Using measured octanol-air partition coefficients to explain environmental partitioning of organochlorine pesticides.

Science.gov (United States)

Shoeib, Mahiba; Harner, Tom

2002-05-01

Octanol-air partition coefficients (Koa) were measured directly for 19 organochlorine (OC) pesticides over the temperature range of 5 to 35 degrees C. Values of log Koa at 25 degrees C ranged over three orders of magnitude, from 7.4 for hexachlorobenzene to 10.1 for 1,1-dichloro-2,2-bis(p-chlorophenyl) ethane. Measured values were compared to values calculated as KowRT/H (where R is the ideal gas constant [8.314 J mol(-1) K(-1)], T is absolute temperature, and H is Henry's law constant) were, in general, larger. Discrepancies of up to three orders of magnitude were observed, highlighting the need for direct measurements of Koa. Plots of Koa versus inverse absolute temperature exhibited a log-linear correlation. Enthalpies of phase transition between octanol and air (deltaHoa) were determined from the temperature slopes and were in the range of 56 to 105 kJ mol(-1) K(-1). Activity coefficients in octanol (gamma(o)) were determined from Koa and reported supercooled liquid vapor pressures (pL(o)), and these were in the range of 0.3 to 12, indicating near-ideal solution behavior. Differences in Koa values for structural isomers of hexachlorocyclohexane were also explored. A Koa-based model was described for predicting the partitioning of OC pesticides to aerosols and used to calculate particulate fractions at 25 and -10 degrees C. The model also agreed well with experimental results for several OC pesticides that were equilibrated with urban aerosols in the laboratory. A log-log regression of the particle-gas partition coefficient versus Koa had a slope near unity, indicating that octanol is a good surrogate for the aerosol organic matter.

Experimental partition determination of octanol-water coefficients of ...

African Journals Online (AJOL)

An electrochemical method based on square wave voltammetry was developed for the measurement of octanol-water partition coefficient, LogP, for ten ferrocene derivatives. Measured LogP values ranged over two orders of magnitude, between 2.18 for 1- ferrocenylethanol and 4.38 for ferrocenyl-2-nitrophenyl.

On L^1-Convergence Of Rees-Stanojević's Sums With Coefficients From The Class K

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Xhevat Z. Krasniqi

2010-12-01

Full Text Available In this paper are considered the modified cosine sums introduced by Rees and Stanojević  with coefficients from the class K. In addition, it is proved that the condition $\\lim_{n\\to \\infty}|a_{n+1}|\\log n= 0$ is a necessary and sufficient condition for the $L^{1}$-convergence of the cosine series. Also, an open problem about $L^{1}$-convergence for the $r-th$ derivative  of the cosine series is presented.

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

Science.gov (United States)

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 ...

Estimation of Partition Coefficients of Benzene, Toluene, Ethylbenzene, and ρ-Xylene by Consecutive Extraction with Solid Phase Microextraction

International Nuclear Information System (INIS)

Eom, In Yong

2011-01-01

The results show that the partition coefficients of the BTEX compound can be estimated using the SPME method under the consecutive extraction mode. The proposed technique is much simpler than previously reported methods. Its novelty is that it eliminated the calibration step in the GC/FID, i. e., liquid injection method. The use of the autosampler for the SPME fiber can facilitate the adoption of consecutive extractions; thus, it allows estimation of the partition coefficients of various analytes. Recently, GC/MS has increasingly been used in analytical laboratories; this may facilitate the identification of an unknown analyte as well as the computation of the corresponding partition coefficients with the proposed method. It is very important to use partition coefficients of organic pollutants to predict their fate in the environment. A liquid-liquid extraction technique was used to determine the partition coefficients of organic compounds between water and organic solvent. The concentration of the target compounds must be determined after equilibrium is established between the two phases. The partition coefficients can be estimated using the capacity factors of HPLC and GC

Determination of the tissue-to-blood partition coefficient for 131iodo-antipyrine in human subcutaneous adipose tissue

DEFF Research Database (Denmark)

Jelnes, R; Astrup, A

1985-01-01

131Iodo-antipyrine (131I-AP) is commonly used for blood flow measurements in adipose tissue. These estimations have been based on the assumption of the tissue-to-blood partition coefficient being 1 ml g-1. No exact determination of the tissue-to-blood partition coefficient for 131I-AP in adipose...... tissue has been carried out. In the present study a partition coefficient of 1.12 +/- 0.06 (mean +/- S.D.) for 131I-AP in adipose tissue has been determined based on the partition coefficient for 131I-AP between lipid-saline (1.24 ml g-1), red blood cells-plasma (0.64 ml g-1), protein-saline (0.19 ml g-1...

Determination of air-loop volume and radon partition coefficient for measuring radon in water sample.

Science.gov (United States)

Lee, Kil Yong; Burnett, William C

A simple method for the direct determination of the air-loop volume in a RAD7 system as well as the radon partition coefficient was developed allowing for an accurate measurement of the radon activity in any type of water. The air-loop volume may be measured directly using an external radon source and an empty bottle with a precisely measured volume. The partition coefficient and activity of radon in the water sample may then be determined via the RAD7 using the determined air-loop volume. Activity ratios instead of absolute activities were used to measure the air-loop volume and the radon partition coefficient. In order to verify this approach, we measured the radon partition coefficient in deionized water in the temperature range of 10-30 °C and compared the values to those calculated from the well-known Weigel equation. The results were within 5 % variance throughout the temperature range. We also applied the approach for measurement of the radon partition coefficient in synthetic saline water (0-75 ppt salinity) as well as tap water. The radon activity of the tap water sample was determined by this method as well as the standard RAD-H 2 O and BigBottle RAD-H 2 O. The results have shown good agreement between this method and the standard methods.

Determination of air-loop volume and radon partition coefficient for measuring radon in water sample

International Nuclear Information System (INIS)

Kil Yong Lee; Burnett, W.C.

2013-01-01

A simple method for the direct determination of the air-loop volume in a RAD7 system as well as the radon partition coefficient was developed allowing for an accurate measurement of the radon activity in any type of water. The air-loop volume may be measured directly using an external radon source and an empty bottle with a precisely measured volume. The partition coefficient and activity of radon in the water sample may then be determined via the RAD7 using the determined air-loop volume. Activity ratios instead of absolute activities were used to measure the air-loop volume and the radon partition coefficient. In order to verify this approach, we measured the radon partition coefficient in deionized water in the temperature range of 10-30 deg C and compared the values to those calculated from the well-known Weigel equation. The results were within 5 % variance throughout the temperature range. We also applied the approach for measurement of the radon partition coefficient in synthetic saline water (0-75 ppt salinity) as well as tap water. The radon activity of the tap water sample was determined by this method as well as the standard RAD-H 2 O and BigBottle RAD-H 2 O. The results have shown good agreement between this method and the standard methods. (author)

Molecular Descriptors Family on Structure Activity Relationships 6. Octanol-Water Partition Coefficient of Polychlorinated Biphenyls

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Lorentz JÄNTSCHI

2006-01-01

Full Text Available Octanol-water partition coefficient of two hundred and six polychlorinated biphenyls was model by the use of an original method based on complex information obtained from compounds structure. The regression analysis shows that best results are obtained in four-varied model (r2 = 0.9168. The prediction ability of the model was studied through leave-one-out analysis (r2cv(loo = 0.9093 and in training and test sets analysis. Modeling the octanol-water partition coefficient of polychlorinated biphenyls by integration of complex structural information provide a stable and performing four-varied model, allowing us to make remarks about relationship between structure of polychlorinated biphenyls and associated octanol-water partition coefficients.

REE partitioning between apatite and melt in a peralkaline volcanic suite, Kenya Rift Valley

Science.gov (United States)

Macdonald, R.; Baginski, B.; Belkin, H.E.; Dzierzanowski, P.; Jezak, L.

