinear mixed model was derived to predict ME partitioning of broiler breeder hens under varied temperature conditions. At 21 wk of age, 192 Ross 708 hens were individually caged within 6 controlled environmental chambers. From 25 to 41 wk, 4 temperature treatments (15°C, 19°C, 23°C, and 27°C) were randomly assigned to the chambers for 2-week periods. Half of the birds in each chamber were fed a high-energy (HE; 2,912 kcal/kg) diet, and half were fed a low-energy (LE; 2,790 kcal/kg) diet. The nonlinear mixed regression model included a normally distributed random term representing individual hen maintenance, a quadratic response to environmental temperature, and linear ADG and egg mass (EM) coefficients. The model assumed that energy requirements for BW gain and egg production were not influenced by environmental temperature because hens were homeothermic, and the cellular processes for associated biochemical processes occurred within a controlled narrow core body temperature range. Residual feed intake (RFI) and residual ME (RME) were used to estimate efficiency. A quadratic effect of environmental temperature on broiler breeder MEm was predicted ( < 0.0001), with a minimum energy expenditure at 24.3°C. Predicted ME at 21°C was 92.5 kcal/kg; requirements for gain and EM were 2.126 and 1.789 kcal/g, respectively

  12. Experimental measurements of zircon/melt trace-element partition coefficients

    NASA Astrophysics Data System (ADS)

    Luo, Yan; Ayers, John C.

    2009-06-01

    Zircon was grown from trace-element doped hydrous peralkaline rhyolite melts with buffered oxygen fugacities in cold-seal experiments at 0.1 and 0.2 GPa and 800 °C and piston-cylinder experiments at 1.5 GPa and 900-1300 °C. Zircon and glass were present in all run products, and small monazite crystals were present in eight of the 12 experiments. Average diameters of zircon crystals ranged from 5 to 20 μm at 800 °C to 30-50 μm at 1300 °C. Zircon crystals have thin rims, and adjacent glass has a narrow (˜1 μm thick) compositional boundary layer. Concentrations obtained through in-situ analysis of cores of run product zircon crystals and melt pools were used to calculate trace-element partition coefficients Dzircon/melt for P, Sc, Ti, V, Y, La, Ce, Pr, Nd, Eu, Gd, Ho, Yb, Lu, Hf, Th, and U. In most cases Lu was the most ( D 12-105) and La the least (0.06-0.95) compatible elements. D values from this study fall within the range of previously measured values for Rare Earth Elements (REE). However, D values measured experimentally show less fractionation than those recently measured using natural phenocryst/matrix pairs. For example, DLu/ DLa measured experimentally in this study range between 27 and 206 compared to a value of 706,522 for a natural zircon/dacite pair [Sano, Y., Terada, K., and Fukuoka, T. 2002 High mass resolution ion microprobe analysis of rare earth elements in silicate glass, apatite and zircon: lack of matrix dependency. Chem. Geol.184, 217-230]. Although D values from this study show good agreement with the lattice strain model, D values from natural phenocryst/matrix pairs combined with measured zircon compositions better reproduce host-rock (magma) compositions of igneous rocks. They also yield more reasonable estimates of magma compositions when combined with compositions of ''out-of-context" zircons. For example, compositions of the Hadean detrital zircons from Jack Hills, Australia yield LREE-enriched magmas when combined with D values

  13. Equations for water-triolein partition coefficients for neutral species; comparison with other water-solvent partitions, and environmental and toxicological processes.

    PubMed

    Abraham, Michael H; Acree, William E

    2016-07-01

    Linear free energy relationships, LFERs, have been constructed for water-triolein partition coefficients for neutral species. It is shown that separate equations are required for wet and dry triolein. From a comparison of the equation coefficients for water-wet triolein with those for 52 other water-solvent systems it is shown that there is little correspondence between triolein and any of the 52 other solvents - only the water-isopropyl myristate system is close to the water-wet triolen system. A comparison of equation coefficients for the water-wet triolein system with LFER coefficients of 16 environmentally important processes shows that wet triolein is not a suitable model for any of the processes, although a number of other water-solvent systems are possible models for some of the environmental processes. A comparison of LFER coefficients with those of 17 aqueous toxicological processes reveals that most of the water-solvent systems, including water-wet triolein, will be poor models for any of the toxicological systems, but the water-lower alcohol systems show promise as models for a number of the toxicological systems. Our method of comparison of coefficients for LFERs that have exactly the same independent variables can be extended to various other types of system. PMID:27038899

  14. What is the correct value for the brain: blood partition coefficient for water

    SciTech Connect

    Herscovitch, P.; Raichle, M.E.

    1984-01-01

    A knowledge of the brain: blood partition coefficient (lambda) for water is usually required for the measurement of cerebral blood flow (CBF) with positron emission tomography (PET) and 0-15 labelled water. The correct calculation of this important parameter from the ratio of brain and blood water contents is reviewed, and the effect of physiological variations in these water contents on lambda is demonstrated. The currently accepted value for whole brain lambda is 0.95-0.96 ml/g, calculated from brain and blood water contents of 77g/100g and 80.5g/100g, respectively. However, this value for lambda is incorrect, because in the calculation the blood water content value was not adjusted for the density of blood. The correct value is 0.91 ml/g. Variations in brain or blood water content affect lambda. Over an hematocrit range of 25% to 55%, lambda varies from 0.86 to 0.93 ml/g, due to a decrease in blood water content. lambda changes with age, and varies regionally in the brain, as brain water content is inversely related to lipid and myelin content. The lambda of the human newborn brain, 1.10 ml/g, is considerably higher than in the adult. Differences in lambda between gray and white matter are well known. However, because of variations in water content, the lambda's of thalamus (0.88 ml/g) and caudate nucleus (0.96 ml/g) are less than that of cerebral cortex (0.99 ml/g), while the lambda of corpus callosum (0.89 ml/g) is greater than that of centrum semiovale (0.83 ml/g). These regional variations in lambda will assume more importance as PET resolution improves. The impact of using an incorrect lambda will depend upon the sensitivity of the particular CBF measurement technique to errors in lambda.

  15. Variations in trace element partition coefficients in sanidine in the Cerro Toledo Rhyolite, Jemez Mountains, New Mexico: Effects of composition, temperature, and volatiles

    SciTech Connect

    Stix, J. ); Gorton, M.P. )

    1990-10-01

    Trace element partition coefficients have been measured for one plagioclase and five sanidine mineral separates from the Cerro Toledo Rhyolite, New Mexico. Sanidine partition coefficients vary substantially and systematically within the Cerro Toledo Rhyolite. Partition coefficients for Ca, Sr, Zn, La, and Eu are lowest in the most evolved rhyolites, whereas Sm and HREE partition coefficients are highest. Rubidium partition coefficients remain constant, while those for Ba, Ce, and Th are variable. Variations of the Sr, Zn, La, and Eu partition coefficients are correlated with the Ca contents and partition coefficients of the sanidines. Calcium may have controlled the distribution of these elements in the sanidine by modifying the feldspar structure. The low Ca partition coefficients in sanidines for the most evolved rhyolites may be the consequence of modification of the melt structure, possibly due to increased volatile contents at the top of the magma chamber(s) during evolution of the Cerro Toledo Rhyolite. The Zn and La partition coefficients between sanidine and melt also may have been controlled by this change in melt structure. Modelling using major elements and the constant Rb partition coefficient for sanidine indicates 70% crystallization of magma during Cerro Toledo Rhyolite time by removal of 68% sanidine and 32% quartz. Estimates of the volume (1) of initial parental magma and (2) of the magma that crystallized during this period are 11,670 km{sup 3} and 8,170 km{sup 3}, respectively. The average intrusion rate of silicic magma during Cerro Toledo Rhyolite activity was 35 {times} 10{sup {minus}3} km{sup 3}/a.

  16. Henry's law behavior in simple systems and in magmas: Criteria for discerning concentration-dependent partition coefficients in nature

    NASA Astrophysics Data System (ADS)

    Watson, E. Bruce

    1985-04-01

    Although numerous questions still surround the topic of Henry's law (HL) as it applies to trace element partitioning, there now exist sufficient experimental data to make some generalizations regarding HL behavior in minerals. The most important of these is that the commonly-observed failure of HL at low concentration occurs at distinctly different levels even for chemically-similar elements in a single mineral. This observation in turn provides a basis for discerning effects of HL failure in natural systems: through examination of element ratios in minerals and rocks, it is possible, in principle, to distinguish HL effects from changes in partition coefficients due to variations in other magmatic parameters such as temperature and the compositions of phases. Initial applications of this approach to plagioclase/ liquid partitioning of REE and to the general behavior of Zr/Hf and Ba/Rb during basalt production suggest that HL usually does hold in nature.

  17. Aqueous solubility, Henry's law constants and air/water partition coefficients of n-octane and two halogenated octanes.

    PubMed

    Sarraute, S; Delepine, H; Costa Gomes, M F; Majer, V

    2004-12-01

    New data on the aqueous solubility of n-octane, 1-chlorooctane and 1-bromooctane are reported between 1 degree C and 45 degrees C. Henry's law constants, K(H), and air/water partition coefficients, K(AW), were calculated by associating the measured solubility values to vapor pressures taken from literature. The mole fraction aqueous solubility varies between (1.13-1.60)x10(-7) for n-octane with a minimum at approximately 23 degrees C, (3.99-5.07)x10(-7) for 1-chlorooctane increasing monotonically with temperature and (1.60-3.44)x10(-7) for 1-bromooctane with a minimum near 18 degrees C. The calculated air-water partition coefficients increase with temperature and are two orders of magnitude lower for the halogenated derivatives compared to octane. The precision of the results, taken as the average absolute deviations of the aqueous solubility, the Henry's law constants, or the air/water partition coefficients, from appropriate smoothing equations as a function of temperature is of 3% for n-octane and of 2% and 4% for 1-chlorooctane and 1-bromooctane, respectively. A new apparatus based on the dynamic saturation column method was used for the solubility measurements. Test measurements with n-octane indicated the capability of measuring solubilities between 10(-6) and 10(-10) in mole fraction, with an estimated accuracy better than +/-10%. A thorough thermodynamic analysis of converting measured data to air/water partition coefficients is presented. PMID:15519399

  18. The influence of plant species on the plant/air partitioning coefficients of PCBs and chlorinated benzenes

    SciTech Connect

    Koemp, P.; McLachlan, M.S.

    1995-12-31

    The plant/air partitioning coefficients (K{sub PA}) of pentachlorobenzene, hexachlorobenzene and 16 PCB congeners were determined in five different grass and herb species common to Central Europe (Lolium multiflorum, Trifolium repens, Plantago lanceolata, Crepis biennis, Achillea millefolium). The measurements were conducted between 5 C and 35 C using a solid phase fugacity meter. Octanol/air partition coefficients (K{sub OA}) were also measured over a similar temperature range. In all cases an excellent linear relationship between log K{sub PA} and log K{sub OA} was observed (r{sup 2} between 0.80 and 0.99). However, while the slope of this relationship was 1 for Lolium multiflorum (ryegrass), in agreement with previous work, the slopes of the log K{sub PA} vs. log K{sub OA} plot were less than 1 for the other 4 species, lying as low as 0.49 for Achillea millefolium (yarrow). Large differences in the enthalpy of phase change (plant/air) were also observed between the different species, but these differences were not related to the differences in the partition coefficients. These observations demonstrate that the contaminant storage properties of plants are variable, and that the lipophilic compartment in some plants is considerably more polar than octanol. This places constraints on the applicability of current models of plant uptake, almost all of which assume that the lipophilic compartment behaves like octanol, and reinforces the need for more research into the contaminant storage properties of plants.

  19. COMPARISON OF THE OCTANOL-AIR PARTITION COEFFICIENT AND LIQUID-PHASE VAPOR PRESSURE AS DESCRIPTORS FOR PARTICLE/GAS PARTITIONING USING LABORATORY AND FIELD DATA FOR PCBS AND PCNS

    EPA Science Inventory

    The conventional Junge-Pankow adsorption model uses the sub-cooled liquid vapor pressure (pLo) as a correlation parameter for gas/particle interactions. An alternative is the octanol-air partition coefficient (Koa) absorption model. Log-log plots of the particle-gas partition c...

  20. Cyclic voltammetric technique for the determination of the critical micelle concentration of surfactants, self-diffusion coefficient of micelles, and partition coefficient of an electrochemical probe

    SciTech Connect

    Mandal, A.B.; Nair, B.U. )

    1991-10-31

    Critical micelle concentrations (cmc) of cetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC) surfactants in aqueous solution have been determined by using the cyclic voltammetric technique. (Co(en){sub 3})(ClO{sub 4}){sub 3} has been used as the redox-active electrochemical probe. The cmc values so obtained for the surfactants were found to be in good agreement with the literature values. The partition coefficient, K, of the electrochemical probe between water and surfactants in nonmicellar and micellar states was estimated using the peak current, i{sub p} and half-wave potential, E{sub 1/2} values. The self-diffusion coefficient, D{sub m}, interaction parameter, k{sub f}, and hydrodynamic radius of the micelles were also estimated. The results suggest that the probe is sensitive to the nature of surfactant as well as surfactant concentration.

  1. Improved prediction of octanol-water partition coefficients from liquid-solute water solubilities and molar volumes

    USGS Publications Warehouse

    Chiou, C.T.; Schmedding, D.W.; Manes, M.

    2005-01-01

    A volume-fraction-based solvent-water partition model for dilute solutes, in which the partition coefficient shows a dependence on solute molar volume (V??), is adapted to predict the octanol-water partition coefficient (K ow) from the liquid or supercooled-liquid solute water solubility (Sw), or vice versa. The established correlation is tested for a wide range of industrial compounds and pesticides (e.g., halogenated aliphatic hydrocarbons, alkylbenzenes, halogenated benzenes, ethers, esters, PAHs, PCBs, organochlorines, organophosphates, carbamates, and amidesureas-triazines), which comprise a total of 215 test compounds spanning about 10 orders of magnitude in Sw and 8.5 orders of magnitude in Kow. Except for phenols and alcohols, which require special considerations of the Kow data, the correlation predicts the Kow within 0.1 log units for most compounds, much independent of the compound type or the magnitude in K ow. With reliable Sw and V data for compounds of interest, the correlation provides an effective means for either predicting the unavailable log Kow values or verifying the reliability of the reported log Kow data. ?? 2005 American Chemical Society.

  2. Determination of Aroma Compound Partition Coefficients in Aqueous, Polysaccharide, and Dairy Matrices Using the Phase Ratio Variation Method: A Review and Modeling Approach.

    PubMed

    Heilig, Andrej; Sonne, Alina; Schieberle, Peter; Hinrichs, Jörg

    2016-06-01

    The partition of aroma compounds between a matrix and a gas phase describes an individual compound's specific affinity toward the matrix constituents affecting orthonasal sensory perception. The static headspace phase ratio variation (PRV) method has been increasingly applied by various authors to determine the equilibrium partition coefficient K in aqueous, polysaccharide, and dairy matrices. However, reported partition coefficients are difficult to relate and compare due to different experimental conditions, e.g., aroma compound selection, matrix composition, equilibration temperature. Due to its specific advantages, the PRV method is supposed to find more frequent application in the future, this Review aims to summarize, evaluate, compare, and relate the currently available data on PRV-determined partition coefficients. This process was designed to specify the potentials and the limitations as well as the consistency of the PRV method, and to identify open fields of research in aroma compound partitioning in food-related, especially dairy matrices. PMID:27182770

  3. An empirical study of statistical properties of variance partition coefficients for multi-level logistic regression models

    USGS Publications Warehouse

    Li, J.; Gray, B.R.; Bates, D.M.

    2008-01-01

    Partitioning the variance of a response by design levels is challenging for binomial and other discrete outcomes. Goldstein (2003) proposed four definitions for variance partitioning coefficients (VPC) under a two-level logistic regression model. In this study, we explicitly derived formulae for multi-level logistic regression model and subsequently studied the distributional properties of the calculated VPCs. Using simulations and a vegetation dataset, we demonstrated associations between different VPC definitions, the importance of methods for estimating VPCs (by comparing VPC obtained using Laplace and penalized quasilikehood methods), and bivariate dependence between VPCs calculated at different levels. Such an empirical study lends an immediate support to wider applications of VPC in scientific data analysis.

  4. Experimental mineral/liquid partition coefficients of the rare earth elements /REE/, Sc and Sr for perovskite, spinel and melilite

    NASA Technical Reports Server (NTRS)

    Nagasawa, H.; Schreiber, H. D.; Morris, R. V.

    1980-01-01

    Experimental determinations of the mineral/liquid partition coefficients of REE (La, Sm, Eu, Gd, Tb, Yb and Lu), Sc and Sr are reported for the minerals perovskite, spinel and melilite in synthetic systems. Perovskite concentrates light REE with respect to the residual liquid but shows no preference for heavy REE. Spinel greatly discriminates against the incorporation of REE, especially light REE, into its crystal structure. The partition of REE into melilite from a silicate liquid is quite dependent upon both the bulk melt and melilite solid-solution (gehlenite and akermanite components) compositions. As such, melilite can be enriched in REE or will reject REE with corresponding strong negative or strong positive Eu anomalies, respectively.

  5. Estimation of air concentrations and profiles for polychlorinated dibenzo-p-dioxins and dibenzofurans from calculated vegetation-air partition coefficients

    SciTech Connect

    Kjeller, L.O.; Rappe, C.; Jones, K.C.

    1995-12-31

    Air concentrations of vapor and particulate phase polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are predicted by use of calculated plant-air partition coefficients. The plant-air interaction is reduced to an octanol-air distribution at equilibrium. Partition coefficients are deduced from the fugacity approach and calculated from congener group average data of solubility, vapor pressure and octanol-water partition coefficient. Calculated partition coefficients were used for prediction of the PCDD/F levels and congener profile in air from archived herbage collected pre- and post-1940. Before 1940 the air had a fly ash or combustion derived PCDD/F composition. After 1940 Hp and OCDD/F are superimposed on the combustion pattern, reflection of their release from the extensive use of polychlorinated compounds, notably penta chlorophenol, but also related compounds.

  6. Prediction of ecotoxicological behavior of chemicals: relationship between n-octanol/water partition coefficient and bioaccumulation of organic chemicals by alga Chlorella

    SciTech Connect

    Geyer, H.; Politzki, G.; Freitag, D.

    1984-01-01

    The bioaccumulation potential of organic chemicals by the green alga Chlorella fusca was determined. A quantitative relationship was found to exist between the lipophilicity (n-octanol/water partition coefficient) of the chemicals and the bioaccumulation factor.

  7. Comparisons of polymer/gas partition coefficients calculated from responses of thickness shear mode and surface acoustic wave vapor sensors.

    PubMed

    Grate, J W; Kaganove, S N; Bhethanabotla, V R

    1998-01-01

    Apparent partition coefficients, K, for the sorption of toluene by four different polymer thin films on thickness shear mode (TSM) and surface acoustic wave (SAW) devices are compared. The polymers examined were poly(isobutylene) (PIB), poly(epichlorohydrin) (PECH), poly(butadiene) (PBD), and poly(dimethylsiloxane) (PDMS). Independent data on partition coefficients for toluene in these polymers were compiled for comparison, and TSM sensor measurements were made using both oscillator and impedance analysis methods. K values from SAW sensor measurements were about twice those calculated from TSM sensor measurements when the polymers were PIB and PECH, and they were also at least twice the values of the independent partition coefficient data, which is interpreted as indicating that the SAW sensor responds to polymer modulus changes as well as to mass changes. K values from SAW and TSM measurements were in agreement with each other and with independent data when the polymer was PBD. Similarly, K values from the PDMS-coated SAW sensor were not much larger than values from independent measurements. These results indicate that modulus effects were not contributing to the SAW sensor responses in the cases of PBD and PDMS. However, K values from the PDMS-coated TSM device were larger than the values from the SAW device or independent measurements, and the impedance analyzer results indicated that this sensor using our sample of PDMS at the applied thickness did not behave as a simple mass sensor. Differences in behavior among the test polymers on SAW devices are interpreted in terms of their differing viscoelastic properties. PMID:21644612

  8. Trace element abundances in megacrysts and their host basalts - Constraints on partition coefficients and megacryst genesis

    NASA Technical Reports Server (NTRS)

    Irving, A. J.; Frey, F. A.

    1984-01-01

    Rare earth and other trace element abundances are determined in megacrysts of clinopyroxene, orthopyroxene, amphibole, mica, anorthoclase, apatite and zircon, as well as their host basalts, in an effort to gather data on mineral/melt trace element partitioning during the high pressure petrogenesis of basic rocks. Phase equilibria, major element partitioning and isotopic ratio considerations indicate that while most of the pyroxene and amphibole megacrysts may have been in equilibrium with their host magmas at high pressures, mica, anorthoclase, apatite, and zircon megacrysts are unlikely to have formed in equilibrium with their host basalts. It is instead concluded that they were precipitated from more evolved magmas, and have been mixed into their present hosts.

  9. Determination of octanol-water partition coefficients for carbonate esters and other small organic molecules by microemulsion electrokinetic chromatography.

    PubMed

    Østergaard, Jesper; Hansen, Steen Honoré; Larsen, Claus; Schou, Christian; Heegaard, Niels H H

    2003-03-01

    Microemulsion electrokinetic chromatography (MEEKC) was assessed as a tool for determination of octanol-water partition coefficients using 34 solutes encompassing 8 carbonate esters. It was confirmed that microemulsions containing 1.44-2.88% w/w SDS, 6.49% w/w 1-butanol, and 0.82% w/w n-heptane constitute a good model of octanol-water partitioning in the pH range of 1.4-7.4. Use of the migration index concept led to improved repeatability of the MEEKC method compared to the use of retention factors. Using a dynamical coating, a high electroosmotic flow at pH 1.4 and 4.75 was achieved expanding the practical pH working range of the MEEKC system. The correlation obtained between the migration index and log P was unaffected by pH indicating that the properties of the microemulsion droplets and, thus, partitioning are independent of pH. No evidence for congeneric behavior was found for the sample set comprising solutes with different hydrogen bonding properties suggesting that simple reference compounds can be used as calibrators. Lipophilicity estimates for the series of carbonate esters were obtained. The increase in lipophilicity with chain length was smaller than expected from the Hansch substituent constant, pi. PMID:12658693

  10. The effect of oil-water partition coefficient on the distribution and cellular uptake of liposome-encapsulated gold nanoparticles.

    PubMed

    Bao, Quan-Ying; Liu, Ai-Yun; Ma, Yu; Chen, Huan; Hong, Jin; Shen, Wen-Bin; Zhang, Can; Ding, Ya

    2016-10-01

    The shape, size, and surface features of nanoparticles greatly influence the structure and properties of resulting hybrid nanosystems. In this work, gold nanoparticles (GNPs) were modified via S-Au covalent bonding by glycol monomethyl ether thioctate with poly(ethylene glycol) methyl ether of different molecular weights (i.e., 350, 550, and 750Da). These modified GNPs (i.e., GNP350, GNP550, and GNP750) showed different oil-water partition coefficients (Kp), as detected using inductively coupled plasma-atomic emission spectroscopy. The different Kp values of the gold conjugates (i.e., 13.98, 2.11, and 0.036 for GNP350, GNP550, and GNP750, respectively) resulted in different conjugate localization within liposomes, as observed by transmission electron microscopy. In addition, the cellular uptake of hybrid liposomes co-encapsulating gold conjugates and Nile red was evaluated using intracellular fluorescence intensity. The results indicated that precise GNP localization in the hydrophilic or hydrophobic liposome cavity could be achieved by regulating the GNP oil-water partition coefficient via surface modification; such localization could further affect the properties and functions of hybrid liposomes, including their cellular uptake profiles. This study furthers the understanding not only of the interaction between liposomes and inorganic nanoparticles but also of adjusting liposome-gold hybrid nanostructure properties via the surface chemistry of gold materials. PMID:27400242

  11. Determining octanol-water partition coefficients for extremely hydrophobic chemicals by combining "slow stirring" and solid-phase microextraction.

    PubMed

    Jonker, Michiel T O

    2016-06-01

    Octanol-water partition coefficients (KOW ) are widely used in fate and effects modeling of chemicals. Still, high-quality experimental KOW data are scarce, in particular for very hydrophobic chemicals. This hampers reliable assessments of several fate and effect parameters and the development and validation of new models. One reason for the limited availability of experimental values may relate to the challenging nature of KOW measurements. In the present study, KOW values for 13 polycyclic aromatic hydrocarbons were determined with the gold standard "slow-stirring" method (log KOW 4.6-7.2). These values were then used as reference data for the development of an alternative method for measuring KOW . This approach combined slow stirring and equilibrium sampling of the extremely low aqueous concentrations with polydimethylsiloxane-coated solid-phase microextraction fibers, applying experimentally determined fiber-water partition coefficients. It resulted in KOW values matching the slow-stirring data very well. Therefore, the method was subsequently applied to a series of 17 moderately to extremely hydrophobic petrochemical compounds. The obtained KOW values spanned almost 6 orders of magnitude, with the highest value measuring 10(10.6) . The present study demonstrates that the hydrophobicity domain within which experimental KOW measurements are possible can be extended with the help of solid-phase microextraction and that experimentally determined KOW values can exceed the proposed upper limit of 10(9) . Environ Toxicol Chem 2016;35:1371-1377. © 2015 SETAC. PMID:26550770

  12. Feasibility of a simple laboratory approach for determining temperature influence on SPMD-air partition coefficients of selected compounds

    NASA Astrophysics Data System (ADS)

    Cicenaite, Aurelija; Huckins, James N.; Alvarez, David A.; Cranor, Walter L.; Gale, Robert W.; Kauneliene, Violeta; Bergqvist, Per-Anders

    Semipermeable membrane devices (SPMDs) are a widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics and partition coefficients of an analyte in a SPMD are mediated by its physicochemical properties and certain environmental conditions. Controlled laboratory experiments are used for determining the SPMD-air ( Ksa's) partition coefficients and the exchange kinetics of organic vapors. This study focused on determining a simple approach for measuring equilibrium Ksa's for naphthalene (Naph), o-chlorophenol ( o-CPh) and p-dichlorobenzene ( p-DCB) over a wide range of temperatures. SPMDs were exposed to test chemical vapors in small, gas-tight chambers at four different temperatures (-16, -4, 22 and 40 °C). The exposure times ranged from 6 h to 28 d depending on test temperature. Ksa's or non-equilibrium concentrations in SPMDs were determined for all compounds, temperatures and exposure periods with the exception of Naph, which could not be quantified in SPMDs until 4 weeks at the -16 °C temperature. To perform this study the assumption of constant and saturated atmospheric concentrations in test chambers was made. It could influence the results, which suggest that flow through experimental system and performance reference compounds should be used for SPMD calibration.

  13. Feasibility of a simple laboratory approach for determining temperature influence on SPMD–air partition coefficients of selected compounds

    USGS Publications Warehouse

    Cicenaite, Aurelija; Huckins, James N.; Alvarez, David A.; Cranor, Walter L.; Gale, Robert W.; Kauneliene, Violeta; Bergqvist, Per-Anders

    2007-01-01

    Semipermeable membrane devices (SPMDs) are a widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics and partition coefficients of an analyte in a SPMD are mediated by its physicochemical properties and certain environmental conditions. Controlled laboratory experiments are used for determining the SPMD–air (Ksa's) partition coefficients and the exchange kinetics of organic vapors. This study focused on determining a simple approach for measuring equilibrium Ksa's for naphthalene (Naph), o-chlorophenol (o-CPh) and p-dichlorobenzene (p-DCB) over a wide range of temperatures. SPMDs were exposed to test chemical vapors in small, gas-tight chambers at four different temperatures (−16, −4, 22 and 40 °C). The exposure times ranged from 6 h to 28 d depending on test temperature. Ksa's or non-equilibrium concentrations in SPMDs were determined for all compounds, temperatures and exposure periods with the exception of Naph, which could not be quantified in SPMDs until 4 weeks at the −16 °C temperature. To perform this study the assumption of constant and saturated atmospheric concentrations in test chambers was made. It could influence the results, which suggest that flow through experimental system and performance reference compounds should be used for SPMD calibration.

  14. Feasibility of a simple laboratory approach for determining temperature influence on SPMD-air partition coefficients of selected compounds

    USGS Publications Warehouse

    Cicenaite, A.; Huckins, J.N.; Alvarez, D.A.; Cranor, W.L.; Gale, R.W.; Kauneliene, V.; Bergqvist, P.-A.

    2007-01-01

    Semipermeable membrane devices (SPMDs) are a widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics and partition coefficients of an analyte in a SPMD are mediated by its physicochemical properties and certain environmental conditions. Controlled laboratory experiments are used for determining the SPMD-air (Ksa's) partition coefficients and the exchange kinetics of organic vapors. This study focused on determining a simple approach for measuring equilibrium Ksa's for naphthalene (Naph), o-chlorophenol (o-CPh) and p-dichlorobenzene (p-DCB) over a wide range of temperatures. SPMDs were exposed to test chemical vapors in small, gas-tight chambers at four different temperatures (-16, -4, 22 and 40 ??C). The exposure times ranged from 6 h to 28 d depending on test temperature. Ksa's or non-equilibrium concentrations in SPMDs were determined for all compounds, temperatures and exposure periods with the exception of Naph, which could not be quantified in SPMDs until 4 weeks at the -16 ??C temperature. To perform this study the assumption of constant and saturated atmospheric concentrations in test chambers was made. It could influence the results, which suggest that flow through experimental system and performance reference compounds should be used for SPMD calibration. ?? 2006 Elsevier Ltd. All rights reserved.

  15. Determination of silicone rubber and low-density polyethylene diffusion and polymer/water partition coefficients for emerging contaminants.

    PubMed

    Pintado-Herrera, Marina G; Lara-Martín, Pablo A; González-Mazo, Eduardo; Allan, Ian J

    2016-09-01

    There is a growing interest in assessing the concentration and distribution of new nonregulated organic compounds (emerging contaminants) in the environment. The measurement of freely dissolved concentrations using conventional approaches is challenging because of the low concentrations that may be encountered and their temporally variable emissions. Absorption-based passive sampling enables the estimation of freely dissolved concentrations of hydrophobic contaminants of emerging concern in water. In the present study, calibration was undertaken for 2 polymers, low-density polyethylene (LDPE) and silicone rubber for 11 fragrances, 5 endocrine-disrupting compounds, 7 ultraviolet (UV) filters, and 8 organophosphate flame retardant compounds. Batch experiments were performed to estimate contaminant diffusion coefficients in the polymers (Dp ), which in general decreased with increasing molecular weight. The values for fragrances, endocrine-disrupting compounds, and UV filters were in ranges similar to those previously reported for polycyclic aromatic hydrocarbons, but were 1 order of magnitude lower for organophosphate flame retardant compounds. Silicone rubber had higher Dp values than LDPE and was therefore selected for further experiments to calculate polymer/water partition coefficients (KPW ). The authors observed a positive correlation between log KPW and log octanol/water partition coefficient values. Field testing of silicone rubber passive samplers was undertaken though exposure in the River Alna (Norway) for an exposure time of 21 d to estimate freely dissolved concentration. Some fragrances and UV filters were predominant over other emerging and regulated contaminants, at levels up to 1600 ng L(-1) for galaxolide and 448 ng L(-1) for octocrylene. Environ Toxicol Chem 2016;35:2162-2172. © 2016 SETAC. PMID:26833936

  16. Temperature dependence of the particle/gas partition coefficient: An application to predict indoor gas-phase concentrations of semi-volatile organic compounds.

    PubMed

    Wei, Wenjuan; Mandin, Corinne; Blanchard, Olivier; Mercier, Fabien; Pelletier, Maud; Le Bot, Barbara; Glorennec, Philippe; Ramalho, Olivier

    2016-09-01

    The indoor gas-phase concentrations of semi-volatile organic compounds (SVOCs) can be predicted from their respective concentrations in airborne particles by applying the particle/gas partitioning equilibrium. The temperature used for partitioning is often set to 25°C. However, indoor temperatures frequently differ from this reference value. This assumption may result in errors in the predicted equilibrium gas-phase SVOC concentrations. To improve the prediction model, the temperature dependence of the particle/gas partition coefficient must be addressed. In this paper, a theoretical relationship between the particle/gas partition coefficient and temperature was developed based on the SVOC absorptive mechanism. The SVOC particle/gas partition coefficients predicted by employing the derived theoretical relationship agree well with the experimental data retrieved from the literature (R>0.93). The influence of temperature on the equilibrium gas-phase SVOC concentration was quantified by a dimensionless analysis of the derived relationship between the SVOC particle/gas partition coefficient and temperature. The predicted equilibrium gas-phase SVOC concentration decreased by between 31% and 53% when the temperature was lowered by 6°C, while it increased by up to 750% when the indoor temperature increased from 15°C to 30°C. PMID:27152992

  17. The Effect of fO2 on Partition Coefficients of U and Th between Garnet and Silicate Melt

    NASA Astrophysics Data System (ADS)

    Huang, F.; He, Z.; Schmidt, M. W.; Li, Q.

    2014-12-01

    Garnet is one of the most important minerals controlling partitioning of U and Th in the upper mantle. U is redox sensitive, while Th is tetra-valent at redox conditions of the silicate Earth. U-series disequilibria have provided a unique tool to constrain the time-scales and processes of magmatism at convergent margins. Variation of garnet/meltDU/Th with fO2 is critical to understand U-series disequilibria in arc lavas. However, there is still no systematic experimental study about the effect of fO2 on partitioning of U and Th between garnet and melt. Here we present experiments on partitioning of U, Th, Zr, Hf, Nb, Ta, and REE between garnet and silicate melts at various fO2. The starting material was hydrous haplo-basalt. The piston cylinder experiments were performed with Pt double capsules with C-CO, MnO-Mn3O4 (MM), and hematite-magnetite (HM) buffers at 3 GPa and 1185-1230 oC. The experiments produced garnets with diameters > 50μm and quenched melt. Major elements were measured by EMPA at ETH Zurich. Trace elements were determined using LA-ICP-MS at Northwestern University (Xi'an, China) and SIMS (Cameca1280 at the Institute of Geology and Geophysics, Beijing, China), producing consistent partition coefficient data for U and Th. With fO2 increasing from CCO to MM and HM, garnet/meltDU decreases from 0.041 to 0.005, while garnet/meltDTh ranges from 0.003 to 0.007 without correlation with fO2. Notably, garnet/meltDTh/U increases from 0.136 at CCO to 0.41 at HM. Our results indicate that U is still more compatible than Th in garnet even at the highest fO2 considered for the subarc mantle wedge (~NNO). Therefore, we predict that if garnet is the dominant phase controlling U-Th partitioning during melting of the mantle wedge, melts would still have 230Th excess over 238U. This explains why most young continental arc lavas have 230Th excess. If clinopyroxene is the dominant residual phase during mantle melting, U could be more incompatible than Th at high fO2

  18. 40 CFR 799.6756 - TSCA partition coefficient (n-octanol/water), generator column method.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    .../water), generator column method. 799.6756 Section 799.6756 Protection of Environment ENVIRONMENTAL... coefficient (n-octanol/water), generator column method. (a) Scope—(1) Applicability. This section is intended... tissue. (v) This section describes a method for determining the Kow based on the dynamic coupled...

  19. 40 CFR 799.6756 - TSCA partition coefficient (n-octanol/water), generator column method.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    .../water), generator column method. 799.6756 Section 799.6756 Protection of Environment ENVIRONMENTAL... coefficient (n-octanol/water), generator column method. (a) Scope—(1) Applicability. This section is intended... tissue. (v) This section describes a method for determining the Kow based on the dynamic coupled...

  20. 40 CFR 799.6756 - TSCA partition coefficient (n-octanol/water), generator column method.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    .../water), generator column method. 799.6756 Section 799.6756 Protection of Environment ENVIRONMENTAL... coefficient (n-octanol/water), generator column method. (a) Scope—(1) Applicability. This section is intended... liquid chromatographic (DCCLC) technique, a technique commonly referred to as the generator column...

  1. 40 CFR 799.6756 - TSCA partition coefficient (n-octanol/water), generator column method.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    .../water), generator column method. 799.6756 Section 799.6756 Protection of Environment ENVIRONMENTAL... coefficient (n-octanol/water), generator column method. (a) Scope—(1) Applicability. This section is intended... liquid chromatographic (DCCLC) technique, a technique commonly referred to as the generator column...

  2. 40 CFR 799.6756 - TSCA partition coefficient (n-octanol/water), generator column method.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    .../water), generator column method. 799.6756 Section 799.6756 Protection of Environment ENVIRONMENTAL... coefficient (n-octanol/water), generator column method. (a) Scope—(1) Applicability. This section is intended... liquid chromatographic (DCCLC) technique, a technique commonly referred to as the generator column...

  3. The Fragment Constant Method for Predicting Octanol-Air Partition Coefficients of Persistent Organic Pollutants at Different Temperatures

    NASA Astrophysics Data System (ADS)

    Li, Xuehua; Chen, Jingwen; Zhang, Li; Qiao, Xianliang; Huang, Liping

    2006-09-01

    The octanol-air partition coefficient (KOA) is a key physicochemical parameter for describing the partition of organic pollutants between air and environmental organic phases. Experimental determination of KOA is costly and time consuming, and sometimes restricted by lack of sufficiently pure chemicals. There is a need to develop a simple but accurate method to estimate KOA. In the present study, a fragment constant model based on five fragment constants and one structural correction factor, was developed for predicting logKOA at temperatures ranging from 10 to 40°C. The model was validated as successful by statistical analysis and external experimental logKOA data. Compared to other quantitative structure-property relationship methods, the present model has the advantage that it is much easier to implement. As aromatic compounds that contain C, H, O, Cl, and Br atoms, were included in the training set used to develop the model, the current fragment model applies to a wide range of chlorinated and brominated aromatic pollutants, such as chlorobenzenes, polychlorinated naphthalenes, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans, polycyclic aromatic hydrocarbons, and polybrominated diphenyl ethers, all of which are typical persistent organic pollutants. Further study is necessary to expand the utility of the method to all halogenated aliphatic and aromatic compounds.

  4. Variation of penicillin acylase partition coefficient with phase volume ratio in poly(ethylene glycol)-sodium citrate aqueous two-phase systems.

    PubMed

    Marcos, J C; Fonseca, L P; Ramalho, M T; Cabral, J M

    1998-06-26

    The influence of phase volume ratio on partition and purification of penicillin acylase from Escherichia coli on poly(ethylene glycol)-sodium citrate aqueous two-phase systems was studied. In PEG 1000 systems both partition coefficients of the enzyme and total protein increased with decreasing phase volume ratio. However, in PEG 3350 containing NaCl, penicillin acylase follows a reverse trend, while total protein behaves in the same way. Implications for protein purification designs are discussed. PMID:9699998

  5. Chromatographic determination of octanol-water partition coefficients (K/sub ow/'s) for 58 polychlorinated biphenyl congeners

    SciTech Connect

    Rapaport, R.A.; Eisenreich, S.J.

    1984-03-01

    Octanol-water partition coefficients of 58 poly-chlorinated biphenyl (PCB) congeners have been determined by reverse-phase C/sub 18/ high-performance liquid chromatography (HPLC) of Aroclor 1242 and 1254 mixtures. High-resolution glass capillary gas-liquid chromatography was used for the detection of the eluted individual congeners. Some PCB congeners behaved atypically from other organics on reverse-phase HPLC, and empirically derived correction factors were used to adjust K/sub ow/ values. Congener log K/sub ow/ values for PCB's ranged from an average of 4.5 for N/sub Cl/ = 1 to 8.1 for N/sub Cl/ = 7. The environmental implications of PCB K/sub ow/ values and congener behavior on the C /sub 18/ reverse-phase column are discussed. 35 references.

  6. Mobility of Heavy Metals (Pb, Cd, Zn) in the Pampeano and Puelche Aquifers, Argentina: Partition and Retardation Coefficients.

    PubMed

    Jakomin, L M; Marbán, L; Grondona, S; Glok Galli, M; Martínez, D E

    2015-09-01

    The prediction about metals behaviour in soil requires knowledge on their solid-liquid partitioning. Usually it is expressed with an empirical distribution coefficient or Kd, which gives the ratio of the metal concentration in the solid phase to that in the solution. Kd values have been determined for Zn, Pb and Cd from samples representing the two most exploited aquifers in Argentina, Pampeano and Puelche, at three different locations in the province of Buenos Aires. The Pampeano aquifer presented higher Kd values than the Puelche aquifer. Comparing Kd values, different relationships could be observed: (a) Pampeano aquifer: Pb > Zn > Cd, and (b) Puelche aquifer: Pb > Cd > Zn. Kd for Cd seems to be linked to cationic exchange capacity, but solid phases precipitation can be more determining for Pb and Zn. PMID:26183386

  7. Partition coefficients and phase behavior for non-toxic ice inhibitors from quantum mechanical calculations and molecular dynamics simulations

    SciTech Connect

    Trohalaki, S.; Pachter, R.

    1996-10-01

    In our continuing efforts to design new anti-icing compounds for jet fuel, aircraft wings, and runways, we report values of the water-hexadecane partition coefficient calculated using AMSOL and COSMO and compare with experimental results whenever possible. In addition, we present phase-behavior results as predicted from the so-called mean-field lattice-gas Flory-Huggins (FH) theory. The FH interaction parameter, related to the cohesive energy density and the Hildebrand solubility parameter, was obtained from equilibrium molecular dynamics (NM) trajectories of mixed and de-mixed systems. Radial distribution functions for intermolecular oxygen-oxygen separations for hydrogen-bond donors and acceptors were also calculated from the MD trajectories. Integration over the peak indicative of hydrogen bonding yields the average number of nearest-neighbor water molecules, which correlates with the anti-icing performance.

  8. Inferences about radionuclide mobility in soils based on the solid/liquid partition coefficients and soil properties.

    PubMed

    Sohlenius, Gustav; Saetre, Peter; Nordén, Sara; Grolander, Sara; Sheppard, Steve

    2013-05-01

    To assist transport modeling in assessments of the radiological impact of a geological repository for radioactive wastes, the mobility of various elements was studied in arable and wetland soils in the Forsmark region, Sweden. Pore water and total element contents were determined for five types of unconsolidated deposits (regolith), spanning a wide range of soil properties with respect to pH and organic matter content. Two soil depths were sampled to capture element mobility in regolith layers affected and unaffected by soil-forming processes. The solid/liquid partition coefficients (K d values) for most elements varied significantly among regolith types. For most elements, the observed variations in K d values could be explained by variations in soil properties. For many elements, mobility increased with decreasing soil pH. The results provide a significant addition of data on radionuclide retention in soils, taking account of soil properties and processes. PMID:23619799

  9. Effects of SO2 and pH on blood-gas partition coefficients of inert gases.

    PubMed

    Yamaguchi, K; Mori, M; Kawai, A; Asano, K; Takasugi, T; Umeda, A; Yokoyama, T

    1990-01-01

    Potential effects of SO2 and of pH on blood-gas partition coefficients, lambda, for inert gases, including SF6, ethane, cyclopropane, halothane, diethyl ether, acetone and N2, were systematically investigated using human blood. Measurements on lambda were performed at 37 degrees C in conditions of varied SO2 and pH using gas chromatography. Incorporating the experimental data on lambda, multiple inert gas elimination was applied to 18 patients with varied chronic lung diseases, in order to estimate the effects of SO2 and of pH on both inert gas exchange and resultant recovery of VA/Q distribution in the lung. For this purpose, the data obtained by the procedure of multiple inert gas elimination were analyzed with the classical approach but allowance was made for lambda of the indicator gas to vary according to exchange of O2 and of CO2 in the pulmonary capillary. Among the gases studied, ethane, cyclopropane, halothane and diethyl ether showed significantly smaller lambda values in the oxygenated blood than in deoxygenated blood, whereas SF6, acetone and N2 were little dependent on SO2. An increase in lambda was found for ethane and a decrease for halothane with increasing pH in the blood. The other gases were not significantly influenced by pH. In spite of these experimental findings, regional difference of either SO2 or pH in the lung did not exert important influence on the inert gas exchange or on the predicted VA/Q distribution. In conclusion, blood-gas partition coefficients of some inert gases are consistently altered by SO2 and pH, but their possible effects on inert gas exchange seem to be negligible. PMID:1965757

  10. The Effect of Pressure on Siderophile-Element (Ni, Co, Mo, W, and P) Metal-Silicate Partition Coefficients

    NASA Astrophysics Data System (ADS)

    Righter, K.; Drake, M. J.

    1995-09-01

    Quantification of the effect of pressure on siderophile element metal-silicate partition coefficients (D) is essential in modelling the accretion histories of the the Earth and terrestrial planets [1], as metal-silicate equilibria may have been set over a range of pressures [2]. We report siderophile element partition coefficients from metal-silicate equilibrium experiments done at 10 and 15 kb, and 1300 degrees C. These new results show that metal-silicate partition coefficients for Ni (Fig. 1), Co, and P decrease with increasing pressure (at constant T and relative fO(sub)2), while those for Mo and W increase. Experiments were done in a 1/2" piston cylinder apparatus, with T, P and fO(sub)2 controlled and monitored as described in a previous study [3]. Synthetic basalt [see 3] powder, doped with 5 wt% levels of either MoO3, WO3 or apatite, was loaded into Fe54Ni29Co17 or Fe64Ni36 tubing, which was closed either by welding or plugging the open ends with small, tapered caps of the same alloy composition. The samples were quenched after 4 to 6 hrs. The metal and glass in the run products are then analyzed by electron microprobe to obtain a solid metal/liquid silicate (SM/LS) partition coefficient for a given element (D = wt% element in metal/ wt% element in glass). For several experiments, NiS was added as a sulfur source, and thus stabilizing a sulfur-bearing metallic liquid. For these experiments, both solid metal/ liquid silicate and liquid metal/ liquid silicate (LM/LS) partition coefficients are reported (Table 1). In order to isolate the effect of pressure on siderophile element partition coefficients, we have compared our results at high pressures to calculated 1 bar values at the same T and fO(sub)2 as our experiments (based on experiments of [4 - 11]; see results for Ni in Fig. 1; data from [3] and this study). The effect of pressure and other intensive variables on metal-silicate D's can be quantified using the thermodynamically-based relation: lnD (metal

  11. Partition coefficients of aroma compounds between polyethylene and aqueous ethanol and their estimation using UNIFAC and GCFEOS. (Volumes I and II)

    SciTech Connect

    Baner, A.L. III.

    1993-01-01

    Partition coefficients were measured for n-alkanes and 13 different aroma compounds (isoamylacetate, d-limonene, camphor, linalylacetate, L-menthol, dimethylbenzyl-carbinol, citronellol, phenylethylalcholo, diphenylmethane, diphenyloxide, eugenol, [tau]-undelacotne) at dilute concentrations between aqueous ethanol solutions (100%, 66% and 33% for n-alkanes; 100%, 75%, 50%, 35% w/w) and nitrogen at 25[degrees]C using a gas stripping column method. Partition coefficients for n-alkanes (octane, nonane, decane, dodecane, tetradecane, hexadecane, octadecane, eicosane, docosane) and the aromas were also measured between low density polyethylene, high density polyethylene and ethanol and aqueous ethanol liquid phases (100%, 75%, 50% and 35% ethanol w/w) at 10[degrees], 25[degrees] and 40[degrees]C using an equilibrium sorption method. No significant differences were found for polyethylene samples with different crystallinities and very little temperature effect was seen for the polymer/liquid partition coefficients. The polymer/liquid partition coefficients were most affected by the chemical nature of the mixture. The liquid/gas and polymer/liquid partition coefficients were estimated using UNIFAC with UNIFAC-FV and using the Group-contribution Flory Equation-of-State (GCFEOS). UNIFAC and GCFEOS are useful for qualitative estimations. Significant quantitative differences between the experimental data and the estimations were found for the liquid/gas and polymer/liquid partition coefficients of some solutes, in particular middle polarity aroma compounds. A correlation of the size of estimation error with increasing molecular weight was observed for the n-alkanes and phenols. The variances between experimental and estimated values are explained in terms of the methods' group-contribution additivity and solution of groups assumptions and the methods' semi-empirical nature. UNIFAC gave more consistent and on average better quantitative estimations the GCFEOS.

  12. Determination of aragonite trace element partition coefficients from speleothem calcite-aragonite transitions

    NASA Astrophysics Data System (ADS)

    Wassenburg, Jasper A.; Scholz, Denis; Jochum, Klaus Peter; Cheng, Hai; Oster, Jessica; Immenhauser, Adrian; Richter, Detlev K.; Haeger, Tobias; Hoffmann, Dirk; Breitenbach, Sebastian F. M.

    2016-04-01

    Speleothem trace element variability has often been linked to environmental changes. While research has focused on element incorporation into speleothem calcite, our current knowledge of trace element variability in speleothem aragonite is limited to a few studies only. Here we present, to our knowledge, for the first time quantitative estimates of distribution coefficients for speleothem aragonite (DMg, DBa, DSr, and DU). These were derived from ten calcite-to-aragonite transitions from seven speleothems from Morocco, Germany, Spain, France and India. Our calculations indicate the following distribution coefficients: DMg = 1.01E-04 ± 9.0E-05, DBa(Ar) = 0.91 ± 0.53, DSr(Ar) = 1.38 ± 0.53, and DU(Ar) = 6.26 ± 4.53. These results are discussed in the context of speleothem growth rates, Rayleigh distillation effects, temperature, drip water elemental composition and drip water pH. We conclude that speleothem aragonite DMg(Ar) is below one, DSr(Ar) is close to unity, and DU(Ar) is above one. For DBa(Ar), such a conclusion is difficult. Speleothem growth rate may affect aragonite DSr in samples forming at a growth rate lower than 20 μm/a. Our results also indicate that calcite DSr and calcite DBa are affected by the Mg content of calcite. This has important implications for studies attempting to quantify processes like prior calcite precipitation. In particular, DSr and DBa cannot be transferred from caves developed within a limestone host rock to caves developed within a dolostone host rock.

  13. EVALUATION OF REVERSE PHASE LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY FOR ESTIMATION OF N-OCTANOL/WATER PARTITION COEFFICIENTS FOR ORGANIC CHEMICALS

    EPA Science Inventory

    A reverse-phase high pressure liquid chromatography/mass spectrometry (HPLC/MS) method was developed for estimating n-octanol/water partition coefficients (K sub ow) of anthropogenic molecules in complex chemical mixtures (e.g., complex effluents and solid waste leachates). The a...

  14. Bioaccumulation Patterns Of PCBs In A Temperate, Freshwater Food Web And Their Relationshop To The Octanol-Water Partition Coefficient (Presentation)

    EPA Science Inventory

    We investigated polychlorinated biphenyl (PCB) bioaccumulation relative to octanol-water partition coefficient (KOW) and organism tropic position (TP) at the Lake Hartwell Superfund site (South Carolina, USA). We measured PCBs (127 congeners) and stable isotopes (δ

  15. Air-water partition coefficients for a suite of polycyclic aromatic and other C10 through C20 unsaturated hydrocarbons.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-09-18

    The air-water partition coefficients (Kaw) for 86 large polycyclic aromatic hydrocarbons and their unsaturated relatives were estimated using high-level G4(MP2) gas and aqueous phase calculations with the SMD, IEFPCM-UFF, and CPCM solvation models. An extensive method validation effort was undertaken which involved confirming that, via comparisons to experimental enthalpies of formation, gas-phase energies at the G4(MP2) level for the compounds of interest were at or near thermochemical accuracy. Investigations of the three solvation models using a range of neutral and ionic compounds suggested that while no clear preferential solvation model could be chosen in advance for accurate Kaw estimates of the target compounds, the employment of increasingly higher levels of theory would result in lower Kaw errors. Subsequent calculations on the polycyclic aromatic and unsaturated hydrocarbons at the G4(MP2) level revealed excellent agreement for the IEFPCM-UFF and CPCM models against limited available experimental data. The IEFPCM-UFF-G4(MP2) and CPCM-G4(MP2) solvation energy calculation approaches are anticipated to give Kaw estimates within typical experimental ranges, each having general Kaw errors of less than 0.5 log10 units. When applied to other large organic compounds, the method should allow development of a broad and reliable Kaw database for multimedia environmental modeling efforts on various contaminants. PMID:27336293

  16. Using solid-phase microextraction to determine partition coefficients to humic acids and bioavailable concentrations of hydrophobic chemicals

    SciTech Connect

    Ramos, E.U.; Meijer, S.N.; Vaes, W.H.J.; Verhaar, H.J.M.; Hermens, J.L.M.

    1998-11-01

    In the current study, the suitability of negligible depletion solid-phase microextraction (nd-SPME) to determine free fractions of chemicals in aquatic environments was explored. The potential interferences of the dissolved matrix (i.e., humic acids) with the SPME measurements were tested. Results show that nd-SPME measures only the freely dissolved fraction and that the measurements are not disturbed by the humic acids. In addition, nd-SPME was used to determine partition coefficients between dissolved organic carbon and water for four hydrophobic chemicals. Obtained values are in excellent agreement with previously reported data. Finally, the bioaccumulation of hexachlorobenzene and PCB 77 to Daphnia magna was determined in the presence and absence of humic acids. The bioconcentration factors (BCF) were calculated based on total as well as on free concentration. Lower BCF values are obtained in the presence of humic acids using total concentrations, whereas equal BCFs are found using free concentrations measured with nd-SPME. Therefore, the authors can conclude that negligible depletion SPME is a good technique to determine bioavailable concentrations of hydrophobic chemicals in aquatic environments.

  17. QSPR models for predicting generator-column-derived octanol/water and octanol/air partition coefficients of polychlorinated biphenyls.

    PubMed

    Yuan, Jintao; Yu, Shuling; Zhang, Ting; Yuan, Xuejie; Cao, Yunyuan; Yu, Xingchen; Yang, Xuan; Yao, Wu

    2016-06-01

    Octanol/water (KOW) and octanol/air (KOA) partition coefficients are two important physicochemical properties of organic substances. In current practice, KOW and KOA values of some polychlorinated biphenyls (PCBs) are measured using generator column method. Quantitative structure-property relationship (QSPR) models can serve as a valuable alternative method of replacing or reducing experimental steps in the determination of KOW and KOA. In this paper, two different methods, i.e., multiple linear regression based on dragon descriptors and hologram quantitative structure-activity relationship, were used to predict generator-column-derived log KOW and log KOA values of PCBs. The predictive ability of the developed models was validated using a test set, and the performances of all generated models were compared with those of three previously reported models. All results indicated that the proposed models were robust and satisfactory and can thus be used as alternative models for the rapid assessment of the KOW and KOA of PCBs. PMID:26943944

  18. A Colorful Laboratory Investigation of Hydrophobic Interactions, the Partition Coefficient, Gibbs Energy of Transfer, and the Effect of Hofmeister Salts

    ERIC Educational Resources Information Center

    McCain, Daniel F.; Allgood, Ottie E.; Cox, Jacob T.; Falconi, Audrey E.; Kim, Michael J.; Shih, Wei-Yu

    2012-01-01

    Only a few pedagogical experiments have been published dealing specifically with the hydrophobic interaction though it plays a central role in biochemistry. A set of experiments is presented in which students partition a variety of colorful indicator dyes in biphasic water/organic solvent mixtures. Students monitor the partitioning visually and…

  19. Removal of dissolved organic carbon by aquifer material: Correlations between column parameters, sorption isotherms and octanol-water partition coefficient.

    PubMed

    Pradhan, Snigdhendubala; Boernick, Hilmar; Kumar, Pradeep; Mehrotra, Indu

    2016-07-15

    The correlation between octanol-water partition coefficient (KOW) and the transport of aqueous samples containing single organic compound is well documented. The concept of the KOW of river water containing the mixture of organics was evolved by Pradhan et al. (2015). The present study aims at determining the KOW and sorption parameters of synthetic aqueous samples and river water to finding out the correlation, if any. The laboratory scale columns packed with aquifer materials were fed with synthetic and river water samples. Under the operating conditions, the compounds in the samples did not separate, and all the samples that contain more than one organic compound yielded a single breakthrough curve. Breakthrough curves simulated from sorption isotherms were compared with those from the column runs. The sorption parameters such as retardation factor (Rf), height of mass transfer zone (HMTZ), rate of mass transfer zone (RMTZ), breakpoint column capacity (qb) and maximum column capacity (qx) estimated from column runs, sorption isotherms and models developed by Yoon-Nelson, Bohart-Adam and Thomas were in agreement. The empirical correlations were found between the KOW and sorption parameters. The transport of the organics measured as dissolved organic carbon (DOC) through the aquifer can be predicted from the KOW of the river water and other water samples. The novelty of the study is to measure KOW and to envisage the fate of the DOC of the river water, particularly during riverbank filtration. Statistical analysis of the results revealed a fair agreement between the observed and computed values. PMID:27082255

  20. Determination of Organic Partitioning Coefficients in Water-Supercritical CO2 Systems by Simultaneous in Situ UV and Near-Infrared Spectroscopies.

    PubMed

    Bryce, David A; Shao, Hongbo; Cantrell, Kirk J; Thompson, Christopher J

    2016-06-01

    CO2 injected into depleted oil or gas reservoirs for long-term storage has the potential to mobilize organic compounds and distribute them between sediments and reservoir brines. Understanding this process is important when considering health and environmental risks, but little quantitative data currently exists on the partitioning of organics between supercritical CO2 and water. In this work, a high-pressure, in situ measurement capability was developed to assess the distribution of organics between CO2 and water at conditions relevant to deep underground storage of CO2. The apparatus consists of a titanium reactor with quartz windows, near-infrared and UV spectroscopic detectors, and switching valves that facilitate quantitative injection of organic reagents into the pressurized reactor. To demonstrate the utility of the system, partitioning coefficients were determined for benzene in water/supercritical CO2 over the range 35-65 °C and approximately 25-150 bar. Density changes in the CO2 phase with increasing pressure were shown to have dramatic impacts on benzene's partitioning behavior. Our partitioning coefficients were approximately 5-15 times lower than values previously determined by ex situ techniques that are prone to sampling losses. The in situ methodology reported here could be applied to quantify the distribution behavior of a wide range of organic compounds that may be present in geologic CO2 storage scenarios. PMID:27115941

  1. Partition coefficients for REE between garnets and liquids - Implications of non-Henry's Law behaviour for models of basalt origin and evolution

    NASA Technical Reports Server (NTRS)

    Harrison, W. J.

    1981-01-01

    An experimental investigation of Ce, Sm and Tm rare earth element (REE) partition coefficients between coexisting garnets (both natural and synthetic) and hydrous liquids shows that Henry's Law may not be obeyed over a range of REE concentrations of geological relevance. Systematic differences between the three REE and the two garnet compositions may be explained in terms of the differences between REE ionic radii and those of the dodecahedral site into which they substitute, substantiating the Harrison and Wood (1980) model of altervalent substitution. Model calculations demonstrate that significant variation can occur in the rare earth contents of melts produced from a garnet lherzolite, if Henry's Law partition coefficients do not apply for the garnet phase.

  2. Reliability of environmental fate modeling results for POPs based on various methods of determining the air/water partition coefficient (log KAW)

    NASA Astrophysics Data System (ADS)

    Odziomek, K.; Gajewicz, A.; Haranczyk, M.; Puzyn, T.

    2013-07-01

    Air-water partition coefficient (KAW) is one of the key parameters determining environmental behavior of Persistent Organic Pollutants (POPs). Experimentally measured values of KAW are still unavailable for majority of POPs, thus alternative methods of supplying data, including Quantitative Structure-Property Relationships (QSPR) modeling, are often in use. In this paper, applicability of two QSPR methods of predicting KAW were compared with each other in the context of further application of the predicted data in environmental transport and fate studies. According to the first (indirect) method, KAW is calculated from previously predicted values of octanol-water (KOW) and octanol-air (KOA) partition coefficients. In the second (direct) approach, KAW is calculated, based on the estimated value of Henry's law constant (KH) and then adjusted to ensure its consistency with the other two partition coefficients (KOW and KOA). Although the indirect method carries theoretically twice as much error as the direct method, when the predicted values of KAW are then utilized as an input to the environmental fate model The OECD POV and LRTP Screening Tool, ver. 2.2, the indirect method elicits much higher and therefore much more restrictive values of overall persistence (POV) and transfer efficiency (TE) than its equivalent (direct method). High uncertainties related to the application of the direct method result mainly from the necessary adjustment procedure.

  3. A new high-throughput method utilizing porous silica-based nano-composites for the determination of partition coefficients of drug candidates.

    PubMed

    Yu, Chih H; Tam, Kin; Tsang, Shik C

    2011-09-01

    We show that highly porous silica-based nanoparticles prepared via micro-emulsion and sol-gel techniques are stable colloids in aqueous solution. By incorporating a magnetic core into the porous silica nano-composite, it is found that the material can be rapidly separated (precipitated) upon exposure to an external magnetic field. Alternatively, the porous silica nanoparticles without magnetic cores can be equally separated from solution by applying a high-speed centrifugation. Using these silica-based nanostructures a new high-throughput method for the determination of partition coefficient for water/n-octanol is hereby described. First, a tiny quantity of n-octanol phase is pre-absorbed in the porous silica nano-composite colloids, which allows an establishment of interface at nano-scale between the adsorbed n-octanol with the bulk aqueous phase. Organic compounds added to the mixture can therefore undergo a rapid partition between the two phases. The concentration of drug compound in the supernatant in a small vial can be determined by UV-visible absorption spectroscopy. With the adaptation of a robotic liquid handler, a high-throughput technology for the determination of partition coefficients of drug candidates can be employed for drug screening in the industry based on these nano-separation skills. The experimental results clearly suggest that this new method can provide partition coefficient values of potential drug candidates comparable to the conventional shake-flask method but requires much shorter analytical time and lesser quantity of chemicals. PMID:21780284

  4. Setup and validation of shake-flask procedures for the determination of partition coefficients (logD) from low drug amounts.

    PubMed

    Andrés, Axel; Rosés, Martí; Ràfols, Clara; Bosch, Elisabeth; Espinosa, Sonia; Segarra, Víctor; Huerta, Josep M

    2015-08-30

    Several procedures based on the shake-flask method and designed to require a minimum amount of drug for octanol-water partition coefficient determination have been established and developed. The procedures have been validated by a 28 substance set with a lipophilicity range from -2.0 to 4.5 (logD7.4). The experimental partition is carried out using aqueous phases buffered with phosphate (pH 7.4) and n-octanol saturated with buffered water and the analysis is performed by liquid chromatography. In order to have accurate results, four procedures and eight different ratios between phase volumes are proposed. Each procedure has been designed and optimized (for partition ratios) for a specific range of drug lipophilicity (low, regular and high lipophilicity) and solubility (high and low aqueous solubility). The procedures have been developed to minimize the measurement in the octanolic phase. Experimental logD7.4 values obtained from different procedures and partition ratios show a standard deviation lower than 0.3 and there is a nice agreement when these values are compared with the reference literature ones. PMID:25968358

  5. Distributions of the particle/gas and dust/gas partition coefficients for seventy-two semi-volatile organic compounds in indoor environment.

    PubMed

    Wei, Wenjuan; Mandin, Corinne; Blanchard, Olivier; Mercier, Fabien; Pelletier, Maud; Le Bot, Barbara; Glorennec, Philippe; Ramalho, Olivier

    2016-06-01

    Particle/gas and dust/gas partition coefficients (Kp and Kd) are two key parameters that address the partitioning of semi-volatile organic compounds (SVOCs) between gas-phase, airborne particles, and settled dust in indoor environment. A number of empirical equations to calculate the values of Kp and Kd have been reported in the literature. Therefore, the difficulty lies in the selection of a specific empirical equation in a given situation. In this study, we retrieved from the literature 38 empirical equations for calculating Kp and Kd values from the SVOC saturation vapor pressure and octanol/air partition coefficient. These values were calculated for 72 SVOCs: 9 phthalates, 9 polybrominated diphenyl ethers (PBDEs), 11 polychlorinated biphenyls (PCBs), 22 biocides, 14 polycyclic aromatic hydrocarbons (PAHs), 3 alkylphenols, 2 synthetic musks, tributylphosphate, and bisphenol A. The mean and median values of log10Kp or log10Kd for most SVOCs were of the same order of magnitude. The distribution of log10Kp values was fitted to either a normal distribution (for 27 SVOCs) or a log-normal distribution (for 45 SVOCs). This work provides a reference distribution of the log10Kp for 72 SVOCs, and its use may reduce the bias associated with the selection of a specific value or equation. PMID:27016817

  6. Using eddy covariance and flux partitioning to assess basal, soil, and stress coefficients for crop evapotranspiration models

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Current approaches to scheduling crop irrigation using reference evapotranspiration (ET0) recommend using a dual-coefficient approach using basal (Kcb) and soil (Ke) coefficients along with a stress coefficient (Ks) to model crop evapotranspiration (ETc), [e.g. ETc=(Ks*Kcb+Ke)*ET0]. However, indepe...

  7. The Influence of Cooling Rate During Crystallization on the Effective Partitioning Coefficient in High-Entropy Alloys from Al-Ti-Co-Ni-Fe System

    NASA Astrophysics Data System (ADS)

    Górecki, Kamil; Bala, Piotr; Cios, Grzegorz; Koziel, Tomasz; Stępień, Milena; Wieczerzak, Krzysztof

    2016-07-01

    An influence of two different cooling rates on the microstructure and dispersion of the components of high-entropy alloy from Al-Ti-Co-Ni-Fe system has been examined. For investigated alloys, the effective partitioning coefficient has been calculated. This factor indicates the degree of segregation of elements and allows for the specification of the differences between dendrites and interdendritic regions. The obtained results allow for the conclusion that the cooling rate substantially affect the growth of dendrites and the volume fraction of interdendritic regions as well as the partitioning of elements in the alloy. Furthermore, the obtained results made it possible to compare the influence of the cooling rate and the chemical composition on the dispersion of the alloying elements.

  8. The Influence of Cooling Rate During Crystallization on the Effective Partitioning Coefficient in High-Entropy Alloys from Al-Ti-Co-Ni-Fe System

    NASA Astrophysics Data System (ADS)

    Górecki, Kamil; Bala, Piotr; Cios, Grzegorz; Koziel, Tomasz; Stępień, Milena; Wieczerzak, Krzysztof

    2016-04-01

    An influence of two different cooling rates on the microstructure and dispersion of the components of high-entropy alloy from Al-Ti-Co-Ni-Fe system has been examined. For investigated alloys, the effective partitioning coefficient has been calculated. This factor indicates the degree of segregation of elements and allows for the specification of the differences between dendrites and interdendritic regions. The obtained results allow for the conclusion that the cooling rate substantially affect the growth of dendrites and the volume fraction of interdendritic regions as well as the partitioning of elements in the alloy. Furthermore, the obtained results made it possible to compare the influence of the cooling rate and the chemical composition on the dispersion of the alloying elements.

  9. Derivation of the ion temperature partition coefficient {beta}{sub {parallel}} from the study of ion frictional heating events

    SciTech Connect

    McCrea, I.W.; Lester, M.; Robinson, T.R.; Wade, N.M.; Jones, T.B.; St. Maurice, J.P.

    1993-09-01

    Analyzing data from the EISCAT CP-0 experiment the authors report on values of the ion temperature partition function {beta}{sub {parallel}}. The measurements are made parallel to the geomagnetic field, and therefore the line-of-sight thermal velocity is well approximated by a maxwellian distribution. This gives a fairly straight forward way to study ion energy balance in the F region.

  10. Determination of membrane cholesterol partition coefficient using a lipid vesicle-cyclodextrin binary system: effect of phospholipid acyl chain unsaturation and headgroup composition.

    PubMed Central

    Niu, Shui-Lin; Litman, Burton J

    2002-01-01

    Lateral domain or raft formation in biological membranes is often discussed in terms of cholesterol-lipid interactions. Preferential interactions of cholesterol with lipids, varying in headgroup and acyl chain unsaturation, were studied by measuring the partition coefficient for cholesterol in unilamellar vesicles. A novel vesicle-cyclodextrin system was used, which precludes the possibility of cross-contamination between donor-acceptor vesicles or the need to modify one of the vesicle populations. Variation in phospholipid headgroup resulted in cholesterol partitioning in the order of sphingomyelin (SM) > phosphatidylserine > phosphatidylcholine (PC) > phosphatidylenthanolamine (PE), spanning a range of partition DeltaG of -1181 cal/mol to +683 cal/mol for SM and PE, respectively. Among the acyl chains examined, the order of cholesterol partitioning was 18:0(stearic acid),18:1n-9(oleic acid) PC > di18:1n-9PC > di18:1n-12(petroselenic acid) PC > di18:2n-6(linoleic acid) PC > 16:0(palmitic acid),22:6n-3(DHA) PC > di18:3n-3(alpha-linolenic acid) PC > di22:6n-3PC with a range in partition DeltaG of 913 cal/mol. Our results suggest that the large differences observed in cholesterol-lipid interactions contribute to the forces responsible for lateral domain formation in plasma membranes. These differences may also be responsible for the heterogeneous cholesterol distribution in cellular membranes, where cholesterol is highly enriched in plasma membranes and relatively depleted in intracellular membranes. PMID:12496107

  11. Experimental determination of the partition coefficient for Ba in Neogloboquadrina dutertrei suggests calcification occurs in a Ba-enriched microenvironment

    NASA Astrophysics Data System (ADS)

    Fehrenbacher, J. S.; Russell, A. D.; Davis, C. V.; Spero, H. J.; Chu, E.

    2015-12-01

    The Ba/Ca ratio in several spinose planktic foraminifer species varies as a function of the Ba/Ca concentration of seawater and is not affected by other parameters such as the seawater salinity, temperature and pH (Honisch et al., 2011). Since seawater Ba concentration is linearly related to Ba in nearshore environments, Ba/Ca ratios in spinose species shows promise as an indicator of past changes in monsoon strength and river runoff (e. g. Weldeab et al. 2007). In contrast, the non-spinose foraminifers often have intrashell variability in Ba/Ca, with Ba/Ca ratios much higher than expected for the range of Ba concentrations observed in the ocean. Furthermore, the Ba/Ca ratio can vary by over a factor of 10 within a single specimen. This suggests either 1) the partition coefficient for Ba in non-spinose species differs from that determined for spinose species, or 2) non-spinose species calcify in a micro-environment that is enriched in Ba. We conducted experiments on live specimens to determine the partition coefficient for Ba in the non-spinose foraminifer N. dutertrei. Specimens were collected via plankton net from the Southern California Bight and cultured at the Wrigley Marine Science Center, Santa Catalina Island during the summer of 2013-2015. We use isotopically labeled seawater (87Sr) to identify discrete portions of calcite that grew in culture. We use laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for trace element analyses and to identify ocean grown vs. culture grown calcite. We show that the partition coefficient is similar to the spinose species: N. dutertrei incorporates Ba as a function of seawater chemistry. We conclude from these observations that N. dutertrei forms its calcite from fluids enriched in Ba, and hypothesize that this process occurs via attachment to organic-rich particles such as marine snow.

  12. Characterizing PUF disk passive air samplers for alkyl-substituted PAHs: Measured and modelled PUF-AIR partition coefficients with COSMO-RS.

    PubMed

    Parnis, J Mark; Eng, Anita; Mackay, Donald; Harner, Tom

    2016-02-01

    Isomers of alkyl-substituted polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes are modelled with COSMO-RS theory to determine the effectiveness and accuracy of this approach for estimation of isomer-specific partition coefficients between air and polyurethane foam (PUF), i.e., KPUF-AIR. Isomer-specific equilibrium partitioning coefficients for a series of 23 unsubstituted and isomeric alkyl-substituted PAHs and dibenzothiophenes were measured at 22 °C. This data was used to determine the accuracy of estimated values using COSMO-RS, which is isomer specific, and the Global Atmospheric Passive Sampling (GAPS) template approach, which treats all alkyl-substitutions as a single species of a given side-chain carbon number. A recently developed oligomer-based model for PUF was employed, which consisted of a 1:1 condensed pair of 2,4-toluene-diisocyanide and glycerol. The COSMO-RS approach resulted in a significant reduction in the RMS error associated with simple PAHs and dibenzothiophene compared with the GAPS template approach. When used with alkylated PAHs and dibenzothiophenes grouped into carbon-number categories, the GAPS template approach gave lower RMS error (0.72) compared to the COSMO-RS result (0.87) when the latter estimates were averaged within the carbon-number-based categories. When the isomer-specific experimental results were used, the COSMO-RS approach resulted in a 21% reduction in RMS error with respect to the GAPS template approach, with a 0.57 RMS error for all alkylated PAHs and dibenzothiophenes studied. The results demonstrate that COSMO-RS theory is effective in generating isomer-specific PUF-air partition coefficients, supporting the application of PUF-based passive samplers for monitoring and research studies of polycyclic aromatic compounds (PACs) in air. PMID:26692513

  13. First-principles, structure-based transdermal transport model to evaluate lipid partition and diffusion coefficients of hydrophobic permeants solely from stratum corneum permeation experiments.

    PubMed

    Kushner, Joseph; Deen, William; Blankschtein, Daniel; Langer, Robert

    2007-12-01

    To account for the effect of branched, parallel transport pathways in the intercellular domain of the stratum corneum (SC) on the passive transdermal transport of hydrophobic permeants, we have developed, from first-principles, a new theoretical model-the Two-Tortuosity Model. This new model requires two tortuosity factors to account for: (1) the effective diffusion path length, and (2) the total volume of the branched, parallel transport pathways present in the SC intercellular domain, both of which may be evaluated from known values of the SC structure. After validating the Two-Tortuosity model with simulated SC diffusion experiments in FEMLAB (a finite element software package), the vehicle-bilayer partition coefficient, K(b), and the lipid bilayer diffusion coefficient, D(b), in untreated human SC were evaluated using this new model for two hydrophobic permeants, naphthol (K(b) = 225 +/- 42, D(b) = 1.7 x 10(-7) +/- 0.3 x 10(-7) cm(2)/s) and testosterone (K(b) = 92 +/- 29, D(b) = 1.9 x 10(-8) +/- 0.5 x 10(-8) cm(2)/s). The results presented in this paper demonstrate that this new method to evaluate K(b) and D(b) is comparable to, and simpler than, previous methods, in which SC permeation experiments were combined with octanol-water partition experiments, or with SC solute release experiments, to evaluate K(b) and D(b). PMID:17887175

  14. Prediction of blood:air and fat:air partition coefficients of volatile organic compounds for the interpretation of data in breath gas analysis6

    PubMed Central

    Kramer, Christian; Mochalski, Paweł; Unterkofler, Karl; Agapiou, Agapios; Ruzsanyi, Veronika; Liedl, Klaus R

    2016-01-01

    In this article, a database of blood:air and fat:air partition coefficients (λb:a and λf:a) is reported for estimating 1678 volatile organic compounds recently reported to appear in the volatilome of the healthy human. For this purpose, a quantitative structure-property relationship (QSPR) approach was applied and a novel method for Henry’s law constants prediction developed. A random forest model based on Molecular Operating Environment 2D (MOE2D) descriptors based on 2619 literature-reported Henry’s constant values was built. The calculated Henry’s law constants correlate very well (R2test = 0.967) with the available experimental data. Blood:air and fat:air partition coefficients were calculated according to the method proposed by Poulin and Krishnan using the estimated Henry’s constant values. The obtained values correlate reasonably well with the experimentally determined ones for a test set of 90 VOCs (R2 = 0.95). The provided data aim to fill in the literature data gap and further assist the interpretation of results in studies of the human volatilome. PMID:26815030

  15. Prediction of blood:air and fat:air partition coefficients of volatile organic compounds for the interpretation of data in breath gas analysis.

    PubMed

    Kramer, Christian; Mochalski, Paweł; Unterkofler, Karl; Agapiou, Agapios; Ruzsanyi, Veronika; Liedl, Klaus R

    2016-03-01

    In this article, a database of blood:air and fat:air partition coefficients (λ b:a and λ f:a) is reported for estimating 1678 volatile organic compounds recently reported to appear in the volatilome of the healthy human. For this purpose, a quantitative structure-property relationship (QSPR) approach was applied and a novel method for Henry's law constants prediction developed. A random forest model based on Molecular Operating Environment 2D (MOE2D) descriptors based on 2619 literature-reported Henry's constant values was built. The calculated Henry's law constants correlate very well (R(2) test  =  0.967) with the available experimental data. Blood:air and fat:air partition coefficients were calculated according to the method proposed by Poulin and Krishnan using the estimated Henry's constant values. The obtained values correlate reasonably well with the experimentally determined ones for a test set of 90 VOCs (R(2)  =  0.95). The provided data aim to fill in the literature data gap and further assist the interpretation of results in studies of the human volatilome. PMID:26815030

  16. Zirconium, hafnium, and rare earth element partition coefficients for ilmenite and other minerals in high-Ti lunar mare basalts - An experimental study

    NASA Technical Reports Server (NTRS)

    Mckay, G.; Wagstaff, J.; Yang, S.-R.

    1986-01-01

    Partition coefficients were determined for Gd, Lu, Hf and Zr among ilmenite, armalcolite, and synthetic high-Ti mare basaltic melts at temperatures from 1122 deg to 1150 deg, and at oxygen fugacities of IW x 10 exp 0.5, by in situ analysis with an electron microprobe, using samples doped to present concentration levels. Coefficients for Zr were also measured for samples containing 600-1600 ppm Zr using this microprobe. In addition, coefficients were determined for Hf and Zr between chromian ulvospinel and melt, for Hf between pigeonite and melt, and for Lu between olivine and melt by microprobe analysis of samples doped to present levels. Values measured using the microprobe were in agreement with the values measured by analyzing mineral separates from the same run products by isotope dilution. Coefficient values for ilmenite are less than 0.01 for the LREE, are around 0.1 for the HREE, and are several times greater than this for Zr and Hf.

  17. Determination of Sr and Ba partition coefficients between apatite from fish ( Sparus aurata) and seawater: The influence of temperature

    NASA Astrophysics Data System (ADS)

    Balter, Vincent; Lécuyer, Christophe

    2010-06-01

    The Sr/Ca and Ba/Ca ratios in inorganic apatite are strongly dependent on the temperature of the aqueous medium during precipitation. If valid in biogenic apatite, these thermometers would offer the advantage of being more resistant to diagenesis than those calibrated on biogenic calcite and aragonite. We have reared seabreams ( Sparus aurata) in tanks with controlled conditions during experiments lasting for more than 2 years at 13, 17, 23 and 27 °C, in order to determine the variations in Sr and Ba partitioning relative to Ca ( DSr and DBa, respectively) between seawater and fish apatitic hard tissues (i.e. teeth and bones), as a function of temperature. The sensitivity of the Sr and Ba thermometers (i.e. ∂ DSr/∂ T and ∂ DBa/∂ T, respectively), are similar in bone ( ∂Db-wSr/∂ T = 0.0036 ± 0.0003 and ∂Db-wBa/∂ T = 0.0134 ± 0.0026, respectively) and enamel ( ∂De-wSr/∂ T = 0.0037 ± 0.0005 and ∂De-wBa/∂ T = 0.0107 ± 0.0026, respectively). The positive values of ∂ DSr/∂ T and ∂ DBa/∂ T in bone and enamel indicate that DSr and DBa increase with increasing temperature, a pattern opposite to that observed for inorganic apatite. This distinct thermodependent trace element partitioning between inorganic and organic apatite and water highlights the contradictory effects of the crystal-chemical and biological controls on the partitioning of Ca, Sr and Ba in vertebrate organisms. Taking into account the diet Sr/Ca and Ba/Ca values, it is shown that the bone Ba/Ca signature of fish can be explained by Ca-biopurification and inorganic apatite precipitation, whereas both of these processes fail to predict the bone Sr/Ca values. Therefore, the metabolism of Ca as a function of temperature still needs to be fully understood. However, the biogenic Sr thermometer is used to calculate an average seawater temperature of 30.6 °C using the Sr/Ca compositions of fossil shark teeth at the Cretaceous/Tertiary boundary, and a typical seawater Sr

  18. Partition coefficient of a surfactant between aggregates and solution: application to the micelle-vesicle transition of egg phosphatidylcholine and octyl beta-D-glucopyranoside.

    PubMed Central

    Paternostre, M; Meyer, O; Grabielle-Madelmont, C; Lesieur, S; Ghanam, M; Ollivon, M

    1995-01-01

    The mechanism of the solubilization of egg phosphatidylcholine containing 10% (M/M) of egg phosphatidic acid unilamellar vesicles by the nonionic detergent, octyl beta-D-glucopyranoside, has been investigated at both molecular and supramolecular levels by using fluorescence and turbidity measurements. In the lamellar region of the transition, the solubilization process has been shown to be first a function of the initial size before reaching an equilibrium aggregation state at the end of this region (the onset of the micellization process). The analysis during the solubilization process of the evolution of both the fluorescence energy transfer between N-(7-nitro-2,1,3-benzoxadiazol-4-yl)-phosphatidylethanolamine (NBD-PE) and N-(lissamine rhodamine B sulfonyl)-phosphatidylethanolamine (Rho-PE) and the fluorescence of 6-dodecanoyl-2-dimethylaminoaphtalene (Laurdan) has allowed us to determine the evolution of the detergent partitioning between the aqueous and the lipidic phases, i.e., the evolution of the molar fraction of OG in the aggregates (XOG/Lip) with its monomeric detergent concentration in equilibrium ([OG]H2O), throughout the vesicle-to-micelle transition without isolating the aqueous medium from the aggregates. The curve described by XOG/Lip versus [OG]H2O shows that the partition coefficient of OG is changing throughout the solubilization process. From this curve, which tends to a value of 1/(critical micellar concentration), five different domains have been delimited: two in the lamellar part of the transition (for 0 < [OG]H2O < 15.6 mM), one in the micellization part, and finally two in the pure micellar region (for 16.5 < [OG]H2O < 21 mM). The first domain in the lamellar part of the transition is characterized by a continuous variation of the partition coefficient. In the second domain, a linear relation relates XOG/Lip and [OG]H2O, indicating the existence of a biphasic domain for which the detergent presents a constant partition coefficient of 18

  19. Experimental determination of the partitioning coefficient and volatility of important BVOC oxidation products using the Aerosol Collection Module (ACM) coupled to a PTR-ToF-MS

    NASA Astrophysics Data System (ADS)

    Gkatzelis, G.; Hohaus, T.; Tillmann, R.; Schmitt, S. H.; Yu, Z.; Schlag, P.; Wegener, R.; Kaminski, M.; Kiendler-Scharr, A.

    2015-12-01

    Atmospheric aerosol can alter the Earth's radiative budget and global climate but can also affect human health. A dominant contributor to the submicrometer particulate matter (PM) is organic aerosol (OA). OA can be either directly emitted through e.g. combustion processes (primary OA) or formed through the oxidation of organic gases (secondary organic aerosol, SOA). A detailed understanding of SOA formation is of importance as it constitutes a major contribution to the total OA. The partitioning between the gas and particle phase as well as the volatility of individual components of SOA is yet poorly understood adding uncertainties and thus complicating climate modelling. In this work, a new experimental methodology was used for compound-specific analysis of organic aerosol. The Aerosol Collection Module (ACM) is a newly developed instrument that deploys an aerodynamic lens to separate the gas and particle phase of an aerosol. The particle phase is directed to a cooled sampling surface. After collection particles are thermally desorbed and transferred to a detector for further analysis. In the present work, the ACM was coupled to a Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS) to detect and quantify organic compounds partitioning between the gas and particle phase. This experimental approach was used in a set of experiments at the atmosphere simulation chamber SAPHIR to investigate SOA formation. Ozone oxidation with subsequent photochemical aging of β-pinene, limonene and real plant emissions from Pinus sylvestris (Scots pine) were studied. Simultaneous measurement of the gas and particle phase using the ACM-PTR-ToF-MS allows to report partitioning coefficients of important BVOC oxidation products. Additionally, volatility trends and changes of the SOA with photochemical aging are investigated and compared for all systems studied.

  20. Radionuclide bioconcentration factors and sediment partition coefficients in Arctic Seas subject to contamination from dumped nuclear wastes

    SciTech Connect

    Fisher, N.S. . Marine Sciences Research Center); Fowler, S.W.; Boisson, F.; Carroll, J. . Marine Environment Lab.); Rissanen, K. ); Salbu, B. . Lab. for Analytical Chemistry); Sazykina, T.G. ); Sjoeblom, K.L. )

    1999-06-15

    The disposal of large quantities of radioactive wastes in Arctic Seas by the former Soviet Union has prompted interest in the behavior of long-lived radionuclides in polar waters. Previous studies on the interactions of radionuclides prominent in radioactive wastes have focused on temperate waters; the extent to which the bioconcentration factors and sediment partitioning from these earlier studies could be applied to risk assessment analyses involving high latitude systems is unknown. Here the authors present concentrations in seawater and calculated in situ bioconcentration factors for [sup 90]Sr, [sup 137]Cs, and [sup 239+240]Pu (the three most important radionuclides in Arctic risk assessment models) in macroalgae, crustaceans, bivalve molluscs, sea birds, and marine mammals as well as sediment K[sub d] values for 13 radionuclides and other elements in samples taken from the Kara and Barents Seas. The data analysis shows that, typically, values for polar and temperate waters are comparable, but exceptions include 10-fold higher concentration factors for [sup 239+240]Pu in Arctic brown macroalgae, 10-fold lower K[sub d] values for [sup 90]Sr in Kara Sea sediment than in typical temperate coastal sediment, and 100-fold greater Ru K[sub d] values in Kara Sea sediment. For most elements application of temperate water bioconcentration factors and K[sub d] values to Arctic marine systems appears to be valid.

  1. Estimation of trace element concentrations in the lunar magma ocean using mineral- and metal-silicate melt partition coefficients

    NASA Astrophysics Data System (ADS)

    Sharp, Miriam; Righter, Kevin; Walker, Richard J.

    2015-04-01

    This study uses experimentally determined plagioclase-melt D values to estimate the trace element concentrations of Sr, Hf, Ga, W, Mo, Ru, Pd, Au, Ni, and Co in a crystallizing lunar magma ocean at the point of plagioclase flotation. Similarly, experimentally determined metal-silicate partition experiments combined with a composition model for the Moon are used to constrain the concentrations of W, Mo, Ru, Pd, Au, Ni, and Co in the lunar magma ocean at the time of core formation. The metal-silicate derived lunar mantle estimates are generally consistent with previous estimates for the concentration of these elements in the lunar mantle. Plagioclase-melt derived concentrations for Sr, Ga, Ru, Pd, Au, Ni, and Co are also consistent with prior estimates. Estimates for Hf, W, and Mo, however, are higher. These elements may be concentrated in the residual liquid during fractional crystallization due to their incompatibility. Alternatively, the apparent enrichment could reflect the inappropriate use of bulk anorthosite data, rather than data for plagioclase separates.

  2. An in vitro spectrometric method for determining the partition coefficients of non-steroidal anti-inflammatory drugs into human erythrocyte ghost membranes

    NASA Astrophysics Data System (ADS)

    Omran, Ahmed A.

    2013-03-01

    Usefulness of second derivative spectrophotometry for determining the partition coefficients (Kps) of four non-steroidal anti-inflammatory drugs (NSAIDs) between human erythrocyte ghost (HEG) membranes and buffer at simulated physiological conditions (pH = 7.4, 37 °C) has been adequately emphasized. In the absorption spectra for each of the investigated NSAIDs, λmax was red-shifted in presence of HEG membranes, indicating that NSAIDs have the nature of metachromasy between lipid bilayer and water. Further quantitative spectral data for calculating Kps could not be obtained from the absorption spectra because of the presence of background signal impacts of HEG lipid bilayers. Second derivative spectra were calculated from absorption spectra and fortunately showed three isosbestic derivative points for each NSAID, indicating without doubt that the background signals were entirely eliminated. From the relation between the derivative intensity change (ΔD) induced by addition of HEG membranes, Kps were calculated and obtained with RSD of below 6%. Fractions of partitioned NSAIDs are in well-harmony with that derived from the experimental values. Moreover, validity of the proposed method was confirmed. Conclusively, the second derivative spectrometry has proven to be a facile, reliable and more expeditious method to obtain in vitro Kps of drugs to HEG without previous separation.

  3. Novel chamber to measure equilibrium soil-air partitioning coefficients of low-volatility organic chemicals under conditions of varying temperature and soil moisture.

    PubMed

    Wolters, André; Linnemann, Volker; Smith, Kilian E C; Klingelmann, Eva; Park, Byung-Jun; Vereecken, Harry

    2008-07-01

    The need to determine soil-air partitioning coefficients (K(SA)) of low-volatility organic chemicals as a measure of their distribution in the soil surface after release into the environment resulted in the development of a novel chamber system, which has been filed for patent. A major advantage of this pseudo-static system is that sufficient time can be factored into the experiment to ensure that the system has achieved equilibrium. In a highly precise method, the air is collected in adsorption tubes and subsequently liberated in a thermodesorption system for the quantitation of the adsorbed compound. The precision of the method is great enough that even the effects of temperature and soil moisture on the soil-air partitioning of very low-volatility compounds can be quantified. Because of analytical detection limits, quantitation of these influences has not been possible to date. Functionality of the setup was illustrated by measurements on the fungicide fenpropimorph. K(SA) values of fenpropimorph displayed a negative relationship with temperature and soil moisture. The type of application (spraying or incorporation) and the use of formulated compounds was shown to have a major impact on the measured K(SA) values. Comparison with calculations using an estimation method revealed that the use of experimentally determined K(SA) values will facilitate a more adequate consideration of volatilization in recent model approaches. PMID:18678019

  4. New insight into pesticide partition coefficient Kd for modelling pesticide fluvial transport: application to an agricultural catchment in south-western France.

    PubMed

    Boithias, Laurie; Sauvage, Sabine; Merlina, Georges; Jean, Séverine; Probst, Jean-Luc; Sánchez Pérez, José Miguel

    2014-03-01

    Pesticides applied on crops are leached with rainfall to groundwater and surface water. They threat the aquatic environment and may render water unfit for human consumption. Pesticide partitioning is one of the pesticide fate processes in the environment that should be properly formalised in pesticide fate models. Based on the analysis of 7 pesticide molecules (alachlor, atrazine, atrazine's transformation product deethylatrazine or DEA, isoproturon, tebuconazole and trifluralin) sampled from July 2009 to October 2010 at the outlet of the river Save (south-western France), the objectives of this study were (1) to check which of the environmental factors (discharge, pH, concentrations of total suspended matter (TSM), dissolved organic carbon (DOC) and particulate organic carbon (POC) could control the pesticide sorption dynamic, and (2) to establish a relationship between environmental factors, the partition coefficient Kd and the octanol/water distribution coefficient Kow. The comparison of physico-chemical parameters values during low flow and high flow shows that discharge, TSM and POC are the factors most likely controlling the pesticide sorption processes in the Save river network, especially for lower values of TSM (below 13mgL(-1)). We therefore express Kd depending on the widely literature-related variable Kow and on the commonly simulated variable TSM concentration. The equation can be implemented in any model describing the fluvial transport and fate of pesticides in both dissolved and sorbed phases, thus, Kd becomes a variable in time and space. The Kd calculation method can be applied to a wide range of catchments and organic contaminants. PMID:24275149

  5. Mg-perovskite/silicate melt partition coefficients in the CMS system at 2430 C and 226 Kbars

    NASA Technical Reports Server (NTRS)

    Mcfarlane, Elisabeth A.; Drake, Michael J.; Gasparik, Tibor

    1992-01-01

    The partitioning of elements among lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements has been reported, and these results as well as interpretations based on them have generated controversy. The first set of direct measurements on a synthetic system in the CaO-MgO-SiO2 (CMS) is reported. An experiment was conducted at Stony Brook, using the USSA-2000 split sphere anvil apparatus. An experiment in the CMS system doped with oxides of Al, Ti, Sc, and Sm and run at a nominal temperature of 2380 C and pressure of 226 kbars is reported. Nominal temperatures were measured with a W 3 percent Re/W 25 percent Re thermocouple. The hot spot temperature, where the liquidus is located, is estimated to be at 2430 C. A 10 mm MgO octahedron was used in concert with 4 mm truncation edge lengths on the WC cubes. The sample was contained in a Re capsule which was inserted into a LaCrO3 furnace. Pressure was calibrated at 2000 C. Run duration was approximately 3 minutes. The charge was mounted in epoxy and analyzed using a CAMECA SX-50 electron microprobe. Standard operating conditions were employed, although counting time for the less abundant elements was increased to improved counting statistics. The melt is unquenchable, and forms a dendritic intergrowth of quench crystals and residual melt. It was analyzed using a 30 micron raster. The structural identity of the Mg-perovskite phase was confirmed using x ray microdiffractometry. The results of the investigation are presented.

  6. Study of the partition coefficients Kp/f of seven model migrants from LDPE polymer in contact with food simulants.

    PubMed

    Paseiro-Cerrato, Rafael; Tongchat, Chinawat; Franz, Roland

    2016-05-01

    This study evaluated the influence of parameters such as temperature and type of low-density polyethylene (LDPE) film on the log Kp/f values of seven model migrants in food simulants. Two different types of LDPE films contaminated by extrusion and immersion were placed in contact with three food simulants including 20% ethanol, 50% ethanol and olive oil under several time-temperature conditions. Results suggest that most log Kp/f values are little affected by these parameters in this study. In addition, the relation between log Kp/f and log Po/w was established for each food simulant and regression lines, as well as correlation coefficients, were calculated. Correlations were compared with data from real foodstuffs. Data presented in this study could be valuable in assigning certain foods to particular food simulants as well as predicting the mass transfer of potential migrants into different types of food or food simulants, avoiding tedious and expensive laboratory analysis. The results could be especially useful for regulatory agencies as well as for the food industry. PMID:26998811

  7. Linear solvation energy relationship of the limiting partition coefficient of organic solutes between water and activated carbon

    USGS Publications Warehouse

    Luehrs, Dean C.; Hickey, James P.; Nilsen, Peter E.; Godbole, K.A.; Rogers, Tony N.

    1995-01-01

    A linear solvation energy relationship has been found for 353 values of the limiting adsorption coefficients of diverse chemicals:  log K = −0.37 + 0.0341Vi − 1.07β + D + 0.65P with R = 0.951, s = 0.51, n = 353, and F = 818.0, where Vi is the intrinsic molar volume; β is a measure of the hydrogen bond acceptor strength of the solute; D is an index parameter for the research group which includes the effects of the different types of carbon used, the temperature, and the length of time allowed for the adsorption equilibrium to be established; and P is an index parameter for the flatness of the molecule. P is defined to be unity if there is an aromatic system in the molecule or if there is a double bond or series of conjugated double bonds with no more that one non-hydrogen atom beyond the double bond and zero otherwise. A slightly better fit is obtained if the two-thirds power of Vi is used as a measure of the surface area in place of the volume term:  log K = −1.75 + 0.227V2/3 − 1.10β + D + 0.60P with R = 0.954, s = 0.49, n = 353, and F = 895.39. This is the first quantitative measure of the effect of the shape of the molecule on its tendency to be adsorbed on activated carbon.

  8. QSPR study on the octanol/air partition coefficient of polybrominated diphenyl ethers by using molecular distance-edge vector index

    PubMed Central

    2014-01-01

    Background The quantitative structure property relationship (QSPR) for octanol/air partition coefficient (KOA) of polybrominated diphenyl ethers (PBDEs) was investigated. Molecular distance-edge vector (MDEV) index was used as the structural descriptor of PBDEs. The quantitative relationship between the MDEV index and the lgKOA of PBDEs was modeled by multivariate linear regression (MLR) and artificial neural network (ANN) respectively. Leave one out cross validation and external validation was carried out to assess the predictive ability of the developed models. The investigated 22 PBDEs were randomly split into two groups: Group I, which comprises 16 PBDEs, and Group II, which comprises 6 PBDEs. Results The MLR model and the ANN model for predicting the KOA of PBDEs were established. For the MLR model, the prediction root mean square relative error (RMSRE) of leave one out cross validation and external validation is 2.82 and 2.95, respectively. For the L-ANN model, the prediction RMSRE of leave one out cross validation and external validation is 2.55 and 2.69, respectively. Conclusion The developed MLR and ANN model are practicable and easy-to-use for predicting the KOA of PBDEs. The MDEV index of PBDEs is shown to be quantitatively related to the KOA of PBDEs. MLR and ANN are both practicable for modeling the quantitative relationship between the MDEV index and the KOA of PBDEs. The prediction accuracy of the ANN model is slightly higher than that of the MLR model. The obtained ANN model shoud be a more promising model for studying the octanol/air partition behavior of PBDEs. PMID:24959199

  9. Experimental Determination of Trace Element Partition Co-efficients in High-MgO arc Basalts at 1.15 GPa, 1235° C.

    NASA Astrophysics Data System (ADS)

    Blundy, J.; McDade, P.; Wood, B.

    2001-12-01

    Island arc basalts are chemical hybrids of melts and fluids derived from subducted slab material and mantle wedge peridotite. In terms of their trace elements, island arc basalts are characterised by enrichment in LILEs relative to REEs and, in particular, relative to the HFSEs. Depletion of HFSEs has been attributed to a variety of subduction related processes most of which infer retention of HFSEs in a titanate phase (e.g. rutile) in the subducting slab during dehydration andor partial melting. However the relative contribution of such phases is unknown because the ability of the silicate mantle wedge peridotite itself to fractionate HFSEs is currently unquantified. Peridotite partial melting in the mantle wedge is a significantly different process to that responsible for melt generation beneath mid-ocean ridges in that melting takes place in the presence of a slab-derived H2O-rich fluid. Addition of water and other components to peridotite both lowers the melting temperature and alters the melting reactions. Trace element partitioning between mineral and melt is primarily a function of phase composition, pressure and temperature. Since pressure and temperature affect different valence cations to differing extents (Wood & Blundy, 1997; Blundy & Green, 2000) it is possible that the unusual low-T melting in the wedge is characterised by quite different HFSEREE fractionations than the relatively high-T melting responsible for MORB generation. Accurate determination of partition co-efficients (Ds) at pressures and temperatures relevant to melt production are thus imperative for characterising processes involved in generating primary arc magmas from the wedge, and in particular establishing the baseline effect of peridotite in generating HFSE fractionations. In this study we determine Ds for REEs, LILEs and HFSEs between cpx, opx and melt at 1235oC, 1.15 GPa, and melt water contents of{ ~}1.5 wt%. These PT conditions correspond with the point of multiple phase

  10. The search for reliable aqueous solubility (Sw) and octanol-water partition coefficient (Kow) data for hydrophobic organic compounds; DDT and DDE as a case study

    USGS Publications Warehouse

    Pontolillo, James; Eganhouse, R.P.

    2001-01-01

    The accurate determination of an organic contaminant?s physico-chemical properties is essential for predicting its environmental impact and fate. Approximately 700 publications (1944?2001) were reviewed and all known aqueous solubilities (Sw) and octanol-water partition coefficients (Kow) for the organochlorine pesticide, DDT, and its persistent metabolite, DDE were compiled and examined. Two problems are evident with the available database: 1) egregious errors in reporting data and references, and 2) poor data quality and/or inadequate documentation of procedures. The published literature (particularly the collative literature such as compilation articles and handbooks) is characterized by a preponderance of unnecessary data duplication. Numerous data and citation errors are also present in the literature. The percentage of original Sw and Kow data in compilations has decreased with time, and in the most recent publications (1994?97) it composes only 6?26 percent of the reported data. The variability of original DDT/DDE Sw and Kow data spans 2?4 orders of magnitude, and there is little indication that the uncertainty in these properties has declined over the last 5 decades. A criteria-based evaluation of DDT/DDE Sw and Kow data sources shows that 95?100 percent of the database literature is of poor or unevaluatable quality. The accuracy and reliability of the vast majority of the data are unknown due to inadequate documentation of the methods of determination used by the authors. [For example, estimates of precision have been reported for only 20 percent of experimental Sw data and 10 percent of experimental Kow data.] Computational methods for estimating these parameters have been increasingly substituted for direct or indirect experimental determination despite the fact that the data used for model development and validation may be of unknown reliability. Because of the prevalence of errors, the lack of methodological documentation, and unsatisfactory data

  11. Linear modeling of the soil-water partition coefficient normalized to organic carbon content by reversed-phase thin-layer chromatography.

    PubMed

    Andrić, Filip; Šegan, Sandra; Dramićanin, Aleksandra; Majstorović, Helena; Milojković-Opsenica, Dušanka

    2016-08-01

    Soil-water partition coefficient normalized to the organic carbon content (KOC) is one of the crucial properties influencing the fate of organic compounds in the environment. Chromatographic methods are well established alternative for direct sorption techniques used for KOC determination. The present work proposes reversed-phase thin-layer chromatography (RP-TLC) as a simpler, yet equally accurate method as officially recommended HPLC technique. Several TLC systems were studied including octadecyl-(RP18) and cyano-(CN) modified silica layers in combination with methanol-water and acetonitrile-water mixtures as mobile phases. In total 50 compounds of different molecular shape, size, and various ability to establish specific interactions were selected (phenols, beznodiazepines, triazine herbicides, and polyaromatic hydrocarbons). Calibration set of 29 compounds with known logKOC values determined by sorption experiments was used to build simple univariate calibrations, Principal Component Regression (PCR) and Partial Least Squares (PLS) models between logKOC and TLC retention parameters. Models exhibit good statistical performance, indicating that CN-layers contribute better to logKOC modeling than RP18-silica. The most promising TLC methods, officially recommended HPLC method, and four in silico estimation approaches have been compared by non-parametric Sum of Ranking Differences approach (SRD). The best estimations of logKOC values were achieved by simple univariate calibration of TLC retention data involving CN-silica layers and moderate content of methanol (40-50%v/v). They were ranked far well compared to the officially recommended HPLC method which was ranked in the middle. The worst estimates have been obtained from in silico computations based on octanol-water partition coefficient. Linear Solvation Energy Relationship study revealed that increased polarity of CN-layers over RP18 in combination with methanol-water mixtures is the key to better modeling of

  12. Potential of the octanol-water partition coefficient (logP) to predict the dermal penetration behaviour of amphiphilic compounds in aqueous solutions.