2009-01-01

Electron microprobe analyses are presented for fluorapatite phenocrysts from a benmoreite-peralkaline rhyolite volcanic suite from the Kenya Rift Valley. The rocks have previously been well characterized petrographically and their crystallization conditions are reasonably well known. The REE contents in the M site increase towards the rhyolites, with a maximum britholite component of ~35 mol.%. Chondrite-normalized REE patterns are rather flat between La and Sm and then decrease towards Yb. Sodium and Fe occupy up to 1% and 4%, respectively, of the M site. The major coupled substitution is REE3+ + Si4+ ??? Ca2+ + P5+. The substitution REE3+ + Na+ ??? 2Ca2+ has been of minor importance. The relatively large Fe contents were perhaps facilitated by the low fo2 conditions of crystallization. Zoning is ubiquitous and resulted from both fractional crystallization and magma mixing. Apatites in some rhyolites are relatively Y-depleted, perhaps reflecting crystallization from melts which had precipitated zircon. Mineral/glass (melt) ratios for two rhyolites are unusually high, with maxima at Sm (762, 1123). ?? 2008 The Mineralogical Society.

Lipid–water partition coefficients and correlations with uptakes by algae of organic compounds

International Nuclear Information System (INIS)

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

2014-01-01

Graphical abstract: - Highlights: • Partition coefficients of contaminants with lipid triolein (K tw ) are measured. • Measured K tw values are nearly the same as the respective K ow . • Sorption of the contaminants to a dry algal powder is similarly measured. • Algal uptake of a compound occurs primarily by partition into the algal lipid. - Abstract: In view of the scarcity of the lipid–water partition coefficients (K tw ) for organic compounds, the log K tw 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 log K tw 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 log K tw are closely related to their respective log K ow (octanol–water), with log K ow = 1.9 to 6.5. A significant difference is observed between the present and early measured log K tw for compounds with log K ow > ∼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 (log K aw/lipid ) are virtually identical to the respective log K tw values, which manifests the dominant lipid-partition effect of the compounds with algae

Influence of the structure of bile acids on their partition coefficient in dibutyl ether and chloroform

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Sebenji Ana S.

2015-01-01

Full Text Available Bile acids are well known natural surfactants able to modify the per­meability of biological membranes. The logarithm of partition coefficient between, tradi­tionally used, n-octanol and water is a measure of lipophilicity as a predictor of solute membrane partitioning. The aim of this work was to determine partition coefficients of bile acids in a mixture of water and chloroform and dibutyl ether at different pH values and with addition of different concentrations of sodium ions, and to examine the influence of the structure of bile acid nucleus on measured partition coefficients. Partition coefficients of three bile acid salts were determined using shake-flask method and the concentration of bile acids was determined after twelve hours of shaking at the room temperature in aqueous and organic layer using reversed phase HPLC with DAD detector on 210 nm. For all three analysed bile acid salts values of logP are lower in dibutyl ether than in chloroform. At certain pH values, curves representing the dependence of partition coeffi­cient on pH value intersect, and these are the pH values for which partition coefficients are the same for both solvents. Increasing the solution ionic strength, this intersection is shifted toward lower pH values. It is found that, for both organic solvents, after the addition of hy­droxyl group in the steroid nucleus (i.e. if the bile acid is less hydrophobic the value of logP falls, especially if more hydroxyl groups are present. With chloroform as a solvent, system quickly comes to excess with electrolyte ions than with dibutyl ether. [Projekat Ministarstva nauke Republike Srbije, br. 172021

Rees Coextensions of Finite, Negative Tomonoids

Czech Academy of Sciences Publication Activity Database

Petrík, Milan; Vetterlein, T.

2017-01-01

Roč. 27, č. 1 (2017), s. 337-356 ISSN 0955-792X R&D Projects: GA ČR GPP201/12/P055 Grant - others:GA MŠk(CZ) EE2.3.20.0051 Institutional support: RVO:67985807 Keywords : totally ordered monoids * tomonoid partition * Rees coextension Subject RIV: BA - General Mathematics OBOR OECD: Computer sciences, information science, bioinformathics (hardware development to be 2.2, social aspect to be 5.8) Impact factor: 0.909, year: 2016

Partition coefficient n-octanol/water of propranolol and atenolol at different temperatures: Experimental and theoretical studies

International Nuclear Information System (INIS)

Mohsen-Nia, M.; Ebrahimabadi, A.H.; Niknahad, B.

2012-01-01

Highlights: ► n-Octanol/water partition coefficients of propranolol and atenolol were measured. ► The effect of temperature on the partition coefficient was studied. ► The equilibrium data were correlated using the NRTL and UNIQUAC activity models. ► The binary interaction parameters of the activity models were reported. ► It is concluded that propranolol is more hydrophobic than the atenolol at 298.15 K. - Abstract: The n-octanol/water partition coefficients of propranolol and atenolol were experimentally determined by ultraviolet (UV) spectroscopy at T = (298.15, 310.15 and 314.15) K. All measurements were made at the maximum wavelength corresponding to maximum absorption. The results showed that the n-octanol/water partition coefficients of propranolol and atenolol increase with the increase of temperature. The experimental data of this work were also used to examine the phase equilibrium correlating capability of some liquid-phase models. The equilibrium experimental data were correlated using the NRTL and UNIQUAC activity coefficient models and the binary interaction parameters were reported. The average root-mea n-square deviations (RMSD) between the experimental and calculated mass fractions of the (n-octanol + propranolol + water) and (n-octanol + atenolol + water) systems were determined. From the partition coefficients obtained, it is concluded that propranolol (log P ow = 3.12 ± 0.14) is more hydrophobic than the atenolol (log P ow = 0.16 ± 0.01) at T = 298.15 K.

Partition Coefficients of Amino Acids, Peptides, and Enzymes in Dextran + Poly(Ethylene Glycol) + Water Aqueous Two-Phase Systems

Energy Technology Data Exchange (ETDEWEB)

Kakisaka, Keijiro.; Shindo, Takashi.; Iwai, Yoshio.; Arai, Yasuhiko. [Kyushu University, Fukuoka (Japan). Department of Chemical Systems and Engineering

1998-12-01

Partition coefficients are measured for five amino acids(aspartic acid, asparagine, methionine, cysteine and histidine) and tow peptides(glycyl-glycine and hexa-glycine) in dextran + poly(ethylene glycol) + water aqueous two-phase system. The partition coefficients of the amino acids and peptides are aorrelated using the osmotic virial equation. The interaction coefficients contained in the equation can be calculated by hydrophilic group parameters. The partition coefficients of {alpha}-amylase calculated by the osmotic virial equation with the hydrophilic group parameters are in fairly good agreement with the experimental data, though a relatively large discrepancy is shown for {beta}-amylase. (author)

Partition Coefficients of Amino Acids, Peptides, and Enzymes in Dextran + Poly(Ethylene Glycol) + Water Aqueous Two-Phase Systems

Energy Technology Data Exchange (ETDEWEB)

Kakisaka, Keijiro.; Shindo, Takashi.; Iwai, Yoshio.; Arai, Yasuhiko. (Kyushu University, Fukuoka (Japan). Department of Chemical Systems and Engineering)

1998-12-01

Partition coefficients are measured for five amino acids(aspartic acid, asparagine, methionine, cysteine and histidine) and tow peptides(glycyl-glycine and hexa-glycine) in dextran + poly(ethylene glycol) + water aqueous two-phase system. The partition coefficients of the amino acids and peptides are aorrelated using the osmotic virial equation. The interaction coefficients contained in the equation can be calculated by hydrophilic group parameters. The partition coefficients of [alpha]-amylase calculated by the osmotic virial equation with the hydrophilic group parameters are in fairly good agreement with the experimental data, though a relatively large discrepancy is shown for [beta]-amylase. (author)

Lipid–water partition coefficients and correlations with uptakes by algae of organic compounds

Energy Technology Data Exchange (ETDEWEB)

Hung, Wei-Nung [Green Energy and Environment Research Laboratories, Industrial Technology Research Institute, Hsinchu 30011, Taiwan (China); Chiou, Cary T., E-mail: carychio@mail.ncku.edu.tw [Department of Environmental Engineering and Sustainable Environment Research Laboratory, National Cheng Kung University, Tainan 70101, Taiwan (China); U.S. Geological Survey, Denver Federal Center, Denver, CO 80225 (United States); Lin, Tsair-Fuh, E-mail: tflin@mail.ncku.edu.tw [Department of Environmental Engineering and Sustainable Environment Research Laboratory, National Cheng Kung University, Tainan 70101, Taiwan (China)

2014-08-30

Graphical abstract: - Highlights: • Partition coefficients of contaminants with lipid triolein (K{sub tw}) are measured. • Measured K{sub tw} values are nearly the same as the respective K{sub ow}. • Sorption of the contaminants to a dry algal powder is similarly measured. • Algal uptake of a compound occurs primarily by partition into the algal lipid. - Abstract: In view of the scarcity of the lipid–water partition coefficients (K{sub tw}) for organic compounds, the log K{sub tw} 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 log K{sub tw} 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 log K{sub tw} are closely related to their respective log K{sub ow} (octanol–water), with log K{sub ow} = 1.9 to 6.5. A significant difference is observed between the present and early measured log K{sub tw} for compounds with log K{sub ow} > ∼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 (log K{sub aw/lipid}) are virtually identical to the respective log K{sub tw} values, which manifests the dominant lipid-partition effect of the compounds with algae.

New Insights into Trace Element Partitioning in Amphibole from Multiple Regression Analysis, with Application to the Magma Plumbing System of Mt. Lamington (Papua New Guinea)

Science.gov (United States)

Zhang, J.; Humphreys, M.; Cooper, G.; Davidson, J.; Macpherson, C.

2015-12-01

We present a new multiple regression (MR) analysis of published amphibole-melt trace element partitioning data, with the aim of retrieving robust relationships between amphibole crystal-chemical compositions and trace element partition coefficients (D). We examined experimental data for calcic amphiboles of kaersutite, pargasite, tschermakite (Tsch), magnesiohornblende (MgHbl) and magnesiohastingsite (MgHst) compositions crystallized from basanitic-rhyolitic melts (n = 150). The MR analysis demonstrates the varying significance of amphibole major element components assigned to different crystallographic sites (T, M1-3, M4, A) as independent variables in controlling D, and it allows us to retrieve statistically significant relationships for REE, Y, Rb, Sr, Pb, Ti, Zr, Nb (n > 25, R2 > 0.6, p-value Ridolfi & Renzulli 2012) with lower Rb and Sr and higher Pb, relative to a hot, andesitic-dacitic melt (950-1,000±50 ºC; 60-70±5 wt % SiO2) where MgHst are crystallized. REE and Nb contents are similar in both types of melts despite higher REE and Nb in MgHbl-Tsch. Therefore, the REE compositional disparity between MgHst and MgHbl-Tsch is driven by the difference in the DREE, rather than the melt REE concentrations.

OCTANOL/WATER PARTITION COEFFICIENTS AND WATER SOLUBILITIES OF PHTHALATE ESTERS

Science.gov (United States)

Measurements of the octanol/water partition coefficients (K-ow) and water solubilities of di-n-octyl phthalate (DnOP) and di-n-decyl phthalate (DnDP) by the slow-stirring method are reported. The water solubility was also measured for di-n-hexyl phthalate (DnHP). The log K-ow val...

Accurate potentiometric determination of lipid membrane-water partition coefficients and apparent dissociation constants of ionizable drugs: electrostatic corrections.

Science.gov (United States)

Elsayed, Mustafa M A; Vierl, Ulrich; Cevc, Gregor

2009-06-01

Potentiometric lipid membrane-water partition coefficient studies neglect electrostatic interactions to date; this leads to incorrect results. We herein show how to account properly for such interactions in potentiometric data analysis. We conducted potentiometric titration experiments to determine lipid membrane-water partition coefficients of four illustrative drugs, bupivacaine, diclofenac, ketoprofen and terbinafine. We then analyzed the results conventionally and with an improved analytical approach that considers Coulombic electrostatic interactions. The new analytical approach delivers robust partition coefficient values. In contrast, the conventional data analysis yields apparent partition coefficients of the ionized drug forms that depend on experimental conditions (mainly the lipid-drug ratio and the bulk ionic strength). This is due to changing electrostatic effects originating either from bound drug and/or lipid charges. A membrane comprising 10 mol-% mono-charged molecules in a 150 mM (monovalent) electrolyte solution yields results that differ by a factor of 4 from uncharged membranes results. Allowance for the Coulombic electrostatic interactions is a prerequisite for accurate and reliable determination of lipid membrane-water partition coefficients of ionizable drugs from potentiometric titration data. The same conclusion applies to all analytical methods involving drug binding to a surface.

Experimental determination of the partitioning coefficient of β-pinene oxidation products in SOAs.

Science.gov (United States)

Hohaus, Thorsten; Gensch, Iulia; Kimmel, Joel; Worsnop, Douglas R; Kiendler-Scharr, Astrid

2015-06-14

The composition of secondary organic aerosols (SOAs) formed by β-pinene ozonolysis was experimentally investigated in the Juelich aerosol chamber. Partitioning of oxidation products between gas and particles was measured through concurrent concentration measurements in both phases. Partitioning coefficients (Kp) of 2.23 × 10(-5) ± 3.20 × 10(-6) m(3) μg(-1) for nopinone, 4.86 × 10(-4) ± 1.80 × 10(-4) m(3) μg(-1) for apoverbenone, 6.84 × 10(-4) ± 1.52 × 10(-4) m(3) μg(-1) for oxonopinone and 2.00 × 10(-3) ± 1.13 × 10(-3) m(3) μg(-1) for hydroxynopinone were derived, showing higher values for more oxygenated species. The observed Kp values were compared with values predicted using two different semi-empirical approaches. Both methods led to an underestimation of the partitioning coefficients with systematic differences between the methods. Assuming that the deviation between the experiment and the model is due to non-ideality of the mixed solution in particles, activity coefficients of 4.82 × 10(-2) for nopinone, 2.17 × 10(-3) for apoverbenone, 3.09 × 10(-1) for oxonopinone and 7.74 × 10(-1) for hydroxynopinone would result using the vapour pressure estimation technique that leads to higher Kp. We discuss that such large non-ideality for nopinone could arise due to particle phase processes lowering the effective nopinone vapour pressure such as diol- or dimer formation. The observed high partitioning coefficients compared to modelled results imply an underestimation of SOA mass by applying equilibrium conditions.

Octanol-air partition coefficients of polybrominated biphenyls.

Science.gov (United States)

Hongxia, Zhao; Jingwen, Chen; Xie, Quan; Baocheng, Qu; Xinmiao, Liang

2009-03-01

The octanol-air partition coefficients (K(OA)) for PBB15, PBB26, PBB31, PBB49, PBB103 and PBB153 were determined as a function of temperature using a gas chromatographic retention time technique with 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (p,p'-DDT) as a reference substance. The internal energies of phase change from octanol to air (Delta(OA)U) were calculated for the six compounds and were in the range from 74 to 116 kJ mol(-1). Simple regression equations of log K(OA) versus relative retention times (RRTs) on gas chromatography (GC), and log K(OA) versus molecular connectivity indexes (MCI) were obtained, for which the correlation coefficients (r(2)) were greater than 0.985 at 283.15K and 298.15K. Thus the K(OA) values of the remaining PBBs can be predicted by using their RRTs and MCI according to these relationships.

Determination of Partition Coefficients of Selected Model Migrants between Polyethylene and Polypropylene and Nanocomposite Polypropylene

Directory of Open Access Journals (Sweden)

Pablo Otero-Pazos

2016-01-01

Full Text Available Studies on nanoparticles have focused the attention of the researchers because they can produce nanocomposites that exhibit unexpected hybrid properties. Polymeric materials are commonly used in food packaging, but from the standpoint of food safety, one of the main concerns on the use of these materials is the potential migration of low molecular substances from the packaging into the food. The key parameters of this phenomenon are the diffusion and partition coefficients. Studies on migration from food packaging with nanomaterials are very scarce. This study is focused on the determination of partition coefficients of different model migrants between the low-density polyethylene (LDPE and polypropylene (PP and between LDPE and nanocomposite polypropylene (naPP. The results show that the incorporation of nanoparticles in polypropylene increases the mass transport of model migrants from LDPE to naPP. This quantity of migrants absorbed into PP and naPP depends partially on the nature of the polymer and slightly on the chemical features of the migrant. Relation (RPP/naPP between partition coefficient KLDPE/PP and partition coefficient KLDPE/naPP at 60°C and 80°C shows that only BHT at 60°C has a RPP/naPP less than 1. On the other hand, bisphenol A has the highest RPP/naPP with approximately 50 times more.