    PubMed

    Korinth, Gintautas; Wellner, Tanja; Schaller, Karl Heinz; Drexler, Hans

    2012-11-23

    Aqueous amphiphilic compounds may exhibit enhanced skin penetration compared with neat compounds. Conventional models do not predict this percutaneous penetration behaviour. We investigated the potential of the octanol-water partition coefficient (logP) to predict dermal fluxes for eight compounds applied neat and as 50% aqueous solutions in diffusion cell experiments using human skin. Data for seven other compounds were accessed from literature. In total, seven glycol ethers, three alcohols, two glycols, and three other chemicals were considered. Of these 15 compounds, 10 penetrated faster through the skin as aqueous solutions than as neat compounds. The other five compounds exhibited larger fluxes as neat applications. For 13 of the 15 compounds, a consistent relationship was identified between the percutaneous penetration behaviour and the logP. Compared with the neat applications, positive logP were associated with larger fluxes for eight of the diluted compounds, and negative logP were associated with smaller fluxes for five of the diluted compounds. Our study demonstrates that decreases or enhancements in dermal penetration upon aqueous dilution can be predicted for many compounds from the sign of logP (i.e., positive or negative). This approach may be suitable as a first approximation in risk assessments of dermal exposure. PMID:23026264

  13. iLOGP: a simple, robust, and efficient description of n-octanol/water partition coefficient for drug design using the GB/SA approach.

    PubMed

    Daina, Antoine; Michielin, Olivier; Zoete, Vincent

    2014-12-22

    The n-octanol/water partition coefficient (log Po/w) is a key physicochemical parameter for drug discovery, design, and development. Here, we present a physics-based approach that shows a strong linear correlation between the computed solvation free energy in implicit solvents and the experimental log Po/w on a cleansed data set of more than 17,500 molecules. After internal validation by five-fold cross-validation and data randomization, the predictive power of the most interesting multiple linear model, based on two GB/SA parameters solely, was tested on two different external sets of molecules. On the Martel druglike test set, the predictive power of the best model (N = 706, r = 0.64, MAE = 1.18, and RMSE = 1.40) is similar to six well-established empirical methods. On the 17-drug test set, our model outperformed all compared empirical methodologies (N = 17, r = 0.94, MAE = 0.38, and RMSE = 0.52). The physical basis of our original GB/SA approach together with its predictive capacity, computational efficiency (1 to 2 s per molecule), and tridimensional molecular graphics capability lay the foundations for a promising predictor, the implicit log P method (iLOGP), to complement the portfolio of drug design tools developed and provided by the SIB Swiss Institute of Bioinformatics. PMID:25382374

  14. Influence of bioassay volume, water column height, and octanol-water partition coefficient on the toxicity of pesticides to rainbow trout.

    PubMed

    Altinok, Ilhan; Capkin, Erol; Boran, Halis

    2011-06-01

    Effects of water volume and water column height on toxicity of cypermethrin, carbaryl, dichlorvos, tetradifon, maneb, captan, carbosulfan endosulfan and HgCl₂ to juvenile rainbow trout (Oncorhynchus mykiss, 3.2 ± 0.7 g) were evaluated in different glass aquaria under static conditions. When fish were exposed to the chemical compounds in 23 cm water column height (25 L), their mortality ranged between 0% and 58%. At the same water volume, but lower water column height (9 cm), mortality of fish increased significantly and was in a range from 60% to 95%. At the same water column height, toxic effects of chemicals were significantly higher in 25 L water volume than that of 8.5 L, water except maneb which has lowest (-0.45) octanol-water partition coefficient value. Mortality rates ratio of 9 and 23 cm water column height ranged between 1.12 and 90 while mortality rates ratio of 9 and 25 L water volume ranged between 1.20 and 4.0. Because actual exposure concentrations were not affected by either water volume or water column height, we propose that increased pesticides' toxicity was related to an increase in bioassay volume, since more pesticide molecules were able to interact with or accumulate the fish. However, there seem to be no relationship between the effects of water volume, water column height and Kow value of chemicals with regard to toxicity in juvenile rainbow trout. PMID:21528427

  15. Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane.

    PubMed

    Sarraute, Sabine; Mokbel, Ilham; Costa Gomes, Margarida F; Majer, Vladimir; Delepine, Hervé; Jose, Jacques

    2006-09-01

    New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 degrees C and 80 degrees C and 1 degrees C and 40 degrees C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within +/-10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p(sat) varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 degrees C of 5.95 x 10(-7) and 1.92 x 10(-7), respectively). A combination of the two sets of data allowed the calculation of the Henry's law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained. PMID:16530806

  16. Terminology for trace-element partitioning

    SciTech Connect

    Beattie, P. ); Drake, M. ); Jones, J.; McKay, G. ); Leeman, W. ); Longhi, J. ); Nielsen, R. ); Palme, H. ); Shaw, D. ); Takahashi, E. ); Watson, B. )

    1993-04-01

    A self-consistent terminology for partitioning data is presented. Ratios of the concentration of a component in two phases are termed partition coefficients and given the symbol D. Ratios of partition coefficients are termed exchange coefficients and given the symbol K[sub D]. The prefix bulk implies that these coefficients are weighted according to the proportions of coexisting phases. Bulk partition and bulk exchange coefficients are denoted by [bar D] and [ovr K[sub D

  17. Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

    NASA Technical Reports Server (NTRS)

    Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

    2000-01-01

    Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

  18. A strategy for the separation of diterpenoid isomers from the root of Aralia continentalis by countercurrent chromatography: The distribution ratio as a substitute for the partition coefficient and a three-phase solvent system.

    PubMed

    Lee, Kyoung Jin; Song, Kwang Ho; Choi, Wonmin; Kim, Yeong Shik

    2015-08-01

    Aralia continentalis (Araliaceae) is widely used as a medicinal plant in East Asia. Previous studies have indicated that diterpenoid isomers (kaurenoic acid, continentalic acid, and ent-continentalic acid) are the major bioactive compounds of this plant. A new strategy was developed to alleviate difficulties in the separation of these isomers from this plant. A three-phase solvent system was applied to separate the isomers, and furthermore, the distribution ratio (Kc) was introduced as a substitute for the partition coefficient (KD). For compounds exhibiting a single equilibrium, their distributions in two immiscible phases were only affected by the partition coefficient of each solute. However, compounds that have a dissociating functional group (e.g., -COOH) are involved in two types of equilibrium in the two-phase system. In this case, the partitioning behaviors of the solutes are greatly affected by the pH of the solution. A mathematical prediction was applied for adjusting the solutions to the proper pH values. To prevent non-used phase (medium phase) waste, both the stationary phase (upper phase) and mobile phase (lower phase) were prepared on-demand without pre-saturation with the application of (1)H NMR. Each fraction obtained was collected and dried, yielding the following diterpenoid isomers from the 50mg injected sample: kaurenoic acid (19.7mg, yield: 39%) and ent-continentalic acid (21.3mg, yield: 42%). PMID:26138601

  19. Predictions of gas-particle partitioning coefficients (K(P)) of polycyclic aromatic hydrocarbons at various occupational environments of Songkhla Province, Thailand.

    PubMed

    Pongpiachan', S; Thamanu, K; Ho, K F; Lee, S C; Sompongchaiyakul, P

    2009-11-01

    Ambient air samples were collected over periods of 24 hours and 3 hours using a Graseby-Anderson high volume air sampler with PM10 TE-6001 at 15 sampling sites, including an urban residential zone, rural area, industrial factories, waste incinerator, traffic areas and agricultural burning areas in Songkhla Province, Thailand. An analysis of organic carbon and elemental carbon was conducted to estimate the gas-particle partitioning of PAHs using a model proposed by Dachs-Eisenreich. The estimated LogK(P) of PAHs emphasized the risk for lung cancer among outdoor workers in waste incinerators, traffic intersections and bus terminals, suggesting the role of the carbonaceous fraction over the gas-particle partitioning of PAHs. Analysis of f(SC)K(SA)delta(OCT)/F(OM)K(OA) ratios revealed a significant role of adsorption and absorption in unusually high elemental carbon fractions (ie low OC/EC ratio) in fine particles collected at waste incinerators and the abnormally high organic carbon fractions (ie high OC/EC ratio) observed in those fine particles of an urban residential zone, respectively. The dual mode of ab/adsorption tended to dominate the gas-particle partitioning of LMW PAHs collected at the traffic intersections and bus terminal. PMID:20578474

  20. Measurements of octanol-air partition coefficients, vapor pressures and vaporization enthalpies of the (E) and (Z) isomers of the 2-ethylhexyl 4-methoxycinnamate as parameters of environmental impact assessment.

    PubMed

    Pegoraro, César N; Chiappero, Malisa S; Montejano, Hernán A

    2015-11-01

    2-Ethylhexyl 4-methoxycinnamate is one of the UVB blocking agents more widely used in a variety of industrial fields. There are more than one hundred industrial suppliers worldwide. Given the enormous annual consumption of octinoxate, problems that arise due to the accumulation of this compound in nature should be taken into consideration. The GC-RT was used in this work with the aim of determining the vapor pressure, enthalpies of vaporization and octanol-air partition coefficient, for the BBP, DOP, E- and Z-EHMC esters. The results showed that Z-EHMC is almost five times more volatile than E-EHMC. Moreover, BBP, Z-EHMC and E-EHMC can be classified as substances with a relatively low mobility since they lie within the range of 810 and log(PL/Pa)<-4, therefore, a low mobility can be expected. From these parameters, their particle-bound fraction and gas-particle partition coefficient were also derived. PMID:26210018

  1. Experimental Determination of Spinel/Melt, Olivine/Melt, and Pyroxene/Melt Partition Coefficients for Re, Ru, Pd, Au, and Pt

    NASA Technical Reports Server (NTRS)

    Righter, K.; Campbell, A. J.; Humayun, M.

    2003-01-01

    Experimental studies have identified spinels as important hosts phases for many of the highly siderophile elements (HSE). Yet experimental studies involving chromite or Cr-rich spinel have been lacking. Experimental studies of partitioning of HSEs between silicate, oxides and silicate melt are plagued by low solubilities and the presence of small metallic nuggets at oxygen fugacities relevant to magmas, which interfere with analysis of the phases of interest. We have circumvented these problems in two ways: 1) performing experiments at oxidized conditions, which are still relevant to natural systems but in which nuggets are not observed, and 2) analysis of run products with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), allowing a combination of high sensitivity and good spatial resolution.

  2. Air-Liquid Partition Coefficient for a Diverse Set of Organic Compounds: Henry’s Law Constant in Water and Hexadecane

    EPA Science Inventory

    The SPARC vapor pressure and activity coefficient models were coupled to estimate Henry’s Law Constant (HLC) in water and in hexadecane for a wide range of non-polar and polar solute organic compounds without modification to/or additional parameterization of the vapor pressure or...

  3. Uranium in granitic magmas: Part 2. Experimental determination of uranium solubility and fluid-melt partition coefficients in the uranium oxide-haplogranite-H 2O-NaX (X = Cl, F) system at 770°C, 2 kbar

    NASA Astrophysics Data System (ADS)

    Peiffert, Chantal; nguyen-Trung, Chinh; Cuney, Michel

    1996-05-01

    The solubility of uranium oxide was investigated in both aqueous halide (Cl, F) fluid and granitic melt in equilibrium in the system uranium oxide-haplogranite-H 2O-NaCl (0.1-5.0 molal), NaF (0.1-0.5 molal) at 770°C, 2 kbar, and fO 2 conditions controlled by Ni-NiO, Fe 3O 4-Fe 2O 3, and Cu 2O- CuO buffers. Three distinct uranium oxides UO (2+ x) with x = 0.01 ± 0.01; 0.12 ± 0.02; and 0.28 ± 0.02, respec- tively, were obtained in both chloride and fluoride systems, under the three fO 2 conditions cited above. Changes in the composition of aqueous solutions and silicate melt were observed after the runs. These changes were more pronounced for the fluoride-bearing experiments. Quench pH decreased from 5.9 to 2.1 with increasing chloride molality from 0.085-4.38 molal. For fluoride solutions, the decrease of pH from 5.4 to 3.4 corresponded to the increase of fluoride molality from 0.02-0.23 molal. The U solubility in chloride solutions was in the range 10-967 ppm. For the same molality, fluoride solutions appeared to dissolve up to twenty times more uranium than chloride solutions. The increase of halide molality and oxidation led to increase the U solubility. The U solubility in silicate glasses was in the range 10-1.8 × 10 4 ppm and increased with increasing oxidation and halide concentration. In addition, increasing agpaicity also increased U solubility in the chloride system. This effect was not observed in the fluoride system. The chloride concentration in the silicate melt increased from 100-790 ppm with increasing initial aqueous chloride concentration from 0.1-5.0 m. The fluoride concentration in the silicate melt increased from 2.8 × 10 3 to 1.1 × 10 4 ppm with increasing initial fluoride concentra- tion from 0.1-0.5 m. In the chloride system, the partition coefficient of U (log D)(U) fluid/melt) increased from -1.2-0 with increasing agpaicity from 0.92-1.36, for increasing chloride concentration from 0.085-4.38 molal and for increasing fO 2 from 10 -15

  4. Determination of polydimethylsiloxane-water partition coefficients for ten 1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene-related compounds and twelve polychlorinated biphenyls using gas chromatography/mass spectrometry.

    PubMed

    Eganhouse, Robert P

    2016-03-18

    Polymer-water partition coefficients (Kpw) of ten DDT-related compounds were determined in pure water at 25 °C using commercial polydimethylsiloxane-coated optical fiber. Analyte concentrations were measured by thermal desorption-gas chromatography/full scan mass spectrometry (TD-GC/MSFS; fibers) and liquid injection-gas chromatography/selected ion monitoring mass spectrometry (LI-GC/MSSIM; water). Equilibrium was approached from two directions (fiber uptake and depletion) as a means of assessing data concordance. Measured compound-specific log Kpw values ranged from 4.8 to 6.1 with an average difference in log Kpw between the two approaches of 0.05 log units (∼ 12% of Kpw). Comparison of the experimentally-determined log Kpw values with previously published data confirmed the consistency of the results and the reliability of the method. A second experiment was conducted with the same ten DDT-related compounds and twelve selected PCB (polychlorinated biphenyl) congeners under conditions characteristic of a coastal marine field site (viz., seawater, 11°C) that is currently under investigation for DDT and PCB contamination. Equilibration at lower temperature and higher ionic strength resulted in an increase in log Kpw for the DDT-related compounds of 0.28-0.49 log units (61-101% of Kpw), depending on the analyte. The increase in Kpw would have the effect of reducing by approximately half the calculated freely dissolved pore-water concentrations (Cfree). This demonstrates the importance of determining partition coefficients under conditions as they exist in the field. PMID:26898149

  5. Partitioning and lipophilicity in quantitative structure-activity relationships.

    PubMed Central

    Dearden, J C

    1985-01-01

    The history of the relationship of biological activity to partition coefficient and related properties is briefly reviewed. The dominance of partition coefficient in quantitation of structure-activity relationships is emphasized, although the importance of other factors is also demonstrated. Various mathematical models of in vivo transport and binding are discussed; most of these involve partitioning as the primary mechanism of transport. The models describe observed quantitative structure-activity relationships (QSARs) well on the whole, confirming that partitioning is of key importance in in vivo behavior of a xenobiotic. The partition coefficient is shown to correlate with numerous other parameters representing bulk, such as molecular weight, volume and surface area, parachor and calculated indices such as molecular connectivity; this is especially so for apolar molecules, because for polar molecules lipophilicity factors into both bulk and polar or hydrogen bonding components. The relationship of partition coefficient to chromatographic parameters is discussed, and it is shown that such parameters, which are often readily obtainable experimentally, can successfully supplant partition coefficient in QSARs. The relationship of aqueous solubility with partition coefficient is examined in detail. Correlations are observed, even with solid compounds, and these can be used to predict solubility. The additive/constitutive nature of partition coefficient is discussed extensively, as are the available schemes for the calculation of partition coefficient. Finally the use of partition coefficient to provide structural information is considered. It is shown that partition coefficient can be a valuable structural tool, especially if the enthalpy and entropy of partitioning are available. PMID:3905374

  6. Cumulants of partitions

    NASA Astrophysics Data System (ADS)

    Weiss, Christoph; Block, Martin; Holthaus, Martin; Schmieder, Gerald

    2003-02-01

    We utilize the formal equivalence between the number-partitioning problem and a harmonically trapped ideal Bose gas within the microcanonical ensemble for characterizing the probability distribution which governs the number of addends occurring in an unrestricted partition of a natural number n. By deriving accurate asymptotic formulae for its coefficients of skewness and excess, it is shown that this distribution remains non-Gaussian even when n is made arbitrarily large. Both skewness and excess vary substantially before settling to their constant-limiting values for n > 1010.

  7. Partition search

    SciTech Connect

    Ginsberg, M.L.

    1996-12-31

    We introduce a new form of game search called partition search that incorporates dependency analysis, allowing substantial reductions in the portion of the tree that needs to be expanded. Both theoretical results and experimental data are presented. For the game of bridge, partition search provides approximately as much of an improvement over existing methods as {alpha}-{beta} pruning provides over minimax.

  8. Experimental determination of salt partition coefficients between aqueous fluids, ice VI and ice VII: implication for the composition of the deep ocean and the geodynamics of large icy moons and water rich planets

    NASA Astrophysics Data System (ADS)

    Journaux, Baptiste; Daniel, Isabelle; Cardon, Hervé; Petitgirard, Sylvain; Perrillat, Jean-Philippe; Caracas, Razvan; Mezouar, Mohamed

    2015-04-01

    The potential habitability of extraterrestrial large aqueous reservoir in icy moons and exoplanets requires an input of nutrients and chemicals that may come from the rocky part of planetary body. Because of the presence of high pressure (HP) water ices (VI, VII, etc.) between the liquid ocean and the silicates, such interactions are considered to be limited in large icy moons, like Ganymede and Titan, and water rich exoplanets. In the case of salty-rich oceans, recent experimental and modeling works have shown that aqueous fluids can be stable at higher pressures [1, 2]. This can ultimately allow direct interaction with the rocky core of icy moons. This effect is nevertheless limited and for larger bodies such as water rich exoplanets with much higher pressures in their hydrosphere, HP ice should be present between the rocky core and a putative ocean. Salts are highly incompatible with low pressure ice Ih, but recent experimental work has shown that alkali metal and halogen salts are moderately incompatible with ice VII, that can incorporate up to several mol/kg of salts [3, 4, 5]. As far as we know, no similar study has been done on ice VI, a HP ice phase expected inside large icy moons. We present here the first experimental data on the partition coefficient of RbI salt between aqueous fluids, ice VI and ice VII using in-situ synchrotron X-Ray single crystal diffraction and X-Ray fluorescence mapping (ESRF - ID-27 beam line [6]). Our experiment enable us to observe a density inversion between ice VI and the salty fluid, and to measure the values of salt partition coefficients between the aqueous fluid and ice VI (strongly incompatible) and ice VII (moderately incompatible). Using the volumes determined with X-Ray diffraction, we were able to measure the density of salty ice VI and ice VII and determine that salty ice VI is lighter than pure H2O ice VI. These results are very relevant for the study of water rich planetary bodies interior because the partition

  9. Evaluation of the use of partition coefficients and molecular surface properties as predictors of drug absorption: a provisional biopharmaceutical classification of the list of national essential medicines of Pakistan

    PubMed Central

    Shawahna, R.; Rahman, NU.

    2011-01-01

    Background and the purpose of the study Partition coefficients (log D and log P) and molecular surface area (PSA) are potential predictors of the intestinal permeability of drugs. The aim of this investigation was to evaluate and compare these intestinal permeability indicators. Methods Aqueous solubility data were obtained from literature or calculated using ACD/Labs and ALOGPS. Permeability data were predicted based on log P, log D at pH 6.0 (log D6.0), and PSA. Results Metoprolol's log P, log D6.0, and a PSA of <65 Å correctly predicted 55.9%, 50.8% and 54.2% of permeability classes, respectively. Labetalol's log P, log D6.0 and PSA correctly predicted 54.2%, 64.4% and 61% of permeability classes, respectively. Log D6.0 correlated well (81%) with Caco-2 permeability (Papp). Of the list of national essential medicines, 135 orally administered drugs were classified into biopharmaceutical classification system (BCS). Of these, 57 (42.2%), 28 (20.7%), 44 (32.6%), and 6 (4.4%) were class I, II, III and IV respectively. Conclusion Log D6.0 showed better prediction capability than log P. Metoprolol as permeability internal standard was more conservative than labetalol. PMID:22615645

  10. Partition Equilibrium

    NASA Astrophysics Data System (ADS)

    Feldman, Michal; Tennenholtz, Moshe

    We introduce partition equilibrium and study its existence in resource selection games (RSG). In partition equilibrium the agents are partitioned into coalitions, and only deviations by the prescribed coalitions are considered. This is in difference to the classical concept of strong equilibrium according to which any subset of the agents may deviate. In resource selection games, each agent selects a resource from a set of resources, and its payoff is an increasing (or non-decreasing) function of the number of agents selecting its resource. While it has been shown that strong equilibrium exists in resource selection games, these games do not possess super-strong equilibrium, in which a fruitful deviation benefits at least one deviator without hurting any other deviator, even in the case of two identical resources with increasing cost functions. Similarly, strong equilibrium does not exist for that restricted two identical resources setting when the game is played repeatedly. We prove that for any given partition there exists a super-strong equilibrium for resource selection games of identical resources with increasing cost functions; we also show similar existence results for a variety of other classes of resource selection games. For the case of repeated games we identify partitions that guarantee the existence of strong equilibrium. Together, our work introduces a natural concept, which turns out to lead to positive and applicable results in one of the basic domains studied in the literature.

  11. GAS-PARTICLE PARTITIONING OF SEMI-VOLATILE ORGANICS ON ORGANIC AEROSOLS USING A PREDICTIVE ACTIVITY COEFFICIENT MODEL: ANALYSIS OF THE EFFECTS OF PARAMETER CHOICES ON MODEL PERFORMANCE. (R826771)

    EPA Science Inventory

    The partitioning of a diverse set of semivolatile organic compounds (SOCs) on a variety of organic aerosols was studied using smog chamber experimental data. Existing data on the partitioning of SOCs on aerosols from wood combustion, diesel combustion, and the Polymers as Reference Partitioning Phase: Polymer Calibration for an Analytically Operational Approach To Quantify Multimedia Phase Partitioning.

    PubMed

    Gilbert, Dorothea; Witt, Gesine; Smedes, Foppe; Mayer, Philipp

    2016-06-01

    Polymers are increasingly applied for the enrichment of hydrophobic organic chemicals (HOCs) from various types of samples and media in many analytical partitioning-based measuring techniques. We propose using polymers as a reference partitioning phase and introduce polymer-polymer partitioning as the basis for a deeper insight into partitioning differences of HOCs between polymers, calibrating analytical methods, and consistency checking of existing and calculation of new partition coefficients. Polymer-polymer partition coefficients were determined for polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and organochlorine pesticides (OCPs) by equilibrating 13 silicones, including polydimethylsiloxane (PDMS) and low-density polyethylene (LDPE) in methanol-water solutions. Methanol as cosolvent ensured that all polymers reached equilibrium while its effect on the polymers' properties did not significantly affect silicone-silicone partition coefficients. However, we noticed minor cosolvent effects on determined polymer-polymer partition coefficients. Polymer-polymer partition coefficients near unity confirmed identical absorption capacities of several PDMS materials, whereas larger deviations from unity were indicated within the group of silicones and between silicones and LDPE. Uncertainty in polymer volume due to imprecise coating thickness or the presence of fillers was identified as the source of error for partition coefficients. New polymer-based (LDPE-lipid, PDMS-air) and multimedia partition coefficients (lipid-water, air-water) were calculated by applying the new concept of a polymer as reference partitioning phase and by using polymer-polymer partition coefficients as conversion factors. The present study encourages the use of polymer-polymer partition coefficients, recognizing that polymers can serve as a linking third phase for a quantitative understanding of equilibrium partitioning of HOCs between any two phases. PMID:27115830

  12. New Linear Partitioning Models Based on Experimental Water: Supercritical CO2 Partitioning Data of Selected Organic Compounds.

    PubMed

    Burant, Aniela; Thompson, Christopher; Lowry, Gregory V; Karamalidis, Athanasios K

    2016-05-17

    Partitioning coefficients of organic compounds between water and supercritical CO2 (sc-CO2) are necessary to assess the risk of migration of these chemicals from subsurface CO2 storage sites. Despite the large number of potential organic contaminants, the current data set of published water-sc-CO2 partitioning coefficients is very limited. Here, the partitioning coefficients of thiophene, pyrrole, and anisole were measured in situ over a range of temperatures and pressures using a novel pressurized batch-reactor system with dual spectroscopic detectors: a near-infrared spectrometer for measuring the organic analyte in the CO2 phase and a UV detector for quantifying the analyte in the aqueous phase. Our measured partitioning coefficients followed expected trends based on volatility and aqueous solubility. The partitioning coefficients and literature data were then used to update a published poly parameter linear free-energy relationship and to develop five new linear free-energy relationships for predicting water-sc-CO2 partitioning coefficients. A total of four of the models targeted a single class of organic compounds. Unlike models that utilize Abraham solvation parameters, the new relationships use vapor pressure and aqueous solubility of the organic compound at 25 °C and CO2 density to predict partitioning coefficients over a range of temperature and pressure conditions. The compound class models provide better estimates of partitioning behavior for compounds in that class than does the model built for the entire data set. PMID:27081725

  13. Deep eutectic solvents in countercurrent and centrifugal partition chromatography.

    PubMed

    Roehrer, Simon; Bezold, Franziska; García, Eva Marra; Minceva, Mirjana

    2016-02-19

    Deep eutectic solvents (DESs) were evaluated as solvents in centrifugal partition chromatography, a liquid-liquid chromatography separation technology. To this end, the partition coefficients of ten natural compounds of different hydrophobicity were determined in non-aqueous biphasic systems containing DES. The influence of the composition of DESs and the presence of water in the biphasic system on the partition coefficient were also examined. In addition, several process relevant physical properties of the biphasic system, such as the density and viscosity of the phases, were measured. A mixture of three to four hydrophobic compounds was successfully separated in a centrifugal partition extractor using a heptane/ethanol/DES biphasic system. PMID:26810802

  14. PARTITIONING OF POLYCHLORINATED BIPHENYL CONGENERS IN SEAWATER OF NEW BEDFORD HARBOR, MASSACHUSETTS

    EPA Science Inventory

    The partitioning of polychlorinated biphenyls (PCBS) between particulate and dissolved phases of seawater was examined along a concentration gradient in New Bedford Harbor, MA. egression analysis was used to examine the relationship between the log of the partition coefficients (...

  15. Trace-element partitioning in pantellerites and trachytes

    SciTech Connect

    Mahood, G.A.; Stimac, J.A. )

    1990-08-01

    In order to investigate the effect of increasing melt peralkalinity on partitioning, partition coefficients have been determined using neutron activation analyses of coexisting phenocrysts and glass of five samples from Pantelleria spanning the range trachyte to pantellerite. Alkali feldspar partition coefficients for Fe, Rb, Ba, Sr, and Eu vary with melt peralkalinity due to changes in melt polymerization and to the systematic increase in X{sub or} and decrease in X{sub an} of the feldspar. In going from trachyte to pantellerite, Fe partition coefficients increase from 0.04 to 0.10, presumably because Fe{sup +3} increasingly substitutes in the feldspar tetrahedral site as melt activity of Al declines and Fe concentrations increase. Partition coefficients for trivalent light REEs (rare earth elements) decrease and the partitioning pattern becomes flatter, the most evolved samples having some of the lowest published values for feldspar. The hundredfold decline in Eu partition coefficients (2.5 to 0.024) and the decrease in the size of the positive partitioning anomaly are attributed to increasing Eu{sup 3+}/Eu{sup 2+} in the melt as it becomes more peralkaline, as well as to concomitant decrease in the Ca content of feldspar. As a result, the behavior of Eu during fractional crystallization of peralkaline suites is fundamentally different from that in metaluminous suites; absolute abundances rise and the size of the negative Eu anomaly changes little with fractionation beyond pantelleritic trachyte.

  16. hydrogen partitioning between postperovskite and bridgmanite

    NASA Astrophysics Data System (ADS)

    Townsend, J. P.; Jacobsen, S. D.; Bina, C. R.; Tsuchiya, J.

    2015-12-01

    We present new results from first-principles calculations of phonon spectra of lower mantle phases of MgSiO3 bridgmanite (brg) and postperovskite (ppv) including hydrous defects, and alumino-hydrous defects. We compute the partition coefficient of hydrogen between ppv and brg for hydrous and alumino-hydrous compositions at D" pressures and temperatures from first-principles lattice dynamics simulations and free energy calculations computed under the quasiharmonic approximation. We find that for aluminum free hydrous conditions the hydrogen partition coefficient between ppv and brg ranges from 0.2-0.8 within D". However, in the presence of aluminum the aluminum-hydrogen partition coefficient between ppv and brg is approximately 1.5. In general for a given pressure, lower temperature increases the partitioning of hydrogen into ppv for the aluminous models, but not for the aluminum free models. Because aluminum is is expected to occur in both natural slab and mantle compositions this suggests aluminous-hydrous ppv may be a host for water in D".

  17. DNA Partitioning in Confining Nanofluidic Slits

    NASA Astrophysics Data System (ADS)

    Greenier, Madeline; Levy, Stephen

    We measure the partitioning of double stranded DNA molecules in moderately and strongly confining nanofluidic slit-like structures. Using fluorescent microscopy, the free energy penalty of confinement is inferred by comparing the concentration of DNA molecules in adjoining slits of different depths. These depths range in size from several persistence lengths to the DNA molecule's radius of gyration. The partition coefficient is determined as a function of the slit depth, DNA contour length, and DNA topology. We compare our results to theory and Monte Carlo simulations that predict the loss of free energy for ideal and semiflexible excluded volume polymers confined between parallel plates.

  18. Continuous partition lattice

    PubMed Central

    Björner, Anders

    1987-01-01

    A continuous analogue to the partition lattices is presented. This is the metric completion of the direct limit of a system of embeddings of the finite partition lattices. The construction is analogous to von Neumann's construction of a continuous geometry over a field F from the finite-dimensional projective geometries over F. PMID:16593874

  19. Uranium and rare earth partitioning in Synroc

    SciTech Connect

    Smith, K.L.; Lumpkin, G.R.; Blackford, M.G.

    1993-12-31

    Improved AEM techniques were used to investigate three Synrocs containing 10 wt% simulated HLW and a fourth sample with {approximately}18 wt% simulated HLW. One of the 10 wt% loaded Synrocs also contained an addition of 1.0 wt% Na{sub 2}O and another contained an addition of 2.0 wt% Fe{sub 2}O{sub 3}. This work is part of a larger study initiated with the objective of determining if the bulk composition of Synroc affects the partitioning of elements between individual phases. Results from the four samples in this study show that, as expected, elemental partitioning is mainly controlled by the ionic radius criterion, with smaller Y, Gd, and U ions having a preference for zirconolite and the larger Ce and Nd ions favouring perovskite. Additions of Na and Fe lead to the formation of CAT and loveringite at the expense of rutile or Magneli phases, but only have minor effects on partitioning coefficients. Partitioning coefficients, D{sup Z/P}, for REE, Y, and U in the four Synrocs are the same (within experimental error).

  1. Fuzzy Partition Models for Fitting a Set of Partitions.

    ERIC Educational Resources Information Center

    Gordon, A. D.; Vichi, M.

    2001-01-01

    Describes methods for fitting a fuzzy consensus partition to a set of partitions of the same set of objects. Describes and illustrates three models defining median partitions and compares these methods to an alternative approach to obtaining a consensus fuzzy partition. Discusses interesting differences in the results. (SLD)

  2. Partitioning and parallel radiosity

    NASA Astrophysics Data System (ADS)

    Merzouk, S.; Winkler, C.; Paul, J. C.

    1996-03-01

    This paper proposes a theoretical framework, based on domain subdivision for parallel radiosity. Moreover, three various implementation approaches, taking advantage of partitioning algorithms and global shared memory architecture, are presented.

  3. Microemulsion electrokinetic chromatography as a suitable tool for lipophilicity determination of acidic, neutral, and basic compounds.

    PubMed

    Subirats, Xavier; Yuan, Hui-Ping; Chaves, Verónica; Marzal, Núria; Rosés, Martí

    2016-07-01

    In the present work, several MEEKC systems are studied to assess their suitability for lipophilicity determination of acidic, neutral, and basic compounds. Thus, several microemulsion compositions over a wide range of pH values (from 2.0 to 12.0), containing heptane, 1-butanol and different types and amounts of surfactant (SDS or sodium cholate: from 1.3 to 3.3%) are characterized using Abraham's solvation model. The addition of acetonitrile (up to 10%) is also studied, since it increases the resolution of the technique for the most lipophilic compounds. The system coefficients obtained are very similar to those of the 1-octanol/water, used as the reference lipophilicity index, allowing simple and linear correlations between the 1-octanol/water partition values (log Po/w ) and MEEKC mass distribution ratios (log kMEEKC ). Variations in the microemulsion composition (aqueous buffer, surfactant, concentration of ACN) did not significantly affect the similarity of the MEEKC systems to log Po/w partition. PMID:27126602

  4. Partitioning of K, U, and Th between sulfide and silicate liquids - Implications for radioactive heating of planetary cores

    NASA Technical Reports Server (NTRS)

    Murrell, M. T.; Burnett, D. S.

    1986-01-01

    Experimental partitioning studies are reported of K, U, and Th between silicate and FeFeS liquids designed to test the proposal that actinide partitioning into sulfide liquids is more important then K partitioning in the radioactive heating of planetary cores. For a basaltic liquid at 1450 C and 1.5 GPa, U partitioning into FeFeS liquids is five times greater than K partitioning. A typical value for the liquid partition coefficient for U from a granitic silicate liquid at one atmosphere at 1150 C and low fO2 is about 0.02; the coefficient for Th is similar. At low fO2 and higher temperature, experiments with basaltic liquids produce strong Ca and U partitioning into the sulfide liquid with U coefficient greater than one. The Th coefficient is less strongly affected.

  5. Estimating Uranium Partition Coefficients from Laboratory Adsorption Isotherms

    SciTech Connect

    Hull, Laurence Charles; Grossman, Christopher; Fjeld, R. A.; Coates, C.J.; Elzerman, A.

    2002-08-01

    An estimated 330 metric tons of uranium have been buried in the radioactive waste Subsurface Disposal Area (SDA) at the Idaho National Engineering and Environmental Laboratory (INEEL). An assessment of uranium transport parameters is being performed to decrease the uncertainty in risk and dose predictions derived from computer simulations of uranium fate and transport to the underlying Snake River Plain Aquifer. Uranium adsorption isotherms have been measured in the laboratory and fit with a Freundlich isotherm. The Freundlich n parameter was statistically identical for 14 sediment samples. The Freundlich Kf for seven samples, where material properties have been measured, is correlated to sediment surface area. Based on these empirical observations, a model has been derived for adsorption of uranium on INEEL sedimentary materials using surface complexation theory. The model was then used to predict the range of adsorption conditions to be expected at the SDA. Adsorption in the deep vadose zone is predicted to be stronger than in near-surface sediments because the total dissolved carbonate decreases with depth.

  6. Estimating Uranium Partition Coefficients from Laboratory Adsorption Isotherms

    SciTech Connect

    Hull, L.C.; Grossman, C.; Fjeld, R.A.; Coates, J.T.; Elzerman, A.W.

    2002-05-10

    An estimated 330 metric tons of uranium have been buried in the radioactive waste Subsurface Disposal Area (SDA) at the Idaho National Engineering and Environmental Laboratory (INEEL). An assessment of uranium transport parameters is being performed to decrease the uncertainty in risk and dose predictions derived from computer simulations of uranium fate and transport to the underlying Snake River Plain Aquifer. Uranium adsorption isotherms have been measured in the laboratory and fit with a Freundlich isotherm. The Freundlich n parameter was statistically identical for 14 sediment samples. The Freundlich Kf for seven samples, where material properties have been measured, is correlated to sediment surface area. Based on these empirical observations, a model has been derived for adsorption of uranium on INEEL sedimentary materials using surface complexation theory. The model was then used to predict the range of adsorption conditions to be expected at the SDA. Adsorption in the deep vadose zone is predicted to be stronger than in near-surface sediments because the total dissolved carbonate decreases with depth.

  7. Partition coefficient and molecular flexibility: the concept of lipophilicity space.

    PubMed

    Vistoli, Giulio; Pedretti, Alessandro; Testa, Bernard

    2009-08-01

    The rationale of this study was to investigate molecular flexibility and its influence on physicochemical properties with a view to uncovering additional information on the fuzzy concept of dynamic molecular structure. Indeed, it is now known that computed molecular interaction fields (MIFs) such as molecular electrostatic potentials (MEPs) and lipophilicity potentials (MLPs) are conformation-dependent, as are dipole moments. A database of 125 compounds was used whose conformational space was explored, while conformation-dependent parameters were computed for each non-redundant conformer found in the conformational space of the compounds. These parameters were the virtual log P (log P(MLP), calculated by a MLP approach), the apolar surface area (ASA), polar surface area (PSA), and solvent-accessible surface (SAS). For each compound, the range taken by each parameter (its property space) was divided by the number of rotors taken as an index of flexibility, yielding a parameter termed 'molecular sensitivity'. This parameter was poorly correlated with others (i.e., it contains novel information) and showed the compounds to fall into two broad classes. 'Sensitive' molecules are those whose computed property ranges are markedly sensitive to conformational effects, whereas 'insensitive' (in fact, less sensitive) molecules have property ranges which are comparatively less affected by conformational fluctuations. A pharmacokinetic application is presented. PMID:19697333

  8. Trace element partitioning between ionic crystal and liquid

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Philpotts, J. A.; Yin, L.

    1978-01-01

    The partitioning of trace elements between ionic crystals and the melt has been correlated with lattice energy of the host. The solid-liquid partition coefficient has been expressed in terms of the difference in relative ionic radius of the trace element and the homogeneous and heterogeneous strain of the host lattice. Predictions based on this model appear to be in general agreement with data for alkali nitrates and for rare-earth elements in natural garnet phenocrysts.

  9. Partitioning Breaks Communities

    NASA Astrophysics Data System (ADS)

    Reid, Fergal; McDaid, Aaron; Hurley, Neil

    Considering a clique as a conservative definition of community structure, we examine how graph partitioning algorithms interact with cliques. Many popular community-finding algorithms partition the entire graph into non-overlapping communities. We show that on a wide range of empirical networks, from different domains, significant numbers of cliques are split across the separate partitions produced by these algorithms. We then examine the largest connected component of the subgraph formed by retaining only edges in cliques, and apply partitioning strategies that explicitly minimise the number of cliques split. We further examine several modern overlapping community finding algorithms, in terms of the interaction between cliques and the communities they find, and in terms of the global overlap of the sets of communities they find. We conclude that, due to the connectedness of many networks, any community finding algorithm that produces partitions must fail to find at least some significant structures. Moreover, contrary to traditional intuition, in some empirical networks, strong ties and cliques frequently do cross community boundaries; much community structure is fundamentally overlapping and unpartitionable in nature.

  10. Mantle Mineral/Silicate Melt Partitioning

    NASA Astrophysics Data System (ADS)

    McFarlane, E. A.; Drake, M. J.

    1992-07-01

    Introduction: The partitioning of elements among mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. It has been proposed that the elevated Mg/Si ratio of the upper mantle of the Earth is a consequence of the flotation of olivine into the upper mantle (Agee and Walker, 1988). Agee and Walker (1988) have generated a model via mass balance by assuming average mineral compositions to generate upper mantle peridotite. This model determines that upper mantle peridotite could result from the addition of 32.7% olivine and 0.9% majorite garnet into the upper mantle, and subtraction of 27.6% perovskite from the upper mantle (Agee and Walker, 1988). The present contribution uses experimental data to examine the consequences of such multiple phase fractionations enabling an independent evaluation of the above mentioned model. Here we use Mg-perovskite/melt partition coefficients from both a synthetic and a natural system (KLB-1) obtained from this laboratory. Also used are partition coefficient values for majorite garnet/melt, beta spinel/melt and olivine/melt partitioning (McFarlane et al., 1991b; McFarlane et al., 1992). Multiple phase fractionations are examined using the equilibrium crystallization equation and partition coefficient values. The mineral proportions determined by Agee and Walker (1988) are converted into weight fractions and used to compute a bulk partition coefficient value. Discussion: There has been a significant debate concerning whether measured values of trace element partition coefficients permit large-scale fractionation of liquidus phases from an early terrestrial magma ocean (Kato et al., 1988a,b; Walker and Agee, 1989; Drake, 1989; Drake et al., 1991; McFarlane et al., 1990, 1991). It should be noted that it is unclear which, if any, numerical values of partition coefficients are appropriate for examining this question, and certainly the assumptions for the current model must be more fully

  11. Partition density functional theory

    NASA Astrophysics Data System (ADS)

    Nafziger, Jonathan

    Partition density functional theory (PDFT) is a method for dividing a molecular electronic structure calculation into fragment calculations. The molecular density and energy corresponding to Kohn Sham density-functional theory (KS-DFT) may be exactly recovered from these fragments. Each fragment acts as an isolated system except for the influence of a global one-body 'partition' potential which deforms the fragment densities. In this work, the developments of PDFT are put into the context of other fragment-based density functional methods. We developed three numerical implementations of PDFT: One within the NWChem computational chemistry package using basis sets, and the other two developed from scratch using real-space grids. It is shown that all three of these programs can exactly reproduce a KS-DFT calculation via fragment calculations. The first of our in-house codes handles non-interacting electrons in arbitrary one-dimensional potentials with any number of fragments. This code is used to explore how the exact partition potential changes for different partitionings of the same system and also to study features which determine which systems yield non-integer PDFT occupations and which systems are locked into integer PDFT occupations. The second in-house code, CADMium, performs real-space calculations of diatomic molecules. Features of the exact partition potential are studied for a variety of cases and an analytical formula determining singularities in the partition potential is derived. We introduce an approximation for the non-additive kinetic energy and show how this quantity can be computed exactly. Finally a PDFT functional is developed to address the issues of static correlation and delocalization errors in approximations within DFT. The functional is applied to the dissociation of H2 + and H2.

  12. PERMEATION OF MOUSE SKIN AND SILICONE RUBBER MEMBRANES BY PHENOLS: RELATIONSHIP TO IN VITRO PARTITIONING (JOURNAL VERSION)

    EPA Science Inventory

    A discrepancy has been noted in the relationship between the relative skin permeabilities of phenols and their lipophilicities as expressed in commonly used octanol/water partition coefficients. The permeability coefficients of 4-nitrophenol and several other phenols through skin...

  13. FNAS phase partitions

    NASA Technical Reports Server (NTRS)

    Vanalstine, James M.

    1993-01-01

    Project NAS8-36955 D.O. #100 initially involved the following tasks: (1) evaluation of various coatings' ability to control wall wetting and surface zeta potential expression; (2) testing various methods to mix and control the demixing of phase systems; and (3) videomicroscopic investigation of cell partition. Three complementary areas were identified for modification and extension of the original contract. They were: (1) identification of new supports for column cell partition; (2) electrokinetic detection of protein adsorption; and (3) emulsion studies related to bioseparations.

  14. Recommended Partition Coefficient (Kd) Values for Nuclide Partitioning in the Presence of Cellulose Degradation Products

    SciTech Connect

    Serkiz, S.M.

    2001-02-23

    This report documents the data analysis of the results of the described laboratory studies in order to recommend Kd values for use in Performance Assessment modeling of nuclide transport in the presence of CDP.

  15. Hydrologic transport and partitioning of phosphorus fractions

    NASA Astrophysics Data System (ADS)

    Berretta, C.; Sansalone, J.

    2011-06-01

    SummaryPhosphorus (P) in rainfall-runoff partitions between dissolved and particulate matter (PM) bound phases. This study investigates the transport and partitioning of P to PM fractions in runoff from a landscaped and biogenically-loaded carpark in Gainesville, FL (GNV). Additionally, partitioning and concentration results are compared to a similarly-sized concrete-paved source area of a similar rainfall depth frequency distribution in Baton Rouge, LA (BTR), where in contrast vehicular traffic represents the main source of pollutants. Results illustrate that concentrations of P fractions (dissolved, suspended, settleable and sediment) for GNV are one to two orders of magnitude higher than BTR. Despite these differences the dissolved fraction ( f d) and partitioning coefficient ( K d) distributions are similar, illustrating that P is predominantly bound to PM fractions. Examining PM size fractions, specific capacity for P (PSC) indicates that the P concentration order is suspended > settleable > sediment for GNV, similarly to BTR. For GNV the dominant PM mass fraction is sediment (>75 μm), while the mass of P is distributed predominantly between sediment and suspended (<25 μm) fractions since these PM mass fractions dominated the settleable one. With respect to transport of PM and P fractions the predominance of events for both areas is mass-limited first-flush, although each fraction illustrated unique washoff parameters. However, while transport is predominantly mass-limited, the transport of each PM and P fraction is influenced by separate hydrologic parameters.

  16. New Aperture Partitioning Element

    NASA Astrophysics Data System (ADS)

    Griffin, S.; Calef, B.; Williams, S.

    Postprocessing in an optical system can be aided by adding an optical element to partition the pupil into a number of segments. When imaging through the atmosphere, the recorded data are blurred by temperature-induced variations in the index of refraction along the line of sight. Using speckle imaging techniques developed in the astronomy community, this blurring can be corrected to some degree. The effectiveness of these techniques is diminished by redundant baselines in the pupil. Partitioning the pupil reduces the degree of baseline redundancy, and therefore improves the quality of images that can be obtained from the system. It is possible to implement the described approach on an optical system with a segmented primary mirror, but not very practical. This is because most optical systems do not have segmented primary mirrors, and those that do have relatively low bandwidth positioning of segments due to their large mass and inertia. It is much more practical to position an active aperture partitioning element at an aft optics pupil of the optical system. This paper describes the design, implementation and testing of a new aperture partitioning element that is completely reflective and reconfigurable. The device uses four independent, annular segments that can be positioned with a high degree of accuracy without impacting optical wavefront of each segment. This mirror has been produced and is currently deployed and working on the 3.6 m telescope.

  17. Airborne phthalate partitioning to cotton clothing

    NASA Astrophysics Data System (ADS)

    Morrison, Glenn; Li, Hongwan; Mishra, Santosh; Buechlein, Melissa

    2015-08-01

    Accumulation on indoor surfaces and fabrics can increase dermal uptake and non-dietary ingestion of semi-volatile organic compounds. To better understand the potential for dermal uptake of phthalates from clothing, we measured the mass accumulation on cotton fabrics of two phthalate esters commonly identified in indoor air: diethylphthalate (DEP) and di-n-butyl phthalate (DnBP). In 10-day chamber experiments, we observed strong air-to-cloth partitioning of these phthalates to shirts and jean material. Area-normalized partition coefficients ranged from 209 to 411 (μg/m2)/(μg/m3) for DEP and 2850 to 6580 (μg/m2)/(μg/m3) for DnBP. Clothing volume-normalized partition coefficients averaged 2.6 × 105 (μg/m3)/(μg/m3) for DEP and 3.9 × 106 (μg/m3)/(μg/m3) for DnBP. At equilibrium, we estimate that a typical set of cotton clothing can sorb DnBP from the equivalent of >10,000 m3 of indoor air, thereby substantially decreasing external mass-transfer barriers to dermal uptake. Further, we estimate that a significant fraction of a child's body burden of DnBP may come from mouthing fabric material that has been equilibrated with indoor air.

  18. Partitioning of PAHs in pore water from mangrove wetlands in Shantou, China.

    PubMed

    Cao, Qi min; Wang, Hua; Qin, Jian qiao; Chen, Gui zhu; Zhang, Yong bei

    2015-01-01

    To investigate the trend of selected polycyclic aromatic hydrocarbons (PAHs) partitioning, fifteen pore water samples collected from the sediments of three mangrove wetlands were analyzed, and the partition coefficients and the partition model for the PAHs were determined by the correlation between K(oc) and octanol-water partition coefficient (K(ow)). The results revealed that the mean Kp values in inner mangrove wetlands were between 143 and 1031 L /Kg; the particulate organic carbon (POC) could strongly adsorb low-ring PAHs; the PAHs partitioning was on a obvious trend transported to particle phase. We suggest that the classic equilibrium model of organic carbon normalized (K(p)=K(oc)f(oc)) may be used to predict the trend of the selected PAHs partitioning. PMID:25450913

  19. Detection of community structure in networks based on community coefficients

    NASA Astrophysics Data System (ADS)

    Lu, Hu; Wei, Hui

    2012-12-01

    Determining community structure in networks is fundamental to the analysis of the structural and functional properties of those networks, including social networks, computer networks, and biological networks. Modularity function Q, which was proposed by Newman and Girvan, was once the most widely used criterion for evaluating the partition of a network into communities. However, modularity Q is subject to a serious resolution limit. In this paper, we propose a new function for evaluating the partition of a network into communities. This is called community coefficient C. Using community coefficient C, we can automatically identify the ideal number of communities in the network, without any prior knowledge. We demonstrate that community coefficient C is superior to the modularity Q and does not have a resolution limit. We also compared the two widely used community structure partitioning methods, the hierarchical partitioning algorithm and the normalized cuts (Ncut) spectral partitioning algorithm. We tested these methods on computer-generated networks and real-world networks whose community structures were already known. The Ncut algorithm and community coefficient C were found to produce better results than hierarchical algorithms. Unlike several other community detection methods, the proposed method effectively partitioned the networks into different community structures and indicated the correct number of communities.

  20. High Pressure/Temperature Metal Silicate Partitioning of Tungsten

    NASA Technical Reports Server (NTRS)

    Shofner, G. A.; Danielson, L.; Righter, K.; Campbell, A. J.

    2010-01-01

    The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

  1. PREDICTION OF THE SOLUBILITY, ACTIVITY COEFFICIENT AND LIQUID/LIQUID PARTITION COEFFICIENT OF ORGANIC COMPOUNDS

    EPA Science Inventory

    Solvation models, based on fundamental chemical structure theory, were developed in the SPARC mechanistic tool box to predict a large array of physical properties of organic compounds in water and in non-aqueous solvents strictly from molecular structure. The SPARC self-interact...

  2. In-Situ Characterization of Dense Non-Aqueous Phase Liquids Using Partitioning Tracers

    SciTech Connect

    Gary A. Pope; Daene C. McKinney; Akhil Datta Gupta; Richard E. Jackson; Minquan Jin

    2000-03-20

    Majors advances have been made during the past three years in our research on interwell partitioning tracers tests (PITTs). These advances include (1) progress on the inverse problem of how to estimate the three-dimensional distribution of NAPL in aquifers from the tracer data, (2) the first ever partitioning tracer experiments in dual porosity media, (3) the first modeling of partitioning tracers in dual porosity media (4) experiments with complex NAPLs such as coal tar, (5) the development of an accurate and simple method to predict partition coefficients using the equivalent alkane carbon number approach, (6) partitioning tracer experiments in large model aquifers with permeability layers, (7) the first ever analysis of partitioning tracer data to estimate the change in composition of a NAPL before and after remediation (8) the first ever analysis of partitioning tracer data after a field demonstration of surfactant foam to remediate NAPL and (9) experiments at elevated temperatures .

  3. PARTITIONING, DESORPTION, AND DECHLORINATION OF A PCB CONGENER IN SEDIMENT SLURRY SUPERNATANTS

    EPA Science Inventory

    Partitioning and desorption played specific roles in the dechlorination of 2-chlorobiphenyl (2-ClBP) in sediment slurry supernatants, which are suspensions of disssolved organic matter(DOM). In short-term experiments, the partition coefficient (Kp) was related to the a...

  4. Cell surface energy, contact angles and phase partition. II. Bacterial cells in biphasic aqueous mixtures.

    PubMed

    Gerson, D F; Akit, J

    1980-11-01

    Partition coefficients in biphasic mixtures of poly(ethylene glycol) and Dextran are compared to cell surface energies obtained from contact angles of each liquid phase on cell layers. Linear relationships are observed between these two independent measurements for a variety of bacterial cells. The results demonstrate the importance of interfacial phenomena and contact angles in the phase-partition process. PMID:6159003

  5. Orientation-dependent impurity partitioning of colloidal crystals

    NASA Astrophysics Data System (ADS)

    Nozawa, Jun; Uda, Satoshi; Hu, Sumeng; Fujiwara, Kozo; Koizumi, Haruhiko

    2016-04-01

    Impurity partitioning during colloidal crystallization was investigated for grains with different orientations. Particles of various sizes were doped as impurities during the growth of colloidal polycrystals. The effective partition coefficient, keff, which is the impurity concentration in the solid (CS) divided by that in initial solution (CL), was measured for grains oriented in the [111] and [100] directions normal to the growth direction. The [111]-oriented grains were found to have a larger keff than [100]-oriented grains. This was analyzed by using the Thurmond and Struthers model. Though both [111]- and [100]-oriented grains were face centered cubic (fcc) structures, within several layers of crystals, the volume fraction of [111]-oriented grains was larger than that of [100]-oriented grains, yielding a larger driving force for nucleation, ΔGTr, and thus a larger equilibrium partition coefficient, k0, for [111]-oriented grains.

  6. EMPIRICAL MODELS OF PB AND CD PARTITIONING USING DATA FROM 13 SOILS, SEDIMENTS AND AQUIFER MATERIALS

    EPA Science Inventory

    Lead (Pb) and cadmium (Cd) are two of the most common toxicants found in contaminated environments. Because solubilization of these metallic elements from the solid phase can influence their fate, transport and bioavailability, the partitioning coefficient (Kd) for these metals ...

  7. PARTITIONING OF ORGANIC COMPOUNDS IN OCTANOL-WATER SYSTEMS

    EPA Science Inventory

    When plots of the log of the octanol-water partition coefficients vs log of water solubilities of a wide variety of liquid and solid solutes are modified by converting the solid solubilities to the estimated solubilities of the corresponding supercooled liquids, the differences b...

  8. REE Partitioning in Lunar Minerals

    NASA Technical Reports Server (NTRS)

    Rapp, J. F.; Lapen, T. J.; Draper, D. S.

    2015-01-01

    Rare earth elements (REE) are an extremely useful tool in modeling lunar magmatic processes. Here we present the first experimentally derived plagioclase/melt partition coefficients in lunar compositions covering the entire suite of REE. Positive europium anomalies are ubiquitous in the plagioclase-rich rocks of the lunar highlands, and complementary negative Eu anomalies are found in most lunar basalts. These features are taken as evidence of a large-scale differentiation event, with crystallization of a global-scale lunar magma ocean (LMO) resulting in a plagioclase flotation crust and a mafic lunar interior from which mare basalts were subsequently derived. However, the extent of the Eu anomaly in lunar rocks is variable. Fagan and Neal [1] reported highly anorthitic plagioclase grains in lunar impact melt rock 60635,19 that displayed negative Eu anomalies as well as the more usual positive anomalies. Indeed some grains in the sample are reported to display both positive and negative anomalies. Judging from cathodoluminescence images, these anomalies do not appear to be associated with crystal overgrowths or zones.

  9. Virial expansion coefficients in the harmonic approximation.

    PubMed

    Armstrong, J R; Zinner, N T; Fedorov, D V; Jensen, A S

    2012-08-01

    The virial expansion method is applied within a harmonic approximation to an interacting N-body system of identical fermions. We compute the canonical partition functions for two and three particles to get the two lowest orders in the expansion. The energy spectrum is carefully interpolated to reproduce ground-state properties at low temperature and the noninteracting high-temperature limit of constant virial coefficients. This resembles the smearing of shell effects in finite systems with increasing temperature. Numerical results are discussed for the second and third virial coefficients as functions of dimension, temperature, interaction, and transition temperature between low- and high-energy limits. PMID:23005730

  10. Experimental study of radium partitioning between anorthite and melt at 1 atm

    SciTech Connect

    Miller, S; Burnett, D; Asimow, P; Phinney, D; Hutcheon, I

    2007-03-08

    We present the first experimental radium mineral/melt partitioning data, specifically between anorthite and a CMAS melt at atmospheric pressure. Ion microprobe measurement of coexisting anorthite and glass phases produces a molar D{sub Ra} = 0.040 {+-} 0.006 and D{sub Ra}/D{sub Ba} = 0.23 {+-} 0.05 at 1400 C. Our results indicate that lattice strain partitioning models fit the divalent (Ca, Sr, Ba, Ra) partition coefficient data of this study well, supporting previous work on crustal melting and magma chamber dynamics that has relied on such models to approximate radium partitioning behavior in the absence of experimentally determined values.

  11. Chemical amplification based on fluid partitioning

    DOEpatents

    Anderson, Brian L.; Colston, Jr., Billy W.; Elkin, Chris

    2006-05-09

    A system for nucleic acid amplification of a sample comprises partitioning the sample into partitioned sections and performing PCR on the partitioned sections of the sample. Another embodiment of the invention provides a system for nucleic acid amplification and detection of a sample comprising partitioning the sample into partitioned sections, performing PCR on the partitioned sections of the sample, and detecting and analyzing the partitioned sections of the sample.

  12. Contaminated vadose zone characterization using partitioning gas tracers

    SciTech Connect

    Whitley, G.A. Jr.; McKinney, D.C.; Pope, G.A.; Rouse, B.A.; Deeds, N.E.

    1999-06-01

    This paper describes laboratory research conducted to investigate the performance of partitioning tracers for the detection of nonaqueous-phase liquids (NAPLs) in vadose zones. Once evaluated, the tracers may be used for volume estimation of NAPLs and remediation performance assessment of vadose zones. These laboratory studies used glass chromatography columns packed with: (1) Ottawa sand; and then (2) in a separate experiment, soil extracted from the Chemical Waste Landfill at Sandia National Laboratories. The columns were prepared in a manner that resulted in a three-phase system of air, water, and NAPL in the columns. Conservative and partitioning gas tracers were injected into the columns, and their elution concentrations were analyzed. The method of moments was used to estimate partition coefficients between the air and NAPL phases for each of the tracers. The partition coefficients and retardation factors, also estimated during the study, are used to select appropriate tracers for NAPL detection. This research identified several suitable perfluorocarbon tracers and demonstrated the feasibility of using partitioning tracers as a tool for NAPL detection in the vadose zone.

  13. Metal partitioning and toxicity in sewage sludge

    SciTech Connect

    Carlson-Ekvall, C.E.A.; Morrison, G.M.

    1995-12-31

    Over 20 years of research has failed to provide an unequivocal correlation between chemically extracted metals in sewage sludge applied to agricultural soil and either metal toxicity to soil organisms or crop uptake. Partitioning of metals between phases and species can provide a better estimation of mobility and potential bioavailability. Partition coefficients, K{sub D} for Cd, Cu, Pb and Zn in a sludge/water solution were determined considering the sludge/water solution as a three-phase system (particulate, colloidal and electrochemically available) over a range of pH values, ionic strengths, contact times and sludge/water ratios and compared with the KD values for sludge/water solution as a two-phase system (aqueous phase and particulate phase). Partitioning results were interpreted in terms of metal mobility from sludge to colloids and in terms of potential bioavailability from colloids to electrochemically available. The results show that both mobility and potential bioavailability are high for Zn, while Cu partitions into the mobile colloidal phase which is relatively non-bioavailable. Lead is almost completely bound to the solid phase, and is neither mobile nor bioavailable. A comparison between K, values and toxicity shows that Zn in sludge is more toxic than can be accounted for in the aqueous phase, which can be due to synergistic effects between sludge organics and Zn. Copper demonstrates clear synergism which can be attributed to the formation of lipid-soluble Cu complexes with known sludge components such as LAS, caffeine, myristic acid and nonylphenol.

  14. Boron, beryllium, and lithium, partitioning in olivine

    SciTech Connect

    Neroda, Elizabeth

    1996-05-01

    A one atmosphere experimental study was performed to determine the mineral/melt partition coefficients for B, Be, and Li in forsteritic olivine. Two compositions were chosen along the 1350{degrees}C isotherm, 1b (Fo{sub 17.3} Ab{sub 82.7} An{sub 0} by weight) and 8c (Fo{sub 30} Ab{sub 23.3} An{sub 47.8}, by weight) were then combined in equal amounts to form a composition was doped with 25ppm Li, B, Yb, Nb, Zr, Sr, and Hf, 50ppm Sm, and 100ppm Be, Nd, Ce, and Rb. Electron and ion microprobe analyses showed that the olivine crystals and surrounding glasses were homogeneous with respect to major and trace elements. Partition coefficients calculated from these analyses are as follows: 1b: D{sub B} = 4.41 ({+-} 2.3) E-03, D{sub Be} = 2.86 ({+-} 0.45) E-03, D{sub Li} = 1.54 ({+-} 0.21) E-01, 50/50: D{sub B} = 2.86 ({+-} 0.5) E-03, D{sub Be} = 2.07 ({+-} 0.09) E-03, D{sub Li} = 1.51 ({+-} 0.18) E-01, 8c: D{sub B} = 6.05 ({+-} 1.5) E-03, D{sub Be} = 1.81 ({+-} 0.03) E-03, D{sub Li} = 1.31 ({+-} 0.09) E-01. The results of this study will combined with similar data for other minerals as part of a larger study to understand the partitioning behavior of B, Be, and Li in melting of the upper mantle at subduction zones.

  15. Partitioning of Nb, Mo, Ba, Ce, Pb, Th and U between immiscible carbonate and silicate liquids: Evaluating the effects of P2O5,F, and carbonate composition

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Walker, D.

    1993-01-01

    Previously we have reported carbonate liq./silicate liq. partition coefficients (D) for a standard suite of trace elements (Nb, Mo, Ba, Ce, Pb, Th, and U) and Ra and Pa as well. In brief, we have found that immiscible liquid partitioning is a strong function of temperature. As the critical temperature of the carbonate-silicate solvus is approached, all partition coefficients approach unity. Additionally, for the overwhelming majority of the partitioning elements, InD is a linear function of 'ionic field strength,' z/r, where z is the charge of the partitioned cation and r is its ionic radius.

  16. Uranium in granitic magmas: Part 1. Experimental determination of uranium solubility and fluid-melt partition coefficients in the uranium oxide-haplogranite-H 2O-Na 2CO 3 system at 720-770°C, 2 kbar

    NASA Astrophysics Data System (ADS)

    Peiffert, Chantal; Cuney, Michel; Nguyen-Trung, Chinh

    1994-06-01

    1.1 to 1.5. For α in the range 1.5-1.7, the effect of both ƒo 2 and agpaicity index on the uranium solubility was considerably reduced. The temperature variation in the range 720-770°C had no significant effect on the uranium solubility in either aqueous fluid or silicate melt. The partition coefficient (D fluid/melt) of uranium was in the range 10 -4.0-10 -1.5 and depended on both ƒo 2 and α according to the equation log D fluid/melt = 0.05 log ƒo 2 (bar) - 3.78α + 2.84 . The validity conditions of this equation are similar to those of the preceding one. Results obtained in the present study could be used to predict the geochemical behaviour of uranium during magma fractionation and to further understanding of the formation of uranium ore deposits related to partial melting or fractional crystallization of felsic magmas. The genesis of the Kvanefjeld (Ilimaussaq, Greenland) uranium deposit is discussed.

  17. Factor Scores, Structure Coefficients, and Communality Coefficients

    ERIC Educational Resources Information Center

    Goodwyn, Fara

    2012-01-01

    This paper presents heuristic explanations of factor scores, structure coefficients, and communality coefficients. Common misconceptions regarding these topics are clarified. In addition, (a) the regression (b) Bartlett, (c) Anderson-Rubin, and (d) Thompson methods for calculating factor scores are reviewed. Syntax necessary to execute all four…

  18. Partitioning and diffusion of PBDEs through an HDPE geomembrane.

    PubMed

    Rowe, R Kerry; Saheli, Pooneh T; Rutter, Allison

    2016-09-01

    Polybrominated diphenyl ether (PBDE) has been measured in MSW landfill leachate and its migration through a modern landfill liner has not been investigated previously. To assure environmental protection, it is important to evaluate the efficacy of landfill liners for controlling the release of PBDE to the environment to a negligible level. The partitioning and diffusion of a commercial mixture of PBDEs (DE-71: predominantly containing six congeners) with respect to a high-density polyethylene (HDPE) geomembrane is examined. The results show that the partitioning coefficients of the six congeners in this mixture range from 700,000 to 7,500,000 and the diffusion coefficients range from 1.3 to 6.0×10(-15)m(2)/s depending on the congener. This combination of very high partitioning coefficients and very low diffusion coefficients suggest that a well constructed HDPE geomembrane liner will be an extremely effective barrier for PBDEs with respect to diffusion from a municipal solid waste landfill, as illustrated by an example. The results for pure diffusion scenario showed that the congeners investigated meet the guidelines by at least a factor of three for an effective geomembrane liner where diffusion is the controlling transport mechanism. PMID:27211313

  19. Quantum field theory of partitions

    SciTech Connect

    Bender, C.M.; Brody, D.C.; Meister, B.K.

    1999-07-01

    Given a sequence of numbers {l_brace}a{sub n}{r_brace}, it is always possible to find a set of Feynman rules that reproduce that sequence. For the special case of the partitions of the integers, the appropriate Feynman rules give rise to graphs that represent the partitions in a clear pictorial fashion. These Feynman rules can be used to generate the Bell numbers B(n) and the Stirling numbers S(n,k) that are associated with the partitions of the integers. {copyright} {ital 1999 American Institute of Physics.}

  20. Probabilistic framework for network partition

    NASA Astrophysics Data System (ADS)

    Li, Tiejun; Liu, Jian; E, Weinan

    2009-08-01

    Given a large and complex network, we would like to find the partition of this network into a small number of clusters. This question has been addressed in many different ways. In a previous paper, we proposed a deterministic framework for an optimal partition of a network as well as the associated algorithms. In this paper, we extend this framework to a probabilistic setting, in which each node has a certain probability of belonging to a certain cluster. Two classes of numerical algorithms for such a probabilistic network partition are presented and tested. Application to three representative examples is discussed.

  1. Partitioning ecosystems for sustainability.

    PubMed

    Murray, Martyn G

    2016-03-01

    Decline in the abundance of renewable natural resources (RNRs) coupled with increasing demands of an expanding human population will greatly intensify competition for Earth's natural resources during this century, yet curiously, analytical approaches to the management of productive ecosystems (ecological theory of wildlife harvesting, tragedy of the commons, green economics, and bioeconomics) give only peripheral attention to the driving influence of competition on resource exploitation. Here, I apply resource competition theory (RCT) to the exploitation of RNRs and derive four general policies in support of their sustainable and equitable use: (1) regulate resource extraction technology to avoid damage to the resource base; (2) increase efficiency of resource use and reduce waste at every step in the resource supply chain and distribution network; (3) partition ecosystems with the harvesting niche as the basic organizing principle for sustainable management of natural resources by multiple users; and (4) increase negative feedback between consumer and resource to bring about long-term sustainable use. A simple policy framework demonstrates how RCT integrates with other elements of sustainability science to better manage productive ecosystems. Several problem areas of RNR management are discussed in the light of RCT, including tragedy of the commons, overharvesting, resource collapse, bycatch, single species quotas, and simplification of ecosystems. PMID:27209800

  2. Partitioning of divalent transition elements between octahedral sheets of trioctahedral smectites and water

    NASA Astrophysics Data System (ADS)

    Decarreau, Alain

    1985-07-01

    Using trioctahedral smectites synthesized at low temperature (25 and 75°C). partition coefficients have been determined for M2+ transition metals (Mn, Fe, Co, Ni, Cu, Zn) between octahedral sheets of smectites and water. These coefficients D( M2+- Mg) = ( M2+)/( Mg) solid/( M2+)/( Mg) liquid have high values near 10 4 for Cu, 1000 for Ni, Co, Zn, 300 for Fe and 30 for Mn. All transition metals are strongly stabilized in the magnesian solid phase, even Mn which leads to noncrystallized products. Within the range of experimental uncertainties, it is found that tetrahedral substitution of Si by Al and differences in temperature (from 25 to 75°C) have no influence on partition coefficients. Experimental data are closely related to thermodynamic properties of the cations and on this basis other partition coefficients can be calculated, for the ( M2+ - Fe2+) pair for instance. The behaviour of transition metals is explained using crystal field theory.

  3. Metal/Silicate Partitioning at High Pressures and Temperatures

    NASA Technical Reports Server (NTRS)

    Shofner, G.; Campbell, A.; Danielson, L.; Righter, K.; Rahman, Z.

    2010-01-01

    The behavior of siderophile elements during metal-silicate segregation, and their resulting distributions provide insight into core formation processes. Determination of partition coefficients allows the calculation of element distributions that can be compared to established values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Moderately siderophile elements, including W, are particularly useful in constraining core formation conditions because they are sensitive to variations in T, P, oxygen fugacity (fO2), and silicate composition. To constrain the effect of pressure on W metal/silicate partitioning, we performed experiments at high pressures and temperatures using a multi anvil press (MAP) at NASA Johnson Space Center and laser-heated diamond anvil cells (LHDAC) at the University of Maryland. Starting materials consisted of natural peridotite mixed with Fe and W metals. Pressure conditions in the MAP experiments ranged from 10 to 16 GPa at 2400 K. Pressures in the LHDAC experiments ranged from 26 to 58 GPa, and peak temperatures ranged up to 5000 K. LHDAC experimental run products were sectioned by focused ion beam (FIB) at NASA JSC. Run products were analyzed by electron microprobe using wavelength dispersive spectroscopy. Liquid metal/liquid silicate partition coefficients for W were calculated from element abundances determined by microprobe analyses, and corrected to a common fO2 condition of IW-2 assuming +4 valence for W. Within analytical uncertainties, W partitioning shows a flat trend with increasing pressure from 10 to 16 GPa. At higher pressures, W becomes more siderophile, with an increase in partition coefficient of approximately 0.5 log units.

  4. Partitioning of Nanoparticles into Organic Phases and Model Cells

    SciTech Connect

    Posner, J.D.; Westerhoff, P.; Hou, W-C.

    2011-08-25

    There is a recognized need to understand and predict the fate, transport and bioavailability of engineered nanoparticles (ENPs) in aquatic and soil ecosystems. Recent research focuses on either collection of empirical data (e.g., removal of a specific NP through water or soil matrices under variable experimental conditions) or precise NP characterization (e.g. size, degree of aggregation, morphology, zeta potential, purity, surface chemistry, and stability). However, it is almost impossible to transition from these precise measurements to models suitable to assess the NP behavior in the environment with complex and heterogeneous matrices. For decades, the USEPA has developed and applies basic partitioning parameters (e.g., octanol-water partition coefficients) and models (e.g., EPI Suite, ECOSAR) to predict the environmental fate, bioavailability, and toxicity of organic pollutants (e.g., pesticides, hydrocarbons, etc.). In this project we have investigated the hypothesis that NP partition coefficients between water and organic phases (octanol or lipid bilayer) is highly dependent on their physiochemical properties, aggregation, and presence of natural constituents in aquatic environments (salts, natural organic matter), which may impact their partitioning into biological matrices (bioaccumulation) and human exposure (bioavailability) as well as the eventual usage in modeling the fate and bioavailability of ENPs. In this report, we use the terminology "partitioning" to operationally define the fraction of ENPs distributed among different phases. The mechanisms leading to this partitioning probably involve both chemical force interactions (hydrophobic association, hydrogen bonding, ligand exchange, etc.) and physical forces that bring the ENPs in close contact with the phase interfaces (diffusion, electrostatic interactions, mixing turbulence, etc.). Our work focuses on partitioning, but also provides insight into the relative behavior of ENPs as either "more like

  5. Coefficients for Interrater Agreement.

    ERIC Educational Resources Information Center

    Zegers, Frits E.

    1991-01-01

    The degree of agreement between two raters rating several objects for a single characteristic can be expressed through an association coefficient, such as the Pearson product-moment correlation. How to select an appropriate association coefficient, and the desirable properties and uses of a class of such coefficients--the Euclidean…

  6. Solid Metal-Liquid Metal Partitioning of Pt, Re, and Os: The Effect of Carbon

    NASA Technical Reports Server (NTRS)

    Chabot, N. L.; Campbell, A. J.; Humayun, M.

    2004-01-01

    If the measured Os isotopic ratios are a signature from the Earth's outer core, understanding them is a unique opportunity to understand more about the Earth's core. The distribution of elements between the Earth's solid inner core and the liquid outer core will depend on their solid metal-liquid metal partition coefficients (D). Solid metal-liquid metal partitioning data are loosely consistent with the needed fractionations between Re-Os and Pt-Os to account for the Os isotopic signature; D(Os) is greater than both D(Re) and D(Pt), and the magnitude of the partition coefficients are similar to those needed [e.g. 7, 8]. The pressure in the core, the composition of the core, and the crystal structure of the solid Fe alloy in the inner core may influence the specific values of the partition coefficients. It may thus be possible to use these sensitivities of the partition coefficients to gain insight into the conditions within the Earth's core. In this abstract, we focus on the compositional influence of C, a potential component of the light element in the Earth's core [9], on the partitioning behaviors of Pt, Re, and Os.

  7. Trace element distribution coefficients in alkaline series. [Titanites; bitite

    SciTech Connect

    Lemarchand, F.; Villemant, B.; Calas, G.

    1987-05-01

    Mineral/groundmass partition coefficients for U, Th, Zr, Hf, Ta, Rb, REE, Co and Sc have been systematically measured in olivine, clinopyroxene, amphibole, biotite, Ti-magnetites, titanite, zircon and feldspars, in basaltic to trachytic lavas from alkaline series (Velay, Chaine des Puys: Massif Central, France and Fayal: Azores). Average partition coefficients are defined within the experimental uncertainty for limited compositional ranges (basalt-hawaiite, mugearites, benmoreite-trachyte), and are useful for trace element modelling. The new results for U, Th, Ta, Zr and Hf partition coefficients show contrasting behaviour. They can thus be used as ''key elements'' for identifying fractionating mineral phases in differentiation processes (e.g. Ta and Th for amphibole and mica). Partition coefficient may be calculated using the two-lattice model suggested by NIELSEN (1985). Such values show a considerably reduced chemical dependence in natural systems, relative to weight per cent D values. The residual variations may be accounted for by temperature or volatile influence. This calculation greatly enhances modelling possibilities using trace elements for comparing differentiation series as well as for predicting the behaviour of elements during magmatic differentiation.

  8. Pallasites as a proxy for understanding core-mantle partitioning

    NASA Astrophysics Data System (ADS)

    Mikhail, S.; Crispin, K. L.; Shahar, A.

    2012-12-01

    During planetary differentiation in the core-mantle system the elements that are iron-loving (siderophile) are partitioned into the core, conversely, the rock-loving (lithophile) elements are partitioned into the mantle. However, empirical data from the studies of upper mantle xenoliths and chondritic meteorites are at odds with experimentally calibrated partition coefficients under conditions akin to the early Earth during core-formation. In short, the concentration of moderate to highly siderophile elements in the mantle is too high. This has led to the late-veneer hypothesis, which increases the mantles siderophile element budget post core-formation to explain the observed siderophile element-enrichment. To investigate the need for such a late-veneer, and to also test the experimentally calibrated partition coefficients, we have analyzed pallasite meteorites, thought to come from the core-mantle boundary of planetary bodies. Pallasites are stony-iron meteorites consisting chiefly of olivine within a Fe-Ni metal matrix. We will present the results from the determinations of a variety of siderophile and lithophile trace elements in the olivines ('mantle') and the Fe-Ni alloy ('core') from 9 pallasite meteorites and 1 aubrite meteorite. We discuss the data in light of two notions; (i) siderophile element-enrichment in the mantle requires a late-veneer and (ii) the pallasites share a common parent body.

  9. Graph Partitioning and Sequencing Software

    1995-09-19

    Graph partitioning is a fundemental problem in many scientific contexts. CHACO2.0 is a software package designed to partition and sequence graphs. CHACO2.0 allows for recursive application of several methods for finding small edge separators in weighted graphs. These methods include inertial, spectral, Kernighan Lin and multilevel methods in addition to several simpler strategies. Each of these approaches can be used to partition the graph into two, four, or eight pieces at each level of recursion.more » In addition, the Kernighan Lin method can be used to improve partitions generated by any of the other algorithms. CHACO2.0 can also be used to address various graph sequencing problems, with applications to scientific computing, database design, gene sequencing and other problems.« less

  10. VARIATIONS IN THE SPECTRAL PROPERTIES OF FRESHWATER AND ESTUARINE CDOM CAUSED BY PARTITIONING ONTO RIVER AND ESTUARINE SEDIMENTS

    EPA Science Inventory

    The optical properties and geochemical cycling of chromophoric dissolved organic matter (CDOM) are altered by its sorption to freshwater and estuarine sediments. Measured partition coefficients (Kp) of Satilla River (Georgia) and Cape Fear River estuary (North Carolina) CDOM ran...

  11. Experimental investigations of trace element fractionation in iron meteorites. III - Elemental partitioning in the system Fe-Ni-S-P

    NASA Technical Reports Server (NTRS)

    Malvin, D. J.; Jones, J. H.; Drake, M. J.

    1986-01-01

    Measurements of solid metal/liquid metal trace element partition coefficients, which are used to interpret the crystallization history of magmatic iron meteorite groups differ greatly between different research groups, using different experimental techniques. Specifically, partition coefficients measured utilizing 'static' experiments which approach equilibrium cannot be reconciled with the results of 'dynamic' experiments which mimic fractional crystallization. We report new tests of our 'static' experimental technique and demonstrate that our methodology yields reliable equilibrium values for Ni, P and Ge partition coefficients. Partition coefficients in the Fe-Ni-S-P system are well matched by interpolation between the Fe-Ni-S and Fe-Ni-P subsystems. In contrast, the predictions of 'dynamic' experiments do not agree with our measurements and, consequently, the ability of 'dynamic' experiments to reproduce iron meteorite Ge vs. Ni fractionation trends successfully must be regarded as fortuitous.

  12. Partitioning of Aromatic Constituents into Water from Jet Fuels.

    PubMed

    Tien, Chien-Jung; Shu, Youn-Yuen; Ciou, Shih-Rong; Chen, Colin S

    2015-08-01

    A comprehensive study of the most commonly used jet fuels (i.e., Jet A-1 and JP-8) was performed to properly assess potential contamination of the subsurface environment from a leaking underground storage tank occurred in an airport. The objectives of this study were to evaluate the concentration ranges of the major components in the water-soluble fraction of jet fuels and to estimate the jet fuel-water partition coefficients (K fw) for target compounds using partitioning experiments and a polyparameter linear free-energy relationship (PP-LFER) approach. The average molecular weight of Jet A-1 and JP-8 was estimated to be 161 and 147 g/mole, respectively. The density of Jet A-1 and JP-8 was measured to be 786 and 780 g/L, respectively. The distribution of nonpolar target compounds between the fuel and water phases was described using a two-phase liquid-liquid equilibrium model. Models were derived using Raoult's law convention for the activity coefficients and the liquid solubility. The observed inverse, log-log linear dependence of the K fw values on the aqueous solubility were well predicted by assuming jet fuel to be an ideal solvent mixture. The experimental partition coefficients were generally well reproduced by PP-LFER. PMID:25840956

  13. Estimation of soil sorption coefficients using QSARs

    SciTech Connect

    Doucette, W.J.

    1994-12-31

    Sorption coefficients quantitatively describe the extent to which an organic chemical distributes itself between an environmental solid and the aqueous phase that it is contact with at equilibrium. Because of the difficulty and expense associated with measuring sorption coefficients, estimated values are often used in place of site specific, experimental values for fate modeling. Most reported methods for estimating the sorption of organic chemicals onto environmental solids are based on observation that for many organic chemicals, and in particular neutral hydrophobic organics, sorption is directly proportional to the quantity of organic matter associated with the solid. Normalizing soil or sediment specific sorption coefficients to the organic carbon content of the sorbent yields a new ``constant``, Koc, that is considered unique property of the organic chemical being sorbed. Values of Koc are then typically estimated from correlations between Koc and various descriptors of hydrophobicity such as octanol/water partition coefficients (Kow), aqueous solubility (S), molecular connectivity indices (MCIs) and retention times or capacity factors generated by reverse phase high performance liquid chromatography (RP-HPLC). Group contribution methods have also been described. While the so-called ``Koc approach`` for estimating sorption coefficients is most appropriate for neutral, hydrophobic organic chemicals on environmental solids containing a significant amount of organic matter, it has been applied to a wide variety of chemical and soil types. This presentation will focus on a discussion of the Koc approach, its applicability and limitations. A comparison of several widely used methods for estimating Koc will be presented.

  14. Hornblende-melt trace-element partitioning measured by ion microprobe

    USGS Publications Warehouse

    Sisson, T.W.

    1994-01-01

    Trace-element abundances were measured in situ by ion microprobe in five samples of hornblende and melt ranging from basaltic andesite to high-silica rhyolite. Except for one sample, for which quench overgrowth or disequilibrium is suspected, the abundance ratios show systematic inter-element and inter-sample variations, and probably approach true partition coefficients. Apparent partition coefficients are reported for La, Ce, Nd, Sm, Dy, Er, Yb, Sc, Ti, V, Cr, Sr, Y and Zr. Rare-earth elements (REE) and Y form smooth convex-upward partitioning patterns that rise to higher D-values and become increasingly convex in more evolved samples. Apparent partition coefficients for REE, Y, Ti, V and Cr can be parameterized as functions of the distribution of Ca between hornblende and melt, giving expressions to predict hornblende-melt trace-element partitioning values. These expressions are used to show that heavy REE-enriched hornblende/whole-rock REE abundance patterns in granitoids may result from partial re-equilibration of hornblende and late-stage residual liquids rather than from anomalous partitioning values. ?? 1994.

  15. Partition behaviour of alkylphenols in crude oil/brine systems under subsurface conditions

    NASA Astrophysics Data System (ADS)

    Bennett, B.; Larter, S. R.

    1997-10-01

    Partition of organic solutes between oils and water in the subsurface is an important geochemical process occurring during petroleum migration and reservoiring, during water washing, and during petroleum production. Currently no data exists on the quantitative aspects of the partition process at subsurface conditions for solutes such as phenols and aromatic hydrocarbons which are major components of both oils and waters. We have constructed an equilibration device for oils and waters based on flow injection analysis principles to measure partition coefficients of alkylphenols in crude oil/brine systems under reservoir conditions. Concentrations of C 0C 2 alkylphenols in waters and solid phase extracts of crude oils produced in the device were determined by reverse phase high performance liquid chromatography with electrochemical detection (RP-HPLC-ED), partition coefficients being measured as a function of pressure (25-340 bar), temperature (25-150°C), and water salinity (0-100,000 mg/L sodium chloride) for a variety of oils. Partition coefficients for all compounds decreased with increasing temperature, increased with water salinity and crude oil bulk NSO content, and showed little change with varying pressure. These laboratory measurements, determined under conditions close to those typically encountered in petroleum reservoirs, suggest temperature, water salinity, and crude oil bulk NSO content will have important influence on oil-water partition processes in the subsurface during migration and water washing.

  16. Designing lipids for selective partitioning into liquid ordered membrane domains.

    PubMed

    Momin, Noor; Lee, Stacey; Gadok, Avinash K; Busch, David J; Bachand, George D; Hayden, Carl C; Stachowiak, Jeanne C; Sasaki, Darryl Y

    2015-04-28

    Self-organization of lipid molecules into specific membrane phases is key to the development of hierarchical molecular assemblies that mimic cellular structures. While the packing interaction of the lipid tails should provide the major driving force to direct lipid partitioning to ordered or disordered membrane domains, numerous examples show that the headgroup and spacer play important but undefined roles. We report here the development of several new biotinylated lipids that examine the role of spacer chemistry and structure on membrane phase partitioning. The new lipids were prepared with varying lengths of low molecular weight polyethylene glycol (EGn) spacers to examine how spacer hydrophilicity and length influence their partitioning behavior following binding with FITC-labeled streptavidin in liquid ordered (Lo) and liquid disordered (Ld) phase coexisting membranes. Partitioning coefficients (Kp Lo/Ld) of the biotinylated lipids were determined using fluorescence measurements in studies with giant unilamellar vesicles (GUVs). Compared against DPPE-biotin, DPPE-cap-biotin, and DSPE-PEG2000-biotin lipids, the new dipalmityl-EGn-biotin lipids exhibited markedly enhanced partitioning into liquid ordered domains, achieving Kp of up to 7.3 with a decaethylene glycol spacer (DP-EG10-biotin). We further demonstrated biological relevance of the lipids with selective partitioning to lipid raft-like domains observed in giant plasma membrane vesicles (GPMVs) derived from mammalian cells. Our results found that the spacer group not only plays a pivotal role for designing lipids with phase selectivity but may also influence the structural order of the domain assemblies. PMID:25772372

  17. New Instrumentation for Phase Partitioning

    NASA Technical Reports Server (NTRS)

    Harris, J. M.

    1985-01-01

    Cells and molecules can be purified by partitioning between the two immiscible liquid phases formed by aqueous solutions of poly/ethylene glycol and dextran. Such purification can be more selective, higher yielding, and less destructive to sensitive biological materials than other available techniques. Earth's gravitational field is a hindering factor as it causes sedimentation of particles to be purified and shear-induced particle randomization. The present proposal is directed toward developing new instrumentation for performing phase partitioning both on Earth and in microgravity.

  18. Rectilinear partitioning of irregular data parallel computations

    NASA Technical Reports Server (NTRS)

    Nicol, David M.

    1991-01-01

    New mapping algorithms for domain oriented data-parallel computations, where the workload is distributed irregularly throughout the domain, but exhibits localized communication patterns are described. Researchers consider the problem of partitioning the domain for parallel processing in such a way that the workload on the most heavily loaded processor is minimized, subject to the constraint that the partition be perfectly rectilinear. Rectilinear partitions are useful on architectures that have a fast local mesh network. Discussed here is an improved algorithm for finding the optimal partitioning in one dimension, new algorithms for partitioning in two dimensions, and optimal partitioning in three dimensions. The application of these algorithms to real problems are discussed.

  19. An experimental study of trace element partitioning between olivine, orthopyroxene and melt in chondrules - Equilibrium values and kinetic effects

    NASA Technical Reports Server (NTRS)

    Kennedy, A. K.; Lofgren, G. E.; Wasserburg, G. J.

    1993-01-01

    Mineral/melt partition coefficients were measured using an ion microprobe for 32 elements in orthopyroxene and olivine in equilibrium and dynamic crystallization experiments on compositions corresponding to chondrules. The mineral/melt partition coefficients calculated from the measured concentrations for both olivine and orthopyroxene show very little change between equilibrium experiments and dynamic experiments with cooling rates of up to 100 C/h. The results provide a self-consistent set of partition coefficients that can be used in thermodynamic models of equilibrium and kinetic partitioning between olivine, orthopyroxene, and melt. These data can be used in models of partial melting and crystal fractionation in olivine- and orthopyroxene-rich systems, such as chondrules. The results may also be applicable to mantle peridotites, komatiitic and picritic lavas, and ultramafic intrusions.

  20. Unsupervised segmentation of MRI knees using image partition forests

    NASA Astrophysics Data System (ADS)

    Marčan, Marija; Voiculescu, Irina

    2016-03-01

    Nowadays many people are affected by arthritis, a condition of the joints with limited prevention measures, but with various options of treatment the most radical of which is surgical. In order for surgery to be successful, it can make use of careful analysis of patient-based models generated from medical images, usually by manual segmentation. In this work we show how to automate the segmentation of a crucial and complex joint -- the knee. To achieve this goal we rely on our novel way of representing a 3D voxel volume as a hierarchical structure of partitions which we have named Image Partition Forest (IPF). The IPF contains several partition layers of increasing coarseness, with partitions nested across layers in the form of adjacency graphs. On the basis of a set of properties (size, mean intensity, coordinates) of each node in the IPF we classify nodes into different features. Values indicating whether or not any particular node belongs to the femur or tibia are assigned through node filtering and node-based region growing. So far we have evaluated our method on 15 MRI knee images. Our unsupervised segmentation compared against a hand-segmented gold standard has achieved an average Dice similarity coefficient of 0.95 for femur and 0.93 for tibia, and an average symmetric surface distance of 0.98 mm for femur and 0.73 mm for tibia. The paper also discusses ways to introduce stricter morphological and spatial conditioning in the bone labelling process.

  1. Monomial Crystals and Partition Crystals

    NASA Astrophysics Data System (ADS)

    Tingley, Peter

    2010-04-01

    Recently Fayers introduced a large family of combinatorial realizations of the fundamental crystal B(Λ0) for ^sln, where the vertices are indexed by certain partitions. He showed that special cases of this construction agree with the Misra-Miwa realization and with Berg's ladder crystal. Here we show that another special case is naturally isomorphic to a realization using Nakajima's monomial crystal.

  2. Set covering, partition and packing

    SciTech Connect

    Hulme, B.L.; Baca, L.S.

    1984-03-01

    Set covering problems are known to be solvable by Boolean algebraic methods. This report shows that set partition and set packing problems can be solved by the same algebraic methods because these problems can be converted into covering problems. Many applications are possible including security patrol assignment which is used as an example.

  3. METAL PARTITIONING IN COMBUSTION PROCESSES

    EPA Science Inventory

    This article summarizes ongoing research efforts at the National Risk Management Research Laboratory of the U.S. Environmental Protection Agency examining [high temperature] metal behavior within combustion environments. The partitioning of non-volatile (Cr and Ni), semi-volatil...

  4. Diffusion and Partitioning of Fluorescent Lipid Probes in Phospholipid Monolayers

    PubMed Central

    Gudmand, M.; Fidorra, Matthias; Bjørnholm, T.; Heimburg, T.

    2009-01-01

    The pressure-dependent diffusion and partitioning of single lipid fluorophores in DMPC and DPPC monolayers were investigated with the use of a custom-made monolayer trough mounted on a combined fluorescence correlation spectroscopy (FCS) and wide-field microscopy setup. It is shown that lipid diffusion, which is essential for the function of biological membranes, is heavily influenced by the lateral pressure and phase of the lipid structure. Both of these may change dynamically during, e.g., protein adsorption and desorption processes. Using FCS, we measured lipid diffusion coefficients over a wide range of lateral pressures in DMPC monolayers and fitted them to a free-area model as well as the direct experimental observable mean molecular area. FCS measurements on DPPC monolayers were also performed below the onset of the phase transition (Π < 5 mN/m). At higher pressures, FCS was not applicable for measuring diffusion coefficients in DPPC monolayers. Single-molecule fluorescence microscopy and differential scanning calorimetry clearly showed that this was due to heterogeneous partitioning of the lipid fluorophores in condensed phases. The results were compared with dye partitioning in giant lipid vesicles. These findings are significant in relation to the application of lipid fluorophores to study diffusion in both model systems and biological systems. PMID:19486682

  5. Bitplane Image Coding With Parallel Coefficient Processing.

    PubMed

    Auli-Llinas, Francesc; Enfedaque, Pablo; Moure, Juan C; Sanchez, Victor

    2016-01-01

    Image coding systems have been traditionally tailored for multiple instruction, multiple data (MIMD) computing. In general, they partition the (transformed) image in codeblocks that can be coded in the cores of MIMD-based processors. Each core executes a sequential flow of instructions to process the coefficients in the codeblock, independently and asynchronously from the others cores. Bitplane coding is a common strategy to code such data. Most of its mechanisms require sequential processing of the coefficients. The last years have seen the upraising of processing accelerators with enhanced computational performance and power efficiency whose architecture is mainly based on the single instruction, multiple data (SIMD) principle. SIMD computing refers to the execution of the same instruction to multiple data in a lockstep synchronous way. Unfortunately, current bitplane coding strategies cannot fully profit from such processors due to inherently sequential coding task. This paper presents bitplane image coding with parallel coefficient (BPC-PaCo) processing, a coding method that can process many coefficients within a codeblock in parallel and synchronously. To this end, the scanning order, the context formation, the probability model, and the arithmetic coder of the coding engine have been re-formulated. The experimental results suggest that the penalization in coding performance of BPC-PaCo with respect to the traditional strategies is almost negligible. PMID:26441420

  6. Coefficients of Effective Length.

    ERIC Educational Resources Information Center

    Edwards, Roger H.

    1981-01-01

    Under certain conditions, a validity Coefficient of Effective Length (CEL) can produce highly misleading results. A modified coefficent is suggested for use when empirical studies indicate that underlying assumptions have been violated. (Author/BW)

  7. Partitioning of olive oil antioxidants between oil and water phases.

    PubMed

    Rodis, Panayotis S; Karathanos, Vaios T; Mantzavinou, Antonia

    2002-01-30

    The partition coefficient (K(p)) of the natural phenolic antioxidant compounds in the olive fruit between aqueous and olive oil phases was determined. The antioxidants of olive oil are either present in the olive fruit or formed during the olive oil extraction process. The antioxidants impart stability to and determine properties of the oil and are valuable from the nutritional point of view. The olive oil antioxidants are amphiphilic in nature and are more soluble in the water than in the oil phase. Consequently, a large amount of the antioxidants is lost with the wastewater during processing. The determination of antioxidants was performed using HPLC, and the K(p) was estimated to be from as low as 0.0006 for oleuropein to a maximum of 1.5 for 3,4-DHPEA-EA (di-hydroxy-phenyl-ethanol-elenolic acid, oleuropein aglycon). Henry's law fitted very well to the experimental data. The partition coefficients were also estimated by applying the activity coefficients of the antioxidants in the two phases using a predictive group contribution method, the UNIFAC equation. The K(p) values estimated with UNIFAC method were of the same order of magnitude but varied from the experimental values. Nevertheless, this method may be a rough predictive tool for process optimization or design. Because the K(p) values were very low, some changes in the process are recommended in order to achieve a higher concentration of antioxidants in the oil. A temperature increase may lead to increasing the partition coefficient. Also, limiting the quantity of water during oil extraction could be a basis for designing alternative processes for increasing the antioxidant concentration in the olive oil. PMID:11804535

  8. Some trees with partition dimension three

    NASA Astrophysics Data System (ADS)

    Fredlina, Ketut Queena; Baskoro, Edy Tri

    2016-02-01

    The concept of partition dimension of a graph was introduced by Chartrand, E. Salehi and P. Zhang (1998) [2]. Let G(V, E) be a connected graph. For S ⊆ V (G) and v ∈ V (G), define the distance d(v, S) from v to S is min{d(v, x)|x ∈ S}. Let Π be an ordered partition of V (G) and Π = {S1, S2, ..., Sk }. The representation r(v|Π) of vertex v with respect to Π is (d(v, S1), d(v, S2), ..., d(v, Sk)). If the representations of all vertices are distinct, then the partition Π is called a resolving partition of G. The partition dimension of G is the minimum k such that G has a resolving partition with k partition classes. In this paper, we characterize some classes of trees with partition dimension three, namely olive trees, weeds, and centipedes.

  9. Equilibrium partitioning of Ficoll in composite hydrogels.

    PubMed

    Kosto, Kimberly B; Panuganti, Swapna; Deen, William M

    2004-09-15

    Equilibrium partition coefficients (phi, the concentration in the gel divided by that in free solution) of fluorescein-labeled Ficolls in pure agarose and agarose-dextran composite gels were measured as a function of gel composition and Ficoll size. The four narrow fractions of Ficoll, a spherical polysaccharide, had Stokes-Einstein radii ranging from 2.7 to 5.9 nm. Gels with agarose volume fractions of 0.040 and 0.080 were studied, with dextran volume fractions (calculated as if the chain were a long fiber) up to 0.011. As expected, phi generally decreased as the Ficoll size increased (for a given gel composition) or as the amount of dextran incorporated into the gel increased (for a given agarose concentration and Ficoll size). The decrease in phi that accompanied dextran addition was predicted well by an excluded volume theory in which agarose and dextran were both treated as rigid, straight, randomly positioned and oriented fibers. Modeling dextran as a spherical coil within a fibrous agarose gel produced much less accurate predictions. The diffusional permeabilities of these gels were assessed by combining the current partitioning data with relative diffusivities (Kd, the diffusivity in the gel divided by that in free solution) reported previously. The values of phi Kd for a synthetic gel with 8.0% agarose and 1.1% dextran (by volume) were found to be very similar to those for the glomerular basement membrane, a physiologically important material which also has a total solids content of approximately 10%. PMID:15341852

  10. Traceds: An Experimental Trace Element Partitioning Database

    NASA Astrophysics Data System (ADS)

    Nielsen, R. L.; Ghiorso, M. S.

    2014-12-01

    calibration datasets, for petrologists to find appropriate partition coefficients, and to help reviewers evaluate models submitted for publication. As an additional benefit, we hope that this investigation will help to set new publication standards for experimental data. The database will be assessable at the portal lepr.ofm-research.org.

  11. Partitioning of differently sized poly(ethylene glycol)s into OmpF porin.

    PubMed Central

    Rostovtseva, Tatiana K; Nestorovich, Ekaterina M; Bezrukov, Sergey M

    2002-01-01

    To understand the physics of polymer equilibrium and dynamics in the confines of ion channel pores, we study partitioning of poly(ethylene glycol)s (PEGs) of different molecular weights into the bacterial porin, OmpF. Thermodynamic and kinetic parameters of partitioning are deduced from the effects of polymer addition on ion currents through single OmpF channels reconstituted into planar lipid bilayer membranes. The equilibrium partition coefficient is inferred from the average reduction of channel conductance in the presence of PEG; rates of polymer exchange between the pore and the bulk are estimated from PEG-induced conductance noise. Partition coefficient as a function of polymer weight is best fitted by a "compressed exponential" with the compression factor of 1.65. This finding demonstrates that PEG partitioning into the OmpF channel pore has sharper dependence on polymer molecular weight than predictions of hard-sphere, random-flight, or scaling models. A 1360-Da polymer separates regimes of partitioning and exclusion. Comparison of its characteristic size with the size of a 2200-Da polymer previously found to separate these regimes for the alpha-toxin shows good agreement with the x-ray structural data for these channels. The PEG-induced conductance noise is compatible with the polymer mobility reduced inside the OmpF pore by an order of magnitude relatively to its value in bulk solution. PMID:11751305

  12. Partitioning of Organic Contaminants and Tracer Compounds in a CO2-Brine System at High Salinities

    NASA Astrophysics Data System (ADS)

    Thomas, B.; Kharaka, Y. K.; Rosenbauer, R. J.; Janesko, D.; Trutna, J.

    2011-12-01

    Nonionic chemical species including gases and organic compounds partition between the fluid CO2 phase and the aqueous phase in geologic carbon sequestration systems. The injection and migration of CO2 in geologic carbon sequestration systems covers a wide range of pressure and temperature, so it is important to understand the partitioning of these compounds at various P-T conditions and salinities. Geochemical data is particularly lacking for the partitioning of organic contaminant compounds and tracer compounds between highly saline brines and CO2. Most groundwater is relatively low in organic contaminants; however, groundwater associated with hydrocarbon migration pathways, enhanced oil recovery (EOR), and hydrocarbon storage or extraction can contain high concentrations of known organic contaminants. CO2 injection in these systems may therefore be more likely to result in partitioning of contaminants into the CO2 phase that could, upon migration, represent an important risk to groundwater resources. We present the experimental apparatus and determination of partition coefficients between brine and CO2 for a suite of compounds including benzene, toluene, ethylbenzene, xylene (BTEX), and low molecular weight polynuclear aromatic hydrocarbons (PAHs). In addition, partition coefficients are determined for the important gas phase tracer compounds: SF6 and Krypton covering a P-T envelope consistent with CO2 injection and plume migration to the near surface.

  13. The effect of sulphur in silicate melt on partitioning of Ni and other trace elements

    NASA Astrophysics Data System (ADS)

    Wood, Bernard; Kiseeva, Ekaterina; Wohlers, Anke

    2016-04-01

    It has been suggested that variations in the sulphur contents of silicate melts affect the partitioning of trace chalcophile elements, particularly Ni, between silicate melt and crystalline phases such as olivine [1]. The general idea is that Ni (and other elements) complex with sulphur dissolved in the melt, thereby stabilising Ni in the melt and reducing the olivine-melt partition coefficient DNi. More recent experiments lead to the assertion that any sulphur effect, if present is small and can be ignored [2]. Experiments aimed at addressing this problem have, however, struggled with the difficulty that the maximum S contents of olivine- precipitating melts do not exceed ~0.5% even at sulphide saturation. Any effect is therefore difficult to establish unequivocally. Here we have taken advantage of the fact that experiments under strongly reducing conditions, where FeO activity in the silicate melt is very low lead to much higher concentrations of S than those associated with olivine precipitation. We have therefore investigated partitioning between sulphide melts and haplobasaltic silicate melt at concentrations of FeO between 0.3 and 10 weight% in order to investigate the "sulphur-effect" on partitioning. At the lowest FeO contents we are able to drive the S content of the melt to 10 weight% enabling the effects to be unequivocally established. We find that partitioning of strongly lithophile elements Nb, Ta, U, REE partition more strongly out of silicate melt as its S content increases. The effect is, surprisingly, predominantly due to the effect of S on the activity coefficient of FeO in the melt. In contrast strongly chalcophile Ni, Cu, Ag partition more strongly into the melt as its S content increases. This is due to a dramatic lowering of the activity coefficients of these elements in the silicate as S increases. Elements which show little effect of S include Pb, Co and In. The results enable us to predict the effects of sulphur on olivine-melt and

  14. Fluorescent solute-partitioning characterization of layered soft contact lenses.

    PubMed

    Dursch, T J; Liu, D E; Oh, Y; Radke, C J

    2015-03-01

    Partitioning of aqueous packaging, wetting, and care-solution agents into and out of soft contact lenses (SCLs) is important for improving wear comfort and also for characterizing lens physico-chemical properties. We illustrate both features of partitioning by application of fluorescent-solute partitioning into DAILIES TOTAL1® (delefilcon A) water-gradient SCLs, which exhibit a layered structure of a silicone-hydrogel (SiHy) core sandwiched between thin surface-gel layers. Two-photon fluorescence confocal laser-scanning microscopy and attenuated total-reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) characterize the lens and assess uptake profiles of six prototypical fluorescent solutes. Comparison of solute uptake in a SiHy-core prototype lens (i.e., O2OPTIX(TM)) validates the core SiHy structure of DAILIESTOTAL1®. To establish surface-layer charge, partition coefficients and water contents are obtained for aqueous pH values of 4 and 7.4. Solute fluorescence-intensity profiles clearly confirm a layered structure for the DAILIES TOTAL1® lenses. In all cases, aqueous solute partition coefficients are greater in the surface layers than in the SiHy core, signifying higher water in the surface gels. ATR-FTIR confirms surface-layer mass water contents of 82±3%. Water uptake and hydrophilic-solute uptake at pH 4 compared with that at pH 7.4 reveal that the surface-gel layers are anionic at physiologic pH 7.4, whereas both the SiHy core and O2OPTIX™ (lotrafilcon B) are nonionic. We successfully confirm the layered structure of DAILIES TOTAL1®, consisting of an 80-μm-thick SiHy core surrounded by 10-μm-thick polyelectrolyte surface-gel layers of significantly greater water content and aqueous solute uptake compared with the core. Accordingly, fluorescent-solute partitioning in SCLs provides information on gel structure and composition, in addition to quantifying uptake and release amounts and rates. PMID:25484335

  15. Liquid-air partition coefficients of 1,1-difluoroethane (HFC152a), 1,1,1-trifluoroethane (HFC143a), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1,1,2,2-pentafluoroethane (HFC125) and 1,1,1,3,3-pentafluoropropane (HFC245fa).