Zircon/fluid trace element partition coefficients measured by recrystallization of Mud Tank zircon at 1.5 GPa and 800-1000 °C

Science.gov (United States)

Ayers, John C.; Peters, Timothy J.

2018-02-01

Hydrothermal zircon grains have trace element characteristics such as low Th/U, high U, and high rare earth element (REE) concentrations that distinguish them from magmatic, metamorphic, and altered zircon grains, but it is unclear whether these characteristics result from distinctive fluid compositions or zircon/fluid fractionation effects. New experiments aimed at measuring zircon/fluid trace element partition coefficients Dz/f involved recrystallizing natural Mud Tank zircon with low trace element concentrations in the presence of H2O, 1 m NaOH, or 1 m HCl doped with ∼1000 ppm of rare earth elements (REE), Y, U and Th and ∼500 ppm of Li, B, P, Nb, Ba, Hf, and Ta. Experiments were run for 168 h at 1.5 GPa, 800-1000 °C, and fO2 = NNO in a piston cylinder apparatus using the double capsule method. LA-ICP-MS analysis shows that run product zircon crystals have much higher trace element concentrations than in Mud Tank zircon starting material. Dz/f values were estimated from run product zircon analyses and bulk composition using mass balance. Most elements behave incompatibly, with median Dz/f being highest for Hf = 8 and lowest for B = 0.02. Addition of NaOH or HCl had little influence on Dz/f values. Dz/f for LREE are anomalously high, likely due to contamination of run product zircon with quenched solutes enriched in incompatible elements, so DLREE were estimated using lattice strain theory. Brice curves for +3 ions yield zircon/fluid DLu/DLa of ∼800-5000. A Brice curve fit to +4 ions yielded DCe4+ values. Estimated concentrations of Ce3+ and Ce4+ show that the average Ce4+/Ce3+ in zircon of 27 is much higher than in fluid of 0.02. Th and U show little fractionation, with median DTh/DU = 0.7, indicating that the low Th/U in natural hydrothermal zircon is inherited from the fluid. Natural fluid compositions estimated from measured Dz/f and published compositions of hydrothermal zircon grains from aplite and eclogite reflect the mineralogy of the host rock, e

[Determination of equilibrium solubility and n-octanol/water partition coefficient of pulchinenosiden D by HPLC].

Science.gov (United States)

Rao, Xiao-Yong; Yin, Shan; Zhang, Guo-Song; Luo, Xiao-Jian; Jian, Hui; Feng, Yu-Lin; Yang, Shi-Lin

2014-05-01

To determine the equilibrium solubility of pulchinenosiden D in different solvents and its n-octanol/water partition coefficients. Combining shaking flask method and high performance liquid chromatography (HPLC) to detect the n-octanol/water partition coefficients of pulchinenosiden D, the equilibrium solubility of pulchinenosiden D in six organic solvents and different pH buffer solution were determined by HPLC analysis. n-Octanol/water partition coefficients of pulchinenosiden D in different pH were greater than zero, the equilibrium solubility of pulchinenosiden D was increased with increase the pH of the buffer solution. The maximum equilibrium solubility of pulchinenosiden D was 255.89 g x L(-1) in methanol, and minimum equilibrium solubility of pulchinenosiden D was 0.20 g x L(-1) in acetonitrile. Under gastrointestinal physiological conditions, pulchinenosiden D exists in molecular state and it has good absorption but poor water-solubility, so increasing the dissolution rate of pulchinenosiden D may enhance its bioavailability.

Determination of partition coefficients of biomolecules in a microfluidic aqueous two phase system platform using fluorescence microscopy.

Science.gov (United States)

Silva, D F C; Azevedo, A M; Fernandes, P; Chu, V; Conde, J P; Aires-Barros, M R

2017-03-03

Aqueous two phase systems (ATPS) offer great potential for selective separation of a wide range of biomolecules by exploring differences in molecular solubility in each of the two immiscible phases. However, ATPS use has been limited due to the difficulty in predicting the behavior of a given biomolecule in the partition environment together with the empirical and time-consuming techniques that are used for the determination of partition and extraction parameters. In this work, a fast and novel technique based on a microfluidic platform and using fluorescence microscopy was developed to determine the partition coefficients of biomolecules in different ATPS. This method consists of using a microfluidic device with a single microchannel and three inlets. In two of the inlets, solutions containing the ATPS forming components were loaded while the third inlet was fed with the FITC tagged biomolecule of interest prepared in milli-Q water. Using fluorescence microscopy, it was possible to follow the location of the FITC-tagged biomolecule and, by simply varying the pumping rates of the solutions, to quickly test a wide variety of ATPS compositions. The ATPS system is allowed 4min for stabilization and fluorescence micrographs are used to determine the partition coefficient.The partition coefficients obtained were shown to be consistent with results from macroscale ATPS partition. This process allows for faster screening of partition coefficients using only a few microliters of material for each ATPS composition and is amenable to automation. The partitioning behavior of several biomolecules with molecular weights (MW) ranging from 5.8 to 150kDa, and isoelectric points (pI) ranging from 4.7 to 6.4 was investigated, as well as the effect of the molecular weight of the polymer ATPS component. Copyright © 2016 Elsevier B.V. All rights reserved.

Octanol-Water Partition Coefficient from 3D-RISM-KH Molecular Theory of Solvation with Partial Molar Volume Correction.

Science.gov (United States)

Huang, WenJuan; Blinov, Nikolay; Kovalenko, Andriy

2015-04-30

The octanol-water partition coefficient is an important physical-chemical characteristic widely used to describe hydrophobic/hydrophilic properties of chemical compounds. The partition coefficient is related to the transfer free energy of a compound from water to octanol. Here, we introduce a new protocol for prediction of the partition coefficient based on the statistical-mechanical, 3D-RISM-KH molecular theory of solvation. It was shown recently that with the compound-solvent correlation functions obtained from the 3D-RISM-KH molecular theory of solvation, the free energy functional supplemented with the correction linearly related to the partial molar volume obtained from the Kirkwood-Buff/3D-RISM theory, also called the "universal correction" (UC), provides accurate prediction of the hydration free energy of small compounds, compared to explicit solvent molecular dynamics [ Palmer , D. S. ; J. Phys.: Condens. Matter 2010 , 22 , 492101 ]. Here we report that with the UC reparametrized accordingly this theory also provides an excellent agreement with the experimental data for the solvation free energy in nonpolar solvent (1-octanol) and so accurately predicts the octanol-water partition coefficient. The performance of the Kovalenko-Hirata (KH) and Gaussian fluctuation (GF) functionals of the solvation free energy, with and without UC, is tested on a large library of small compounds with diverse functional groups. The best agreement with the experimental data for octanol-water partition coefficients is obtained with the KH-UC solvation free energy functional.

Buckminsterfullerene's (C60) octanol-water partition coefficient (Kow) and aqueous solubility.

Science.gov (United States)

Jafvert, Chad T; Kulkarni, Pradnya P

2008-08-15

To assess the risk and fate of fullerene C60 in the environment, its water solubility and partition coefficients in various systems are useful. In this study, the log Kow of C60 was measured to be 6.67, and the toluene-water partition coefficient was measured at log Ktw = 8.44. From these values and the respective solubilities of C60 in water-saturated octanol and water-saturated toluene, C60's aqueous solubility was calculated at 7.96 ng/L(1.11 x 10(-11) M) for the organic solvent-saturated aqueous phase. Additionally, the solubility of C60 was measured in mixtures of ethanol-water and tetrahydrofuran-water and modeled with Wohl's equation to confirm the accuracy of the calculated solubility value. Results of a generator column experiment strongly support the hypothesis that clusters form at aqueous concentrations below or near this calculated solubility. The Kow value is compared to those of other hydrophobic organic compounds, and bioconcentration factors for C60 were estimated on the basis of Kow.

SAMPL5: 3D-RISM partition coefficient calculations with partial molar volume corrections and solute conformational sampling

Science.gov (United States)

Luchko, Tyler; Blinov, Nikolay; Limon, Garrett C.; Joyce, Kevin P.; Kovalenko, Andriy

2016-11-01

Implicit solvent methods for classical molecular modeling are frequently used to provide fast, physics-based hydration free energies of macromolecules. Less commonly considered is the transferability of these methods to other solvents. The Statistical Assessment of Modeling of Proteins and Ligands 5 (SAMPL5) distribution coefficient dataset and the accompanying explicit solvent partition coefficient reference calculations provide a direct test of solvent model transferability. Here we use the 3D reference interaction site model (3D-RISM) statistical-mechanical solvation theory, with a well tested water model and a new united atom cyclohexane model, to calculate partition coefficients for the SAMPL5 dataset. The cyclohexane model performed well in training and testing (R=0.98 for amino acid neutral side chain analogues) but only if a parameterized solvation free energy correction was used. In contrast, the same protocol, using single solute conformations, performed poorly on the SAMPL5 dataset, obtaining R=0.73 compared to the reference partition coefficients, likely due to the much larger solute sizes. Including solute conformational sampling through molecular dynamics coupled with 3D-RISM (MD/3D-RISM) improved agreement with the reference calculation to R=0.93. Since our initial calculations only considered partition coefficients and not distribution coefficients, solute sampling provided little benefit comparing against experiment, where ionized and tautomer states are more important. Applying a simple pK_{ {a}} correction improved agreement with experiment from R=0.54 to R=0.66, despite a small number of outliers. Better agreement is possible by accounting for tautomers and improving the ionization correction.

SAMPL5: 3D-RISM partition coefficient calculations with partial molar volume corrections and solute conformational sampling.

Science.gov (United States)

Luchko, Tyler; Blinov, Nikolay; Limon, Garrett C; Joyce, Kevin P; Kovalenko, Andriy

2016-11-01

Implicit solvent methods for classical molecular modeling are frequently used to provide fast, physics-based hydration free energies of macromolecules. Less commonly considered is the transferability of these methods to other solvents. The Statistical Assessment of Modeling of Proteins and Ligands 5 (SAMPL5) distribution coefficient dataset and the accompanying explicit solvent partition coefficient reference calculations provide a direct test of solvent model transferability. Here we use the 3D reference interaction site model (3D-RISM) statistical-mechanical solvation theory, with a well tested water model and a new united atom cyclohexane model, to calculate partition coefficients for the SAMPL5 dataset. The cyclohexane model performed well in training and testing ([Formula: see text] for amino acid neutral side chain analogues) but only if a parameterized solvation free energy correction was used. In contrast, the same protocol, using single solute conformations, performed poorly on the SAMPL5 dataset, obtaining [Formula: see text] compared to the reference partition coefficients, likely due to the much larger solute sizes. Including solute conformational sampling through molecular dynamics coupled with 3D-RISM (MD/3D-RISM) improved agreement with the reference calculation to [Formula: see text]. Since our initial calculations only considered partition coefficients and not distribution coefficients, solute sampling provided little benefit comparing against experiment, where ionized and tautomer states are more important. Applying a simple [Formula: see text] correction improved agreement with experiment from [Formula: see text] to [Formula: see text], despite a small number of outliers. Better agreement is possible by accounting for tautomers and improving the ionization correction.

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

Science.gov (United States)

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...

Gender- and Age-Specific REE and REE/FFM Distributions in Healthy Chinese Adults

Directory of Open Access Journals (Sweden)

Yu Cheng

2016-09-01

Full Text Available Basic data on the resting energy expenditure (REE of healthy populations are currently rare, especially for developing countries. The aims of the present study were to describe gender- and age-specific REE distributions and to evaluate the relationships among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. This cross-sectional survey included 540 subjects (343 women and 197 men, 20–79 years old. REE was measured by indirect calorimetry and expressed as kcal/day/kg total body weight. The data were presented as the means and percentiles for REE and the REE to fat-free mass (FFM ratio; differences were described by gender and age. Partial correlation analysis was used to analyze the correlations between REE, tertiles of REE/FFM, and glycolipid metabolism and eating behaviors. In this study, we confirmed a decline in REE with age in women (p = 0.000 and men (p = 0.000, and we found that men have a higher REE (p = 0.000 and lower REE/FFM (p = 0.021 than women. Furthermore, we observed no associations among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. In conclusion, the results presented here may be useful to clinicians and nutritionists for comparing healthy and ill subjects and identifying changes in REE that are related to aging, malnutrition, and chronic diseases.

Gender- and Age-Specific REE and REE/FFM Distributions in Healthy Chinese Adults.

Science.gov (United States)

Cheng, Yu; Yang, Xue; Na, Li-Xin; Li, Ying; Sun, Chang-Hao

2016-09-01

Basic data on the resting energy expenditure (REE) of healthy populations are currently rare, especially for developing countries. The aims of the present study were to describe gender- and age-specific REE distributions and to evaluate the relationships among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. This cross-sectional survey included 540 subjects (343 women and 197 men, 20-79 years old). REE was measured by indirect calorimetry and expressed as kcal/day/kg total body weight. The data were presented as the means and percentiles for REE and the REE to fat-free mass (FFM) ratio; differences were described by gender and age. Partial correlation analysis was used to analyze the correlations between REE, tertiles of REE/FFM, and glycolipid metabolism and eating behaviors. In this study, we confirmed a decline in REE with age in women (p = 0.000) and men (p = 0.000), and we found that men have a higher REE (p = 0.000) and lower REE/FFM (p = 0.021) than women. Furthermore, we observed no associations among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. In conclusion, the results presented here may be useful to clinicians and nutritionists for comparing healthy and ill subjects and identifying changes in REE that are related to aging, malnutrition, and chronic diseases.

Direct calculation of 1-octanol-water partition coefficients from adaptive biasing force molecular dynamics simulations.

Science.gov (United States)

Bhatnagar, Navendu; Kamath, Ganesh; Chelst, Issac; Potoff, Jeffrey J

2012-07-07

The 1-octanol-water partition coefficient log K(ow) of a solute is a key parameter used in the prediction of a wide variety of complex phenomena such as drug availability and bioaccumulation potential of trace contaminants. In this work, adaptive biasing force molecular dynamics simulations are used to determine absolute free energies of hydration, solvation, and 1-octanol-water partition coefficients for n-alkanes from methane to octane. Two approaches are evaluated; the direct transfer of the solute from 1-octanol to water phase, and separate transfers of the solute from the water or 1-octanol phase to vacuum, with both methods yielding statistically indistinguishable results. Calculations performed with the TIP4P and SPC∕E water models and the TraPPE united-atom force field for n-alkanes show that the choice of water model has a negligible effect on predicted free energies of transfer and partition coefficients for n-alkanes. A comparison of calculations using wet and dry octanol phases shows that the predictions for log K(ow) using wet octanol are 0.2-0.4 log units lower than for dry octanol, although this is within the statistical uncertainty of the calculation.

Octanol-water partition coefficients for predicting the effects of tannins in ruminant nutrition.

Science.gov (United States)

Mueller-Harvey, Irene; Mlambo, Victor; Sikosana, Joe L N; Smith, Tim; Owen, Emyr; Brown, Ron H

2007-07-11

Tannins can cause beneficial or harmful nutritional effects, but their great diversity has until now prevented a rational distinction between tannin structures and their nutritional responses. An attempt has been made to study this problem by examining the octanol-water solubilities of tannins. A relatively simple HPLC method has been developed for screening mixtures of plant tannins for their octanol-water partition coefficients (Kow coefficients). Tannins were isolated from the fruits and leaves of different Acacia, Calliandra, Dichrostachys, and Piliostigma species, which are known to produce beneficial or harmful effects. The Kow coefficients of these tannins ranged from 0.061 to 13.9, average coefficients of variation were 9.2% and recoveries were 107%. Acacia nilotica fruits and leaves had the highest Kow coefficients, that is, 2.0 and 13.9, respectively. These A. nilotica products also have high concentrations of tannins. The combined effects of high octanol solubilities and high tannin concentrations may explain their negative effects on animal nutrition and health. It is known that compounds with high octanol solubilities are more easily absorbed into tissues, and it is, therefore, proposed that such compounds are more likely to cause toxicity problems especially if consumed in large quantities. According to the literature, tannins in human foods tend to have low Kow coefficients, and this was confirmed for the tannins in Piliostigma thonningii fruits. Therefore, unconventional feeds or browse products should be screened not only for their tannin concentrations but also for low octanol-water partition coefficients in order to identify nutritionally safe feeds and to avoid potentially toxic feeds.