    PubMed

    Ernstgård, Lena; Lind, Birger; Andersen, Melvin E; Johanson, Gunnar

    2010-01-01

    Blood-air and tissue-blood coefficients (lambda) are essential to characterize the uptake and disposition of volatile substances, e.g. by physiologically based pharmacokinetic (PBPK) modelling. Highly volatile chemicals, including many hydrofluorocarbons (HFC) have low solubility in liquid media. These characteristics pose challenges for determining lambda values. A modified head-space vial equilibrium method was used to determine lambda values for five widely used HFCs. The method is based on automated head-space gas chromatography and injection of equal amount of chemical in two head-space vials with identical air phase volumes but different volumes of the liquid phase. The liquids used were water (physiological saline), fresh human blood, and olive oil. The average lambda values (n = 8) were as follows: 1,1-difluoroethane (HFC152a) - 1.08 (blood-air), 1.11 (water-air) and 5.6 (oil-air); 1,1,1-trifluoroethane (HFC143a) - 0.15, 0.15 and 1.90; 1,1,1,2-tetrafluoroethane (HFC134a) - 0.36, 0.35 and 3.5; 1,1,1,2,2-pentafluoroethane (HFC125) - 0.083, 0.074 and 1.71; and 1,1,1,3,3-pentafluoropropane (HFC245fa) - 0.62, 0.58 and 12.1. The lambda values appeared to be concentration-independent in the investigated range (2-200 ppm). In spite of the low lambda values, the method errors were modest, with coefficients of variation of 9, 11 and 10% for water, blood and oil, respectively. PMID:19701883

  16. Influence of the partitioning of osmolytes by the cytoplasm on the passive response of cells to osmotic loading.

    PubMed

    Albro, Michael B; Petersen, Leah E; Li, Roland; Hung, Clark T; Ateshian, Gerard A

    2009-12-01

    Due to the dense organization of organelles, cytoskeletal elements, and protein complexes that make up the intracellular environment, it is likely that membrane-permeant solutes may be excluded from a fraction of the interstitial space of the cytoplasm via steric restrictions, electrostatic interactions, and other long-range intermolecular forces. This study investigates the hypothesis that the intracellular partitioning of membrane-permeant solutes manifests itself as a partial volume recovery in response to hyperosmotic loading, based on prior theoretical and biomimetic experimental studies. Osmotic loading experiments are performed on immature bovine chondrocytes using culture conditions where regulatory volume responses are shown to be insignificant. Osmotic loading with membrane-permeant glycerol (92 Da) and urea (60 Da) are observed to produce partial volume recoveries consistent with the proposed hypothesis, whereas loading with 1,2-propanediol (76 Da) produces complete volume recovery. Combining these experimental results with the previous theoretical framework produces a measure for the intracellular partition coefficient of each of these solutes. At 1000 mOsm, 1,2-propanediol is the only osmolyte to yield a partition coefficient not statistically different from unity, kappa(p)(i) = 1.00 +/- 0.02. For glycerol, the partition coefficient increases with osmolarity from kappa(p)(i) = 0.48 +/- 0.19 at 200 mOsm to kappa(p)(i) = 0.80 +/- 0.07 at 1000 mOsm; urea exhibits no such dependence, with an average value of kappa(p)(i) = 0.87 +/- 0.07 for all osmolarities from 200 to 1000 mOsm. The finding that intracellular partitioning of membrane-permeant solutes manifests itself as a partial volume recovery under osmotic loading offers a simple method for characterizing the partition coefficient. These measurements suggest that significant partitioning may occur even for small membrane-permeant osmolytes. Furthermore, a positive correlation is observed, suggesting

  17. Measuring Seebeck Coefficient

    NASA Technical Reports Server (NTRS)

    Snyder, G. Jeffrey (Inventor)

    2015-01-01

    A high temperature Seebeck coefficient measurement apparatus and method with various features to minimize typical sources of errors is described. Common sources of temperature and voltage measurement errors which may impact accurate measurement are identified and reduced. Applying the identified principles, a high temperature Seebeck measurement apparatus and method employing a uniaxial, four-point geometry is described to operate from room temperature up to 1300K. These techniques for non-destructive Seebeck coefficient measurements are simple to operate, and are suitable for bulk samples with a broad range of physical types and shapes.

  18. Experimental determination of U and Th partitioning between clinopyroxene and natural and synthetic basaltic liquid

    NASA Technical Reports Server (NTRS)

    Latourrette, T. Z.; Burnett, D. S.

    1992-01-01

    Experimental measurements of U and the partition coefficients between clinopyroxene and synthetic and natural basaltic liquid are presented. The results demonstrate that crystal-liquid U-Th fractionation is fO2-dependent and that U in terrestrial magmas is not entirely tetravalent. During partial melting, the liquid will have a Th/U ratio less than the clinopyroxene in the source. The observed U-238 - Th-230 disequilibrium in MORB requires that the partial melt should have a U/Th ratio greater than the bulk source and therefore cannot result from clinopyroxene-liquid partitioning. Further, the magnitudes of the measured partition coefficients are too small to generate significant U-Th fractionation in either direction. Assuming that clinopyroxene contains the bulk of the U and Th in the MORB source, the results indicate that U-238 - Th-230 disequilibrium in MORB may not be caused by partial melting at all.

  19. Influence of pressure derivative of partition function on thermodynamic properties of non-local thermodynamic equilibrium thermal plasma

    NASA Astrophysics Data System (ADS)

    Singh, Gurpreet; Sharma, Rohit; Singh, Kuldip

    2015-09-01

    Thermodynamic properties (compressibility coefficient Z γ , specific heat at constant volume c v , adiabatic coefficient γ a , isentropic coefficient γ i s e n , and sound speed c s ) of non-local thermodynamic equilibrium hydrogen thermal plasma have been investigated for different values of pressure and non-equilibrium parameter θ (=Te/Th) in the electron temperature range from 6000 K to 60 000 K. In order to estimate the influence of pressure derivative of partition function on thermodynamic properties, two cases have been considered: (a) in which pressure derivative of partition function is taken into account in the expressions and (b) without pressure derivative of partition function in their expressions. Here, the case (b) represents expressions already available in literature. It has been observed that the temperature from which pressure derivative of partition function starts influencing a given thermodynamic property increases with increase of pressure and non-equilibrium parameter θ. Thermodynamic property in the case (a) is always greater than its value in the case (b) for compressibility coefficient and specific heat at constant volume, whereas for adiabatic coefficient, isentropic coefficient, and sound speed, its value in the case (a) is always less than its value in the case (b). For a given value of θ, the relationship of compressibility coefficient with degree of ionization depends upon pressure in the case (a), whereas it is independent of pressure in the case (b). Relative deviation between the two cases shows that the influence of pressure derivative of partition function is significantly large and increases with the augmentation of pressure and θ for compressibility coefficient, specific heat at constant volume, and adiabatic coefficient, whereas for isentropic coefficient and sound speed, it is marginal even at high values of pressure and non-equilibrium parameter θ.

  20. Bounding the Bogoliubov coefficients

    SciTech Connect

    Boonserm, Petarpa; Visser, Matt

    2008-11-15

    While over the last century or more considerable effort has been put into the problem of finding approximate solutions for wave equations in general, and quantum mechanical problems in particular, it appears that as yet relatively little work seems to have been put into the complementary problem of establishing rigourous bounds on the exact solutions. We have in mind either bounds on parametric amplification and the related quantum phenomenon of particle production (as encoded in the Bogoliubov coefficients), or bounds on transmission and reflection coefficients. Modifying and streamlining an approach developed by one of the present authors [M. Visser, Phys. Rev. A 59 (1999) 427-438, (arXiv:quant-ph/9901030)], we investigate this question by developing a formal but exact solution for the appropriate second-order linear ODE in terms of a time-ordered exponential of 2x2 matrices, then relating the Bogoliubov coefficients to certain invariants of this matrix. By bounding the matrix in an appropriate manner, we can thereby bound the Bogoliubov coefficients.

  1. Nickel and Cobalt Partitioning Between Spinel and Basaltic Melt: Applications to Planetary Basalt Suites

    NASA Technical Reports Server (NTRS)

    Righter, K.

    2002-01-01

    New experimental spinel/melt partition coefficients for Ni and Co have been measured in basalt samples with natural levels of Ni and Co, are lower than previous high doping experiments, and are applied to several planetary basalt suites. Additional information is contained in the original extended abstract.

  2. A Henry's Law Test for Experimental Partitioning Studies of Iron Meteorites

    NASA Technical Reports Server (NTRS)

    Chabot, N. L.; Campbell, A. J.; Humayun, M.; Agee, C. B.

    2001-01-01

    Low-level doped solid metal/liquid metal experiments analyzed by laser ablation ICP-MS allow Henry's Law to be tested. The results indicate Henry's Law is obeyed and the experimental partition coefficients can be applied to iron meteorites. Additional information is contained in the original extended abstract.

  3. Evidence for equilibrium conditions during the partitioning of nickel between olivine and komatiite liquids.

    USGS Publications Warehouse

    Budahn, J.R.

    1986-01-01

    Olivine-liquid partition coefficients for Ni(DNi), calculated from Ni vs MgO abundance variations in komatiite series basalts, compare favourably with experimentally determined values, if Ni variations in olivine-controlled basalts can be modelled with an equation that assumes equilibrium between the entire olivine crystal and its coexisting liquid.-J.A.Z.

  4. Temperature and composition dependencies of trace element partitioning - Olivine/melt and low-Ca pyroxene/melt

    NASA Technical Reports Server (NTRS)

    Colson, R. O.; Mckay, G. A.; Taylor, L. A.

    1988-01-01

    This paper presents a systematic thermodynamic analysis of the effects of temperature and composition on olivine/melt and low-Ca pyroxene/melt partitioning. Experiments were conducted in several synthetic basalts with a wide range of Fe/Mg, determining partition coefficients for Eu, Ca, Mn, Fe, Ni, Sm, Cd, Y, Yb, Sc, Al, Zr, and Ti and modeling accurately the changes in free energy for trace element exchange between crystal and melt as functions of the trace element size and charge. On the basis of this model, partition coefficients for olivine/melt and low-Ca pyroxene/melt can be predicted for a wide range of elements over a variety of basaltic bulk compositions and temperatures. Moreover, variations in partition coeffeicients during crystallization or melting can be modeled on the basis of changes in temperature and major element chemistry.

  5. Cylindric partitions, {{\\boldsymbol{ W }}}_{r} characters and the Andrews-Gordon-Bressoud identities

    NASA Astrophysics Data System (ADS)

    Foda, O.; Welsh, T. A.

    2016-04-01

    We study the Andrews-Gordon-Bressoud (AGB) generalisations of the Rogers-Ramanujan q-series identities in the context of cylindric partitions. We recall the definition of r-cylindric partitions, and provide a simple proof of Borodin’s product expression for their generating functions, that can be regarded as a limiting case of an unpublished proof by Krattenthaler. We also recall the relationships between the r-cylindric partition generating functions, the principal characters of {\\hat{{sl}}}r algebras, the {{\\boldsymbol{ M }}}r r,r+d minimal model characters of {{\\boldsymbol{ W }}}r algebras, and the r-string abaci generating functions, providing simple proofs for each. We then set r = 2, and use two-cylindric partitions to re-derive the AGB identities as follows. Firstly, we use Borodin’s product expression for the generating functions of the two-cylindric partitions with infinitely long parts, to obtain the product sides of the AGB identities, times a factor {(q;q)}∞ -1, which is the generating function of ordinary partitions. Next, we obtain a bijection from the two-cylindric partitions, via two-string abaci, into decorated versions of Bressoud’s restricted lattice paths. Extending Bressoud’s method of transforming between restricted paths that obey different restrictions, we obtain sum expressions with manifestly non-negative coefficients for the generating functions of the two-cylindric partitions which contains a factor {(q;q)}∞ -1. Equating the product and sum expressions of the same two-cylindric partitions, and canceling a factor of {(q;q)}∞ -1 on each side, we obtain the AGB identities.

  6. About Thinning Invariant Partition Structures

    NASA Astrophysics Data System (ADS)

    Starr, Shannon; Vermesi, Brigitta; Wei, Ang

    2012-08-01

    Bernoulli- p thinning has been well-studied for point processes. Here we consider three other cases: (1) sequences ( X 1, X 2,…); (2) gaps of such sequences ( X n+1- X 1) n∈ℕ; (3) partition structures. For the first case we characterize the distributions which are simultaneously invariant under Bernoulli- p thinning for all p∈(0,1]. Based on this, we make conjectures for the latter two cases, and provide a potential approach for proof. We explain the relation to spin glasses, which is complementary to important previous work of Aizenman and Ruzmaikina, Arguin, and Shkolnikov.

  7. Influence of residual surfactants on DNAPL characterization using partitioning tracers

    NASA Astrophysics Data System (ADS)

    Cho, Jaehyun; Annable, Michael D.; Rao, P. Suresh C.

    2004-08-01

    The partitioning tracer technique is among the DNAPL source-zone characterization methods being evaluated, while surfactant in-situ flushing is receiving attention as an innovative technology for enhanced source-zone cleanup. Here, we examine in batch and column experiments the magnitude of artifacts introduced in estimating DNAPL content when residual surfactants are present. The batch equilibrium tests, using residual surfactants ranging from 0.05 to 0.5 wt.%, showed that as the surfactant concentrations increased, the tracer partition coefficients decreased linearly for sodium hexadecyl diphenyl oxide disulfonate (DowFax 8390), increased linearly for polyoxyethylene (10) oleyl ether (Brij 97), and decreased slightly or exhibited no observable trend for sodium dihexyl sulfosuccinate (AMA 80). Results from column tests using clean sand with residual DowFax 8390 and Tetrachloroethylene (PCE) were consistent with those of batch tests. In the presence of DowFax 8390 (less than 0.5 wt.%), the PCE saturations were underestimated by up to 20%. Adsorbed surfactants on a loamy sand with positively charged oxides showed false indications of PCE saturation based on partitioning tracers in the absence of PCE. Using no surfactant (background soil) gave a false PCE saturation of 0.0004, while soil contacted by AMA 80, Brij 97, and DowFax 8390 gave false PCE saturations of 0.0024, 0.043, and 0.23, respectively.

  8. Uranium partitioning under acidic conditions in a sandy soil aquifer

    SciTech Connect

    Johnson, W.H. |; Serkiz, S.M.; Johnson, L.M.

    1995-07-01

    The partitioning of uranium in an aquifer down gradient of two large mixed waste sites was examined with respect to the solution and soil chemistry (e.g., pH redox potential and contaminant concentration) and aqueous-phase chemical speciation. This involved generation of field-derived, batch sorption, and reactive mineral surface sorption data. Field-derived distribution coefficients for uranium at these waste sites were found to vary between 0.40 and 15,000. Based on thermodynamic speciation modeling and a comparison of field and laboratory data, gibbsite is a potential reactive mineral surface present in modified soils at the sites. Uranium partitioning data are presented from field samples and laboratory studies of background soil and the mineral surface gibbsite. Mechanistic and empirical sorption models fit to the field-derived uranium partitioning data show an improvement of over two orders of magnitude, as measured by the normalized sum of errors squared, when compared with the single K{sub d} model used in previous risk work. Models fit to batch sorption data provided a better fit of sorbed uranium than do models fit to the field-derived data.

  9. On some trees having partition dimension four

    NASA Astrophysics Data System (ADS)

    Ida Bagus Kade Puja Arimbawa, K.; Baskoro, Edy Tri

    2016-02-01

    In 1998, G. Chartrand, E. Salehi and P. Zhang introduced the notion of partition dimension of a graph. Since then, the study of this graph parameter has received much attention. A number of results have been obtained to know the values of partition dimensions of various classes of graphs. However, for some particular classes of graphs, finding of their partition dimensions is still not completely solved, for instances a class of general tree. In this paper, we study the properties of trees having partition dimension 4. In particular, we show that, for olive trees O(n), its partition dimension is equal to 4 if and only if 8 ≤ n ≤ 17. We also characterize all centipede trees having partition dimension 4.

  10. Sediment-porewater partitioning of polynuclear aromatic hydrocarbons (PAHs)

    SciTech Connect

    Maruya, K.A.; Risebrough, R.W.; Horne, A.J.

    1996-10-01

    Quantifying the distribution of hydrophobic organic compounds between contaminated sediment and interstitial water is key to understanding their fate and effects in aquatic ecosystems. Sampling during the wet and dry-seasons in San Francisco Bay has revealed that the extent of partitioning, measured as the apparent sediment organic carbon-porewater distribution coefficient (K{sub oc}{prime}), was positively correlated with the octanol-water distribution coefficient (K{sub ow}) for a suite of pyrogenically-derived, 2-6 ring PAHs. In addition, sediment PAHs (organic carbon basis) were associated with the silt fraction and organic carbon content. Moreover, K{sub oc}{prime} decreased along an intertidal gradient and was an order of magnitude higher during the wet season when runoff into the Bay was high. Our results provide evidence that substrate heterogeneity, a factor not accounted for in simple equilibrium models, can significantly alter the distribution of PAHs in this environment.

  11. The grand partition function of dilute biregular solutions

    NASA Astrophysics Data System (ADS)

    Nagamori, Meguru; Ito, Kimihisa; Tokuda, Motonori

    1994-10-01

    It has been demonstrated that the grand partition function (GPF) of biregular solutions contains in one single equation such thermodynamic principles as Henry's law, Raoult's law, the Gibbs-Duhem relation, Raoultian activity coefficients and their finite power series, Wagner's rec-iprocity, Schenck-Frohberg-Steinmetz's interchange, Lupis-Elliott's additivity, Mori-Morooka's disparity, and Darken's quadratic formalism. The logarithm of the Raoultian activity coefficient of species i, In γi should not be expressed by the Taylor series expansion, lest its truncation infringe the Gibbs-Duhem equation. The GPF methodology establishes that In γi, is not a vector but a scalar point function, free from any path dependence. While Darken's quadratic formalism employs three parameters to describe a ternary solution, the present biregularity approximation offers an alternative using seven empirical parameters, in case better accuracy is needed.

  12. Chemical amplification based on fluid partitioning in an immiscible liquid

    DOEpatents

    Anderson, Brian L.; Colston, Bill W.; Elkin, Christopher J.

    2010-09-28

    A system for nucleic acid amplification of a sample comprises partitioning the sample into partitioned sections and performing PCR on the partitioned sections of the sample. Another embodiment of the invention provides a system for nucleic acid amplification and detection of a sample comprising partitioning the sample into partitioned sections, performing PCR on the partitioned sections of the sample, and detecting and analyzing the partitioned sections of the sample.

  13. Displaying multimedia environmental partitioning by triangular diagrams

    SciTech Connect

    Lee, S.C.; Mackay, D.

    1995-11-01

    It is suggested that equilateral triangular diagrams are a useful method of depicting the equilibrium partitioning of organic chemicals among the three primary environmental media of the atmosphere, the hydrosphere, and the organosphere (natural organic matter and biotic lipids and waxes). The technique is useful for grouping chemicals into classes according to their partitioning tendencies, for depicting the incremental effects of substituents such as alkyl groups and chlorine, and for showing how partitioning changes in response to changes in temperature.

  14. Partition of ionized and neutral halogenated phenols between octanol and water, lipid membranes and water, and sarcoplasmic reticulum and water

    NASA Astrophysics Data System (ADS)

    Word, Robert Campbell

    An understanding of the distribution of toxic compounds between biological and aqueous media is important to assessing their toxicology and risk to the environment. Of great interest to this problem is the validity of a critical environmental parameter: the octanol-water partition coefficient. Since the usefulness of this parameter has been questioned, we measured the octanol-water, lipid membrane-water, alkane-water, and biomembrane-water partition of nine halogenated phenols (2,4,6-trifluorophenol, pentafluorophenol, 2,4,6-trichlorophenol, 2,3,4,5-tetrachlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol, 2,4,6-tribromophenol, pentabromophenol, and 2,4,6-triiodophenol). We have addressed the role of halophenol charge, concentration, and size as well as ionic strength, membrane composition, and temperature in partition and free energy of transfer of halophenols. We have confirmed that octanol-water and membrane-water partition coefficients of neutral halophenols are similar. In contrast, we found that membrane-water partition coefficients of ionized halophenols are 800 times greater than octanol-water partition coefficients. Membrane-water partition exhibits saturation effects that we have modeled using Langmuir isotherms and the Grahame solution to the Gouy-Chapman model of an electrical double layer. The model supports the hypothesis that neutral halophenols saturate membranes via space-filling whereas ionized halophenols saturate membranes electrostatically. The octanol-water partition coefficient of ionized 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP) is proportional to ionic strength. This finding is consistent with a cation-TeCP- ion-pair transfer mechanism that maintains electroneutrality of the phases. In contrast, an increase in ionic strength reduces membrane electrostatic saturation, consistent with counter-ion screening of membrane surface charge. Membrane-water partition of 2,3,4,6-TeCP is nearly independent of lipid acyl length and carbonyl dipole

  15. Seasonality and interspecies differences in particle/gas partitioning of PAHs observed by the Integrated Atmospheric Deposition Network (IADN)

    NASA Astrophysics Data System (ADS)

    Galarneau, Elisabeth; Bidleman, Terry F.; Blanchard, Pierrette

    This study presents partitioning data from eight locations in the Laurentian Great Lakes region collected by the Integrated Atmospheric Deposition Network (IADN) over periods ranging from 1 to 6 years. Particle/gas partitioning varies sufficiently between sites in the Great Lakes region to preclude the use of a uniform temperature dependence for its description. Site-specific parameters for describing partitioning as a function of inverse temperature are presented. Relationships between partitioning of appreciably semivolatile PAHs and saturated vapour pressure at Chicago (IIT) and Sturgeon Point (STP) demonstrate that anthracene, benz[a]anthracene and retene behave differently than phenanthrene, fluoranthene, pyrene and chrysene+triphenylene. Possible reasons for these differences include interspecies variations in the fraction of atmospherically non-exchangeable, though analytically extractable, PAHs on particles and differences in soot-air partition coefficients as they relate to saturated vapour pressure. The observed interspecies differences are not consistent with sampling artefacts such as filter adsorption or sorbent breakthrough. At IIT, but not at STP, values of the slope of the relationship between the log partition coefficient and log vapour pressure vary in a manner opposing the annual temperature cycle. A comparison of partitioning calculated by a combined absorption/adsorption model shows good predictability at Chicago but underestimates values at a rural site (Eagle Harbor, EGH) by an order of magnitude.

  16. Understanding viral partitioning in two-phase aqueous nonionic micellar systems: 2. Effect of entrained micelle-poor domains.

    PubMed

    Kamei, Daniel T; King, Jonathan A; Wang, Daniel I C; Blankschtein, Daniel

    2002-04-20

    Unlike the partitioning behavior of hydrophilic, water-soluble proteins, the partitioning behavior of viruses in the two-phase aqueous nonionic n-decyl tetra(ethylene oxide) (C10E4) micellar system cannot be fully explained using the excluded-volume theory developed recently by our group. A central assumption underlying the excluded-volume theory--that macroscopic phase separation equilibrium is attained--was therefore challenged experimentally and theoretically. Photographs of the two-phase aqueous C10E4 micellar system were taken for different volume ratios to demonstrate that the entrainment of micelle-poor (virus-rich) domains in the macroscopic, top, micelle-rich phase decreases with a decrease in the volume ratio. Partitioning experiments were then conducted with the model virus bacteriophage P22 and the model protein cytochrome c at different operating temperatures for different volume ratios. For bacteriophage P22, the measured viral partition coefficient at each temperature decreased by about an order of magnitude when the volume ratio was decreased from 10 to 0.1, which clearly indicated that entrainment is an important factor influencing viral partitioning. For cytochrome c, the measured protein partition coefficient did not change, which demonstrated that this entrainment effect negligibly influences protein partitioning. A new theoretical description of partitioning was also developed that combines the excluded-volume theory with this entrainment effect. In this theory, one fitted parameter--the volume fraction of entrained micelle-poor domains in the macroscopic, top, micelle-rich phase--is used to account for the entrainment. To fit this parameter, only a single partitioning experiment is required for a given volume ratio, irrespectively of the partitioning solute. The new theoretical description of partitioning yielded very good quantitative predictions of the viral partition coefficients. Accordingly, it can be concluded that the primary mechanisms

  17. Parameters of photosynthetic energy partitioning.

    PubMed

    Lazár, Dušan

    2015-03-01

    Almost every laboratory dealing with plant physiology, photosynthesis research, remote sensing, and plant phenotyping possesses a fluorometer to measure a kind of chlorophyll (Chl) fluorescence induction (FLI). When the slow Chl FLI is measured with addition of saturating pulses and far-red illumination, the so-called quenching analysis followed by the so-called relaxation analysis in darkness can be realized. These measurements then serve for evaluation of the so-called energy partitioning, that is, calculation of quantum yields of photochemical and of different types of non-photochemical processes. Several theories have been suggested for photosynthetic energy partitioning. The current work aims to summarize all the existing theories, namely their equations for the quantum yields, their meaning and their assumptions. In the framework of these theories it is also found here that the well-known NPQ parameter ( [Formula: see text] ; Bilger and Björkman, 1990) equals the ratio of the quantum yield of regulatory light-induced non-photochemical quenching to the quantum yield of constitutive non-regulatory non-photochemical quenching (ΦNPQ/Φf,D). A similar relationship is also found here for the PQ parameter (ΦP/Φf,D). PMID:25569797

  18. Mass partitioning effects in diffusion transport.

    PubMed

    Kojic, Milos; Milosevic, Miljan; Wu, Suhong; Blanco, Elvin; Ferrari, Mauro; Ziemys, Arturas

    2015-08-28

    Frequent mass exchange takes place in a heterogeneous environment among several phases, where mass partitioning may occur at the interface of phases. Analytical and computational methods for diffusion do not usually incorporate molecule partitioning masking the true picture of mass transport. Here we present a computational finite element methodology to calculate diffusion mass transport with a partitioning phenomenon included and the analysis of the effects of partitioning. Our numerical results showed that partitioning controls equilibrated mass distribution as expected from analytical solutions. The experimental validation of mass release from drug-loaded nanoparticles showed that partitioning might even dominate in some cases with respect to diffusion itself. The analysis of diffusion kinetics in the parameter space of partitioning and diffusivity showed that partitioning is an extremely important parameter in systems, where mass diffusivity is fast and that the concentration of nanoparticles can control payload retention inside nanoparticles. The computational and experimental results suggest that partitioning and physiochemical properties of phases play an important, if not crucial, role in diffusion transport and should be included in the studies of mass transport processes. PMID:26204522

  19. Rare Earth Element Partitioning in Lunar Minerals: An Experimental Study

    NASA Technical Reports Server (NTRS)

    McIntosh, E. C.; Rapp, J. F.; Draper, D. S.

    2016-01-01

    The partitioning behavior of rare earth elements (REE) between minerals and melts is widely used to interpret the petrogenesis and geologic context of terrestrial and extra-terrestrial samples. REE are important tools for modelling the evolution of the lunar interior. The ubiquitous negative Eu anomaly in lunar basalts is one of the main lines of evidence to support the lunar magma ocean (LMO) hypothesis, by which the plagioclase-rich lunar highlands were formed as a flotation crust during differentiation of a global-scale magma ocean. The separation of plagioclase from the mafic cumulates is thought to be the source of the Eu depletion, as Eu is very compatible in plagioclase. Lunar basalts and volcanic glasses are commonly depleted in light REEs (LREE), and more enriched in heavy REEs (HREE). However, there is very little experimental data available on REE partitioning between lunar minerals and melts. In order to interpret the source of these distinctive REE patterns, and to model lunar petrogenetic processes, REE partition coefficients (D) between lunar minerals and melts are needed at conditions relevant to lunar processes. New data on D(sub REE) for plagioclase, and pyroxenes are now available, but there is limited available data for olivine/melt D(sub REE), particularly at pressures higher than 1 bar, and in Fe-rich and reduced compositions - all conditions relevant to the lunar mantle. Based on terrestrial data, REE are highly incompatible in olivine (i.e. D much less than 1), however olivine is the predominant mineral in the lunar interior, so it is important to understand whether it is capable of storing even small amounts of REE, and how the REEs might be fractionatied, in order to understand the trace element budget of the lunar interior. This abstract presents results from high-pressure and temperature experiments investigating REE partitioning between olivine and melt in a composition relevant to lunar magmatism.

  20. Partition, orientation and mobility of ubiquinones in a lipid bilayer.

    PubMed

    Galassi, Vanesa Viviana; Arantes, Guilherme Menegon

    2015-12-01

    Ubiquinone is the universal mobile charge carrier involved in biological electron transfer processes. Its redox properties and biological function depend on the molecular partition and lateral diffusion over biological membranes. However, ubiquinone localization and dynamics within lipid bilayers are long debated and still uncertain. Here we present molecular dynamics simulations of several ubiquinone homologs with variable isoprenoid tail lengths complexed to phosphatidylcholine bilayers. Initially, a new force-field parametrization for ubiquinone is derived from and compared to high level quantum chemical data. Free energy profiles for ubiquinone insertion in the lipid bilayer are obtained with the new force-field. The profiles allow for the determination of the equilibrium location of ubiquinone in the membrane as well as for the validation of the simulation model by direct comparison with experimental partition coefficients. A detailed analysis of structural properties and interactions shows that the ubiquinone polar head group is localized at the water-bilayer interface at the same depth of the lipid glycerol groups and oriented normal to the membrane plane. Both the localization and orientation of ubiquinone head groups do not change significantly when increasing the number of isoprenoid units. The isoprenoid tail is extended and packed with the lipid acyl chains. For ubiquinones with long tails, the terminal isoprenoid units have high flexibility. Calculated ubiquinone diffusion coefficients are similar to that found for the phosphatidylcholine lipid. These results may have further implications for the mechanisms of ubiquinone transport and binding to respiratory and photosynthetic protein complexes. PMID:26255075

  1. Constraints on light noble gas partitioning at the conditions of spinel-peridotite melting

    NASA Astrophysics Data System (ADS)

    Jackson, Colin R. M.; Parman, Stephen W.; Kelley, Simon P.; Cooper, Reid F.

    2013-12-01

    Helium partitioning between olivine, orthopyroxene, clinopyroxene, and spinel and basaltic melt has been experimentally determined under upper mantle melting conditions (up to 20 kbar and 1450 °C). Under the conditions explored, helium partition coefficients are similar in all minerals investigated (KdHe˜10-4), suggesting He is evenly distributed between the minerals of spinel peridotite. This is in contrast to most incompatible elements, which are concentrated in clinopyroxene in spinel peridotite. The studied minerals have different concentrations of point defects, but similar He solubility, providing no evidence for He partitioning onto specific defects sites (e.g. cation vacancies). Upper limits on the partition coefficients for Ne and Ar have also been determined, constraining these elements to be moderately to highly incompatible in olivine at the conditions of spinel peridotite melting (<10-2 and <10-3, respectively). Helium partitioning in peridotite minerals varies little within the range of temperatures, pressures, and mineral compositions explored in this study. Reported partition coefficients, in combination with previous work, suggest that moderate to high degree mantle melting is not an efficient mechanism for increasing (U+Th)/He, (U+Th)/Ne, or K/Ar of the depleted mantle (DMM) through time, and consequently, supports the argument that recycling of oceanic crust is largely responsible for the relatively strong radiogenic noble gas signatures in the depleted mantle. Mantle residues with lowered (U+Th)/He, (U+Th)/Ne, and K/Ar may be produced through large extents of melting, but concentrations of noble gases will be low, unless noble gas solubility in solids deviate from Henry's Law at high fugacity.

  2. Mapping environmental partitioning properties of nonpolar complex mixtures by use of GC × GC.

    PubMed

    Nabi, Deedar; Gros, Jonas; Dimitriou-Christidis, Petros; Arey, J Samuel

    2014-06-17

    Comprehensive two-dimensional gas chromatography (GC × GC) is effective for separating and quantifying nonpolar organic chemicals in complex mixtures. Here we present a model to estimate 11 environmental partitioning properties for nonpolar analytes based on GC × GC chromatogram retention time information. The considered partitioning properties span several phases including pure liquid, air, water, octanol, hexadecane, particle natural organic matter, dissolved organic matter, and organism lipids. The model training set and test sets are based on a literature compilation of 648 individual experimental partitioning property data. For a test set of 50 nonpolar environmental contaminants, predicted partition coefficients exhibit root-mean-squared errors ranging from 0.19 to 0.48 log unit, outperforming Abraham-type solvation models for the same chemical set. The approach is applicable to nonpolar organic chemicals containing C, H, F, Cl, Br, and I, having boiling points ≤402 °C. The presented model is calibrated, easy to apply, and requires the user only to identify a small set of known analytes that adapt the model to the GC × GC instrument program. The analyst can thus map partitioning property estimates onto GC × GC chromatograms of complex mixtures. For example, analyzed nonpolar chemicals can be screened for long-range transport potential, aquatic bioaccumulation potential, arctic contamination potential, and other characteristic partitioning behaviors. PMID:24901063

  3. Particle-Dissolved Phase Partition of Polychlorinated Biphenyls in High Altitude Alpine Lakes.

    PubMed

    Nellier, Yann-Michel; Perga, Marie-Elodie; Cottin, Nathalie; Fanget, Philippe; Naffrechoux, Emmanuel

    2015-08-18

    We investigated whether polychlorinated biphenyls (PCBs) partitioning between the dissolved and particulate phases in two high altitude alpine lakes was determined by the quantity, size structure, or composition of suspended particles. Within- and between-lakes differences in water-particulate phase partition coefficient (Kp) were not related to total suspended matter, phytoplankton biomass, or taxonomic composition. Yet, a seasonal relationship between Kp and Kow was detected for both lakes, revealing equilibrium of PCBs partition when lakes were ice covered. On the contrary, PCBs partitioning between particles and water appeared kinetically limited during the open water season. Partition is therefore mainly governed by thermodynamic laws during the ice-covered period, while none of the tested physical or biological parameters seemed to explain the distribution of these particle-reactive contaminants in the open water period. PCBs were always mainly associated with particulate matter, but partitioning within different particulate size-fractions varied between seasons and between years during open water periods. When ice cover is absent, PCBs were mainly adsorbed on microplankton, the largest phytoplanktonic size fraction, which is the least likely to get grazed by pelagic microconsumers. PMID:26189929

  4. Actinide crystal-liquid partitioning for clinopyroxene and Ca3/PO4/2

    NASA Technical Reports Server (NTRS)

    Benjamin, T.; Heuser, W. R.; Burnett, D. S.; Seitz, M. G.

    1980-01-01

    Coefficients for the partitioning of the actinide elements Th, U and Pu, which are used as indicators of r-process nucleosynthesis and the ages of meteorite and lunar samples, between diopsidic clinopyroxene, whitlockite and silicate liquid at 20 kbar are measured. Fission and alpha track radiography techniques are employed to detect element concentrations in synthetic crystals made using spiked starting materials, under the assumptions of equilibrium partitioning at the crystal-liquid interface and actinide zoning. Analysis of the data indicates results to be consistent with interface equilibrium except at high cooling rates. Th/U/Pu partition coefficients of about 0.002/0.002/O.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. The greater incorporation of Pu into the crystalline phases is attributed to the importance of trivalent Pu, and the similarity of its partition coefficient into clinopyroxene to that of the light rare earths supports the concept of Pu/rare earth dating.

  5. Laboratory actinide partitioning - Whitlockite/liquid and influence of actinide concentration levels

    NASA Technical Reports Server (NTRS)

    Benjamin, T. M.; Jones, J. H.; Heuser, W. R.; Burnett, D. S.

    1983-01-01

    The partition coefficients between synthetic whitlockite (beta Ca-phosphate) and coexisting silicate melts are determined for the actinide elements Th, U and Pu. Experiments were performed at 1 bar pressure and 1250 C at oxygen fugacities from 10 to the -8.5 to 10 to the -0.7 bars, and partitioning was determined from trace element radiography combined with conventional electron microprobe analysis. Results show Pu to be more readily incorporated into crystalline phases than U or Th under reducing conditions, which is attributed to the observation that Pu exists primarily in the trivalent state, while U and Th are tetravalent. Corrected partition coefficients for whitlockite of 3.6, less than or equal to 0.6, 1.2, 0.5 and less than or equal to 0.002 are estimated for Pu(+3), Pu(+4), Th(+4), U(+4) and U(+6), respectively. Experiments performed at trace levels and percent levels of UO2 indicate that Si is involved in U substitution in whitlockite, and show a reduced partition coefficient at higher concentrations of U that can be explained by effects on melt structure or the fraction of tetravalent U.

  6. Synthesis, characterization, and liposome partition of a novel tetracycline derivative using the ionic liquids framework.

    PubMed

    Alves, Filipa; Oliveira, Filipe S; Schröder, Bernd; Matos, Carla; Marrucho, Isabel M

    2013-05-01

    Recently, efforts have been put on the development of new drug formulations using ionic liquid framework. In this work, two different species of abroad-spectrum polyketide antibiotic, tetracycline, are studied in terms of some important properties for antibiotics such as solubility in water and hydrophilic-hydrophobic balance. Tetracycline was used as cation, whereas docusate, a biocompatible anion, which enables the tailoring of the hydrophilicity of salts, was chosen as the anion. The developed innovative ion pair, tetracycline docusate, was characterized in terms of its thermal stability, water solubility, octanol-water, and liposome-water partition coefficients, using UV-vis spectrophotometry because of the absorbance of tetracycline around 270 nm. Egg yolk phosphatidylcholine liposomes were used as cell membrane models, and the interactions of both tetracycline hydrochloride and tetracycline docusate with the liposomes were quantified by determination of the partition coefficient using derivative spectrophotometry. A theoretical model based on simple partition drugs between two different media was used to determine the partition coefficient in liposomes. PMID:23450634

  7. Laboratory characterization of non-aqueous phase liquid/tracer interaction in support of a vadose zone partitioning interwell tracer test

    NASA Astrophysics Data System (ADS)

    Deeds, Neil E.; McKinney, Daene C.; Pope, Gary A.

    2000-01-01

    Contaminant characterization is important for successful remediation of non-aqueous phase liquids (NAPLs) in the unsaturated zone. A partitioning interwell tracer test (PITT) can provide a good estimate of average subsurface NAPL saturations. Screening experiments were completed in the laboratory to evaluate several gas tracers for a PITT study to be completed in the vadose zone at Kirtland Air Force Base in Albuquerque, NM. Four perfluorocarbon tracers were found to be suitable for this PITT. Further laboratory column studies were completed using contaminated field soil to measure the partition coefficients between the tracers and the NAPL. The results from the column studies showed that the air/NAPL tracer partition coefficients ranged from 8.8±0.6 to 71±3. This range of partition coefficients is suitable for detection of NAPL saturations in the field of 0.002 to 0.14.

  8. Assimilate partitioning during reproductive growth

    SciTech Connect

    Finazzo, S.F.; Davenport, T.L.

    1987-04-01

    Leaves having various phyllotactic relationships to fruitlets were labeled for 1 hour with 10/sub r/Ci of /sup 14/CO/sub 2/. Fruitlets were also labeled. Fruitlets did fix /sup 14/CO/sub 2/. Translocation of radioactivity from the peel into the fruit occurred slowly and to a limited extent. No evidence of translocation out of the fruitlets was observed. Assimilate partitioning in avocado was strongly influenced by phyllotaxy. If a fruit and the labeled leaf had the same phyllotaxy then greater than 95% of the radiolabel was present in this fruit. When the fruit did not have the same phyllotaxy as the labeled leaf, the radiolabel distribution was skewed with 70% of the label going to a single adjacent position. Avocado fruitlets exhibit uniform labeling throughout a particular tissue. In avocado, assimilates preferentially move from leaves to fruits with the same phyllotaxy.

  9. Building Ecology and Partition Design. Technical Bulletin.

    ERIC Educational Resources Information Center

    Maryland State Dept. of Education, Baltimore.

    This bulletin is intended as a resource for school system facility planners and architects who design schools. Ways in which decision makers can incorporate environmental concerns in the design of school buildings are detailed. Focus is on the design of interior partition systems. Partition systems in schools serve several purposes; they define…

  10. A Partitioning Technique for Defining Instructional Groups.

    ERIC Educational Resources Information Center

    Baker, Frank B.; Hubert, Lawrence J.

    1979-01-01

    A technique is presented for partitioning N students into K groups of fixed sizes using a given measure of proximity for all student pairs. The measure of proximity is typically calculated from a set of variables and constitutes the data needed for a criterion of partition "fit." (Author)

  11. Multimedia environmental chemical partitioning from molecular information.

    PubMed

    Martínez, Izacar; Grifoll, Jordi; Giralt, Francesc; Rallo, Robert

    2010-12-15

    The prospect of assessing the environmental distribution of chemicals directly from their molecular information was analyzed. Multimedia chemical partitioning of 455 chemicals, expressed in dimensionless compartmental mass ratios, was predicted by SimpleBox 3, a Level III Fugacity model, together with the propagation of reported uncertainty for key physicochemical and transport properties, and degradation rates. Chemicals, some registered in priority lists, were selected according to the availability of experimental property data to minimize the influence of predicted information in model development. Chemicals were emitted in air or water in a fixed geographical scenario representing the Netherlands and characterized by five compartments (air, water, sediments, soil and vegetation). Quantitative structure-fate relationship (QSFR) models to predict mass ratios in different compartments were developed with support vector regression algorithms. A set of molecular descriptors, including the molecular weight and 38 counts of molecular constituents were adopted to characterize the chemical space. Out of the 455 chemicals, 375 were used for training and testing the QSFR models, while 80 were excluded from model development and were used as an external validation set. Training and test chemicals were selected and the domain of applicability (DOA) of the QSFRs established by means of self-organizing maps according to structural similarity. Best results were obtained with QSFR models developed for chemicals belonging to either the class [C] and [C; O], or the class with at least one heteroatom different than oxygen in the structure. These two class-specific models, with respectively 146 and 229 chemicals, showed a predictive squared coefficient of q(2) ≥ 0.90 both for air and water, which respectively dropped to q(2)≈ 0.70 and 0.40 for outlying chemicals. Prediction errors were of the same order of magnitude as the deviations associated to the uncertainty of the

  12. Purification of biomaterials by phase partitioning

    NASA Technical Reports Server (NTRS)

    Harris, J. M.

    1984-01-01

    A technique which is particularly suited to microgravity environments and which is potentially more powerful than electrophoresis is phase partitioning. Phase partitioning is purification by partitioning between the two immiscible aqueous layers formed by solution of the polymers poly(ethylene glycol) and dextran in water. This technique proved to be very useful for separations in one-g but is limited for cells because the cells are more dense than the phase solutions thus tend to sediment to the bottom of the container before reaching equilibrium with the preferred phase. There are three phases to work in this area: synthesis of new polymers for affinity phase partitioning; development of automated apparatus for ground-based separations; and design of apparatus for performing simple phase partitioning space experiments, including examination of mechanisms for separating phases in the absence of gravity.

  13. Bicriterion methods for partitioning dissimilarity matrices.

    PubMed

    Brusco, Michael J; Cradit, J Dennis

    2005-11-01

    Partitioning indices associated with the within-cluster sums of pairwise dissimilarities often exhibit a systematic bias towards clusters of a particular size, whereas minimization of the partition diameter (i.e. the maximum dissimilarity element across all pairs of objects within the same cluster) does not typically have this problem. However, when the partition-diameter criterion is used, there is often a myriad of alternative optimal solutions that can vary significantly with respect to their substantive interpretation. We propose a bicriterion partitioning approach that considers both diameter and within-cluster sums in the optimization problem and facilitates selection from among the alternative optima. We developed several MATLAB-based exchange algorithms that rapidly provide excellent solutions to bicriterion partitioning problems. These algorithms were evaluated using synthetic data sets, as well as an empirical dissimilarity matrix. PMID:16293203

  14. Cell partition in two phase polymer systems

    NASA Technical Reports Server (NTRS)

    Brooks, D. E.

    1979-01-01

    Aqueous phase-separated polymer solutions can be used as support media for the partition of biological macromolecules, organelles and cells. Cell separations using the technique have proven to be extremely sensitive to cell surface properties but application of the systems are limited to cells or aggregates which do not significantly while the phases are settling. Partition in zero g in principle removes this limitation but an external driving force must be applied to induce the phases to separate since their density difference disappears. We have recently shown that an applied electric field can supply the necessary driving force. We are proposing to utilize the NASA FES to study field-driven phase separation and cell partition on the ground and in zero g to help define the separation/partition process, with the ultimate goal being to develop partition as a zero g cell separation technique.

  15. Dense Subgraph Partition of Positive Hypergraphs.

    PubMed

    Liu, Hairong; Latecki, Longin Jan; Yan, Shuicheng

    2015-03-01

    In this paper, we present a novel partition framework, called dense subgraph partition (DSP), to automatically, precisely and efficiently decompose a positive hypergraph into dense subgraphs. A positive hypergraph is a graph or hypergraph whose edges, except self-loops, have positive weights. We first define the concepts of core subgraph, conditional core subgraph, and disjoint partition of a conditional core subgraph, then define DSP based on them. The result of DSP is an ordered list of dense subgraphs with decreasing densities, which uncovers all underlying clusters, as well as outliers. A divide-and-conquer algorithm, called min-partition evolution, is proposed to efficiently compute the partition. DSP has many appealing properties. First, it is a nonparametric partition and it reveals all meaningful clusters in a bottom-up way. Second, it has an exact and efficient solution, called min-partition evolution algorithm. The min-partition evolution algorithm is a divide-and-conquer algorithm, thus time-efficient and memory-friendly, and suitable for parallel processing. Third, it is a unified partition framework for a broad range of graphs and hypergraphs. We also establish its relationship with the densest k-subgraph problem (DkS), an NP-hard but fundamental problem in graph theory, and prove that DSP gives precise solutions to DkS for all kin a graph-dependent set, called critical k-set. To our best knowledge, this is a strong result which has not been reported before. Moreover, as our experimental results show, for sparse graphs, especially web graphs, the size of critical k-set is close to the number of vertices in the graph. We test the proposed partition framework on various tasks, and the experimental results clearly illustrate its advantages. PMID:26353260

  16. Stability of coefficients in the Kronecker product of a hook and a rectangle

    NASA Astrophysics Data System (ADS)

    Ballantine, Cristina M.; Hallahan, William T.

    2016-02-01

    We use recent work of Jonah Blasiak (2012 arXiv:1209.2018) to prove a stability result for the coefficients in the Kronecker product of two Schur functions: one indexed by a hook partition and one indexed by a rectangle partition. We also give nearly sharp bounds for the size of the partition starting with which the Kronecker coefficients are stable. Moreover, we show that once the bound is reached, no new Schur functions appear in the decomposition of Kronecker product. We call this property superstability. Thus, one can recover the Schur decomposition of the Kronecker product from the smallest case in which the superstability holds. The bound for superstability is sharp. Our study of this particular case of the Kronecker product is motivated by its usefulness for the understanding of the quantum Hall effect (Scharf T et al 1994 J. Phys. A: Math. Gen 27 4211-9).

  17. Vanadium Partitioning Among Phases Relevant to Eucrite Petrogenesis

    NASA Astrophysics Data System (ADS)

    Hanson, B. Z.; Jones, J. H.; Mittlefehldt, D. W.; Jurewicz, A. J. G.

    1995-09-01

    Scandium, V, and Cr are depleted in eucrites compared to other lithophile refractory trace elements, and, therefore, understanding these depletions is important to deciphering the origin of eucrites. Previously, we have reported Sc partitioning experiments relevant to eucrite petrogenesis [1] and V concentrations in partial melts of the Murchison chondrite [2]. The Sc experiments indicated that eucrites such as Sioux County were generated by about 20% partial melting of a source whose residual phases were dominated by olivine. Additionally, our V analyses of the Murchison glasses were very similar to those measured for the Sioux County eucrite. This was particularly gratifying, since the major element concentrations of our 1180 degrees C Murchison glass were also very similar to those of eucrites [3]. Because the solid residua of the Murchison experiments were also dominated by olivine, there was apparent qualitative agreement between the inferences from both Sc and V. Previously, Sc partition coefficients for olivine and pyroxene at 1190-1200 degrees C have allowed us to model eucrite petrogenesis by assuming that eucrites such as Sioux County are simple partial melts [1]. Newly acquired V partition coefficients (Table 1) allow us to perform a similar calculation for V (Table 2). Vanadium analyses were corrected for Ti interference, and the similarity of partition coefficients from different experiments gives us confidence in the results. In addition, lnD versus 1/T regressions give good fits with r^2 > 0.99. Thus, partial melting models may be tested, using our experimental partition coefficients, by independently modeling Sc and V depletions. The assumptions necessary may be summarized: Eucrites such as Sioux County are produced by equilibrium partial melting of a source region and this source has approximately CM chondrite relative abundances of refractory lithophile elements. With this proviso, we have a system of four equations and four unknowns: one equation

  18. Averaging Internal Consistency Reliability Coefficients

    ERIC Educational Resources Information Center

    Feldt, Leonard S.; Charter, Richard A.

    2006-01-01

    Seven approaches to averaging reliability coefficients are presented. Each approach starts with a unique definition of the concept of "average," and no approach is more correct than the others. Six of the approaches are applicable to internal consistency coefficients. The seventh approach is specific to alternate-forms coefficients. Although the…

  19. Defining Noble Gas Partitioning for Carbon Capture and Storage Environments

    NASA Astrophysics Data System (ADS)

    Warr, O.; Masters, A.; Rochelle, C.; Ballentine, C. J.

    2014-12-01

    For viable CCS implementation variables such as CO2 dissolution rates, reactions with the host rock and the extent of groundwater interaction must be accurately constrained. Noble gases play an important role in these systems [e.g. 1,2]. Their application, however, requires accurate Henry's constants within dense CO2-H2O systems. Current interpretations use pure noble gas-H2O partitioning data [3,4] and assume CO2-noble gas interactions are negligible, even at high (>700 kg/m3) CO2 densities [2]. To test this assumption we experimentally determined noble gas CO2-H2O partitioning for the 170-656 kg/m3 CO2 density range; representative of most CCS environments. Contrary to assumption, CO2 density significantly affected noble gas partition coefficients. For helium, increasing CO2 density resulted in a negative deviation trend from CO2-free values whilst for argon, krypton and xenon strong, positive deviations were observed. At 656 kg/m3 these deviations were -35%, 74%, 114% and 321% respectively. This is interpreted as the CO2 phase acting as a polar solvent inducing polarisation in the noble gases. Deviation trends are well defined using a 2nd order polynomial. The effect of a dense CO2 phase can now be incorporated into existing noble gas models. We also present results from a Gibbs-Ensemble Monte Carlo molecular simulation to model partitioning for this binary system. This fundamental technique makes predictions based on the pair-potentials of interaction between the molecules. Here it gives the phase compositions and Henry coefficients for noble gases. With a proven ability in accurately replicating both the CO2-H2O system and low pressure noble gas Henry constants the focus is now on fully optimising the model to match high pressure observations. [1] Gilfillan et al. (2009) Nature 458 614-618 [2] Gilfillan et al. (2008) GCA 72 1174-1198 [3] Crovetto et al. (1982) J.Chem.Phys. 76 1077-1086 [4] Ballentine et al. in Porcelli et al. (eds.) (2002) Rev.Min.Geo. 47 539-614.