Ionization constants by curve fitting: determination of partition and distribution coefficients of acids and bases and their ions.

Science.gov (United States)

Clarke, F H; Cahoon, N M

1987-08-01

A convenient procedure has been developed for the determination of partition and distribution coefficients. The method involves the potentiometric titration of the compound, first in water and then in a rapidly stirred mixture of water and octanol. An automatic titrator is used, and the data is collected and analyzed by curve fitting on a microcomputer with 64 K of memory. The method is rapid and accurate for compounds with pKa values between 4 and 10. Partition coefficients can be measured for monoprotic and diprotic acids and bases. The partition coefficients of the neutral compound and its ion(s) can be determined by varying the ratio of octanol to water. Distribution coefficients calculated over a wide range of pH values are presented graphically as "distribution profiles". It is shown that subtraction of the titration curve of solvent alone from that of the compound in the solvent offers advantages for pKa determination by curve fitting for compounds of low aqueous solubility.

Apparent partition coefficient in octanol-water and binding percentage to BSA of 153Sm(113,117Snm) complexes

International Nuclear Information System (INIS)

Yang Yuqing; Luo Shunzhong; Wang Guanquan; He Jiaheng; Bing Wenzeng; Pu Manfei; Wei Hongyuan; Wang Wenjin

2004-01-01

Apparent partition coefficient in octanol-water and binding percentage to BSA of 153 Sm-NTMP, 153 Sm-HEDTMP, 153 Sm-DCTMP, 153 Sm-EDTMP, 153 Sm-DTPMP, 113,117 Sn m -EDTMP, 113,117 Sn m -HEDTMP, 113,117 Sn m -DTPMP are measured. The results show that there is a linear relationship between the relative magnitude of the apparent partition coefficient in octanol-water and the relative magnitude of the binding percentage to BSA of these 153 Sm( 113,117 Sn m ) complexes. This linear relationship provides a new method for determination of the apparent partition coefficient in octanol-water of 153 Sm( 113,117 Sn m ) complexes of this kind. This linear relationship also implicates that hydrophobic force plays an important role in the binding of 153 Sm( 113,117 Sn m ) complexes to BSA

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

Science.gov (United States)

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...

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

Science.gov (United States)

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

QSPR modeling of octanol/water partition coefficient for vitamins by optimal descriptors calculated with SMILES.

Science.gov (United States)

Toropov, A A; Toropova, A P; Raska, I

2008-04-01

Simplified molecular input line entry system (SMILES) has been utilized in constructing quantitative structure-property relationships (QSPR) for octanol/water partition coefficient of vitamins and organic compounds of different classes by optimal descriptors. Statistical characteristics of the best model (vitamins) are the following: n=17, R(2)=0.9841, s=0.634, F=931 (training set); n=7, R(2)=0.9928, s=0.773, F=690 (test set). Using this approach for modeling octanol/water partition coefficient for a set of organic compounds gives a model that is statistically characterized by n=69, R(2)=0.9872, s=0.156, F=5184 (training set) and n=70, R(2)=0.9841, s=0.179, F=4195 (test set).

Determination of Partition coefficients for a Mixture of Volatile Organic Compounds in Rats and Humans at Different Life Stages

National Research Council Canada - National Science Library

Mahle, Deidre A; Gearhart, Jeffrey M; Godfrey, Richard J; Mattie, David R; Cook, Robert S; Grisby, Claude C

2004-01-01

.... Partition coefficients (PCs) are an integral component of pharmacokinetic models and determining differences in tissue partitioning of volatile organic chemicals across life stages can help reduce the uncertainty in risk assessment...

The double isotope technique for in vivo determination of the tissue-to-blood partition coefficient for xenon in human subcutaneous adipose tissue--an evaluation

DEFF Research Database (Denmark)

Jelnes, Rolf; Astrup, A; Bülow, J

1985-01-01

the partition coefficient found by the double isotope technique, significantly lower values are obtained than if the in vitro determined coefficient is used. This difference is explained mainly by local dilution when injecting xenon subcutaneously. In short-term studies, utilization of the double isotope...... technique reduces the coefficient of variation on average flow determinations, thus an improvement in accuracy of local blood flow estimation can be obtained compared to the method in which an average partition coefficient is used. For long-term studies a partition coefficient of 7.5 ml g-1 seems valid.......Local subcutaneous 133xenon (133Xe) elimination was registered in the human forefoot in 34 patients. The tissue/blood partition coefficient for Xe was estimated individually by simultaneous registration of 133Xe and [131I]antipyrine ([131I]AP) washout from the same local depot. When measured...

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

Science.gov (United States)

2010-07-01

... using the CLogP3 computer program in paragraph (e)(9) of this section. 4 Hawker and Connell (1988... (B) Constant temperature bath with circulation pump-bath and capable of controlling temperature to 25...-partition coefficient correlation. Environmental Science and Technology 14:1227-1229 (1980). (2) Bruggemann...

Effectiveness of water-air and octanol-air partition coefficients to predict lipophilic flavor release behavior from O/W emulsions.

Science.gov (United States)

Tamaru, Shunji; Igura, Noriyuki; Shimoda, Mitsuya

2018-01-15

Flavor release from food matrices depends on the partition of volatile flavor compounds between the food matrix and the vapor phase. Thus, we herein investigated the relationship between released flavor concentrations and three different partition coefficients, namely octanol-water, octanol-air, and water-air, which represented the oil, water, and air phases present in emulsions. Limonene, 2-methylpyrazine, nonanal, benzaldehyde, ethyl benzoate, α-terpineol, benzyl alcohol, and octanoic acid were employed. The released concentrations of these flavor compounds from oil-in-water (O/W) emulsions were measured under equilibrium using static headspace gas chromatography. The results indicated that water-air and octanol-air partition coefficients correlated with the logarithms of the released concentrations in the headspace for highly lipophilic flavor compounds. Moreover, the same tendency was observed over various oil volume ratios in the emulsions. Our findings therefore suggest that octanol-air and water-air partition coefficients can be used to predict the released concentration of lipophilic flavor compounds from O/W emulsions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simple Method to Determine the Partition Coefficient of Naphthenic Acid in Oil/Water

DEFF Research Database (Denmark)

Bitsch-Larsen, Anders; Andersen, Simon Ivar

2008-01-01

The partition coefficient for technical grade naphthenic acid in water/n-decane at 295 K has been determined (K-wo = 2.1 center dot 10(-4)) using a simple experimental technique with large extraction volumes (0.09 m(3) of water). Furthermore, nonequilibrium values at different pH values...

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

Science.gov (United States)

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.

REE controls in ultramafic hosted MOR hydrothermal systems: An experimental study at elevated temperature and pressure

Science.gov (United States)

Allen, Douglas E.; Seyfried, W. E.

2005-02-01

A hydrothermal experiment involving peridotite and a coexisting aqueous fluid was conducted to assess the role of dissolved Cl - and redox on REE mobility at 400°C, 500 bars. Data show that the onset of reducing conditions enhances the stability of soluble Eu +2 species. Moreover, Eu +2 forms strong aqueous complexes with dissolved Cl - at virtually all redox conditions. Thus, high Cl - concentrations and reducing conditions can combine to reinforce Eu mobility. Except for La, trivalent REE are not greatly affected by fluid speciation under the chemical and physical condition considered, suggesting control by secondary mineral-fluid partitioning. LREE enrichment and positive Eu anomalies observed in fluids from the experiment are remarkably similar to patterns of REE mobility in vent fluids issuing from basalt- and peridotite-hosted hydrothermal systems. This suggests that the chondrite normalized REE patterns are influenced greatly by fluid speciation effects and secondary mineral formation processes. Accordingly, caution must be exercised when using REE in hydrothermal vent fluids to infer REE sources in subseafloor reaction zones from which the fluids are derived. Although vent fluid patterns having LREE enrichment and positive Eu anomalies are typically interpreted to suggest plagioclase recrystallization reactions, this need not always be the case.