  20. PREDICTING SOIL SORPTION COEFFICIENTS OF ORGANIC CHEMICALS USING A NEURAL NETWORK MODEL

    EPA Science Inventory

    The soil/sediment adsorption partition coefficient normalized to organic carbon (Koc) is extensively used to assess the fate of organic chemicals in hazardous waste sites. Several attempts have been made to estimate the value of Koc from chemical structure ...

  1. Growth rate controlled barium partitioning in calcite and aragonite

    NASA Astrophysics Data System (ADS)

    Goetschl, Katja Elisabeth; Mavromatis, Vasileios; Baldermann, Andre; Purgstaller, Bettina; Dietzel, Martin

    2016-04-01

    The barium (Ba) content and the Ba/Ca molar ratios in biogenic and abiotic carbonates have been widely used from the scientific community as a geochemical proxy especially in marine and early diagenetic settings. The Ba content of carbonate minerals has been earlier associated to changes in oceanic circulation that may have been caused by upwelling, changes in weathering regimes and river-runoff as well as melt water discharge. The physicochemical controls of Ba ion incorporation in the two most abundant CaCO3 polymorphs found in Earth's surface environments, i.e. calcite and aragonite, have adequately been studied only for calcite. These earlier studies (i.e. [1]) suggest that at increasing growth rate, Ba partitioning in calcite is increasing as well. In contrast, to date the effect of growth rate on the partitioning of Ba in aragonite remains questionable, despite the fact that this mineral phase is the predominant carbonate-forming polymorph in shallow marine environments. To shed light on the mechanisms controlling Ba ion uptake in carbonates in this study we performed steady-state Ba co-precipitation experiments with calcite and aragonite at 25°C. The obtained results for the partitioning of Ba in calcite are in good agreement with those reported earlier by [1], whereas those for aragonite indicate a reduction of Ba partitioning at elevated aragonite growth rates, with the partitioning coefficient value between solid and fluid to be approaching the unity. This finding is good agreement with the formation of a solid solution in the aragonite-witherite system, owing to the isostructural crystallography of the two mineral phases. Moreover, our data set provides new insights that are required for reconstructing the evolution of the Ba content of pristine marine versus diagenetically altered carbonate minerals commonly occurring in marine subfloor settings, as the thermodynamically less stable aragonite will transform to calcite enriched in Ba, whilst affecting

  2. Partition features and renaturation enhancement of chymosin in aqueous two-phase systems.

    PubMed

    Reh, Georgina; Spelzini, Dario; Tubío, Gisela; Picó, Guillermo; Farruggia, Beatriz

    2007-12-01

    Aqueous two-phase systems of polyethylene glycol (molecular mass 1450, 3350 and 6000)-phosphate and polyethylene-polypropylene oxide (molecular mass 8400)-maltodextrin systems were used in order to study the partition features of recombinant chymosin from inclusion bodies. These systems in the presence of 8M urea were used for the solubilization of inclusion bodies containing recombinant chymosin and for the oxidative renaturation of this protein. Recombinant chymosin showed to be partitioned in favour of the top phase in all studied systems with a partition coefficient between 4 and 6. The recovery of the chymosin biological activity was 32% in the polyethylene-polypropylene oxide, while in the polyethylene glycol-phosphate the recovery was 50-59%. The results indicate that the liquid-liquid extraction would be an adequate tool able to isolate and concentrate chymosin from inclusion bodies with a yield of biological activity higher than that obtained from the standard method (43%). PMID:17988962

  3. Chemical Partition of the Radiative Decay Rate of Luminescence of Europium Complexes

    NASA Astrophysics Data System (ADS)

    Lima, Nathalia B. D.; Dutra, José Diogo L.; Gonçalves, Simone M. C.; Freire, Ricardo O.; Simas, Alfredo M.

    2016-02-01

    The spontaneous emission coefficient, Arad, a global molecular property, is one of the most important quantities related to the luminescence of complexes of lanthanide ions. In this work, by suitable algebraic transformations of the matrices involved, we introduce a partition that allows us to compute, for the first time, the individual effects of each ligand on Arad, a property of the molecule as a whole. Such a chemical partition thus opens possibilities for the comprehension of the role of each of the ligands and their interactions on the luminescence of europium coordination compounds. As an example, we applied the chemical partition to the case of repeating non-ionic ligand ternary complexes of europium(III) with DBM, TTA, and BTFA, showing that it allowed us to correctly order, in an a priori manner, the non-obvious pair combinations of non-ionic ligands that led to mixed-ligand compounds with larger values of Arad.

  4. Chemical Partition of the Radiative Decay Rate of Luminescence of Europium Complexes

    PubMed Central

    Lima, Nathalia B. D.; Dutra, José Diogo L.; Gonçalves, Simone M. C.; Freire, Ricardo O.; Simas, Alfredo M.

    2016-01-01

    The spontaneous emission coefficient, Arad, a global molecular property, is one of the most important quantities related to the luminescence of complexes of lanthanide ions. In this work, by suitable algebraic transformations of the matrices involved, we introduce a partition that allows us to compute, for the first time, the individual effects of each ligand on Arad, a property of the molecule as a whole. Such a chemical partition thus opens possibilities for the comprehension of the role of each of the ligands and their interactions on the luminescence of europium coordination compounds. As an example, we applied the chemical partition to the case of repeating non-ionic ligand ternary complexes of europium(III) with DBM, TTA, and BTFA, showing that it allowed us to correctly order, in an a priori manner, the non-obvious pair combinations of non-ionic ligands that led to mixed-ligand compounds with larger values of Arad. PMID:26892900

  5. Partitioning of flight data for aerodynamic modeling of aircraft at high angles of attack

    NASA Technical Reports Server (NTRS)

    Batterson, James G.; Klein, Vladislav

    1987-01-01

    It is sometimes necessary to determine aerodynamic model structure and estimate associated stability and control derivatives for airplanes from flight data that cover a large range of angle of attack or sideslip. One method of dealing with that problem is through data partitioning. The main purpose of this paper is to provide an explanation of a data partitioning procedure and its application and to discuss both the power and limitations of that procedure for the analysis of large maneuvers of aircraft. The partitioning methodology is shown to provide estimates for coefficients of those regressors that are well excited in the aircraft motion. In particular, primary lateral stability and damping derivatives are identified throughout the maneuver ranges.

  6. Selecting optimal partitioning schemes for phylogenomic datasets

    PubMed Central

    2014-01-01

    Background Partitioning involves estimating independent models of molecular evolution for different subsets of sites in a sequence alignment, and has been shown to improve phylogenetic inference. Current methods for estimating best-fit partitioning schemes, however, are only computationally feasible with datasets of fewer than 100 loci. This is a problem because datasets with thousands of loci are increasingly common in phylogenetics. Methods We develop two novel methods for estimating best-fit partitioning schemes on large phylogenomic datasets: strict and relaxed hierarchical clustering. These methods use information from the underlying data to cluster together similar subsets of sites in an alignment, and build on clustering approaches that have been proposed elsewhere. Results We compare the performance of our methods to each other, and to existing methods for selecting partitioning schemes. We demonstrate that while strict hierarchical clustering has the best computational efficiency on very large datasets, relaxed hierarchical clustering provides scalable efficiency and returns dramatically better partitioning schemes as assessed by common criteria such as AICc and BIC scores. Conclusions These two methods provide the best current approaches to inferring partitioning schemes for very large datasets. We provide free open-source implementations of the methods in the PartitionFinder software. We hope that the use of these methods will help to improve the inferences made from large phylogenomic datasets. PMID:24742000

  7. The gas/particle partitioning of polycyclic aromatic hydrocarbons collected at a sub-Arctic site in Canada

    NASA Astrophysics Data System (ADS)

    Sofowote, Uwayemi M.; Hung, Hayley; Rastogi, Ankit K.; Westgate, John N.; Su, Yushan; Sverko, Ed; D'Sa, Ivy; Roach, Pat; Fellin, Phil; McCarry, Brian E.

    2010-12-01

    Polycyclic aromatic hydrocarbons (PAH) were measured in air samples at a remote air monitoring site established in the Yukon Territory, Canada as part of a global project (International Polar Year; IPY) to study the potential for atmospheric long-range transport of anthropogenic pollutants to the Arctic. Gas- and particle-phase PAH were collected in polyurethane foam plugs and on glass fibre filters respectively from August 2007 to October 2009. PAH concentrations were found to be highest in the winter months and lowest in summer. The gas/particle partitioning coefficients of 3-5 ringed PAH were computed and seasonal averages were compared. In the summer time, lower molecular mass PAH exhibited relatively higher partitioning into the particle-phase. This particle-phase partitioning led to the shallowest slopes being recorded during summer for the log-log correlation plots between the PAH partition coefficients and their sub-cooled vapour pressures. Air mass back trajectories suggest that local impacts may be more important during the summer time which is marked by increased camping activities at camping sites in the proximity of the sampling station. In conclusion, both summer and wintertime variations in PAH concentrations and gas/particle partitioning are considered to be source- and phototransformation-dependent rather than dependent on temperature-driven shifts in equilibrium partitioning.

  8. Evaluation of log K{sub ow} and tissue lipid content as predictors of chemical partitioning to fish tissues

    SciTech Connect

    Bertelsen, S.L.; Gallinat, C.A.; Elonen, C.M.; Hoffman, A.D.; Nichols, J.W.

    1998-08-01

    In vitro equilibrium chemical partition coefficients were determined for six chemicals in selected tissues from four species of fish. Log-transformed values were then regressed in stepwise fashion against chemical log octanol/water partition coefficient (K{sub ow}) and the log of tissue lipid content to derive a series of linear one- and two-variable models. Equations derived for fat indicate that n-octanol is a good surrogate for nonpolar lipid in the range of chemical log K{sub ow} tested (1.46 < log K{sub ow} < 4.04). These equations also support the conclusion that previously developed K{sub ow}-bioconcentration factor relationships are largely a reflection of chemical accumulation in fat. Fitted slope and intercept terms for lean tissues differed from those expected from chemical partitioning to lipid only and were instead consistent with the suggestion that partitioning to nonlipid-nonwater cellular constituents contributes substantially to chemical accumulation. A general equation is presented for prediction of tissue/water and blood/water partitioning from chemical log K{sub ow} and tissue (or blood) lipid content. It is suggested, however, that tissue- and blood-specific equations be used to estimate the tissue/blood partitioning relationships needed for kinetic modeling efforts.

  9. The gas/particle partitioning of nitro- and oxy-polycyclic aromatic hydrocarbons in the atmosphere of northern China

    NASA Astrophysics Data System (ADS)

    Li, Wei; Shen, Guofeng; Yuan, Chenyi; Wang, Chen; Shen, Huizhong; Jiang, Huai; Zhang, Yanyan; Chen, Yuanchen; Su, Shu; Lin, Nan; Tao, Shu

    2016-05-01

    The gas/particle partitioning of nitro-polycyclic aromatic hydrocarbons (nPAHs) and oxy-PAHs (oPAHs) is pivotal to estimate their environmental fate. Simultaneously measured atmospheric concentrations of nPAHs and oPAHs in both gaseous and particulate phases at 18 sites in northern China make it possible to investigate their partitioning process in a large region. The gas/particle partitioning coefficients (Kp) in this study were higher than those measured in the emission exhausts. The Kp for most individual nPAHs was higher than those for their corresponding parent PAHs. Generally higher Kp values were found at rural field sites compared to values in the rural villages and cities. Temperature, subcooled liquid-vapor pressure (Pl0) and octanol-air partition coefficient (Koa) were all significantly correlated with Kp. The slope values between log Kp and log Pl0, ranging from - 0.54 to - 0.34, indicate that the equilibrium of gas/particle partitioning might not be reached, which could be also revealed from a positive correlation between log Kp and particulate matter (PM) concentrations. Underestimation commonly exists in all three partitioning models, but the predicted values of Kp from the dual model are closer to the measured Kp for derivative PAHs in northern China.

  10. Gas/Aerosol partitioning: a simplified method for global modeling

    NASA Astrophysics Data System (ADS)

    Metzger, S. M.

    2000-09-01

    The main focus of this thesis is the development of a simplified method to routinely calculate gas/aerosol partitioning of multicomponent aerosols and aerosol associated water within global atmospheric chemistry and climate models. Atmospheric aerosols are usually multicomponent mixtures, partly composed of acids (e.g. H2SO4, HNO3), their salts (e.g. (NH4)2SO4, NH4NO3, respectively), and water. Because these acids and salts are highly hygroscopic, water, that is associated with aerosols in humid environments, often exceeds the total dry aerosol mass. Both the total dry aerosol mass and the aerosol associated water are important for the role of atmospheric aerosols in climate change simulations. Still, multicomponent aerosols are not yet routinely calculated within global atmospheric chemistry or climate models. The reason is that these particles, especially volatile aerosol compounds, require a complex and computationally expensive thermodynamical treatment. For instance, the aerosol associated water depends on the composition of the aerosol, which is determined by the gas/liquid/solid partitioning, in turn strongly dependent on temperature, relative humidity, and the presence of pre-existing aerosol particles. Based on thermodynamical relations such a simplified method has been derived. This method is based on the assumptions generally made by the modeling of multicomponent aerosols, but uses an alternative approach for the calculation of the aerosol activity and activity coefficients. This alternative approach relates activity coefficients to the ambient relative humidity, according to the vapor pressure reduction and the generalization of Raoult s law. This relationship, or simplification, is a consequence of the assumption that the aerosol composition and the aerosol associated water are in thermodynamic equilibrium with the ambient relative humidity, which determines the solute activity and, hence, activity coefficients of a multicomponent aerosol mixture

  11. Experimental partitioning of Zr, Ti, and Nb between silicate liquid and a complex noble metal alloy and the partitioning of Ti between perovskite and platinum metal

    NASA Technical Reports Server (NTRS)

    Jurewicz, Stephen R.; Jones, John H.

    1993-01-01

    El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.

  12. A unified algorithm for predicting partition coefficients for PBPK modeling of drugs and environmental chemicals

    SciTech Connect

    Peyret, Thomas; Poulin, Patrick; Krishnan, Kannan

    2010-12-15

    The algorithms in the literature focusing to predict tissue:blood PC (P{sub tb}) for environmental chemicals and tissue:plasma PC based on total (K{sub p}) or unbound concentration (K{sub pu}) for drugs differ in their consideration of binding to hemoglobin, plasma proteins and charged phospholipids. The objective of the present study was to develop a unified algorithm such that P{sub tb}, K{sub p} and K{sub pu} for both drugs and environmental chemicals could be predicted. The development of the unified algorithm was accomplished by integrating all mechanistic algorithms previously published to compute the PCs. Furthermore, the algorithm was structured in such a way as to facilitate predictions of the distribution of organic compounds at the macro (i.e. whole tissue) and micro (i.e. cells and fluids) levels. The resulting unified algorithm was applied to compute the rat P{sub tb}, K{sub p} or K{sub pu} of muscle (n = 174), liver (n = 139) and adipose tissue (n = 141) for acidic, neutral, zwitterionic and basic drugs as well as ketones, acetate esters, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons and ethers. The unified algorithm reproduced adequately the values predicted previously by the published algorithms for a total of 142 drugs and chemicals. The sensitivity analysis demonstrated the relative importance of the various compound properties reflective of specific mechanistic determinants relevant to prediction of PC values of drugs and environmental chemicals. Overall, the present unified algorithm uniquely facilitates the computation of macro and micro level PCs for developing organ and cellular-level PBPK models for both chemicals and drugs.

  13. Partition Coefficients of Selected Compounds Using Ion Exchange Separation of Cesium From High Level Waste

    SciTech Connect

    Toth, James J.; Blanchard, David L.; Arm, Stuart T.; Urie, Michael W.

    2004-04-24

    The removal of cesium radioisotope (137Cs) from the High Level Waste stored in underground storage tanks at the Hanford site is a formidable chemical separations challenge for the Waste Treatment Plant. An eluatable organic-based ion exchange resin was selected as the baseline technology (1). The baseline technology design employs a proprietary macrocyclic weak-acid ion exchange resin to adsorb the cesium (137Cs) during the process loading cycle in a fixed bed column design. Following loading, the cesium is eluted from the resin using a nitric acid eluant. Previous work provided limited understanding of the performance of the resin, processed with actual wastes, and under multiple load and elute conditions, which are required for the ion exchange technology to be underpinned sufficiently for resolution of all process-related design issues before flowsheet and construction drawings can be released. By performing multiple ion exchange column tests with waste feeds, and measuring the chemical and radionuclide compositions of the waste feeds, column effluents and column eluants, ion exchange stream composition information can be provided for supporting resolution of selected design issues.

  14. 40 CFR 799.6755 - TSCA partition coefficient (n-octanol/water), shake flask method.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) Prerequisites. Suitable analytical method, dissociation constant, water solubility, and hydrolysis (preliminary... or by use of published solubilities of the test substance in the pure solvents. Alternatively, it...

  15. 40 CFR 799.6755 - TSCA partition coefficient (n-octanol/water), shake flask method.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) Prerequisites. Suitable analytical method, dissociation constant, water solubility, and hydrolysis (preliminary... or by use of published solubilities of the test substance in the pure solvents. Alternatively, it...

  16. 40 CFR 799.6755 - TSCA partition coefficient (n-octanol/water), shake flask method.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) Prerequisites. Suitable analytical method, dissociation constant, water solubility, and hydrolysis (preliminary... or by use of published solubilities of the test substance in the pure solvents. Alternatively, it...

  17. 40 CFR 799.6755 - TSCA partition coefficient (n-octanol/water), shake flask method.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...) Prerequisites. Suitable analytical method, dissociation constant, water solubility, and hydrolysis (preliminary... or by use of published solubilities of the test substance in the pure solvents. Alternatively, it...

  18. 40 CFR 799.6755 - TSCA partition coefficient (n-octanol/water), shake flask method.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... acid and base, drying, and distilling. More sophisticated methods will be required to separate the n... usually given in the form of its logarithm to base 10 (log P). In this case n-octanol and water: Equation... reported. (ix) The mean P from all determinations should also be expressed as its logarithm (base 10)....

  19. Determining Passive Sampler Partition Coefficients for Dissolved-phase Organic Contaminants

    EPA Science Inventory

    Passive samplers are used for environmental and analytical purposes to measure dissolved nonionic organic contaminants (NOCs) by absorption from a contaminated medium into a clean phase, usually in the form of a synthetic organic film. Recently developed passive sampler techniqu...

  20. Drag Coefficient of Hexadecane Particles

    NASA Astrophysics Data System (ADS)

    Nakao, Yoshinobu; Hishida, Makoto; Kajimoto, Sadaaki; Tanaka, Gaku

    This paper deals with the drag coefficient of solidified hexadecane particles and their free rising velocity in liquid. The drag coefficient was experimentally investigated in Reynolds number range of about 40-300. The present experimental results are summarized in the following; (1) the drag coefficient of solidified hexadecane particles formed in liquid coolant by direct contact cooling is higher than that of a smooth surface sphere, this high drag coefficient seems to be attributed to the non-smooth surface of the solidified hexadecane particles, (2) experimental correlation for the drag coefficient of the solidified hexadecane particles was proposed, (3 ) the measured rising velocity of the solidified hexadecane particle agrees well with the calculated one, (4) the drag coefficients of hexadecane particles that were made by pouring hexadecane liquid into a solid hollow sphere agreed well with the drag coefficient of smooth surface sphere.

  1. Gas/particle partitioning of 2-methyltetrols and levoglucosan at an urban site in Denver.

    PubMed

    Xie, Mingjie; Hannigan, Michael P; Barsanti, Kelley C

    2014-01-01

    In this study, a medium volume sampler incorporating quartz fiber filters (QFFs) and a polyurethane foam (PUF)/XAD/PUF sandwich (PXP) was used to collect 2-methyltetrols (isoprene tracer) and levoglucosan (biomass burning tracer) in gaseous and particle (PM2.5) phases. The measured gas/particle (G/P) partitioning coefficients (Kp,OMm) of 2-methyltetrols and levoglucosan were calculated and compared to their predicted G/P partitioning coefficients (Kp,OMt) based on an absorptive partitioning theory. The breakthrough experiments showed that gas-phase 2-methyltetrols and levoglucosan could be collected using the PXP or PUF adsorbent alone, with low breakthrough; however, the recoveries of levoglucosan in PXP samples were lower than 70% (average of 51.9–63.3%). The concentration ratios of 2-methyltetrols and levoglucosan in the gas phase to those in the particle phase were often close to or higher than unity in summer, indicating that these polar species are semi-volatile and their G/P partitioning should be considered when applying particle-phase data for source apportionment. The Kp,OMm values of 2-methyltetrols had small variability in summer Denver, which was ascribed to large variations in concentrations of particulate organic matter (5.14 ± 3.29 μg m–3) and small changes in ambient temperature (21.8 ± 4.05 °C). The regression between log Kp,OMm and log Kp,OMt suggested that the absorptive G/P partitioning theory could reasonably predict the measured G/P partitioning of levoglucosan in ambient samples. PMID:24517510

  2. EARTH’S CORE FORMATION: NEW CONSTRAINTS FROM SIDEROPHILE ELEMENTS PARTITIONING (Invited)

    NASA Astrophysics Data System (ADS)

    Siebert, J.; Corgne, A.; Ryerson, F. J.

    2009-12-01

    The abundances of siderophile elements in the Earth’s mantle are the result of core formation in the early Earth. Many variables are involved in the prediction of metal/silicate siderophile partition coefficients during core segregation: pressure, temperature, oxygen fugacity, silicate and metal compositions. Despite publications of numerous results of metal-silicate experiments, the experimental database and predictive expressions for elements partitioning are hampered by a lack of systematic study to separate and evaluate the effects of each variable. Only a relatively complete experimental database that describes Ni and Co partitioning now exists but is not sufficient to unambiguously decide between the most popular model for core formation with a single stage core-mantle equilibration at the bottom of a deep magma ocean (e.g. Li and Agee, 2001) and more recent alternative models (e.g. Wade and Wood, 2005; Rubie et al., 2007). In this experimental work, systematic study of metal-silicate partitioning is presented for elements normally regarded as moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta). New results are obtained for elements whose partitioning behavior is usually poorly constrained and not integrated into any accretion or core formation models. A new piston-cylinder design assembly allows us to present a suite of isobaric partitioning experiments at 3 GPa within a temperature range from 1600 to 2600 C and over a range of relative oxygen fugacity from IW-1.5 to IW-3.5. Silicate melts range from basaltic to peridotite in composition. The individual effect of pressure is also investigated through a combination of piston cylinder and multi anvil isothermal experiments from 0.5 to 18 GPa at 1900 C. Absolute measurements of partitioning coefficients combining EMP and LA-ICPMS analytical methods are provided. Moreover, thermodynamic calculations were performed to assess the effects

  3. Partitioning of regular computation on multiprocessor systems

    NASA Technical Reports Server (NTRS)

    Lee, Fung Fung

    1988-01-01

    Problem partitioning of regular computation over two dimensional meshes on multiprocessor systems is examined. The regular computation model considered involves repetitive evaluation of values at each mesh point with local communication. The computational workload and the communication pattern are the same at each mesh point. The regular computation model arises in numerical solutions of partial differential equations and simulations of cellular automata. Given a communication pattern, a systematic way to generate a family of partitions is presented. The influence of various partitioning schemes on performance is compared on the basis of computation to communication ratio.

  4. Convex Regression with Interpretable Sharp Partitions

    PubMed Central

    Petersen, Ashley; Simon, Noah; Witten, Daniela

    2016-01-01

    We consider the problem of predicting an outcome variable on the basis of a small number of covariates, using an interpretable yet non-additive model. We propose convex regression with interpretable sharp partitions (CRISP) for this task. CRISP partitions the covariate space into blocks in a data-adaptive way, and fits a mean model within each block. Unlike other partitioning methods, CRISP is fit using a non-greedy approach by solving a convex optimization problem, resulting in low-variance fits. We explore the properties of CRISP, and evaluate its performance in a simulation study and on a housing price data set.

  5. Quantum Dilogarithms and Partition q-Series

    NASA Astrophysics Data System (ADS)

    Kato, Akishi; Terashima, Yuji

    2015-08-01

    In our previous work (Kato and Terashima, Commun Math Phys. arXiv:1403.6569, 2014), we introduced the partition q-series for mutation loop γ—a loop in exchange quiver. In this paper, we show that for a certain class of mutation sequences, called reddening sequences, the graded version of partition q-series essentially coincides with the ordered product of quantum dilogarithm associated with each mutation; the partition q-series provides a state-sum description of combinatorial Donaldson-Thomas invariants introduced by Keller.

  6. How pervasive is the Hirshfeld partitioning?

    SciTech Connect

    Heidar-Zadeh, Farnaz; Ayers, Paul W.

    2015-01-28

    One can partition the molecular density into its atomic contributions by minimizing the divergence of the atom-in-molecule densities from their corresponding reference pro-atomic densities, subject to the constraint that the sum of the atom-in-molecule densities is the total molecular density. We expose conditions on the divergence measure that are necessary, and sufficient, to recover the popular Hirshfeld partitioning. Specifically, among all local measures of the divergence between two probability distribution functions, the Hirshfeld partitioning is obtained only for f-divergences.

  7. Phase behavior and component partitioning in low water content amorphous carbohydrates and their potential impact on encapsulation of flavors.

    PubMed

    Gunning, Y M; Parker, R; Ring, S G; Rigby, N M; Wegg, B; Blake, A

    2000-02-01

    The compositions at which amorphous ethanol-maltose-water mixtures exhibit liquid-liquid separation have been determined in the temperature range from 20 to 80 degrees C. At water contents below approximately 20% w/w two phases were observed, with the maltose-rich phase slightly richer in water. Partition coefficients of organic nonelectrolytes ranging in hydrophobicity from 1, 2-ethanediol and 1,2-propanediol to benzyl alcohol and propyl acetate have been measured for octanol/sorbitol, benzyl alcohol/sorbitol, and 1-butanol/sorbitol mixtures. Linear correlations were found between the log partition coefficients in the various solvent systems. Replacing water with sorbitol results in more organic partitioning into the octanol. Replacing octanol with benzyl alcohol or 1-butanol also results in more organic partitioning into the hydrophobic phase. The results establish a relationship with partition coefficients for octanol/water mixtures, which are well studied experimentally and for which predictive approaches exist. The implications of these results for flavor retention and encapsulation are discussed. PMID:10691646

  8. Partitioning technique for open systems

    NASA Astrophysics Data System (ADS)

    Brändas, Erkki J.

    2010-11-01

    The focus of the present contribution is essentially confined to three research areas carried out during the author's turns as visiting (assistant, associate and full) professor at the University of Florida's Quantum Theory Project, QTP. The first two topics relate to perturbation theory and spectral theory for self-adjoint operators in Hilbert space. The third subject concerns analytic extensions to non-self-adjoint problems, where particular consequences of the occurrence of continuous energy spectra are measured. In these studies general partitioning methods serve as general cover for perturbation-, variational- and general matrix theory. In addition we follow up associated inferences for the time dependent problem as well as recent results and conclusions of a rather general yet surprising character. Although the author spent most of his times at QTP during visits in the 1970s and 1980s, collaborations with department members and shorter stays continued through later decades. Nevertheless the impact must be somewhat fragmentary, yet it is hoped that the present account is sufficiently self-contained to be realistic and constructive.

  9. Lipid partitioning during cardiac stress.

    PubMed

    Kolwicz, Stephen C

    2016-10-01

    It is well documented that fatty acids serve as the primary fuel substrate for the contracting myocardium. However, extensive research has identified significant changes in the myocardial oxidation of fatty acids during acute or chronic cardiac stress. As a result, the redistribution or partitioning of fatty acids due to metabolic derangements could have biological implications. Fatty acids can be stored as triacylglycerols, serve as critical components for biosynthesis of phospholipid membranes, and form the potent signaling molecules, diacylglycerol and ceramides. Therefore, the contribution of lipid metabolism to health and disease is more intricate than a balance of uptake and oxidation. In this review, the available data regarding alterations that occur in endogenous cardiac lipid pathways during the pathological stressors of ischemia-reperfusion and pathological hypertrophy/heart failure are highlighted. In addition, changes in endogenous lipids observed in exercise training models are presented for comparison. This article is part of a Special Issue entitled: Heart Lipid Metabolism edited by G.D. Lopaschuk. PMID:27040509

  10. HPAM: Hirshfeld Partitioned Atomic Multipoles

    PubMed Central

    Elking, Dennis M.; Perera, Lalith; Pedersen, Lee G.

    2011-01-01

    An implementation of the Hirshfeld (HD) and Hirshfeld-Iterated (HD-I) atomic charge density partitioning schemes is described. Atomic charges and atomic multipoles are calculated from the HD and HD-I atomic charge densities for arbitrary atomic multipole rank lmax on molecules of arbitrary shape and size. The HD and HD-I atomic charges/multipoles are tested by comparing molecular multipole moments and the electrostatic potential (ESP) surrounding a molecule with their reference ab initio values. In general, the HD-I atomic charges/multipoles are found to better reproduce ab initio electrostatic properties over HD atomic charges/multipoles. A systematic increase in precision for reproducing ab initio electrostatic properties is demonstrated by increasing the atomic multipole rank from lmax = 0 (atomic charges) to lmax = 4 (atomic hexadecapoles). Both HD and HD-I atomic multipoles up to rank lmax are shown to exactly reproduce ab initio molecular multipole moments of rank L for L ≤ lmax. In addition, molecular dipole moments calculated by HD, HD-I, and ChelpG atomic charges only (lmax = 0) are compared with reference ab initio values. Significant errors in reproducing ab initio molecular dipole moments are found if only HD or HD-I atomic charges used. PMID:22140274

  11. Energy partitioning schemes: a dilemma.

    PubMed

    Mayer, I

    2007-01-01

    Two closely related energy partitioning schemes, in which the total energy is presented as a sum of atomic and diatomic contributions by using the "atomic decomposition of identity", are compared on the example of N,N-dimethylformamide, a simple but chemically rich molecule. Both schemes account for different intramolecular interactions, for instance they identify the weak C-H...O intramolecular interactions, but give completely different numbers. (The energy decomposition scheme based on the virial theorem is also considered.) The comparison of the two schemes resulted in a dilemma which is especially striking when these schemes are applied for molecules distorted from their equilibrium structures: one either gets numbers which are "on the chemical scale" and have quite appealing values at the equilibrium molecular geometries, but exhibiting a counter-intuitive distance dependence (the two-center energy components increase in absolute value with the increase of the interatomic distances)--or numbers with too large absolute values but "correct" distance behaviour. The problem is connected with the quick decay of the diatomic kinetic energy components. PMID:17328441

  12. Protein partition between the different phases comprising poly(ethylene glycol)-salt aqueous two-phase systems, hydrophobic interaction chromatography and precipitation: a generic description in terms of salting-out effects.

    PubMed

    Huddleston, J; Abelaira, J C; Wang, R; Lyddiatt, A

    1996-05-17

    The solution behaviour of selected proteins has been studied under conditions promoting precipitation, binding to mildly hydrophobic adsorbents or partition. Solvophobic theory may be used to describe these forms of protein partition. The tendency of a protein to partition therein is dependent upon surface properties of the protein solute mediated by the concentration and nature of added salts. As applied to partitioning in poly(ethylene glycol) (PEG)-salt systems this implies that linear (Brönsted) relationships apply only to proteins partitioned close to the critical point. At longer tie-line lengths protein partitioning is increasingly influenced by salting-out forces. This is confirmed by the observed behaviour of the proteins. The point at which this behaviour changes has been unambiguously defined enabling the direct comparison of phase transition of proteins during partition in all systems. The results obtained show that phase transition during adsorption and partition occur at similar concentrations of salt. This is less than that required to promote precipitation. It appears, from these limited studies, that top-phase preferring proteins are partitioned at salt concentrations above those required to cause adsorption. Proteins preferring the lower phase are partitioned at salt concentrations close to or below those required for adsorption. This raises questions regarding the solvated molecular form of the partitioned proteins and the definition of the partition coefficient. PMID:8798879

  13. Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: A Monte Carlo simulation study

    SciTech Connect

    Quesada-Pérez, Manuel; Maroto-Centeno, José Alberto; Adroher-Benítez, Irene

    2014-05-28

    In this work, the size-exclusion partitioning of neutral solutes in crosslinked polymer networks has been studied through Monte Carlo simulations. Two models that provide user-friendly expressions to predict the partition coefficient have been tested over a wide range of volume fractions: Ogston's model (especially devised for fibrous media) and the pore model. The effects of crosslinking and bond stiffness have also been analyzed. Our results suggest that the fiber model can acceptably account for size-exclusion effects in crosslinked gels. Its predictions are good for large solutes if the fiber diameter is assumed to be the effective monomer diameter. For solutes sizes comparable to the monomer dimensions, a smaller fiber diameter must be used. Regarding the pore model, the partition coefficient is poorly predicted when the pore diameter is estimated as the distance between adjacent crosslinker molecules. On the other hand, our results prove that the pore sizes obtained from the pore model by fitting partitioning data of swollen gels are overestimated.

  14. Metal-silicate partitioning of Ni and Co in a deep magma ocean

    NASA Astrophysics Data System (ADS)

    Siebert, Julien; Badro, James; Antonangeli, Daniele; Ryerson, Frederick J.

    2012-03-01

    The pattern of siderophile (iron-loving) element abundance in the silicate portion of the Earth is a consequence of metal separation during core formation. The apparent excess of nickel and cobalt in mantle-derived rocks has been attributed to metal-silicate equilibration in a deep terrestrial magma ocean. Based on the extrapolation of phase equilibria and metal-silicate partitioning results obtained at lower pressure (P) and temperature (T), previous estimates of the P-T of equilibration are all greater than 25 GPa and 3000 K. Using the laser-heated diamond anvil cell, we have extended metal-silicate partitioning measurements for Ni and Co to 75 GPa and 4400 K, exceeding the liquidus temperatures for both metal and silicate (basalt or peridotite) and, therefore, achieving thermodynamic conditions directly comparable to those of the magma ocean. The metal-silicate partition coefficients of nickel and cobalt decrease with increasing pressure and reach the values required to yield present mantle concentrations at ~ 50 GPa. At these conditions, silicon and oxygen concentrations measured in the metallic liquid allow to solve the seismically constrained core density deficit. Above 60 GPa, the partition coefficients become too low, resulting in an overabundance of Ni and Co in the silicate mantle. Our data therefore support the paradigm of core formation in a deep mama ocean, providing an upper bound for the depth at which Earth's core may have formed, and explaining the main geophysical (density) and geochemical (excess siderophile elements) observables.

  15. Phase partitioning of trace metals in a contaminated estuary influenced by industrial effluent discharge.

    PubMed

    Wang, Wenhao; Wang, Wen-Xiong

    2016-07-01

    Severe trace metal pollution due to industrial effluents releases was found in Jiulong River Estuary, Southern China. In this study, water samples were collected during effluent release events to study the dynamic changes of environmental conditions and metal partitioning among dissolved, particulate and colloidal phases controlled by estuarine mixing. Intermittent effluent discharges during low tide caused decreasing pH and dissolved oxygen, and induced numerous suspended particulate materials and dissolved organic carbon to the estuary. Different behaviors of Cu, Zn, Ni, Cr and Pb in the dissolved fraction against the conservative index salinity indicated different sources, e.g., dissolved Ni from the intermittent effluent. Although total metal concentrations increased markedly following effluent discharges, Cu, Zn, Cr, Pb were predominated by the particulate fraction. Enhanced adsorption onto particulates in the mixing process resulted in elevated partitioning coefficient (Kd) values for Cu and Zn, and the particle concentration effect was not obvious under such anthropogenic impacts. Colloidal proportion of these metals (especially Cu and Zn) showed positive correlations with dissolved or colloidal organic carbon, suggesting the metal-organic complexation. However, the calculated colloidal partitioning coefficients were relatively constant, indicating the excess binding capacity. Overall, the intermittent effluent discharge altered the particulate/dissolved and colloidal/soluble phase partitioning process and may further influence the bioavailability and potential toxicity to aquatic organisms. PMID:27061473

  16. Genetically engineered charge modifications to enhance protein separation in aqueous two-phase systems: Charge directed partitioning

    SciTech Connect

    Luther, J.R.; Glatz, C.E.

    1995-04-05

    This report continues the authors` examination of the effect of genetically engineered charge modifications on the partitioning behavior of proteins in aqueous two-phase extraction. The genetic modifications consisted of the fusion of charged peptide tails to {beta}-galactosidase and charge-change point mutations to T4 lysozyme. In this study, they examined charge directed partitioning behavior in PEG/dextran systems containing small amounts of the charged polymers diethylaminoethyl-dextran (DEAE-dextran) or dextran sulfate. The best results were obtained when attractive forces between the protein and polymer were present. Nearly 100% of the {beta}-galactosidase, which carries a net negative charge, partitioned to the DEAE-dextran-rich phase regardless of whether the phase was dextran or PEG. In these cases, cloudiness of the protein-rich phases suggest that strong charge interactions resulted in protein/polymer aggregation, which may have contribution to the extreme partitioning. Unlike the potential-driven partitioning reported previously, consistent partitioning trends were observed as a result of the fusion tails, with observed shifts in partition coefficient (K{sub p}) of up to 37-fold. However, these changes could not be solely attributed to charge-based interactions.

  17. Comparison of the in situ and desprptipn sediment-water partitioning of polycyclic aromatic hydrocarbons and polychlorinated biphenyls

    USGS Publications Warehouse

    Mcgroddy, S.E.; Farrington, J.W.; Gschwend, P.M.

    1996-01-01

    In situ sediment-porewater partitioning of polycyclic aromatic hydrocarbons (PAHs) measured in three cores from Boston Harbor, MA, has led us to suggest that only a fraction of the total measured sediment PAH concentration is available for equilibrium partitioning (AEP fraction). To test this, aqueous PAH concentrations were measured in laboratory desorption experiments using subsamples of the same Boston Harbor sediments. The observed concentrations were consistentwith what we predicted from the field-derived AEP values: Caqueous=(Csediment ?? AEP)/(foc ?? Koc) where foc is the fraction organic carbon in the sediment and Koc is the organic carbon normalized sediment-water partition coefficient. Equilibrium partitioning models based on the total measured sediment PAH concentrations overestimated the measured aqueous PAH concentrations by as much as 100 times in some cases. Only a small fraction of the sediment phenanthrene and pyrene concentrations (1-40%) appeared to be available for equilibrium partitioning. Both in situ and laboratory desorption aqueous polychlorinated biphenyl (PCB) concentrations were consistent with equilibrium partitioning models and the assumption that 100% of these compounds was available for equilibrium partitioning. These results are particularly important to efforts to predict the environmental mobility and bioavailability of the PAHs.

  18. Atmospheric amines - Part II. Thermodynamic properties and gas/particle partitioning

    NASA Astrophysics Data System (ADS)

    Ge, Xinlei; Wexler, Anthony S.; Clegg, Simon L.

    2011-01-01

    Amines enter the atmosphere from a wide range of sources, but relatively little is known about their atmospheric behavior, especially their role in gas/particle partitioning. In Part I of this work ( Ge et al., 2011) a total of 154 amines, 32 amino acids and urea were identified as occurring in the atmosphere, based upon a survey of the literature. In this work we compile data for the thermodynamic properties of the amines which control gas/particle partitioning (Henry's Law constant, liquid vapor pressure, acid dissociation constant, activity coefficient and solubility in water), and also estimate the solid/gas dissociation constants of their nitrate and chloride salts. Prediction methods for boiling point, liquid vapor pressure, acid dissociation constant and the solubility of the amines in water are evaluated, and used to estimate values of the equilibrium constants where experimental data are lacking. Partitioning of amines into aqueous aerosols is strongly dependent upon pH and is greatest for acidic aerosols. For several common amines the tendency to partition to the particle phase is similar to or greater than that of ammonia. Our results are presented as tables of values of thermodynamic equilibrium constants, which are also incorporated into the Extended Aerosol Inorganics Model ( E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) to enable gas/aerosol partitioning and other calculations to be carried out.

  19. Effects of organic solvents on the partitioning of enzymes in aqueous two-phase systems.

    PubMed

    Johansson, G; Kopperschläger, G

    1987-02-13

    Organic solvents (ethylene glycol, glycerol, dimethyl sulphoxide, dimethylformamide, dioxane, methanol and propanol-2, as well as sucrose and urea) have been included in aqueous two-phase (liquid-liquid) systems comprised of water, dextran and poly(ethylene glycol). The concentration of the organic solvent was in most cases 20% (w/w). The influence of these solvents on the phase-forming properties, the volume ratio, the freezing point and the partitioning of a polymer-bound ligand, Procion Red HE-3B poly(ethylene glycol), has been studied. The partition coefficients for alkaline phosphatase decrease with ethylene glycol, glycerol, sucrose and urea (factors of 0.25-0.5), but increase with the other substances (factors of 1.2-1.6). The temperature effects on the partitioning of alkaline phosphatase from calf intestine as well as of phosphofructokinase from yeast in systems containing ethylene glycol have been studied and compared with partitioning in standard systems, not containing solvents. The possible uses of the above systems for partitioning studies of enzymes are discussed. PMID:2951391

  20. Effect of Sulfur on Siderophile Element Partitioning Between Olivine and Martian Primary Melt

    NASA Technical Reports Server (NTRS)

    Usui, T.; Shearer, C. K.; Righter, K.; Jones, J. H.

    2011-01-01

    Since olivine is a common early crystallizing phase in basaltic magmas that have produced planetary and asteroidal crusts, a number of experimental studies have investigated elemental partitioning between olivine and silicate melt [e.g., 1, 2, 3]. In particular, olivine/melt partition coefficients of Ni and Co (DNi and DCo) have been intensively studied because these elements are preferentially partitioned into olivine and thus provide a uniquely useful insight into the basalt petrogenesis [e.g., 4, 5]. However, none of these experimental studies are consistent with incompatible signatures of Co [e.g., 6, 7, 8] and Ni [7] in olivines from Martian meteorites. Chemical analyses of undegassed MORB samples suggest that S dissolved in silicate melts can reduce DNi up to 50 % compared to S-free experimental systems [9]. High S solubility (up to 4000 ppm) for primitive shergottite melts [10] implies that S might have significantly influenced the Ni and Co partitioning into shergottite olivines. This study conducts melting experiments on Martian magmatic conditions to investigate the effect of S on the partitioning of siderophile elements between olivine and Martian primary melt.

  1. Naphthalene SOA: redox activity and naphthoquinone gas-particle partitioning

    NASA Astrophysics Data System (ADS)

    McWhinney, R. D.; Zhou, S.; Abbatt, J. P. D.

    2013-10-01

    Chamber secondary organic aerosol (SOA) from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox-active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. These results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10-4 m3 μg-1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. Also, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

  2. Reducing variance in batch partitioning measurements

    SciTech Connect

    Mariner, Paul E.

    2010-08-11

    The partitioning experiment is commonly performed with little or no attention to reducing measurement variance. Batch test procedures such as those used to measure K{sub d} values (e.g., ASTM D 4646 and EPA402 -R-99-004A) do not explain how to evaluate measurement uncertainty nor how to minimize measurement variance. In fact, ASTM D 4646 prescribes a sorbent:water ratio that prevents variance minimization. Consequently, the variance of a set of partitioning measurements can be extreme and even absurd. Such data sets, which are commonplace, hamper probabilistic modeling efforts. An error-savvy design requires adjustment of the solution:sorbent ratio so that approximately half of the sorbate partitions to the sorbent. Results of Monte Carlo simulations indicate that this simple step can markedly improve the precision and statistical characterization of partitioning uncertainty.

  3. Cell Partition in Two Polymer Aqueous Phases

    NASA Technical Reports Server (NTRS)

    Harris, J. M.

    1985-01-01

    Partition of biological cells in two phase aqueous polymer systems is recognized as a powerful separation technique which is limited by gravity. The synthesis of new, selective polymer ligand conjugates to be used in affinity partition separations is of interest. The two most commonly used polymers in two phase partitioning are dextran and polyethylene glycol. A thorough review of the chemistry of these polymers was begun, particularly in the area of protein attachment. Preliminary studies indicate the importance in affinity partitioning of minimizing gravity induced randomizing forces in the phase separation process. The PEG-protein conjugates that were prepared appear to be ideally suited for achieving high quality purifications in a microgravity environment. An interesting spin-off of this synthetic work was the observation of catalytic activity for certain of our polymer derivatives.

  4. Connections between groundwater flow and transpiration partitioning.

    PubMed

    Maxwell, Reed M; Condon, Laura E

    2016-07-22

    Understanding freshwater fluxes at continental scales will help us better predict hydrologic response and manage our terrestrial water resources. The partitioning of evapotranspiration into bare soil evaporation and plant transpiration remains a key uncertainty in the terrestrial water balance. We used integrated hydrologic simulations that couple vegetation and land-energy processes with surface and subsurface hydrology to study transpiration partitioning at the continental scale. Both latent heat flux and partitioning are connected to water table depth, and including lateral groundwater flow in the model increases transpiration partitioning from 47 ± 13 to 62 ± 12%. This suggests that lateral groundwater flow, which is generally simplified or excluded in Earth system models, may provide a missing link for reconciling observations and global models of terrestrial water fluxes. PMID:27463671

  5. Connections between groundwater flow and transpiration partitioning

    NASA Astrophysics Data System (ADS)

    Maxwell, Reed M.; Condon, Laura E.

    2016-07-01

    Understanding freshwater fluxes at continental scales will help us better predict hydrologic response and manage our terrestrial water resources. The partitioning of evapotranspiration into bare soil evaporation and plant transpiration remains a key uncertainty in the terrestrial water balance. We used integrated hydrologic simulations that couple vegetation and land-energy processes with surface and subsurface hydrology to study transpiration partitioning at the continental scale. Both latent heat flux and partitioning are connected to water table depth, and including lateral groundwater flow in the model increases transpiration partitioning from 47 ± 13 to 62 ± 12%. This suggests that lateral groundwater flow, which is generally simplified or excluded in Earth system models, may provide a missing link for reconciling observations and global models of terrestrial water fluxes.

  6. Partitioning of heavy metals to suspended solids of the Flint River, Michigan

    SciTech Connect

    McIlroy, L.M.; DePinto, J.V.; Young, T.C.; Martin, S.C.

    1986-01-01

    The sorptive affinity of copper and zinc to suspended river sediments was investigated as a function of pH and adsorbent solids concentration. Water samples from the Flint River in Michigan were centrifuged to yield a composite sediment concentrate used as an adsorbent in experiments determining pH adsorption edges and conditional adsorption isotherms. Copper and zinc exhibited sharp pH adsorption edges at pH values of approximately 4 to 5.5 and 6 to 7, respectively. Both metals exhibited fractional adsorption decreases as total metal in the system increased. Adsorbent concentration increases were shown to cause decreases in measured copper partition coefficients. The indirect relationship between adsorbent concentration and partition coefficient was observed whether the adsorbent was concentrated or diluted without altering bulk solution chemistry. A mathematical formulation that incorporated both the adsorbent mass effects and the separation of sorbed metal into reversible and resistant components satisfactorily described the observations.

  7. Deriving the Hirshfeld partitioning using distance metrics

    SciTech Connect

    Heidar-Zadeh, Farnaz; Ayers, Paul W.; Bultinck, Patrick

    2014-09-07

    The atoms in molecules associated with the Hirshfeld partitioning minimize the generalized Hellinger-Bhattacharya distance to the reference pro-atom densities. Moreover, the reference pro-atoms can be chosen by minimizing the distance between the pro-molecule density and the true molecular density. This provides an alternative to both the heuristic “stockholder” and the mathematical information-theoretic interpretations of the Hirshfeld partitioning. These results extend to any member of the family of f-divergences.

  8. Isorropia Partitioning and Load Balancing Package

    2006-09-01

    Isorropia is a partitioning and load balancing package which interfaces with the Zoltan library. Isorropia can accept input objects such as matrices and matrix-graphs, and repartition/redistribute them into a better data distribution on parallel computers. Isorropia is primarily an interface package, utilizing graph and hypergraph partitioning algorithms that are in the Zoltan library which is a third-party library to Tilinos.

  9. Deriving the Hirshfeld partitioning using distance metrics

    NASA Astrophysics Data System (ADS)

    Heidar-Zadeh, Farnaz; Ayers, Paul W.; Bultinck, Patrick

    2014-09-01

    The atoms in molecules associated with the Hirshfeld partitioning minimize the generalized Hellinger-Bhattacharya distance to the reference pro-atom densities. Moreover, the reference pro-atoms can be chosen by minimizing the distance between the pro-molecule density and the true molecular density. This provides an alternative to both the heuristic "stockholder" and the mathematical information-theoretic interpretations of the Hirshfeld partitioning. These results extend to any member of the family of f-divergences.

  10. Chalcophile element partitioning into magmatic sulphides: the effect of silicate melt composition

    NASA Astrophysics Data System (ADS)

    Kiseeva, Kate; Wood, Bernard

    2016-04-01

    Partitioning of many elements between sulphide and silicate melts is a function of the FeO content of the silicate liquid (Kiseeva and Wood, 2013). The theoretical relationship is a linear one between LogDM (DM=[M]sulph/[M]sil) and -log[FeO] with a slope of n/2, where n is the valency of trace element M. In practice we find that the slope deviates from the theoretical one because of the presence of oxygen in the sulphide. In our recent study we investigated the effects of sulphide composition and temperature on chalcophile element partitioning between sulphide and silicate liquids (Kiseeva and Wood, 2015). We have concluded that partitioning of most chalcophile elements is a strong function of the oxygen (or FeO) content of the sulphide. As expected, lithophile elements partition more strongly into sulphide as its oxygen content increases, while chalcophile elements enter sulphide less readily with increasing oxygen. The effect of Ni and Cu content of sulphide is significantly smaller than the effect of oxygen, while the effects of temperature are large only for a number of elements (such as Ni, Cu, Ag). In this study we show that in addition to the effect of sulphide composition, for certain elements the effect of silicate melt composition on sulphide/silicate partitioning can be quite large. For instance, within the range of NBO/T between 0.5 and 2 the DTlsulph/sil changes in order of magnitude. For the elements, like Pb, partition coefficient does not seem to change much with the silicate melt composition, while for Sb the effect of the silicate melt composition on D is a factor of 3. Partitioning of chalcophile elements into more evolved, alkali-rich and felsic magmas is estimated to be very different from the partitioning into basaltic melts, mainly due to the strong effects of temperature and alkali components. Although it is highly likely that sulphide is in solid form at liquidus temperatures for dacite and rhyolite and thus the partitioning of chalcophile

  11. Automorphic instanton partition functions on Calabi-Yau threefolds

    NASA Astrophysics Data System (ADS)

    Persson, Daniel

    2012-02-01

    We survey recent results on quantum corrections to the hypermultiplet moduli space Script M in type IIA/B string theory on a compact Calabi-Yau threefold X, or, equivalently, the vector multiplet moduli space in type IIB/A on X × S1. Our main focus lies on the problem of resumming the infinite series of D-brane and NS5-brane instantons, using the mathematical machinery of automorphic forms. We review the proposal that when the theory in three dimensions exhibits an arithmetic "U-duality" symmetry G(Bbb Z) the total instanton partition function arises from a certain unitary automorphic representation of G, whose Fourier coefficients reproduce the BPS-degeneracies. In the case of four-dimensional Script N = 2 theories on Bbb R × S1 we argue that the relevant automorphic representation falls in the quaternionic discrete series of G, and that the partition function is a holomorphic section on the twistor space over Script M.

  12. Partitioning studies of coal-tar constitutents in a two-phase contaminated ground-water system

    SciTech Connect

    Rostad, C.E.; Pereira, W.E.; Hult, M.F.

    1985-01-01

    Organic compounds derived from coal-tar wastes in a contaminated aquifer in St. Louis Park, Minnesota, were identified, and their partition coefficients between the tar phase and aqueous phase were determined and compared with the corresponding n-octanol/water partition coefficients. Coal tar contains numerous polycyclic aromatic compounds, many of which are suspected carcinogens or mutagens. Groundwater contamination by these toxic compounds may pose an environmental health hazard in nearby public water-supply wells. Fluid samples from this aquifer developed two phases upon settling: an upper aqueous phase, and a lower oily-tar phase. After separating the phases, polycyclic aromatic compounds in each phase were isolated using complexation with N-methyl-2-pyrrolidone and identified by fused-silica capillary gas chromatography/mass spectrometry. Thirty-one of the polycyclic aromatic compounds were chosen for further study from four different classes: 12 polycyclic aromatic hydrocarbons, 10 nitrogen heterocycles, 5 sulfur heterocycles, and 4 oxygen heterocycles. Within each compounds class, the tar/water partition coefficients of these compounds were reasonable comparable with the respective n-octanol/water partition coefficient.

  13. FATE OF DYES IN AQUATIC SYSTEMS. 1. SOLUBILITY AND PARTITIONING OF SOME HYDROPHOBIC DYES AND RELATED COMPOUNDS

    EPA Science Inventory

    Solubilities and vapor pressures from the literature are combined with calculated octanol/water partition coefficients, K (sub ow), to assess the expected environmental behavior of about 50 dyes. The solubility suggests the potential for a 30- to 150-fold concentration enhancemen...

  14. Partitioning studies of coal-tar constituents in a two-phase contaminated ground-water system

    USGS Publications Warehouse

    Rostad, C.E.; Pereira, W.E.; Hult, M.F.

    1985-01-01

    Organic compounds derived from coal-tar wastes in a contaminated aquifer in St. Louis Park, Minnesota, were identified, and their partition coefficients between the tar phase and aqueous phase were determined and compared with the corresponding n-octanol/water partition coefficients. Coal tar contains numerous polycyclic aromatic compounds, many of which are suspected carcinogens or mutagens. Groundwater contamination by these toxic compounds may pose an environmental health hazard in nearby public water-supply wells. Fluid samples from this aquifer developed two phases upon settling: an upper aqueous phase, and a lower oily-tar phase. After separating the phases, polycyclic aromatic compounds in each phase were isolated using complexation with N-methyl-2-pyrrolidone and identified by fused-silica capillary gas chromatography/mass spectrometry. Thirty-one of the polycyclic aromatic compounds were chosen for further study from four different classes: 12 polycyclic aromatic hydrocarbons, 10 nitrogen heterocycles, 5 sulfur heterocycles, and 4 oxygen heterocycles. Within each compound class, the tar/water partition coefficients of these compounds were reasonably comparable with the respective n-octanol/water partition coefficient.

  15. Quadrature formulas for Fourier coefficients

    NASA Astrophysics Data System (ADS)

    Bojanov, Borislav; Petrova, Guergana

    2009-09-01

    We consider quadrature formulas of high degree of precision for the computation of the Fourier coefficients in expansions of functions with respect to a system of orthogonal polynomials. In particular, we show the uniqueness of a multiple node formula for the Fourier-Tchebycheff coefficients given by Micchelli and Sharma and construct new Gaussian formulas for the Fourier coefficients of a function, based on the values of the function and its derivatives.

  16. Coefficient Alpha: A Reliability Coefficient for the 21st Century?

    ERIC Educational Resources Information Center

    Yang, Yanyun; Green, Samuel B.

    2011-01-01

    Coefficient alpha is almost universally applied to assess reliability of scales in psychology. We argue that researchers should consider alternatives to coefficient alpha. Our preference is for structural equation modeling (SEM) estimates of reliability because they are informative and allow for an empirical evaluation of the assumptions…

  17. PAC91 - PROPERTIES AND COEFFICIENTS 1991

    NASA Technical Reports Server (NTRS)

    Mcbride, B. J.

    1994-01-01

    The two principal functions of PAC91 are to provide a means of generating theoretical thermodynamic functions from molecular constant data and to supply a means of fitting these functions to empirical equations by using a least-squares fit. The coefficients obtained from the fit may then be used to generate a library of thermodynamic data in a uniform and easy-to-use format for use in other computer codes. Several large compilations of selected or calculated thermodynamic data currently exist. Nevertheless, there is a continuing need for additional calculations due to the discovery of new species, the revision of existing molecular constant data and structural parameters, the need for data at temperatures other than those already published, the availability of new or revised heats of formation, dissociation or transition, and the revision of fundamental constants or atomic weights. Calculations may also be needed to compare the results of assuming various possible forms of the partition function. In addition, there is often a preference for thermodynamic data in functional rather than tabular form. In order to satisfy these needs, the PAC91 program can perform any combination of the following: (1) calculate thermodynamic functions (heat capacity, enthalpy, entropy, and Gibbs energy) for any set of 1 to 202 temperatures, (2) obtain a least-squares fit of the first three of these functions (either individually, two at a time, or all three simultaneously) for up to eight temperature intervals, and (3) calculate, as a function of temperature, heats of formation and equilibrium constants from assigned reference elements. The thermodynamic functions for ideal gases may be calculated from molecular constant data using one of several partition function variations provided by the program. For monatomic gases, one of three partition function cutoff techniques may be selected by the user, and unobserved but predicted electronic energy levels may be included by the program

  18. Software Partitioning Schemes for Advanced Simulation Computer Systems. Final Report.

    ERIC Educational Resources Information Center

    Clymer, S. J.

    Conducted to design software partitioning techniques for use by the Air Force to partition a large flight simulator program for optimal execution on alternative configurations, this study resulted in a mathematical model which defines characteristics for an optimal partition, and a manually demonstrated partitioning algorithm design which…

  19. The Perils of Partition: Difficulties in Retrieving Magma Compositions from Chemically Equilibrated Basaltic Meteorites

    NASA Technical Reports Server (NTRS)

    Treiman, Allan H.

    1996-01-01

    The chemical compositions of magmas can be derived from the compositions of their equilibrium minerals through mineral/magma partition coefficients. This method cannot be applied safely to basaltic rocks, either solidified lavas or cumulates, which have chemically equilibrated or partially equilibrated at subsolidus temperatures, i.e., in the absence of magma. Applying mineral/ melt partition coefficients to mineral compositions from such rocks will typically yield 'magma compositions' that are strongly fractionated and unreasonably enriched in incompatible elements (e.g., REE's). In the absence of magma, incompatible elements must go somewhere; they are forced into minerals (e.g., pyroxenes, plagioclase) at abundance levels far beyond those established during normal mineral/magma equilibria. Further, using mineral/magma partition coefficients with such rocks may suggest that different minerals equilibrated with different magmas, and the fractionation sequence of those melts (i.e., enrichment in incompatible elements) may not be consistent with independent constraints on the order of crystallization. Subsolidus equilibration is a reasonable cause for incompatible- element-enriched minerals in some eucrites, diogenites, and martian meteorites and offers a simple alternative to petrogenetic schemes involving highly fractionated magmas or magma infiltration metasomatism.

  20. Partitioning of organophosphorus pesticides into phosphatidylcholine small unilamellar vesicles studied by second-derivative spectrophotometry

    NASA Astrophysics Data System (ADS)

    Takegami, Shigehiko; Kitamura, Keisuke; Ohsugi, Mayuko; Ito, Aya; Kitade, Tatsuya

    2015-06-01

    In order to quantitatively examine the lipophilicity of the widely used organophosphorus pesticides (OPs) chlorfenvinphos (CFVP), chlorpyrifos-methyl (CPFM), diazinon (DZN), fenitrothion (FNT), fenthion (FT), isofenphos (IFP), profenofos (PFF) and pyraclofos (PCF), their partition coefficient (Kp) values between phosphatidylcholine (PC) small unilamellar vesicles (SUVs) and water (liposome-water system) were determined by second-derivative spectrophotometry. The second-derivative spectra of these OPs in the presence of PC SUV showed a bathochromic shift according to the increase in PC concentration and distinct derivative isosbestic points, demonstrating the complete elimination of the residual background signal effects that were observed in the absorption spectra. The Kp values were calculated from the second-derivative intensity change induced by addition of PC SUV and obtained with a good precision of R.S.D. below 10%. The Kp values were in the order of CPFM > FT > PFF > PCF > IFP > CFVP > FNT ⩾ DZN and did not show a linear correlation relationship with the reported partition coefficients obtained using an n-octanol-water system (R2 = 0.530). Also, the results quantitatively clarified the effect of chemical-group substitution in OPs on their lipophilicity. Since the partition coefficient for the liposome-water system is more effective for modeling the quantitative structure-activity relationship than that for the n-octanol-water system, the obtained results are toxicologically important for estimating the accumulation of these OPs in human cell membranes.

  1. Equilibrium partition ratios, densities, and transport phenomena in nickel-base superalloys

    NASA Astrophysics Data System (ADS)

    Sung, Pil Kyung

    To simulate transport phenomena, macrosegregation and segregation defects known as "freckles" during directional solidification of Ni-base superalloys, numerical modeling can be used; hence it is essential to have reasonably accurate values of the thermodynamic and transport properties for the alloys. In this research, therefore, the equilibrium partition ratios of the solutes in the Ni-Al-Ta-Cr quaternary system, as a model alloy, were measured, and the solid- and liquid-densities in Ni-base superalloys. were estimated. Also, the importance of these properties on the sensitivity of the results of numerical simulations was studied. The partition ratios apply to equilibria between melts and gamma-phase in the range of 1615 K to 1694 K, and it was found that the equilibrium partition ratio of Ta varies from approximately 0.6 at dilute Ta to 0.85 at 17 wt.% Ta. For the same range of Ta-contents, the partition ratios of Al and Cr vary much less and range from about 0.92 to 0.96. In addition to the partition ratios, the liquidus temperatures of the liquid in equilibrium with gamma in the Ni-Al-Ta-Cr system were estimated with a multidimensional regression analysis. To calculate the densities of solid Ni-base superalloys as functions of temperature and composition, lattice parameters at 20°C and coefficients of thermal expansion (CTEs) were estimated by combining available data. The CTEs calculated from the regressions result in densities that are within 0.5% error or less for seventeen alloys. To estimate the densities of liquid Ni-base superalloys, the densities and temperature coefficients of density of the liquid transition-metals, which are used as alloy elements in Ni-base superalloys, were applied to a simple correlation. By using this approach, the estimates of the liquid densities of five Ni-base superalloys agree with the measured values to +/-2.5%. Finally, the importance of using reasonably accurate estimates of the transport properties was illustrated by

  2. RADIONUCLIDE RISK COEFFICIENT UNCERTAINTY REPORT

    EPA Science Inventory

    EPA has published excess cancer risk coefficients for the US population in Federal Guidance Report 13 (FGR 13). FGR 13 gives separate risk coefficients for food ingestion, water ingestion, inhalation, and external exposure for each of over 800 radionuclides. Some information on...

  3. Standardized Discriminant Coefficients: A Rejoinder.

    ERIC Educational Resources Information Center

    Mueller, Ralph O.; Cozad, James B.

    1993-01-01

    Although comments of D.J. Nordlund and R. Nagel are welcomed, their arguments are not sufficient to accept the recommendation of using total variance estimates to standardize canonical discriminant function coefficients. If standardized coefficients are used to help interpret a discriminant analysis, pooled within-group variance estimates should…

  4. Temperature and pressure dependence of Ni partitioning between olivine and high-MgO silicate melts

    NASA Astrophysics Data System (ADS)

    Matzen, A. K.; Baker, M. B.; Beckett, J.; Stolper, E. M.

    2010-12-01

    Mantle melting that produces ocean island basalts (OIBs) takes place at temperatures (T) and pressures (P) significantly higher than the conditions at which they erupt or are intruded in the crust/shallow upper mantle [1]. To the degree that the olivine (ol)-liquid (liq) nickel partition coefficient depends on T and P, it is important that models used to describe ol-liq Ni partitioning during mantle melting include data from experiments at elevated T and P. The expressions can then be used in models which aim to reproduce the wide range of Ni contents measured in primitive phenocrysts from OIBs [2]. Available data on Ni partitioning is dominated by 1-atm experiments in which T and liquid composition are highly correlated, making it difficult to separate the effects of these variables on the observed variations in Ni partitioning between ol and liq based on 1-atm experiments alone [3].
    We conducted experiments on a mixture of MORB and olivine at 1 atm (1400°C) and 1-3 GPa (1450-1550°C). We moderated the loss of Ni from the silicate melt to the Pt-enclosed graphite capsule by surrounding the chip of MORB glass with powdered olivine and sintering the assembly at a T below the solidus of the MORB chip. The data presented in this work is from a series of reversed experiments where T and P were increased in such a way that the liquid composition remained approximately constant (MgO ~ 17 wt. %), effectively isolating the effects of T and P from those of liquid composition on the ol-liq partition coefficient. The resulting partition coefficient decreases from ~5 to 3.8 (by wt) as the temperature increases from 1400 to 1550°C. The rate of decrease of the Ni partition coefficient measured in these experiments (~0.5/100°C) is less than that of recent models, which predict a decrease of ~0.1/100°C [4]. Using the results of our experiments we fit a thermodynamic expression to describe the ol-liq Ni-Mg exchange equilibrium as a function of both T and liquid

  5. Specific ion interactions with aromatic rings in aqueous solutions: Comparison of molecular dynamics simulations with a thermodynamic solute partitioning model and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Vincent, Jordan C.; Matt, Sarah M.; Rankin, Blake M.; D'Auria, Raffaella; Freites, J. Alfredo; Ben-Amotz, Dor; Tobias, Douglas J.

    2015-10-01

    Specific ion interactions of KF, and the Na+ salts of SO42-, F-, Cl-, NO3-, I-, and ClO4- with benzene in aqueous solutions were investigated using molecular dynamics simulations and compared with experimental Raman multivariate curve resolution (Raman-MCR) and thermodynamic results. Good agreement is found with the hydration-shell partition coefficients of salts obtained from the thermodynamic analysis and of halogen anions obtained from the Raman-MCR spectra of benzene and pyridine. Larger discrepancies between the simulation and thermodynamic cation partitioning results point to the influence of counter-ion interaction on cation partitioning.

  6. Multi-A Graph Patrolling and Partitioning

    NASA Astrophysics Data System (ADS)

    Elor, Y.; Bruckstein, A. M.

    2012-12-01

    We introduce a novel multi agent patrolling algorithm inspired by the behavior of gas filled balloons. Very low capability ant-like agents are considered with the task of patrolling an unknown area modeled as a graph. While executing the proposed algorithm, the agents dynamically partition the graph between them using simple local interactions, every agent assuming the responsibility for patrolling his subgraph. Balanced graph partition is an emergent behavior due to the local interactions between the agents in the swarm. Extensive simulations on various graphs (environments) showed that the average time to reach a balanced partition is linear with the graph size. The simulations yielded a convincing argument for conjecturing that if the graph being patrolled contains a balanced partition, the agents will find it. However, we could not prove this. Nevertheless, we have proved that if a balanced partition is reached, the maximum time lag between two successive visits to any vertex using the proposed strategy is at most twice the optimal so the patrol quality is at least half the optimal. In case of weighted graphs the patrol quality is at least (1)/(2){lmin}/{lmax} of the optimal where lmax (lmin) is the longest (shortest) edge in the graph.

  7. Determination of soil–water sorption coefficients of volatile methylsiloxanes

    PubMed Central

    Kozerski, Gary E; Xu, Shihe; Miller, Julie; Durham, Jeremy

    2014-01-01

    The sorption behaviors of 4 cyclic and linear volatile methyl siloxane (VMS) compounds between water and organic matter in 3 United Kingdom soils were studied by a batch equilibrium method using13C-enriched sorbates. Sorption and desorption kinetics and isotherms were determined for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), octamethyltrisiloxane (L3), and decamethyltetrasiloxane (L4). Concentrations of [13C]-VMS in the soil and aqueous phases were measured directly by extraction and gas chromatography–mass spectrometry techniques. All VMS compounds were sorbed rapidly, reaching constant distributions in all soils by 24 h. Desorption kinetics were very rapid, with reattainment of equilibrium within 1 h. In the main, linear isotherms were observed for aqueous concentrations at or below 4% of the solubility limits. The average sorption organic carbon partition coefficient (log KOC) values across soils were 4.23 for D4, 5.17 for D5, 4.32 for L3, and 5.13 for L4, with standard deviations of 0.09 to 0.34. Desorption KOC values were systematically greater by 0.1 log units to 0.3 log units. The linear isotherms and low variation in KOC values across soils suggested partitioning-dominated sorption of the VMS. Compared with traditional hydrophobic organic compounds, KOC values for the VMS compounds were significantly lower than expected on the basis of their octanol–water partition coefficients. A linear free energy relationship analysis showed that these differences could be rationalized quantitatively in terms of the inherent characteristics of the VMS compounds, combined with the differences in solvation properties of organic matter and octanol. Environ Toxicol Chem 2014; 33:1937–1945. PMID:24862578

  8. A partition-limited model for the plant uptake of organic contaminants from soil and water

    USGS Publications Warehouse

    Chiou, C.T.; Sheng, G.; Manes, M.

    2001-01-01

    In dealing with the passive transport of organic contaminants from soils to plants (including crops), a partition-limited model is proposed in which (i) the maximum (equilibrium) concentration of a contaminant in any location in the plant is determined by partition equilibrium with its concentration in the soil interstitial water, which in turn is determined essentially by the concentration in the soil organic matter (SOM) and (ii) the extent of approach to partition equilibrium, as measured by the ratio of the contaminant concentrations in plant water and soil interstitial water, ??pt (??? 1), depends on the transport rate of the contaminant in soil water into the plant and the volume of soil water solution that is required for the plant contaminant level to reach equilibrium with the external soil-water phase. Through reasonable estimates of plant organic-water compositions and of contaminant partition coefficients with various plant components, the model accounts for calculated values of ??pt in several published crop-contamination studies, including near-equilibrium values (i.e., ??pt ??? 1) for relatively water-soluble contaminants and lower values for much less soluble contaminants; the differences are attributed to the much higher partition coefficients of the less soluble compounds between plant lipids and plant water, which necessitates much larger volumes of the plant water transport for achieving the equilibrium capacities. The model analysis indicates that for plants with high water contents the plant-water phase acts as the major reservoir for highly water-soluble contaminants. By contrast, the lipid in a plant, even at small amounts, is usually the major reservoir for highly water-insoluble contaminants.

  9. Experimental Study of the Partitioning of Siderophile Elements in a Crystallizing Lunar Magma Ocean

    NASA Technical Reports Server (NTRS)

    Galenas, M.; Righter, K.; Danielson, L.; Pando, K.; Walker, R. J.

    2012-01-01

    The distributions of trace elements between the lunar interior and pristine crustal rocks were controlled by the composition of starting materials, lunar core formation, and crystallization of the lunar magma ocean (LMO) [1]. This study focuses on the partitioning of highly siderophile elements (HSE) including Re, Os, Ir, Ru, Pt, Rh, Pd and Au as well as the moderately siderophile elements Mo and W, and the lithophile elements of Hf and Sr. Our experiments also include Ga, which can be slightly siderophile, but is mostly considered to be chalcophile. Partitioning of these elements is not well known at the conditions of a crystallizing LMO. Previous studies of HSE partitioning in silicate systems have yielded highly variable results for differing oxygen fugacity (fO2) and pressure [2-4]. For example, under certain conditions Pt is compatible in clinopy-roxene [2] and Rh and Ru are compatible in olivine [3]. The silicate compositions used for these experiments were nominally basaltic. Ruthenium, Rh, and Pd are incompatible in plagioclase under these conditions[4]. However, this latter study was done at extremely oxidizing conditions and at atmospheric pressure, possibly limiting the applicability for consideration of conditions of a crystallizing LMO. In this study we address the effects of pressure and oxygen fugacity on the crystal/liquid partition coefficients of these trace elements. We are especially interested in the plagioclase/melt partition coefficients so that it may be possible to use reverse modeling to constrain the concentrations of these elements in the lunar mantle through their abundances in pristine crustal rocks.

  10. Study and modeling of the evolution of gas-liquid partitioning of hydrogen sulfide in model solutions simulating winemaking fermentations.

    PubMed

    Mouret, Jean-Roch; Sablayrolles, Jean-Marie; Farines, Vincent

    2015-04-01

    The knowledge of gas-liquid partitioning of aroma compounds during winemaking fermentation could allow optimization of fermentation management, maximizing concentrations of positive markers of aroma and minimizing formation of molecules, such as hydrogen sulfide (H2S), responsible for defects. In this study, the effect of the main fermentation parameters on the gas-liquid partition coefficients (Ki) of H2S was assessed. The Ki for this highly volatile sulfur compound was measured in water by an original semistatic method developed in this work for the determination of gas-liquid partitioning. This novel method was validated and then used to determine the Ki of H2S in synthetic media simulating must, fermenting musts at various steps of the fermentation process, and wine. Ki values were found to be mainly dependent on the temperature but also varied with the composition of the medium, especially with the glucose concentration. Finally, a model was developed to quantify the gas-liquid partitioning of H2S in synthetic media simulating must to wine. This model allowed a very accurate prediction of the partition coefficient of H2S: the difference between observed and predicted values never exceeded 4%. PMID:25763810

  11. Enzymatic hydrolysis of cellulose in aqueous two-phase systems. 1. Partition of cellulases from Trichoderma reesei

    SciTech Connect

    Tjerneld, F.; Persson, J.; Albertsson, P.A.; Hahn-Haegerdal, B.

    1985-07-01

    The partitioning of endo-..beta..-glucanase, exo-..beta..-glucananse, and ..beta..-glucosidase from Trichoderma reesei QM 9414 in aqueous two-phase systems has been studied with the object of designing a phase system for continuous bioconversion of cellulose. The partitioning of the enzymes in two-phase systems composed of various water soluble polymeric compounds were studied. Systems based on dextran and polyethylene glycol (PEG) were optimal for one sidedly partitioning of the enzymes to the bottom phase. The influence of polymer molecular weights, polymer concentration, ionic composition of the medium, pH, temperature, and adsorption of the enzymes to cellulose on the enyzme partition coefficients (K) were studied. By combining the effects of polymer molecular weight and adsorption to cellulose, K values could be reduced for endo-..beta..-glucanase to 0.02 and for ..beta..-glucosidase to 0.005 at 20 degrees C in a phase system of Dvalues could be reduced for endo-..beta..-glucanase to 0.02 and for ..beta..-glucosidase to 0.005 at 20 degrees C in a phase system of Dextran 40-PEG 40000 in the presence of excess cellulose. At 50 degrees C, K values were increased by a factor of two. In a phase system based on inexpensive crude dextran and PEG, the partition coefficient for endo-..beta..-glucanase was 0.16 and for beta-glucosidase was 0.14 at 20 degrees C with excess cellulose present.

  12. Experimental partitioning studies near the Fe-FeS eutectic, with an emphasis on elements important to iron meteorite chronologies (Pb, Ag, Pd, and Tl)

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Hart, S. R.; Benjamin, T. M.

    1993-01-01

    Partitioning coefficients for metal/sulfide liquid, troilite/sulfide liquid, and schreibersite/sulfide liquid were determined for Ag, Au, Mo, Ni, Pd, and Tl (using EMPA and proton-induced X-ray microprobe and ion microprobe analyses) in order to understand the chronometer systems of iron meteorites. In general, the obtained schreibersite/metal and troilite/metal partition coefficients for 'compatible' elements were quite similar to those inferred from natural assemblages, reinforcing an earlier made conclusion that there is a class of elements for which experimental troilite/metal and schreibersite/metal partition coefficients approximate those inferred from natural samples. The consistency between experimental and natural assemblages, however, was not observed for Ag, Pb, and Tl, indicating that the abundances of these elements determined in 'metal' and 'troilite' separates from iron meteorites are influenced by trace minerals that concentrate incompatible elements.

  13. Characterization of bovine serum albumin partitioning behaviors in polymer-salt aqueous two-phase systems.

    PubMed

    Chow, Yin Hui; Yap, Yee Jiun; Tan, Chin Ping; Anuar, Mohd Shamsul; Tejo, Bimo Ario; Show, Pau Loke; Ariff, Arbakariya Bin; Ng, Eng-Poh; Ling, Tau Chuan

    2015-07-01

    In this paper, a linear relationship is proposed relating the natural logarithm of partition coefficient, ln K for protein partitioning in poly (ethylene glycol) (PEG)-phosphate aqueous two-phase system (ATPS) to the square of tie-line length (TLL(2)). This relationship provides good fits (r(2) > 0.98) to the partition of bovine serum albumin (BSA) in PEG (1450 g/mol, 2000 g/mol, 3350 g/mol, and 4000 g/mol)-phosphate ATPS with TLL of 25.0-50.0% (w/w) at pH 7.0. Results also showed that the plot of ln K against pH for BSA partitioning in the ATPS containing 33.0% (w/w) PEG1450 and 8.0% (w/w) phosphate with varied working pH between 6.0 and 9.0 exhibited a linear relationship which is in good agreement (r(2) = 0.94) with the proposed relationship, ln K = α' pH + β'. These results suggested that both the relationships proposed could be applied to correlate and elucidate the partition behavior of biomolecules in the polymer-salt ATPS. The influence of other system parameters on the partition behavior of BSA was also investigated. An optimum BSA yield of 90.80% in the top phase and K of 2.40 was achieved in an ATPS constituted with 33.0% (w/w) PEG 1450 and 8.0% (w/w) phosphate in the presence of 8.5% (w/w) sodium chloride (NaCl) at pH 9.0 for 0.3% (w/w) BSA load. PMID:25553974

  14. New parallel SOR method by domain partitioning

    SciTech Connect

    Xie, D.; Adams, L.

    1999-07-01

    In this paper the authors propose and analyze a new parallel SOR method, the PSOR method, formulated by using domain partitioning and interprocessor data communication techniques. They prove that the PSOR method has the same asymptotic rate of convergence as the Red/Black (R/B) SOR method for the five-point stencil on both strip and block partitions, and as the four-color (R/B/G/O) SOR method for the nine-point stencil on strip partitions. They also demonstrate the parallel performance of the PSOR method on four different MIMD multiprocessors (a KSR1, an Intel Delta, a Paragon, and an IBM SP2). Finally, they compare the parallel performance of PSOR, R/B SOR, and R/B/G/O SOR. Numerical results on the Paragon indicate that PSOR is more efficient than R/B SOR and R/B/G/O SOR in both computation and interprocessor data communication.

  15. Fourier transform spectrometer controller for partitioned architectures

    NASA Astrophysics Data System (ADS)

    Tamas-Selicean, D.; Keymeulen, D.; Berisford, D.; Carlson, R.; Hand, K.; Pop, P.; Wadsworth, W.; Levy, R.

    The current trend in spacecraft computing is to integrate applications of different criticality levels on the same platform using no separation. This approach increases the complexity of the development, verification and integration processes, with an impact on the whole system life cycle. Researchers at ESA and NASA advocated for the use of partitioned architecture to reduce this complexity. Partitioned architectures rely on platform mechanisms to provide robust temporal and spatial separation between applications. Such architectures have been successfully implemented in several industries, such as avionics and automotive. In this paper we investigate the challenges of developing and the benefits of integrating a scientific instrument, namely a Fourier Transform Spectrometer, in such a partitioned architecture.

  16. Parallel algorithms for dynamically partitioning unstructured grids

    SciTech Connect

    Diniz, P.; Plimpton, S.; Hendrickson, B.; Leland, R.

    1994-10-01

    Grid partitioning is the method of choice for decomposing a wide variety of computational problems into naturally parallel pieces. In problems where computational load on the grid or the grid itself changes as the simulation progresses, the ability to repartition dynamically and in parallel is attractive for achieving higher performance. We describe three algorithms suitable for parallel dynamic load-balancing which attempt to partition unstructured grids so that computational load is balanced and communication is minimized. The execution time of algorithms and the quality of the partitions they generate are compared to results from serial partitioners for two large grids. The integration of the algorithms into a parallel particle simulation is also briefly discussed.

  17. Some comments on molecular partition functions

    SciTech Connect

    Sharp, C.M.

    1987-03-01

    In models of cool stellar atmospheres where molecules are important, molecular spectroscopic data can be used to calculate partition functions, from which equilibrium constants hence abundances can be obtained. In this report, it is shown that simple analytic approximations can be used to calculate very easily the partition functions of diatomic molecules, and comparisons are made for the two particularly important astrophysical molecules, H/sub 2/ and CO, with other work where the partition functions are calculated by explicitly summing over a very large number of energy levels. It is found that these analytic approximations give excellent agreement with more detailed calculations and are certainly adequate for many purposes. This method is very convenient, as only a few spectroscopic constants are needed, and the analytic formulae are very easily evaluated.

  18. On the upscaling of mass transfer rate expressions for interpretation of source zone partitioning tracer tests

    NASA Astrophysics Data System (ADS)

    Boroumand, Ali; Abriola, Linda M.

    2015-02-01

    Analysis of partitioning tracer tests conducted in dense nonaqueous phase liquid (DNAPL) source zones relies on conceptual models that describe mass exchange between the DNAPL and aqueous phases. Such analysis, however, is complicated by the complex distribution of entrapped DNAPL mass and formation heterogeneity. Due to parameter uncertainty in heterogeneous regions and the desire to reduce model complexity, the effect of mass transfer limitations is often neglected, and an equilibrium-based model is typically used to interpret test results. This work explores the consequences of that simplifying assumption on test data interpretation and develops an alternative upscaled modeling approach to quantify effective mass transfer rates. To this end, a series of partitioning tracer tests is numerically simulated in heterogeneous two-dimensional PCE-DNAPL source zones, representative of a range of hydraulic conductivity and DNAPL mass distribution characteristics. The effective mass transfer coefficient corresponding to each test is determined by fitting an upscaled model to the simulated data, and regression analysis is performed to explore the correlation between various source zone metrics and the effective mass transfer coefficient. Results suggest that vertical DNAPL spreading, Reynolds number, pool fraction, and the effective organic phase saturation are the most significant parameters controlling tracer partitioning rates. Finally, a correlation for prediction of the effective (upscaled) mass transfer coefficient is proposed and verified using existing experimental data. The developed upscaled model incorporates the influence of physical heterogeneity on the rate of tracer partitioning and, thus, can be used for the estimation of source zone mass distribution characteristics from tracer test results.

  19. Influence of soil organic matter composition on the partition of organic compounds

    USGS Publications Warehouse

    Rutherford, D.W.; Chiou, C.T.; Klle, D.E.

    1992-01-01

    The sorption at room temperature of benzene and carbon tetrachloride from water on three high-organic-content soils (muck, peat, and extracted peat) and on cellulose was determined in order to evaluate the effect of sorbent polarity on the solute partition coefficients. The isotherms are highly linear for both solutes on all the organic matter samples, which is consistent with a partition model. For both solutes, the extracted peat shows the greatest sorption capacity while the cellulose shows the lowest capacity; the difference correlates with the polar-to-nonpolar group ratio [(O + N)/C] of the sorbent samples. The relative increase of solute partition coefficient (Kom) with a decrease of sample polar content is similar for both solutes, and the limiting sorption capacity on a given organic matter sample is comparable between the solutes. This observation suggests that one can estimate the polarity effect of a sample of soil organic matter (SOM) on Kom of various nonpolar solutes by determining the partition coefficient of single nonpolar solute when compositional analysis of the SOM is not available. The observed dependence of Kom on sample polarity is used to account for the variation of Kom values of individual compounds on different soils that results from change in the polar group content of SOM. On the assumption that the carbon content of SOM in "ordinary soils" is 53-63%, the calculated variation of Kom is a factor of ???3. This value is in agreement with the limit of variation of most Kom data with soils of relatively high SOM contents.

  20. Partition signed social networks via clustering dynamics

    NASA Astrophysics Data System (ADS)

    Wu, Jianshe; Zhang, Long; Li, Yong; Jiao, Yang

    2016-02-01

    Inspired by the dynamics phenomenon occurred in social networks, the WJJLGS model is modified to imitate the clustering dynamics of signed social networks. Analyses show that the clustering dynamics of the model can be applied to partition signed social networks. Traditionally, blockmodel is applied to partition signed networks. In this paper, a detailed dynamics-based algorithm for signed social networks (DBAS) is presented. Simulations on several typical real-world and illustrative networks that have been analyzed by the blockmodel verify the correctness of the proposed algorithm. The efficiency of the algorithm is verified on large scale synthetic networks.

  1. Partitioning SAT Instances for Distributed Solving

    NASA Astrophysics Data System (ADS)

    Hyvärinen, Antti E. J.; Junttila, Tommi; Niemelä, Ilkka

    In this paper we study the problem of solving hard propositional satisfiability problem (SAT) instances in a computing grid or cloud, where run times and communication between parallel running computations are limited.We study analytically an approach where the instance is partitioned iteratively into a tree of subproblems and each node in the tree is solved in parallel.We present new methods for constructing partitions which combine clause learning and lookahead. The methods are incorporated into the iterative approach and its performance is demonstrated with an extensive comparison against the best sequential solvers in the SAT competition 2009 as well as against two efficient parallel solvers.

  2. Wrong Signs in Regression Coefficients

    NASA Technical Reports Server (NTRS)

    McGee, Holly

    1999-01-01

    When using parametric cost estimation, it is important to note the possibility of the regression coefficients having the wrong sign. A wrong sign is defined as a sign on the regression coefficient opposite to the researcher's intuition and experience. Some possible causes for the wrong sign discussed in this paper are a small range of x's, leverage points, missing variables, multicollinearity, and computational error. Additionally, techniques for determining the cause of the wrong sign are given.

  3. Fuel Temperature Coefficient of Reactivity

    SciTech Connect

    Loewe, W.E.

    2001-07-31

    A method for measuring the fuel temperature coefficient of reactivity in a heterogeneous nuclear reactor is presented. The method, which is used during normal operation, requires that calibrated control rods be oscillated in a special way at a high reactor power level. The value of the fuel temperature coefficient of reactivity is found from the measured flux responses to these oscillations. Application of the method in a Savannah River reactor charged with natural uranium is discussed.

  4. The effects of composition and temperature on chalcophile and lithophile element partitioning into magmatic sulphides

    NASA Astrophysics Data System (ADS)

    Kiseeva, Ekaterina S.; Wood, Bernard J.

    2015-08-01

    We develop a comprehensive model to describe trace and minor element partitioning between sulphide liquids and anhydrous silicate liquids of approximately basaltic composition. We are able thereby to account completely for the effects of temperature and sulphide composition on the partitioning of Ag, Cd, Co, Cr, Cu, Ga, Ge, In, Mn, Ni, Pb, Sb, Ti, Tl, V and Zn. The model was developed from partitioning experiments performed in a piston-cylinder apparatus at 1.5 GPa and 1300 to 1700 °C with sulphide compositions covering the quaternary FeSsbnd NiSsbnd CuS0.5sbnd FeO. Partitioning of most elements is a strong function of the oxygen (or FeO) content of the sulphide. This increases linearly with the FeO content of the silicate melt and decreases with Ni content of the sulphide. As expected, lithophile elements partition more strongly into sulphide as its oxygen content increases, while chalcophile elements enter sulphide less readily with increasing oxygen. We parameterised the effects by using the ε-model of non-ideal interactions in metallic liquids. The resulting equation for partition coefficient of an element M between sulphide and silicate liquids can be expressed as We used our model to calculate the amount of sulphide liquid precipitated along the liquid line of descent of MORB melts and find that 70% of silicate crystallisation is accompanied by ∼0.23% of sulphide precipitation. The latter is sufficient to control the melt concentrations of chalcophile elements such as Cu, Ag and Pb. Our partition coefficients and observed chalcophile element concentrations in MORB glasses were used to estimate sulphur solubility in MORB liquids. We obtained between ∼800 ppm (for primitive MORB) and ∼2000 ppm (for evolved MORB), values in reasonable agreement with experimentally-derived models. The experimental data also enable us to reconsider Ce/Pb and Nd/Pb ratios in MORB. We find that constant Ce/Pb and Nd/Pb ratios of 25 and 20, respectively, can be achieved

  5. Partitioning of light lithophile elements during basalt eruptions on Earth and application to Martian shergottites

    NASA Astrophysics Data System (ADS)

    Edmonds, Marie

    2015-02-01

    An enigmatic record of light lithophile element (LLE) zoning in pyroxenes in basaltic shergottite meteorites, whereby LLE concentrations decrease dramatically from the cores to the rims, has been interpreted as being due to partitioning of LLE into a hydrous vapor during magma ascent to the surface on Mars. These trends are used as evidence that Martian basaltic melts are water-rich (McSween et al., 2001). Lithium and boron are light lithophile elements (LLE) that partition into volcanic minerals and into vapor from silicate melts, making them potential tracers of degassing processes during magma ascent to the surface of Earth and of other planets. While LLE degassing behavior is relatively well understood for silica-rich melts, where water and LLE concentrations are relatively high, very little data exists for LLE abundance, heterogeneity and degassing in basaltic melts. The lack of data hampers interpretation of the trends in the shergottite meteorites. Through a geochemical study of LLE, volatile and trace elements in olivine-hosted melt inclusions from Kilauea Volcano, Hawaii, it can be demonstrated that lithium behaves similarly to the light to middle rare Earth elements during melting, magma mixing and fractionation. Considerable heterogeneity in lithium and boron is inherited from mantle-derived primary melts, which is dominant over the fractionation and degassing signal. Lithium and boron are only very weakly volatile in basaltic melt erupted from Kilauea Volcano, with vapor-melt partition coefficients <0.1. Degassing of LLE is further inhibited at high temperatures. Pyroxene and associated melt inclusion LLE concentrations from a range of volcanoes are used to quantify lithium pyroxene-melt partition coefficients, which correlate negatively with melt H2O content, ranging from 0.13 at low water contents to <0.08 at H2O contents >4 wt%. The observed terrestrial LLE partitioning behavior is extrapolated to Martian primitive melts through modeling. The zoning

  6. Bioavailability of endocrine disrupting chemicals (EDCs): Liposome-water partitioning and lipid membrane permeation

    NASA Astrophysics Data System (ADS)

    Kwon, Jung-Hwan

    The bioavailability of endocrine disrupting chemicals (EDCs) is a function of a number of parameters including the ability of the chemical to partition into organic tissue and reach receptor sites within an organism. In this dissertation, equilibrium partition coefficients between water and lipid membrane vesicles and artificial lipid membrane permeability were investigated for evaluating bioavailability of aqueous pollutants. Structurally diverse endocrine disrupting chemicals were chosen as model compounds for partitioning experiments and simple hydrophobic organic chemicals were used for the evaluation of a parallel artificial membrane device developed to mimic bioconcentration rates in fish. Hydrophobic interactions represented by octanol/water partition coefficients (KOWs) were not appropriate for estimating lipid membrane/water partition coefficients (Klipws) for the selected EDCs having a relatively large molar liquid volume (MLV) and containing polar functional groups. Correlations that include MLV and polar surface area (PSA) reduce the predicted value of log K lipw, suggesting that lipid membranes are less favorable than 1-octanol for a hydrophobic solute because of the changes in membrane fluidity and the amount of cholesterol in the lipid bilayers. These results suggested that KOW alone has limited potential for estimating K lipw, and MLV or PSA may be used as additional descriptors for developing quantitative structure-activity relationships (QSARs). The poor correlations between KOW and Klipw observed in this research may be due to the highly organized structure of lipid bilayers. Measured thermodynamic constants demonstrated that the entropy contribution becomes more dominant for more organized liposomes having saturated lipid tails. This implies that entropy-driven partitioning process makes Klipw different from KOW especially for more saturated lipid bilayer membranes. In the parallel artificial membrane system developed, a membrane filter

  7. Influence of carbon partitioning kinetics on final Austenite fraction during quenching and partitioning

    SciTech Connect

    Clarke, Amy J; Speer, John G; Matlock, David K; Rizzo, F C; Edmonds, David V; Santofimia, Maria J

    2009-01-01

    The quenching and partitioning (Q&P) process is a two-stage heat-treatment procedure proposed for producing steel microstructures that contain carbon-enriched retained austenite. In Q&P processing, austenite stabilization is accomplished by carbon partitioning from supersaturated martensite. A quench temperature selection methodology was developed to predict an optimum process quench temperature; extension of this methodology to include carbon partitioning kinetics is developed here. Final austenite fraction is less sensitive to quench temperature than previously predicted, in agreement with experimental results.

  8. Partitioning of Organic Compounds between Crude Oil and Water under Supercritical CO2 Condition

    NASA Astrophysics Data System (ADS)

    Rod, K. A.; Wang, G.

    2015-12-01

    In recent years depleted oil reservoirs have received special interest as carbon storage reservoirs because of their potential to offset costs through collaboration with enhanced oil recovery projects. Leakage of the injected CO2 may occur either as supercritical CO2 or CO2-saturated (brine) water. The injected supercritical CO2 is a nonpolar solvent that can potentially mobilize the residual oil compounds into supercritical CO2 and brine water through phase partitioning. For detailed risk assessment of CO2 leakage, various models can be used to quantify the mass of organic contaminants transported from carbon storage sites to potential receptors such as potable aquifers, in which the partition coefficients of crude oil hydrocarbons between CO2/crude oil/brines for subsurface CO2 sequestration scenarios are the key parameters controlling the fate and transport of organic contaminants along the CO2 leakage pathways. However, the solubilities of many of the oil organic compounds in brines under supercritical CO2 condition have not been yet fully determined. In this study, we developed a novel method to accurately measure the partitioning of crude oil organic compounds (BTEX, PAHs, etc.) between supercritical CO2 and brines and to study the effects of temperature, pressure, salinity, and compound's cosolvency (solubility enhancement) on the partitioning behavior of oil organic compounds along the various CO2 leakage paths in the subsurface.

  9. Effect of electric field on the partitioning behavior of solutes in entropic interaction chromatography.

    PubMed

    Shi, Qing-Hong; Jia, Guo-Dong; Xu, Liang; Sun, Yan

    2013-09-01

    In this study, a novel column design with a round cross-section was proposed to be suitable for a transverse electric field (EF). Additionally, two beads for entropic interaction chromatography (EIC) were prepared by grafting glycidyl methacrylate onto Toyopearl HW-65F (T65F) beads. Solute partitioning was then investigated to elucidate the role of graft polymerization with and without an EF. In a T65F column, solute partitioning was attributed to the distinct pore structure in the beads and was governed by pore flow. Under EF, partition coefficients (Kp) for solutes decreased with increasing EF strength. In the two EIC columns, a decrease of Kp was also observed without an EF while the fractionation windows were extended. It was more pronounced in the EIC column with a high grafting density (T65F-H). This was explained by the decrease in the effective pore size of solutes caused by the steric hindrance of polymer chains. Under an EF, the solutes showed different partitioning behaviours in the T65F-H column. With increasing EF strength, Kp for vitamin B12 and myoglobin was decreased. In contrast, Kp for large solutes increased as a result of concentration polarization on the bead surface. Both behaviors were related to the modulation of graft polymerization to residual charge on the matrix and the pore size of the solutes. PMID:23857725

  10. Evaluation of estimation methods for organic carbon normalized sorption coefficients

    USGS Publications Warehouse

    Baker, James R.; Mihelcic, James R.; Luehrs, Dean C.; Hickey, James P.

    1997-01-01

    A critically evaluated set of 94 soil water partition coefficients normalized to soil organic carbon content (Koc) is presented for 11 classes of organic chemicals. This data set is used to develop and evaluate Koc estimation methods using three different descriptors. The three types of descriptors used in predicting Koc were octanol/water partition coefficient (Kow), molecular connectivity (mXt) and linear solvation energy relationships (LSERs). The best results were obtained estimating Koc from Kow, though a slight improvement in the correlation coefficient was obtained by using a two-parameter regression with Kow and the third order difference term from mXt. Molecular connectivity correlations seemed to be best suited for use with specific chemical classes. The LSER provided a better fit than mXt but not as good as the correlation with Koc. The correlation to predict Koc from Kow was developed for 72 chemicals; log Koc = 0.903* log Kow + 0.094. This correlation accounts for 91% of the variability in the data for chemicals with log Kow ranging from 1.7 to 7.0. The expression to determine the 95% confidence interval on the estimated Koc is provided along with an example for two chemicals of different hydrophobicity showing the confidence interval of the retardation factor determined from the estimated Koc. The data showed that Koc is not likely to be applicable for chemicals with log Kow < 1.7. Finally, the Koc correlation developed using Kow as a descriptor was compared with three nonclass-specific correlations and two 'commonly used' class-specific correlations to determine which method(s) are most suitable.

  11. PARTITIONING OF METALS IN ROTARY KILN INCINERATION

    EPA Science Inventory

    This research project investigated the fate of trace metals in rotary kiln incineration with venturi- and packed tower-scrubber particulate- and acid gas-control. est plan was developed, using a factorial experimental design, to study the partitioning of metals among kiln ash, sc...

  12. Lipid metabolism and nutrient partitioning strategies.

    PubMed

    Morris, A M; Calsbeek, D J; Eckel, R H

    2004-10-01

    The increasing prevalence of overweight and obesity worldwide is daunting and requires prompt attention by the affected, health care profession, government and the pharmaceutical industry. Because overweight/obesity are defined as an excess of adipose tissue mass, all approaches in prevention and treatment must consider redirecting lipid storage in adipose tissue to oxidative metabolism. Lipid partitioning is a complex process that involves interaction between fat and other macronutrients, particularly carbohydrate. In an isocaloric environment, when fat is stored carbohydrate is oxidized and vice versa. Processes that influence fat partitioning in a manner in which weight is maintained must be modified by changes in organ-specific fat transport and metabolism. When therapy is considered, however, changes in lipid partitioning alone will be ineffective unless a negative energy balance is also achieved, i.e. energy expenditure exceeds energy intake. The intent of this review is to focus on molecules including hormones, enzymes, cytokines, membrane transport proteins, and transcription factors directly involved in fat trafficking and partitioning that could be potential drug targets. Some examples of favorably altering body composition by systemic and/or tissue specific modification of these molecules have already been provided with gene knockout and/or transgenic approaches in mice. The translation of this science to humans remains a challenging task. PMID:15544448

  13. Set Partitions and the Multiplication Principle

    ERIC Educational Resources Information Center

    Lockwood, Elise; Caughman, John S., IV

    2016-01-01

    To further understand student thinking in the context of combinatorial enumeration, we examine student work on a problem involving set partitions. In this context, we note some key features of the multiplication principle that were often not attended to by students. We also share a productive way of thinking that emerged for several students who…

  14. UNCERTAINTY IN SOURCE PARTITIONING USING STABLE ISOTOPES

    EPA Science Inventory

    Stable isotope analyses are often used to quantify the contribution of multiple sources to a mixture, such as proportions of food sources in an animal's diet, C3 vs. C4 plant inputs to soil organic carbon, etc. Linear mixing models can be used to partition two sources with a sin...

  15. A review of approaches for evapotranspiration partitioning

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Partitioning of evapotranspiration (ET) into evaporation from the soil surface (E) and transpiration (T) is challenging but important in order to assess biomass production and the allocation of increasingly scarce water resources. Generally T is the desired component with the water being used to enh...

  16. Measure-theoretic sensitivity via finite partitions

    NASA Astrophysics Data System (ADS)

    Li, Jian

    2016-07-01

    For every positive integer n≥slant 2 , we introduce the concept of measure-theoretic n-sensitivity for measure-theoretic dynamical systems via finite measurable partitions, and show that an ergodic system is measure-theoretically n-sensitive but not (n  +  1)-sensitive if and only if its maximal pattern entropy is log n .

  17. Creep-fatigue analysis by Strainrange Partitioning

    NASA Technical Reports Server (NTRS)

    Manson, S. S.; Halford, G. R.; Hirschbere, M. H.

    1973-01-01

    Strainrange Partitioning provides unifying framework for characterizing high-temperature, low-cycle, creep-fatigue properties of metals and alloys. Method offers distinct advantage to designers of immediately providing reliable upper and lower bounds on cyclic life for any type of inelastic strain cycle that may be encountered in service.

  18. Partition function of interacting calorons ensemble

    NASA Astrophysics Data System (ADS)

    Deldar, S.; Kiamari, M.

    2016-01-01

    We present a method for computing the partition function of a caloron ensemble taking into account the interaction of calorons. We focus on caloron-Dirac string interaction and show that the metric that Diakonov and Petrov offered, works well in the limit where this interaction occurs. We suggest computing the correlation function of two polyakov loops by applying Ewald's method.

  19. Quantum chemical modeling of humic acid/air equilibrium partitioning of organic vapors.

    PubMed

    Niederer, Christian; Goss, Kai-Uwe

    2007-05-15

    Classical approaches for predicting soil organic matter partition coefficients of organic compounds require a calibration with experimental partition data and, for good accuracy, experimental compound descriptors. In this study we evaluate the quantum chemical model COSMO-RS in its COSMOtherm implementation for the prediction of about 200 experimental Leonardite humic acid/air partition coefficients without calibration or experimental compound descriptors, but simply based on molecular structures. For this purpose a Leonardite Humic Acid model monomer limited to 31 carbon atoms was derived from 13C NMR analysis, elemental analysis, and acidic function analysis provided in the literature. Altogether the COSMOtherm calculations showed a good performance and we conclude that it may become a very promising tool for the prediction of sorption in soil organic matter for compounds for which the molecular structure is the only reliable information available. COSMOtherm can be expected to be very robust with respectto new and complex compound structures because its calculations are based on a fundamental assessment of the underlying intermolecular forces. In contrast, other empirical models that are also based on the molecular structure of the sorbate have an application domain that is limited by their calibration data set that is often unknown to the user. PMID:17547191

  20. Experimental chlorine partitioning between forsterite, enstatite and aqueous fluid at upper mantle conditions☆

    PubMed Central

    Fabbrizio, Alessandro; Stalder, Roland; Hametner, Kathrin; Günther, Detlef

    2013-01-01

    Cl partition coefficients between forsterite, enstatite and coexisting Cl-bearing aqueous fluids were determined in a series of high pressure and temperature piston cylinder experiments at 2 GPa between 900 and 1300 °C in the system MgO–SiO2–H2O–NaCl–BaO–C±CaCl2±TiO2±Al2O3±F. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA-ICP-MS. The chlorine content of forsterite and enstatite was measured by electron microprobe, and the nature of hydrous defects was investigated by infrared spectroscopy. Partition coefficients show similar incompatibility for Cl in forsterite and enstatite, with DClfo/fl = 0.0012 ± 0.0006, DClen/fl = 0.0018 ± 0.0008 and DClfo/en = 1.43 ± 0.71. The values determined for mineral/fluid partitioning are very similar to previously determined values for mineral/melt. Applying the new mineral/fluid partition coefficients to fluids in subduction zones, a contribution between 0.15% and 20% of the total chlorine from the nominally anhydrous minerals is estimated. Infrared spectra of experimental forsterite show absorption bands at 3525 and 3572 cm−1 that are characteristic for hydroxyl point defects associated with trace Ti substitutions, and strongly suggest that the TiO2 content of the system can influence the chlorine and OH incorporation via the stabilization of Ti-clinohumite-like point defects. The water contents for coexisting forsterite and enstatite in some runs were determined using unpolarized IR spectra and calculated water partition coefficients DH2Ofo/en are between 0.01 and 0.5. PMID:25843971

  1. Transport coefficients of heavy baryons

    NASA Astrophysics Data System (ADS)

    Tolos, Laura; Torres-Rincon, Juan M.; Das, Santosh K.