A New Approach on Estimation of Solubility and n-Octanol/ Water Partition Coefficient for Organohalogen Compounds

Directory of Open Access Journals (Sweden)

Chenzhong Cao

2008-06-01

Full Text Available The aqueous solubility (logW and n-octanol/water partition coefficient (logPOW are important properties for pharmacology, toxicology and medicinal chemistry. Based on an understanding of the dissolution process, the frontier orbital interaction model was suggested in the present paper to describe the solvent-solute interactions of organohalogen compounds and a general three-parameter model was proposed to predict the aqueous solubility and n-octanol/water partition coefficient for the organohalogen compounds containing nonhydrogen-binding interactions. The model has satisfactory prediction accuracy. Furthermore, every item in the model has a very explicit meaning, which should be helpful to understand the structure-solubility relationship and may be provide a new view on estimation of solubility.

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

Energy Technology Data Exchange (ETDEWEB)

Wei, Wenjuan, E-mail: Wenjuan.Wei@cstb.fr [University of Paris-Est, Scientific and Technical Center for Building (CSTB), Health and Comfort Department, French Indoor Air Quality Observatory (OQAI), 84 Avenue Jean Jaurès, Champs sur Marne, 77447 Marne la Vallée Cedex 2 (France); Mandin, Corinne [University of Paris-Est, Scientific and Technical Center for Building (CSTB), Health and Comfort Department, French Indoor Air Quality Observatory (OQAI), 84 Avenue Jean Jaurès, Champs sur Marne, 77447 Marne la Vallée Cedex 2 (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); LERES-Environment and Health Research Laboratory (Irset and EHESP Technologic Platform), Rennes (France); Blanchard, Olivier [EHESP-School of Public Health, Sorbonne Paris Cité, Rennes (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); Mercier, Fabien [EHESP-School of Public Health, Sorbonne Paris Cité, Rennes (France); LERES-Environment and Health Research Laboratory (Irset and EHESP Technologic Platform), Rennes (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); Pelletier, Maud [EHESP-School of Public Health, Sorbonne Paris Cité, Rennes (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); Le Bot, Barbara [EHESP-School of Public Health, Sorbonne Paris Cité, Rennes (France); LERES-Environment and Health Research Laboratory (Irset and EHESP Technologic Platform), Rennes (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); and others

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. - Highlights: • A theoretical relationship between K{sub p} and temperature was developed. • The relationship was based on the SVOC absorptive mechanism. • The temperature impact was quantified by a dimensionless analysis.

Calculation of the octanol-water partition coefficient of armchair polyhex BN nanotubes

Science.gov (United States)

Mohammadinasab, E.; Pérez-Sánchez, H.; Goodarzi, M.

2017-12-01

A predictive model for determination partition coefficient (log P) of armchair polyhex BN nanotubes by using simple descriptors was built. The relationship between the octanol-water log P and quantum chemical descriptors, electric moments, and topological indices of some armchair polyhex BN nanotubes with various lengths and fixed circumference are represented. Based on density functional theory electric moments and physico-chemical properties of those nanotubes are calculated.

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

Science.gov (United States)

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

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 α-pinene-O 3 reaction was augmented by carrying out smog chamber partitioning experiments on aerosols from meat cooking, and catalyzed and uncatalyzed gasoline engine exhaust. Model compositions for aerosols from meat cooking and gasoline combustion emissions were used to calculate activity coefficients for the SOCs in the organic aerosols and the Pankow absorptive gas/particle partitioning model was used to calculate the partitioning coefficient Kp and quantitate the predictive improvements of using the activity coefficient. The slope of the log K p vs. log p L0 correlation for partitioning on aerosols from meat cooking improved from -0.81 to -0.94 after incorporation of activity coefficients iγ om. A stepwise regression analysis of the partitioning model revealed that for the data set used in this study, partitioning predictions on α-pinene-O 3 secondary aerosol and wood combustion aerosol showed statistically significant improvement after incorporation of iγ om, which can be attributed to their overall polarity. The partitioning model was sensitive to changes in aerosol composition when updated compositions for α-pinene-O 3 aerosol and wood combustion aerosol were used. The octanol-air partitioning coefficient's ( KOA) effectiveness as a partitioning correlator over a variety of aerosol types was evaluated. The slope of the log K p- log K OA correlation was not constant over the aerosol types and SOCs used in the study and the use of KOA for partitioning correlations can potentially lead to significant deviations, especially for polar aerosols.

Myocardial T1 mapping and determination of partition coefficients at 3 tesla: comparison between gadobenate dimeglumine and gadofosveset trisodium

Directory of Open Access Journals (Sweden)

Marcelo Souto Nacif

2018-01-01

Full Text Available Abstract Objective: To compare an albumin-bound gadolinium chelate (gadofosveset trisodium and an extracellular contrast agent (gadobenate dimeglumine, in terms of their effects on myocardial longitudinal (T1 relaxation time and partition coefficient. Materials and Methods: Study subjects underwent two imaging sessions for T1 mapping at 3 tesla with a modified look-locker inversion recovery (MOLLI pulse sequence to obtain one pre-contrast T1 map and two post-contrast T1 maps (mean 15 and 21 min, respectively. The partition coefficient was calculated as ΔR1myocardium /ΔR1blood , where R1 is 1/T1. Results: A total of 252 myocardial and blood pool T1 values were obtained in 21 healthy subjects. After gadolinium administration, the myocardial T1 was longer for gadofosveset than for gadobenate, the mean difference between the two contrast agents being −7.6 ± 60 ms (p = 0.41. The inverse was true for the blood pool T1, which was longer for gadobenate than for gadofosveset, the mean difference being 56.5 ± 67 ms (p < 0.001. The partition coefficient (λ was higher for gadobenate than gadofosveset (0.41 vs. 0.33, indicating slower blood pool washout for gadofosveset than for gadobenate. Conclusion: Myocardial T1 times did not differ significantly between gadobenate and gadofosveset. At typical clinical doses of the contrast agents, partition coefficients were significantly lower for the intravascular contrast agent than for the extravascular agent.

Partition coefficients of some purine derivatives and its application to pharmacokinetics.

Science.gov (United States)

Chrzanowska, M; Sobiak, J; Kuehn, M; Dorawa, E; Hermann, T

2009-12-01

Metazathioprine (MAZA), a methylated derivative of azathioprine (AZA), demonstrated the greatest values of apparent and specific partition coefficients in n-octanol/phosphate buffer at pH 5.7 and pH 7.4 among purine derivatives such as 6-mercaptopurine (6-MP), 6-thioguanine (6-TG) and AZA. Introduction of a methyl group into the imidazole ring of AZA increases lipophilic properties of MAZA compared to AZA. Mass balance of purine derivatives in n-octanol and in phosphate buffer indicated their chemical stability in those media.

Determination of partition coefficients using 1 H NMR spectroscopy and time domain complete reduction to amplitude-frequency table (CRAFT) analysis.

Science.gov (United States)

Soulsby, David; Chica, Jeryl A M

2017-08-01

We have developed a simple, direct and novel method for the determination of partition coefficients and partitioning behavior using 1 H NMR spectroscopy combined with time domain complete reduction to amplitude-frequency tables (CRAFT). After partitioning into water and 1-octanol using standard methods, aliquots from each layer are directly analyzed using either proton or selective excitation NMR experiments. Signal amplitudes for each compound from each layer are then extracted directly from the time domain data in an automated fashion and analyzed using the CRAFT software. From these amplitudes, log P and log D 7.4 values can be calculated directly. Phase, baseline and internal standard issues, which can be problematic when Fourier transformed data are used, are unimportant when using time domain data. Furthermore, analytes can contain impurities because only a single resonance is examined and need not be UV active. Using this approach, we examined a variety of pharmaceutically relevant compounds and determined partition coefficients that are in excellent agreement with literature values. To demonstrate the utility of this approach, we also examined salicylic acid in more detail demonstrating an aggregation effect as a function of sample loading and partition coefficient behavior as a function of pH value. This method provides a valuable addition to the medicinal chemist toolbox for determining these important constants. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Polymers as reference partitioning phase: polymer calibration for an analytically operational approach to quantify multimedia phase partitioning

DEFF Research Database (Denmark)

Gilbert, Dorothea; Witt, Gesine; Smedes, Foppe

2016-01-01

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......-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...