    2016-08-01

    We compute the transport coefficients (drag and momentum diffusion) of the low-lying heavy baryons Λc and Λb in a medium of light mesons formed at the later stages of high-energy heavy-ion collisions. We employ the Fokker-Planck approach to obtain the transport coefficients from unitarized baryon-meson interactions based on effective field theories that respect chiral and heavy-quark symmetries. We provide the transport coefficients as a function of temperature and heavy-baryon momentum, and analyze the applicability of certain nonrelativistic estimates. Moreover we compare our outcome for the spatial diffusion coefficient to the one coming from the solution of the Boltzmann-Uehling-Uhlenbeck transport equation, and we find a very good agreement between both calculations. The transport coefficients for Λc and Λb in a thermal bath will be used in a subsequent publication as input in a Langevin evolution code for the generation and propagation of heavy particles in heavy-ion collisions at LHC and RHIC energies.

  2. Characterizing the Solid-Solution Coefficient and Plant Uptake Factor of As, Cd and Pb in California Croplands

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In risk assessment models, the solid-solution partition coefficient (Kd), and plant uptake factor (PUF), are often employed to model the fate and transport of trace elements in soils. The trustworthiness of risk assessments depends on the reliability of the parameters used. In this study, we exami...

  3. Open software tools for eddy covariance flux partitioning

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Agro-ecosystem management and assessment will benefit greatly from the development of reliable techniques for partitioning evapotranspiration (ET) into evaporation (E) and transpiration (T). Among other activities, flux partitioning can aid in evaluating consumptive vs. non-consumptive agricultural...

  4. Sediment-water partitioning of inorganic mercury in estuaries.

    PubMed

    Turner, A; Millward, G E; Le Roux, S M

    2001-12-01

    The sediment-water partitioning and speciation of inorganic mercury have been studied under simulated estuarine conditions by monitoring the hydrophobicity and uptake of dissolved 203Hg(II) in samples from a variety of estuarine environments. A persistent increase in the distribution coefficientwith increasing salinity is inconsistent with inorganic speciation calculations, which predict an increase in the concentration of the soluble HgCl4(2-) complex (or reduction in sediment-water distribution coefficient) with increasing salinity. Partition data are, however, defined by an empirical equation relating to the salting out of nonelectrolytes via electrostriction and are characterized by salting constants between about 1.4 and 2.0 L mol(-1). Salting out of the neutral, covalent chloro-complex, HgCl2(0), is predicted but cannot account for the magnitude of salting out observed. Since Hg(II) strongly complexes with dissolved (and particulate) organic matter in natural environments, of more significance appears to be the salting out of Hg(II)-organic complexes. Operational measurements of the speciation of dissolved Hg(II) using Sep-Pak C18 columns indicate a reduction in the proportion of hydrophobic (C18-retained) dissolved Hg(II) complexes with increasing salinity, both in the presence and absence of suspended particles. Ratios of hydrophobic Hg(ll) before and after particle addition suggest a coupled salting out-sorption mechanism, with the precise nature of Hg(II) species salted out being determined bythe characteristics and concentrations of dissolved and sediment organic matter. PMID:11770766

  5. Partitioning of transition metals between diopside and coexisting silicate liquids. I - Nickel, cobalt, and manganese

    NASA Technical Reports Server (NTRS)

    Lindstrom, D. J.; Weill, D. F.

    1978-01-01

    Distribution coefficients have been found for the partitioning of Ni, Co, and Mn between calcium-rich clinopyroxenes and coexisting silicate liquids. Values are found for the 1110-1360 C temperature range. The breakdown of Henry's Law was not observed. The measured clinopyroxene/liquid distribution coefficients ranged from 1.5-14.0 for Ni, 0.5-2.0 for Co, and 0.3-1.2 for Mn. Analyses of pyroxenes grown from charges differing in the amounts of transition metals indicate that Ni and Co occupy the M1 site of diopside and that Mn occupies the M1 and M2 sites. Equilibrium constants were found in terms of the activities of the components in the liquid and solid phases. These activities are based on the mole fractions. An activity/concentration model was used for the liquid phase in order to explain the variations in the clinopyroxene/liquid coefficients due to bulk composition.

  6. Diffusion coefficients and dissociation constants of enhanced green fluorescent protein binding to free standing membranes.

    PubMed

    Thomas, Franziska A; Visco, Ilaria; Petrášek, Zdeněk; Heinemann, Fabian; Schwille, Petra

    2015-12-01

    Recently, a new and versatile assay to determine the partitioning coefficient [Formula: see text] as a measure for the affinity of peripheral membrane proteins for lipid bilayers was presented in the research article entitled, "Introducing a fluorescence-based standard to quantify protein partitioning into membranes" [1]. Here, the well-characterized binding of hexahistidine-tag (His6) to NTA(Ni) was utilized. Complementarily, this data article reports the average diffusion coefficient [Formula: see text] of His6-tagged enhanced green fluorescent protein (eGFP-His6) and the fluorescent lipid analog ATTO-647N-DOPE in giant unilamellar vesicles (GUVs) containing different amounts of NTA(Ni) lipids. In addition, dissociation constants [Formula: see text] of the NTA(Ni)/eGFP-His6 system are reported. Further, a conversion between [Formula: see text] and [Formula: see text] is provided. PMID:26587560

  7. Analysis of segregation trends observed in iron meteorites using measured distribution coefficients

    NASA Astrophysics Data System (ADS)

    Sellamuthu, R.; Goldstein, J. I.

    1985-02-01

    Fe-Ni alloys of meteoritic composition were solidified by a plane front solidification technique. Distribution coefficients of Ni, P, Ir, Ge, and Cu were determined from the composition data of the plane front solidified alloys. Equations that describe the distribution coefficients (P, Ni, Ir, Ge, and Cu) as a function of S and P content as well as S to P ratio were used to calculate solute partitioning between solid and liquid during the solidification of IIAB, IIIAB, and IVA parent bodies. The calculated P versus Ni, Ir versus Ni, Ge versus Ni, and Cu versus Ni trends are in good agreement with the observed meteorite data for each chemical group. It is concluded that each chemical group formed as a single molten pool in a parent body and that solute partitioning that occurred during solidification is responsible for the observed compositional trends within a single meteorite group.

  8. Analysis of segregation trends observed in iron meteorites using measured distribution coefficients

    NASA Technical Reports Server (NTRS)

    Sellamuthu, R.; Goldstein, J. I.

    1985-01-01

    Fe-Ni alloys of meteoritic composition were solidified by a plane front solidification technique. Distribution coefficients of Ni, P, Ir, Ge, and Cu were determined from the composition data of the plane front solidified alloys. Equations that describe the distribution coefficients (P, Ni, Ir, Ge, and Cu) as a function of S and P content as well as S to P ratio were used to calculate solute partitioning between solid and liquid during the solidification of IIAB, IIIAB, and IVA parent bodies. The calculated P versus Ni, Ir versus Ni, Ge versus Ni, and Cu versus Ni trends are in good agreement with the observed meteorite data for each chemical group. It is concluded that each chemical group formed as a single molten pool in a parent body and that solute partitioning that occurred during solidification is responsible for the observed compositional trends within a single meteorite group.

  9. Tracers in recharge — Effects of partitioning in soils

    NASA Astrophysics Data System (ADS)

    Gerritse, Robert G.; Adeney, John A.

    1992-02-01

    Partitioning among mobile and stationary water phases in a soil measurably reduces movement of a tracer relative to the mobile water phase. The quantity of water infiltrating the soil, however, still follows from the product of the distance travelled by the tracer and average moisture content of the soil over that distance. Partitioning between surface and water phases in a soil by proton and protium exchange has only a small effect on the retention of isotopically labelled water. Partitioning between surface, water and gas phases in a soil, however, strongly decreases diffusive movement of isotopically labelled water in the gas phase. In sandy soils with moisture contents less than 5%, the effective diffusion coefficient in the gas phase can be reduced by a factor between 50 and 5000. As a soil dries out, diffusive movement of 18O labelled water will become larger than of HDO and HTO. Negative charges on soil surfaces repel chloride and bromide. The effect of charge exclusion on movement of Cl - and Br - relative to HDO was measured in small columns for a number of soils from the southwest of Western Australia. Data from these experiments show that in the unsaturated zone of sandy soils, charge exclusion can reduce the pore volume available to Cl - and Br - in the water phase at field capacity by > 20%. Recharge to ground water, if calculated from the position of Cl - or Br - tracers and average moisture in the soil profile, must then be reduced by the same percentage. The effect of charge exclusion in soils on the calculation of recharge from profile data, was evaluated for a practical situation. Significant amounts of bromide from car exhaust gases accumulate in soils in urban areas and can be used to trace water movement. A site was chosen in metropolitan Perth on a sparsely vegetated calcareous sand near the junction of two busy roads. A seasonal effect on bromide accumulation in the soil profile at this site was clearly visible from data on the soil solution

  10. Optimising query execution time in LHCb Bookkeeping System using partition pruning and Partition-Wise joins

    NASA Astrophysics Data System (ADS)

    Mathe, Zoltan; Charpentier, Philippe

    2014-06-01

    The LHCb experiment produces a huge amount of data which has associated metadata such as run number, data taking condition (detector status when the data was taken), simulation condition, etc. The data are stored in files, replicated on the Computing Grid around the world. The LHCb Bookkeeping System provides methods for retrieving datasets based on their metadata. The metadata is stored in a hybrid database model, which is a mixture of Relational and Hierarchical database models and is based on the Oracle Relational Database Management System (RDBMS). The database access has to be reliable and fast. In order to achieve a high timing performance, the tables are partitioned and the queries are executed in parallel. When we store large amounts of data the partition pruning is essential for database performance, because it reduces the amount of data retrieved from the disk and optimises the resource utilisation. This research presented here is focusing on the extended composite partitioning strategy such as range-hash partition, partition pruning and usage of the Partition-Wise joins. The system has to serve thousands of queries per minute, the performance and capability of the system is measured when the above performance optimization techniques are used.

  11. Analysis of internal conversion coefficients

    PubMed

    Coursol; Gorozhankin; Yakushev; Briancon; Vylov

    2000-03-01

    An extensive database has been assembled that contains the three most widely used sets of calculated internal conversion coefficients (ICC): [Hager R.S., Seltzer E.C., 1968. Internal conversion tables. K-, L-, M-shell Conversion coefficients for Z = 30 to Z = 103, Nucl. Data Tables A4, 1-237; Band I.M., Trzhaskovskaya M.B., 1978. Tables of gamma-ray internal conversion coefficients for the K-, L- and M-shells, 10 < or = Z < or = 104, Special Report of Leningrad Nuclear Physics Institute; Rosel F., Fries H.M., Alder K., Pauli H.C., 1978. Internal conversion coefficients for all atomic shells, At. Data Nucl. Data Tables 21, 91-289] and also includes new Dirac Fock calculations [Band I.M. and Trzhaskovskaya M.B., 1993. Internal conversion coefficients for low-energy nuclear transitions, At. Data Nucl. Data Tables 55, 43-61]. This database is linked to a computer program to plot ICCs and their combinations (sums and ratios) as a function of Z and energy, as well as relative deviations of ICC or their combinations for any pair of tabulated data. Examples of these analyses are presented for the K-shell and total ICCs of the gamma-ray standards [Hansen H.H., 1985. Evaluation of K-shell and total internal conversion coefficients for some selected nuclear transitions, Eur. Appl. Res. Rept. Nucl. Sci. Tech. 11.6 (4) 777-816] and for the K-shell and total ICCs of high multipolarity transitions (total, K-, L-, M-shells of E3 and M3 and K-shell of M4). Experimental data sets are also compared with the theoretical values of these specific calculations. PMID:10724406

  12. Seebeck coefficient of one electron

    SciTech Connect

    Durrani, Zahid A. K.

    2014-03-07

    The Seebeck coefficient of one electron, driven thermally into a semiconductor single-electron box, is investigated theoretically. With a finite temperature difference ΔT between the source and charging island, a single electron can charge the island in equilibrium, directly generating a Seebeck effect. Seebeck coefficients for small and finite ΔT are calculated and a thermally driven Coulomb staircase is predicted. Single-electron Seebeck oscillations occur with increasing ΔT, as one electron at a time charges the box. A method is proposed for experimental verification of these effects.

  13. 33. Elevation of Doors / Typical Cement Toilet Partitions / ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    33. Elevation of Doors / Typical Cement Toilet Partitions / Typical Cement Shower Bath Partitions / Typical Marble Shower Bath Partitions / Dispensary Cupboard Supply Room Cupboard Similar / Section / Kitchen Cupboard and Sink / Screened Porch Cupboard (drawing 10) - Whittier State School, Hospital & Receiving Building, 11850 East Whittier Boulevard, Whittier, Los Angeles County, CA

  14. 47 CFR 27.904 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 2 2014-10-01 2014-10-01 false Geographic partitioning and spectrum... partitioning and spectrum disaggregation. An entity that acquires a portion of a 1670-1675 MHz band licensee's geographic area or spectrum subject to a geographic partitioning or spectrum disaggregation agreement...

  15. 47 CFR 95.823 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 5 2013-10-01 2013-10-01 false Geographic partitioning and spectrum... Geographic partitioning and spectrum disaggregation. (a) Eligibility. Parties seeking Commission approval of geographic partitioning or spectrum disaggregation of 218-219 MHz Service system licenses shall request...

  16. 47 CFR 27.805 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 2 2013-10-01 2013-10-01 false Geographic partitioning and spectrum... partitioning and spectrum disaggregation. An entity that acquires a portion of a 1.4 GHz band licensee's geographic area or spectrum subject to a geographic partitioning or spectrum disaggregation agreement...

  17. 47 CFR 27.904 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 2 2013-10-01 2013-10-01 false Geographic partitioning and spectrum... partitioning and spectrum disaggregation. An entity that acquires a portion of a 1670-1675 MHz band licensee's geographic area or spectrum subject to a geographic partitioning or spectrum disaggregation agreement...

  18. 47 CFR 90.911 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 47 Telecommunication 5 2011-10-01 2011-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.911 Partitioned licenses and disaggregated spectrum. (a) Eligibility...) that constitute the partitioned area. (2) Disaggregation. Spectrum may be disaggregated in any...

  19. 47 CFR 27.904 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 47 Telecommunication 2 2011-10-01 2011-10-01 false Geographic partitioning and spectrum... partitioning and spectrum disaggregation. An entity that acquires a portion of a 1670-1675 MHz band licensee's geographic area or spectrum subject to a geographic partitioning or spectrum disaggregation agreement...

  20. 47 CFR 90.911 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 5 2013-10-01 2013-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.911 Partitioned licenses and disaggregated spectrum. (a) Eligibility...) that constitute the partitioned area. (2) Disaggregation. Spectrum may be disaggregated in any...

  1. 47 CFR 95.823 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 5 2012-10-01 2012-10-01 false Geographic partitioning and spectrum... Geographic partitioning and spectrum disaggregation. (a) Eligibility. Parties seeking Commission approval of geographic partitioning or spectrum disaggregation of 218-219 MHz Service system licenses shall request...

  2. 47 CFR 90.911 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 5 2014-10-01 2014-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.911 Partitioned licenses and disaggregated spectrum. (a) Eligibility...) that constitute the partitioned area. (2) Disaggregation. Spectrum may be disaggregated in any...

  3. 47 CFR 90.813 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 5 2012-10-01 2012-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.813 Partitioned licenses and disaggregated spectrum. (a) Eligibility.... Spectrum may be disaggregated in any amount. (3) Combined partitioning and disaggregation. The...

  4. 47 CFR 90.911 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 5 2012-10-01 2012-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.911 Partitioned licenses and disaggregated spectrum. (a) Eligibility...) that constitute the partitioned area. (2) Disaggregation. Spectrum may be disaggregated in any...

  5. 47 CFR 90.813 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 5 2014-10-01 2014-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.813 Partitioned licenses and disaggregated spectrum. (a) Eligibility.... Spectrum may be disaggregated in any amount. (3) Combined partitioning and disaggregation. The...

  6. 47 CFR 90.813 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 5 2013-10-01 2013-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.813 Partitioned licenses and disaggregated spectrum. (a) Eligibility.... Spectrum may be disaggregated in any amount. (3) Combined partitioning and disaggregation. The...

  7. 47 CFR 27.805 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 2 2014-10-01 2014-10-01 false Geographic partitioning and spectrum... partitioning and spectrum disaggregation. An entity that acquires a portion of a 1.4 GHz band licensee's geographic area or spectrum subject to a geographic partitioning or spectrum disaggregation agreement...

  8. 47 CFR 95.823 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 47 Telecommunication 5 2010-10-01 2010-10-01 false Geographic partitioning and spectrum... Geographic partitioning and spectrum disaggregation. (a) Eligibility. Parties seeking Commission approval of geographic partitioning or spectrum disaggregation of 218-219 MHz Service system licenses shall request...

  9. 47 CFR 95.823 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 47 Telecommunication 5 2011-10-01 2011-10-01 false Geographic partitioning and spectrum... Geographic partitioning and spectrum disaggregation. (a) Eligibility. Parties seeking Commission approval of geographic partitioning or spectrum disaggregation of 218-219 MHz Service system licenses shall request...

  10. 47 CFR 90.813 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 47 Telecommunication 5 2010-10-01 2010-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.813 Partitioned licenses and disaggregated spectrum. (a) Eligibility.... Spectrum may be disaggregated in any amount. (3) Combined partitioning and disaggregation. The...

  11. 47 CFR 90.813 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 47 Telecommunication 5 2011-10-01 2011-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.813 Partitioned licenses and disaggregated spectrum. (a) Eligibility.... Spectrum may be disaggregated in any amount. (3) Combined partitioning and disaggregation. The...

  12. 47 CFR 27.805 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 2 2012-10-01 2012-10-01 false Geographic partitioning and spectrum... partitioning and spectrum disaggregation. An entity that acquires a portion of a 1.4 GHz band licensee's geographic area or spectrum subject to a geographic partitioning or spectrum disaggregation agreement...

  13. 47 CFR 90.911 - Partitioned licenses and disaggregated spectrum.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 47 Telecommunication 5 2010-10-01 2010-10-01 false Partitioned licenses and disaggregated spectrum... Specialized Mobile Radio Service § 90.911 Partitioned licenses and disaggregated spectrum. (a) Eligibility...) that constitute the partitioned area. (2) Disaggregation. Spectrum may be disaggregated in any...

  14. 47 CFR 95.823 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 5 2014-10-01 2014-10-01 false Geographic partitioning and spectrum... Geographic partitioning and spectrum disaggregation. (a) Eligibility. Parties seeking Commission approval of geographic partitioning or spectrum disaggregation of 218-219 MHz Service system licenses shall request...

  15. 47 CFR 27.904 - Geographic partitioning and spectrum disaggregation.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 2 2012-10-01 2012-10-01 false Geographic partitioning and spectrum... partitioning and spectrum disaggregation. An entity that acquires a portion of a 1670-1675 MHz band licensee's geographic area or spectrum subject to a geographic partitioning or spectrum disaggregation agreement...

  16. Partitioning of quencher ions in the micellar microenvironment of polyoxyethylene nonyl phenol

    NASA Astrophysics Data System (ADS)

    Ghosh, Sujit Kumar; Khatua, Pijus Kanti; Ghosh, Jayanta Kumar; Bhattacharya, Subhash Chandra

    2005-01-01

    This paper has explored the quenching of fluorescence of the dye safranine T (ST) by the inorganic cations viz Cu 2+, Co 2+, Ni 2+ and Mn 2+ in micellar solutions of the surfactant dioxyethylene nonyl phenol (Igepal CO-210), pentaoxyethylene nonyl phenol (Igepal CO-520) and dodecaoxyethylene nonyl phenol (Igepal CO-720). The quenching results have been calculated in light of stern volmer equation (SV) to evaluate the extent of interaction between the fluorophore (ST) and quencher. The average concentration of the quencher ions in the micelle have been determined. The quenching efficiency of ST by inorganic ions in micellar medium is lower than that in aqueous medium. The results show that the ions get partitioned in the micellar medium. The values of the partition coefficient of the ions decrease with increase in HLB value and number of oxyethylene groups in Igepal.

  17. Alcohol binding to liposomes by 2H NMR and radiolabel binding assays: does partitioning describe binding?

    PubMed Central

    Dubey, A K; Eryomin, V A; Taraschi, T F; Janes, N

    1996-01-01

    Implicit within the concept of membrane-buffer partition coefficients of solutes is a nonspecific solvation mechanism of solute binding. However, (2)H NMR studies of the binding of (2)H(6)-ethanol and [1-(2)H(2)] n-hexanol to phosphatidylcholine vesicles have been interpreted as evidence for two distinct alcohol binding modes. One binding mode was reported to be at the membrane surface. The second mode was reported to be within the bilayer interior. An examination of the (2)H NMR binding studies, together with direct radiolabel binding assays, shows that other interpretations of the data are more plausible. The results are entirely consistent with partitioning (nonspecific binding) as the sole mode of alcohol binding to liposomes, in accord with our previous thermodynamic interpretation of alcohol action in phosphatidylcholine liposomes. PMID:9172754

  18. Evaluation of solubility and partition properties of ampicillin-based ionic liquids.

    PubMed

    Florindo, Catarina; Araújo, João M M; Alves, Filipa; Matos, Carla; Ferraz, Ricardo; Prudêncio, Cristina; Noronha, João Paulo; Petrovski, Željko; Branco, Luís; Rebelo, Luís Paulo N; Marrucho, Isabel M

    2013-11-18

    In order to overcome the problems associated with low water solubility, and consequently low bioavailability of active pharmaceutical ingredients (APIs), herein we explore a modular ionic liquid synthetic strategy for improved APIs. Ionic liquids containing L-ampicillin as active pharmaceutical ingredient anion were prepared using the methodology developed in our previous work, using organic cations selected from substituted ammonium, phosphonium, pyridinium and methylimidazolium salts, with the intent of enhancing the solubility and bioavailability of L-ampicillin forms. In order to evaluate important properties of the synthesized API-ILs, the water solubility at 25 °C and 37 °C (body temperature) as well as octanol-water partition coefficients (Kow's) and HDPC micelles partition at 25 °C were measured. Critical micelle concentrations (CMC's) in water at 25 °C and 37 °C of the pharmaceutical ionic liquids bearing cations with surfactant properties were also determined from ionic conductivity measurements. PMID:23978632

  19. The effect of solid metal composition on solid metal/ liquid metal partitioning of trace elements

    NASA Astrophysics Data System (ADS)

    Rai, N.; van Westrenen, W.

    2010-12-01

    Fundamental understanding of the partitioning behaviour of elements between different core and/or mantle phases is needed to constrain processes of planetary differentiation and evolution. The partitioning behaviour of elements between solid metal and liquid metal in the Fe-S system, of relevance to core crystallisation in planetesimals and the terrestrial planets, has been investigated by several workers [1-6], most of whom [1-5] conclude that variations in partition coefficients can be explained by variations in melt composition. However, recently Stewart et al. [6] showed that the crystal-lattice strain model commonly used to describe silicate mineral - silicate melt partitioning can be applied to partially molten metallic systems. This suggests the structure of the solid metal also plays a role in determining solid metal / molten metal partitioning. Here, we investigate the effect of the structure of the solid metal in the Fe-S system on solid/liquid metal partitioning by obtaining new element partitioning data at pressures between 0.5 and 3 GPa. The effect of the solid metal is isolated from pressure-temperature-melt composition effects by performing experiments at constant P and T with two Fe-S bulk compositions on either side of the eutectic composition. In addition to the effect of solid metal composition we investigate the effects of pressure and S content on trace element partitioning behaviour and the application of the lattice strain model to our results. Starting mixtures were doped with several hundred ppm levels of trace elements Ni, Co, W, Mo, V, Nb, Ta, Sn, Cu, Pb, Zn, Cr, Mn, P, Ge,. Experiments were performed using a QUICKPress piston cylinder apparatus at the VU University, Amsterdam using alumina capsules. Experiments were heated to 1073 K at pressure and allowed to sinter for a duration of 10 hours before the temperature was raised at a rate of 50 K / min to the target value. Preliminary EPMA data for a 1 GPa experiment with FeS as the solid

  20. Influential role of black carbon in the soil-air partitioning of polychlorinated biphenyls (PCBs) in the Indus River Basin, Pakistan.

    PubMed

    Ali, Usman; Syed, Jabir Hussain; Mahmood, Adeel; Li, Jun; Zhang, Gan; Jones, Kevin C; Malik, Riffat Naseem

    2015-09-01

    Levels of polychlorinated biphenyls (PCBs) were assessed in surface soils and passive air samples from the Indus River Basin, and the influential role of black carbon (BC) in the soil-air partitioning process was examined. ∑26-PCBs ranged between 0.002-3.03 pg m(-3) and 0.26-1.89 ng g(-1) for passive air and soil samples, respectively. Lower chlorinated (tri- and tetra-) PCBs were abundant in both air (83.9%) and soil (92.1%) samples. Soil-air partitioning of PCBs was investigated through octanol-air partition coefficients (KOA) and black carbon-air partition coefficients (KBC-A). The results of the paired-t test revealed that both models showed statistically significant agreement between measured and predicted model values for the PCB congeners. Ratios of fBCKBC-AδOCT/fOMKOA>5 explicitly suggested the influential role of black carbon in the retention and soil-air partitioning of PCBs. Lower chlorinated PCBs were strongly adsorbed and retained by black carbon during soil-air partitioning because of their dominance at the sampling sites and planarity effect. PMID:25933089

  1. Experimental Study of Coupling Coefficients for Propulsion on TEA CO2 Laser

    SciTech Connect

    Tan Rongqing; Lin Jun; Hughes, Jeremy; Pakhomov, Andrew V.

    2004-03-30

    The original purpose of this study was to address a partition of propulsive energy between air and metal, when the breakdown is initiated at the metal surface and/or in adjacent air space. Coupling coefficient as a function of air pressure varied in the range 4 mTorr - 1 atm is presented. The experiments were conducted by focusing output pulses of a TEA CO2 laser system (0.2-{mu}s pulsewidth at 10.6 {mu}m wavelength and {approx} 10.0 J energy) on aluminum targets. Coupling coefficients were derived from the pendulum displacements.

  2. Organic peroxides gas-particle partitioning and rapid heterogeneous decomposition on secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Li, H.; Chen, Z. M.; Huang, L. B.; Huang, D.

    2015-10-01

    Organic peroxides, important species in the atmosphere, will promote secondary organic aerosols (SOA) aging, affect HOx radicals cycling, and cause adverse health effects. However, the formation, gas-particle partitioning, and evolution of organic peroxides are extremely complicated and still unclear. In this study, we investigate in the laboratory the production and gas-particle partitioning of peroxides from the ozonolysis of α-pinene, which is one of the major biogenic volatile organic compounds in the atmosphere and is an important precursor for SOA at a global scale. We have determined the molar yields of hydrogen peroxide (H2O2), hydroxymethyl hydroperoxide (HMHP), peroxyformic acid (PFA), peroxyacetic acid (PAA) and total peroxides (TPO, including unknown peroxides) and the fraction of peroxides in SOA. Comparing the gas-phase and particle-phase peroxides, we find that gas-particle partitioning coefficients of PFA and PAA are 104 times higher than theoretical prediction, indicating that organic peroxides play a more important role in the SOA formation than expected previously. Here, we give the partitioning coefficients of TPO as (2-3) × 10-4 m3μg-1. Even so, more than 80 % of the peroxides formed in the reaction remain in the gas phase. Water does not affect the total amount of peroxides in either the gas or particle phase, but can change the distribution of gaseous peroxides. About 18 % gaseous peroxides undergo rapid heterogeneous decomposition on SOA particles in the presence of water vapor, resulting in the additional production of H2O2. This process can partially interpret the unexpected high H2O2 yield under wet conditions. Transformation of organic peroxides to H2O2 also saves OH in the atmosphere, helping to improve the understanding of OH cycling.

  3. Organic peroxides' gas-particle partitioning and rapid heterogeneous decomposition on secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Li, Huan; Chen, Zhongming; Huang, Liubin; Huang, Dao

    2016-02-01

    Organic peroxides, important species in the atmosphere, promote secondary organic aerosol (SOA) aging, affect HOx radicals cycling, and cause adverse health effects. However, the formation, gas-particle partitioning, and evolution of organic peroxides are complicated and still unclear. In this study, we investigated in the laboratory the production and gas-particle partitioning of peroxides from the ozonolysis of α-pinene, which is one of the major biogenic volatile organic compounds in the atmosphere and an important precursor for SOA at a global scale. We have determined the molar yields of hydrogen peroxide (H2O2), hydromethyl hydroperoxide (HMHP), peroxyformic acid (PFA), peroxyacetic acid (PAA), and total peroxides (TPOs, including unknown peroxides) and the fraction of peroxides in α-pinene/O3 SOA. Comparing the gas-phase peroxides with the particle-phase peroxides, we find that gas-particle partitioning coefficients of PFA and PAA are 104 times higher than the values from the theoretical prediction, indicating that organic peroxides play a more important role in SOA formation than previously expected. Here, the partitioning coefficients of TPO were determined to be as high as (2-3) × 10-4 m3 µg-1. Even so, more than 80 % of the peroxides formed in the reaction remain in the gas phase. Water changes the distribution of gaseous peroxides, while it does not affect the total amount of peroxides in either the gas or the particle phase. Approx. 18 % of gaseous peroxides undergo rapid heterogeneous decomposition on SOA particles in the presence of water vapor, resulting in the additional production of H2O2. This process can partially explain the unexpectedly high H2O2 yields under wet conditions. Transformation of organic peroxides to H2O2 also preserves OH in the atmosphere, helping to improve the understanding of OH cycling.

  4. Rare earth and high field strength element partitioning between iron-rich clinopyroxenes and felsic liquids

    NASA Astrophysics Data System (ADS)

    Olin, P. H.; Wolff, J. A.

    2010-11-01

    Rare earth elements are commonly assumed to substitute only for Ca in clinopyroxene because of the similarity of ionic radii for REE3+ and Ca2+ in eightfold coordination. The assumption is valid for Mg-rich clinopyroxenes for which observed mineral/melt partition coefficients are readily predicted by the lattice strain model for substitution onto a single site (e.g., Wood and Blundy 1997). We show that natural Fe-rich pyroxenes in both silica-undersaturated and silica-oversaturated magmatic systems deviate from this behavior. Salites (Mg# 48-59) in phonolites from Tenerife, ferrohedenbergites (Mg# 14.2-16.2) from the rhyolitic Bandelier Tuff, and ferroaugites (Mg# 9.6-32) from the rhyolitic Rattlesnake Tuff have higher heavy REE contents than predicted by single-site substitution. The ionic radius of Fe2+ in sixfold coordination is substantially greater than that of Mg2+; hence, we propose that, in Fe-rich clinopyroxenes, heavy REE are significantly partitioned between eightfold Ca sites and sixfold Fe and Mg sites such that Yb and Lu exist dominantly in sixfold coordination. We also outline a REE-based method of identifying pyroxene/melt pairs in systems with multiple liquid and crystal populations, based upon the assumption that LREE and MREE reside exclusively in eightfold coordination in pyroxene. Contrary to expectations, interpolation of mineral/melt partition coefficient data for heavy REE does not predict the behavior of Y. We speculate that mass fractionation effects play a role in mineral/melt lithophile trace element partitioning that is detectable among pairs of isovalent elements with near-identical radii, such as Y and Ho, Zr and Hf, and Nb and Ta.

  5. The partitioning of trace elements between clinopyroxene and trachybasaltic melt during rapid cooling and crystal growth

    NASA Astrophysics Data System (ADS)

    Mollo, S.; Blundy, J. D.; Iezzi, G.; Scarlato, P.; Langone, A.

    2013-12-01

    We present the variation in trace element partition coefficients measured at the interface between rapidly cooled clinopyroxene crystals and co-existing melts. Results indicate that, as the cooling rate is increased, clinopyroxene crystals are progressively depleted in Si, Ca and Mg counterbalanced by enrichments in Al (mainly tetrahedral Aliv), Na and Ti. Partition coefficients (Ds) for rare earth elements (REE), high field strength elements (HFSE) and transition elements (TE) increase with increasing cooling rate, in response to clinopyroxene compositional variations. The entry of REE into the M2 site is facilitated by a coupled substitution where either Na substitutes for Ca on the M2 site or Aliv substitutes for Si in the tetrahedral site. The latter substitution reflects an increased ease of locally balancing the excess charge at M2 as the number of surrounding Aliv atoms increases. Due to the lower concentration of Ca in rapidly cooled clinopyroxenes, divalent large ion lithophile elements (LILE) on M2 decrease at the expense of monovalent cations. Conversely, higher concentrations of HFSE and TE on the M1 site are facilitated as the average charge on this site increases with the replacement of divalent-charged cations by Alvi. Although crystallization kinetics modify clinopyroxene composition, deviations from equilibrium partitioning are insufficient to change the tendency of a trace element to be compatible or incompatible. Consequently, there are regular relationships between ionic radius, valence of the trace element and D. At both equilibrium and cooling rate conditions, Ds for isovalent cations define parabola-like curves when plotted against ionic radius, consistent with the lattice strain model, demonstrating that the partitioning of trace elements is driven by charge balance mechanisms; cation substitution reactions can be treated in terms of the energetics of the various charge-imbalanced configurations.

  6. Metal-silicate partitioning during core formation on super-Earths

    NASA Astrophysics Data System (ADS)

    Schaefer, L. K.; Jacobsen, S. B.; Petaev, M. I.; Sasselov, D. D.; Remo, J. L.

    2015-12-01

    Separation of the Earth into a rocky mantle and metallic Fe core is a problem long studied in the planetary science community (e.g. [1]). The timing of core formation influences the abundances of the siderophile elements found in the Earth's mantle, and the mechanism of core formation influences the degree of chemical equilibration between the rocky mantle and the core at the time of metal separation. However, limited work has been done on formation of metallic cores and its effects on mantle chemistry in rocky planets larger than the Earth. Super-Earths, exoplanets with masses up to ~ 5 Earth masses and radii up to ~1.6-1.7 Earth radii, have significantly larger internal pressures and consequently higher internal temperatures than the Earth, therefore conclusions from Earth-centric studies of core formation may be erroneous. Partitioning coefficients for many of the relevant elements (e.g. Fe, Ni, Si, O, etc.) are available in the literature, but only to relatively low pressures. The relevant pressures for super-Earths are significantly larger. However, data on Fe-O-Ni-Si partitioning at pressures (200-500 GPa) and temperatures relevant to super-Earths have been measured by laser-induced shocks with the ZBL laser at Sandia National Laboratory with a method described in [2]. We will present a model which integrates this data with lower pressure partition coefficients from the literature (e.g. [3],[4],[5]), with special emphasis on Fe and O, to describe partitioning behavior at high pressures and discuss its implications for core size and composition on rocky super-Earths. [1] Ringwood, A.E. (1977) Geochem. J. 11, 111-135. [2] Remo, J.L., Petaev, M.I., Jacobsen, S. B. (2008) LPSC abstract, 1420. [3] Frost, D.J. et al. (2010) JGR, B02202. [4] Kombayashi, T. (2014) JGR, 4164-4177. [5] Rubie, D.C. et al. (2011) EPSL, 301, 31-42. [5

  7. Integer Solutions of Binomial Coefficients

    ERIC Educational Resources Information Center

    Gilbertson, Nicholas J.

    2016-01-01

    A good formula is like a good story, rich in description, powerful in communication, and eye-opening to readers. The formula presented in this article for determining the coefficients of the binomial expansion of (x + y)n is one such "good read." The beauty of this formula is in its simplicity--both describing a quantitative situation…

  8. Prediction of stream volatilization coefficients

    USGS Publications Warehouse

    Rathbun, Ronald E.

    1990-01-01

    Equations are developed for predicting the liquid-film and gas-film reference-substance parameters for quantifying volatilization of organic solutes from streams. Molecular weight and molecular-diffusion coefficients of the solute are used as correlating parameters. Equations for predicting molecular-diffusion coefficients of organic solutes in water and air are developed, with molecular weight and molal volume as parameters. Mean absolute errors of prediction for diffusion coefficients in water are 9.97% for the molecular-weight equation, 6.45% for the molal-volume equation. The mean absolute error for the diffusion coefficient in air is 5.79% for the molal-volume equation. Molecular weight is not a satisfactory correlating parameter for diffusion in air because two equations are necessary to describe the values in the data set. The best predictive equation for the liquid-film reference-substance parameter has a mean absolute error of 5.74%, with molal volume as the correlating parameter. The best equation for the gas-film parameter has a mean absolute error of 7.80%, with molecular weight as the correlating parameter.

  9. Tables of the coefficients A

    NASA Technical Reports Server (NTRS)

    Chandra, N.

    1974-01-01

    Numerical coefficients required to express the angular distribution for the rotationally elastic or inelastic scattering of electrons from a diatomic molecule were tabulated for the case of nitrogen and in the energy range from 0.20 eV to 10.0 eV. Five different rotational states are considered.

  10. Estimating the Polyserial Correlation Coefficient.

    ERIC Educational Resources Information Center

    Bedrick, Edward J.; Breslin, Frederick C.

    1996-01-01

    Simple noniterative estimators of the polyserial correlation coefficient are developed by exploiting a general relationship between the polyserial correlation and the point polyserial correlation to give extensions of the biserial estimators of K. Pearson (1909), H. E. Brogden (1949), and F. M. Lord (1963) to the multicategory setting. (SLD)

  11. Trace Element Partitioning under Crustal and Uppermost Mantle Conditions: The Influences of Ionic Radius, Cation Charge, Pressure, and Temperature

    NASA Astrophysics Data System (ADS)

    Wood, B. J.; Blundy, J. D.

    2003-12-01

    The controls on partitioning of trace elements between crystals and silicate melts were initially the subject of crystal-chemical, rather than petrogenetic interest. Goldschmidt (1937) systematized his observations of elemental concentrations in minerals as a means of understanding and predicting element behavior during crystallization from liquids or gases. Thus, he proposed his three "rules" of element partitioning, which may be summarized as follows: (i) Any two ions of the same charge and very similar ionic radius have essentially the same crystal-liquid partition coefficient (D=[i]xtl/[i]liq, where [i] refers to the concentration of element i). (ii) If there is a small difference of ionic radius, the smaller ion enters the crystal preferentially, e.g., DMg2+>DFe2+, DK+>DRb+>DCs+. (iii) For ions of similar radius but different charges, the ion with the higher charge enters the crystal preferentially, i.e., DSc3+>DMg2+>DLi+, DCa2+>DNa+, and DBa2+>DK+. These principles were taught to generations of students and, as we will show below, under certain circumstances, retain a degree of validity. They are neither, however, universally correct nor do they have any quantitative applicability. The aim of this chapter is to summarize the ways in which Goldschmidt's work has been amplified through a combination of theory and experimental measurement in order to quantify crystal-liquid partitioning behavior.Since the development of accurate methods of determining element concentration at the ppm level, the trace-element contents of igneous rocks have frequently been used to model their chemical evolution. These studies use estimated crystal-liquid partition coefficients together with solutions for the differential equations describing, e.g., fractional crystallization or fractional melting (Schilling and Winchester, 1967; Gast, 1968; Shaw, 1970) to model evolution of the melt during precipitation or dissolution of the crystalline phases. Generally, because of lack of data

  12. Experimental investigation of the partitioning of phosphorus between metal and silicate phases - Implications for the earth, moon and eucrite parent body

    NASA Astrophysics Data System (ADS)

    Newsom, H. E.; Drake, M. J.

    1983-01-01

    An experimental study is reported of the partitioning of Phosphorus between solid metal and basaltic silicate liquid as a function of temperature and oxygen fugacity and of the implications for the earth, moon and eucrite parent body (EPB). The relationship established between the partition coefficient and the fugacity is given at 1190 C by log D(P) = -1.12 log fO2 - 15.95 and by log D(P) = -1.53 log fO2 17.73 at 1300 C. The partition coefficient D(P) was determined, and it is found to be consistent with a valence state of 5 for P in the molten silicate. Using the determined coefficient the low P/La ratios of the earth, moon, and eucrites relative to C1 chondrites can be explained. The lowering of the P/La ratio in the eucrites relative to Cl chondrite by a factor of 40 can be explained by partitioning P into 20-25 wt% sulfur-bearing metallic liquid corresponding to 5-25% of the total metal plus silicate system. The low P/La and W/La ratios in the moon may be explained by the partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. These observations are consistent with independent formation of the moon and the earth.

  13. Partitioning of Si and platinum group elements between liquid and solid Fe-Si alloys

    NASA Astrophysics Data System (ADS)

    Morard, G.; Siebert, J.; Badro, J.

    2014-05-01

    Crystallization of the Earth's inner core fractionates major and minor elements between the solid and liquid metal, leaving physical and geochemical imprints on the Earth's core. For example, the density jump observed at the Inner Core Boundary (ICB) is related to the preferential partitioning of lighter elements in the liquid outer core. The fractionation of Os, Re and Pt between liquid and solid during inner core crystallization has been invoked as a process that explains the observed Os isotopic signature of mantle plume-derived lavas (Brandon et al., 1998; Brandon and Walker, 2005) in terms of core-mantle interaction. In this article we measured partitioning of Si, Os, Re and Pt between liquid and solid metal. Isobaric (2 GPa) experiments were conducted in a piston-cylinder press at temperatures between 1250 °C and 1600 °C in which an imposed thermal gradient through the sample provided solid-liquid coexistence in the Fe-Si system. We determined the narrow melting loop in the Fe-Si system using Si partitioning values and showed that order-disorder transition in the Fe-Si solid phases can have a large effect on Si partitioning. We also found constant partition coefficients (DOs, DPt, DRe) between liquid and solid metal, for Si concentrations ranging from 2 to 12 wt%. The compact structure of Fe-Si liquid alloys is compatible with incorporation of Si and platinum group elements (PGEs) elements precluding solid-liquid fractionation. Such phase diagram properties are relevant for other light elements such as S and C at high pressure and is not consistent with inter-elemental fractionation of PGEs during metal crystallization at Earth's inner core conditions. We therefore propose that the peculiar Os isotopic signature observed in plume-derived lavas is more likely explained by mantle source heterogeneity (Meibom et al., 2002; Baker and Krogh Jensen, 2004; Luguet et al., 2008).

  14. Platinum partitioning between metal and silicate melts: Core formation, late veneer and the nanonuggets issue

    NASA Astrophysics Data System (ADS)

    Médard, Etienne; Schmidt, Max W.; Wälle, Markus; Keller, Nicole S.; Günther, Detlef

    2015-08-01

    High-pressure, high-temperature experiments have been performed at ∼1.2 GPa and 1360-2100 °C to investigate the partitioning of Pt between a silicate melt and a metallic melt. Our experiments indicate that nanonuggets encountered in previous experiments are experimental artifacts, formed at high temperature by oversaturation caused by high oxygen fugacity during the initial stages of an experiment. Experiments at high-acceleration using a centrifuging piston-cylinder show that nanonuggets can be removed by gravity during the experiment. Formation of nanonuggets can also be avoided by using initially reduced starting materials. The presence of iron is also a key element in reducing the formation of nanonuggets. Our nanonugget-free data are broadly consistent with previous nanonuggets-filtered data, and suggest that Pt partitioning becomes independent of oxygen fugacity below an oxygen fugacity of at least IW+2. Pt is thus possibly dissolved as a neutral species (or even an anionic species) at low fO2, instead of the more common Pt2+ species present at higher fO2. Due to low concentration, the nature of this species cannot be determined, but atomic Pt or Pt- are possible options. Under core-formation conditions, Pt partitioning between metal and silicate is mostly independent of oxygen fugacity, silicate melt composition, and pressure. Partition coefficient during core formation can be expressed by the following equation: log DPtMmetal/silicate = 1.0348 + 14698 / T (in weight units). Calculations indicate that the Pt content (and by extension the Highly Siderophile Elements content) of the Earth's mantle cannot be explained by equilibrium partitioning during core formation, requiring further addition of HSE to the mantle. The mass of this late veneer is approximately 0.4% of the total mass of the Earth (or 0.6% of the mass of the mantle).

  15. Partitioning and matrix-specific toxicity of bifenthrin among sediments and leaf-sourced organic matter.

    PubMed

    Maul, Jonathan D; Trimble, Andrew J; Lydy, Michael J

    2008-04-01

    Synthetic pyrethroids readily partition from the aqueous to the solid phase in aquatic systems. Previous work has focused on pyrethroid partitioning to sediment matrices. Within many aquatic systems, however, other carbon-containing materials are present and can be critically important to certain invertebrate species and ecosystem functioning. For example, some invertebrates readily process leaf material, and these processes may represent an additional route of contaminant exposure. To our knowledge, estimates for partitioning of pyrethroids to these nondissolved organic matter matrices and associated toxicity have not been examined. The objectives of the present study were to examine variation in organic carbon (OC)-based partition coefficient (K(OC)) among three size fractions of particulate organic matter from sugar maple (Acer saccharum) leaf litter and sediments for the pyrethroid insecticide bifenthrin and to examine variation in toxicity to Hyalella azteca among bifenthrin-bound organic matter matrices and sediment. Log K(OC) of [(14)C]bifenthrin was greatest within sediment (6.63+/-0.23; mean +/- standard deviation throughout) and lowest in coarse particulate leaf material (4.86+/-0.03). The H. azteca median lethal concentration was 0.07, 0.11, and 0.15 microg/g OC for leaf material, sediment, and a 50% mix of leaf and sediment, respectively. Nonoverlapping 95% confidence intervals occurred between the leaf treatment and the leaf-sediment treatment. This pattern was supported in an additional experiment, and at 0.22 microg/g OC, H. azteca survival was greater in the leaf-sediment mixture than in sediment or in leaf material alone (F=29.5, p<0.0001). In systems that contain sediment and leaf material, both greater partitioning of bifenthrin to the sediment fraction and preferential use of leaf substrates may drive H. azteca survival. PMID:18333691

  16. CAP: A Computer Code for Generating Tabular Thermodynamic Functions from NASA Lewis Coefficients. Revised

    NASA Technical Reports Server (NTRS)

    Zehe, Michael J.; Gordon, Sanford; McBride, Bonnie J.

    2002-01-01

    For several decades the NASA Glenn Research Center has been providing a file of thermodynamic data for use in several computer programs. These data are in the form of least-squares coefficients that have been calculated from tabular thermodynamic data by means of the NASA Properties and Coefficients (PAC) program. The source thermodynamic data are obtained from the literature or from standard compilations. Most gas-phase thermodynamic functions are calculated by the authors from molecular constant data using ideal gas partition functions. The Coefficients and Properties (CAP) program described in this report permits the generation of tabulated thermodynamic functions from the NASA least-squares coefficients. CAP provides considerable flexibility in the output format, the number of temperatures to be tabulated, and the energy units of the calculated properties. This report provides a detailed description of input preparation, examples of input and output for several species, and a listing of all species in the current NASA Glenn thermodynamic data file.

  17. CAP: A Computer Code for Generating Tabular Thermodynamic Functions from NASA Lewis Coefficients

    NASA Technical Reports Server (NTRS)

    Zehe, Michael J.; Gordon, Sanford; McBride, Bonnie J.

    2001-01-01

    For several decades the NASA Glenn Research Center has been providing a file of thermodynamic data for use in several computer programs. These data are in the form of least-squares coefficients that have been calculated from tabular thermodynamic data by means of the NASA Properties and Coefficients (PAC) program. The source thermodynamic data are obtained from the literature or from standard compilations. Most gas-phase thermodynamic functions are calculated by the authors from molecular constant data using ideal gas partition functions. The Coefficients and Properties (CAP) program described in this report permits the generation of tabulated thermodynamic functions from the NASA least-squares coefficients. CAP provides considerable flexibility in the output format, the number of temperatures to be tabulated, and the energy units of the calculated properties. This report provides a detailed description of input preparation, examples of input and output for several species, and a listing of all species in the current NASA Glenn thermodynamic data file.

  18. Bipartite graph partitioning and data clustering

    SciTech Connect

    Zha, Hongyuan; He, Xiaofeng; Ding, Chris; Gu, Ming; Simon, Horst D.

    2001-05-07

    Many data types arising from data mining applications can be modeled as bipartite graphs, examples include terms and documents in a text corpus, customers and purchasing items in market basket analysis and reviewers and movies in a movie recommender system. In this paper, the authors propose a new data clustering method based on partitioning the underlying biopartite graph. The partition is constructed by minimizing a normalized sum of edge weights between unmatched pairs of vertices of the bipartite graph. They show that an approximate solution to the minimization problem can be obtained by computing a partial singular value decomposition (SVD) of the associated edge weight matrix of the bipartite graph. They point out the connection of their clustering algorithm to correspondence analysis used in multivariate analysis. They also briefly discuss the issue of assigning data objects to multiple clusters. In the experimental results, they apply their clustering algorithm to the problem of document clustering to illustrate its effectiveness and efficiency.

  19. Number Partitioning via Quantum Adiabatic Computation

    NASA Technical Reports Server (NTRS)

    Smelyanskiy, Vadim N.; Toussaint, Udo; Clancy, Daniel (Technical Monitor)

    2002-01-01

    We study both analytically and numerically the complexity of the adiabatic quantum evolution algorithm applied to random instances of combinatorial optimization problems. We use as an example the NP-complete set partition problem and obtain an asymptotic expression for the minimal gap separating the ground and exited states of a system during the execution of the algorithm. We show that for computationally hard problem instances the size of the minimal gap scales exponentially with the problem size. This result is in qualitative agreement with the direct numerical simulation of the algorithm for small instances of the set partition problem. We describe the statistical properties of the optimization problem that are responsible for the exponential behavior of the algorithm.

  20. Analysis of fractals with combined partition

    NASA Astrophysics Data System (ADS)

    Dedovich, T. G.; Tokarev, M. V.

    2016-03-01

    The space—time properties in the general theory of relativity, as well as the discreteness and non-Archimedean property of space in the quantum theory of gravitation, are discussed. It is emphasized that the properties of bodies in non-Archimedean spaces coincide with the properties of the field of P-adic numbers and fractals. It is suggested that parton showers, used for describing interactions between particles and nuclei at high energies, have a fractal structure. A mechanism of fractal formation with combined partition is considered. The modified SePaC method is offered for the analysis of such fractals. The BC, PaC, and SePaC methods for determining a fractal dimension and other fractal characteristics (numbers of levels and values of a base of forming a fractal) are considered. It is found that the SePaC method has advantages for the analysis of fractals with combined partition.