A critical compilation and review of default soil solid/liquid partition coefficients, Kd, for use in environmental assessments

International Nuclear Information System (INIS)

Thibault, D.H.; Sheppard, M.I.; Smith, P.A.

1990-03-01

Environmental assessments of the Canadian concept for disposal of nuclear fuel waste in plutonic rock formations require analyses of the migration of nuclides from the disposal vault to the biosphere. Analyses of nuclide migration via groundwater through the geosphere, unconsolidated overburden and soil use models requiring solid/liquid partition coefficients (K d ) to describe the interaction of the nuclides with the solid materials. This report presents element-specific soil solid/liquid partition coefficients based on a detailed survey of the literature. Values for clays, silt, sand and organic soils are summarized. Partition coefficients for the following elements are presented: americium, antimony, arsenic, barium, boron, cadmium, calcium, carbon, cerium, cesium, chromium, cobalt, copper, curium, europium, iodine, iron, lead, lithium, manganese, molybdenum, neptunium, nickel, niobium, palladium, phosphorus, plutonium, polonium, radium, ruthenium, samarium, selenium, silver, strontium, technetium, tellurium, terbium, thorium, tin, tritium, uranium, zinc, and zirconium. The values compiled in this study are compared with earlier K d value compendiums and are the values recommended for the use in the soil, deep sediment and overburden models for the Environmental Impact Statement on the concept for disposal of Canada's nuclear fuel waste

QSPR modeling of octanol/water partition coefficient of antineoplastic agents by balance of correlations.

Science.gov (United States)

Toropov, Andrey A; Toropova, Alla P; Raska, Ivan; Benfenati, Emilio

2010-04-01

Three different splits into the subtraining set (n = 22), the set of calibration (n = 21), and the test set (n = 12) of 55 antineoplastic agents have been examined. By the correlation balance of SMILES-based optimal descriptors quite satisfactory models for the octanol/water partition coefficient have been obtained on all three splits. The correlation balance is the optimization of a one-variable model with a target function that provides both the maximal values of the correlation coefficient for the subtraining and calibration set and the minimum of the difference between the above-mentioned correlation coefficients. Thus, the calibration set is a preliminary test set. Copyright (c) 2009 Elsevier Masson SAS. All rights reserved.

Determination of solid-liquid partition coefficients (Kd) for the herbicides inspiration and trifluralin in five UK agricultural soils

International Nuclear Information System (INIS)

Cooke, Cindy M.; Shaw, George; Collins, Chris D.

2004-01-01

Isoproturon and trifluralin are herbicides of contrasting chemical characters and modes of action. Standard batch sorption procedures were carried out to investigate the individual sorption behaviour of 14 C-isoproturon and 14 C-trifluralin in five agricultural soils (1.8-4.2% OC), and the soil solid-liquid partition coefficients (K d values) were determined. Trifluralin exhibited strong partitioning to the soil solid phase (K d range 106-294) and low desorption potential, thus should not pose a threat to sensitive waters via leaching, although particle erosion and preferential flow pathways may facilitate transport. For isoproturon, soil adsorption was low (K d range 1.96-5.75) and desorption was high, suggesting a high leaching potential, consistent with isoproturon being the most frequently found pesticide in UK surface waters. Soil partitioning was directly related to soil organic carbon (OC) content. Accumulation isotherms were modelled using a dual-phase adsorption model to estimate adsorption and desorption rate coefficients. Associations between herbicides and soil humic substances were also shown using gel filtration chromatography. - Capsule: Herbicide soil sorption described by a dual-phase adsorption model reflected soil partitioning, as influenced by soil OC and humic substances

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

Science.gov (United States)

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...

Partition coefficients of methylated DNA bases obtained from free energy calculations with molecular electron density derived atomic charges.

Science.gov (United States)

Lara, A; Riquelme, M; Vöhringer-Martinez, E

2018-05-11

Partition coefficients serve in various areas as pharmacology and environmental sciences to predict the hydrophobicity of different substances. Recently, they have also been used to address the accuracy of force fields for various organic compounds and specifically the methylated DNA bases. In this study, atomic charges were derived by different partitioning methods (Hirshfeld and Minimal Basis Iterative Stockholder) directly from the electron density obtained by electronic structure calculations in a vacuum, with an implicit solvation model or with explicit solvation taking the dynamics of the solute and the solvent into account. To test the ability of these charges to describe electrostatic interactions in force fields for condensed phases, the original atomic charges of the AMBER99 force field were replaced with the new atomic charges and combined with different solvent models to obtain the hydration and chloroform solvation free energies by molecular dynamics simulations. Chloroform-water partition coefficients derived from the obtained free energies were compared to experimental and previously reported values obtained with the GAFF or the AMBER-99 force field. The results show that good agreement with experimental data is obtained when the polarization of the electron density by the solvent has been taken into account, and when the energy needed to polarize the electron density of the solute has been considered in the transfer free energy. These results were further confirmed by hydration free energies of polar and aromatic amino acid side chain analogs. Comparison of the two partitioning methods, Hirshfeld-I and Minimal Basis Iterative Stockholder (MBIS), revealed some deficiencies in the Hirshfeld-I method related to the unstable isolated anionic nitrogen pro-atom used in the method. Hydration free energies and partitioning coefficients obtained with atomic charges from the MBIS partitioning method accounting for polarization by the implicit solvation model

Determination and importance of temperature dependence of retention coefficient (RPHPLC) in QSAR model of nitrazepams' partition coefficient in bile acid micelles.

Science.gov (United States)

Posa, Mihalj; Pilipović, Ana; Lalić, Mladena; Popović, Jovan

2011-02-15

Linear dependence between temperature (t) and retention coefficient (k, reversed phase HPLC) of bile acids is obtained. Parameters (a, intercept and b, slope) of the linear function k=f(t) highly correlate with bile acids' structures. Investigated bile acids form linear congeneric groups on a principal component (calculated from k=f(t)) score plot that are in accordance with conformations of the hydroxyl and oxo groups in a bile acid steroid skeleton. Partition coefficient (K(p)) of nitrazepam in bile acids' micelles is investigated. Nitrazepam molecules incorporated in micelles show modified bioavailability (depo effect, higher permeability, etc.). Using multiple linear regression method QSAR models of nitrazepams' partition coefficient, K(p) are derived on the temperatures of 25°C and 37°C. For deriving linear regression models on both temperatures experimentally obtained lipophilicity parameters are included (PC1 from data k=f(t)) and in silico descriptors of the shape of a molecule while on the higher temperature molecular polarisation is introduced. This indicates the fact that the incorporation mechanism of nitrazepam in BA micelles changes on the higher temperatures. QSAR models are derived using partial least squares method as well. Experimental parameters k=f(t) are shown to be significant predictive variables. Both QSAR models are validated using cross validation and internal validation method. PLS models have slightly higher predictive capability than MLR models. Copyright © 2010 Elsevier B.V. All rights reserved.

Field determination and QSPR prediction of equilibrium-status soil/vegetation partition coefficient of PCDD/Fs.

Science.gov (United States)

Li, Li; Wang, Qiang; Qiu, Xinghua; Dong, Yian; Jia, Shenglan; Hu, Jianxin

2014-07-15

Characterizing pseudo equilibrium-status soil/vegetation partition coefficient KSV, the quotient of respective concentrations in soil and vegetation of a certain substance at remote background areas, is essential in ecological risk assessment, however few previous attempts have been made for field determination and developing validated and reproducible structure-based estimates. In this study, KSV was calculated based on measurements of seventeen 2,3,7,8-substituted PCDD/F congeners in soil and moss (Dicranum angustum), and rouzi grass (Thylacospermum caespitosum) of two background sites, Ny-Ålesund of the Arctic and Zhangmu-Nyalam region of the Tibet Plateau, respectively. By both fugacity modeling and stepwise regression of field data, the air-water partition coefficient (KAW) and aqueous solubility (SW) were identified as the influential physicochemical properties. Furthermore, validated quantitative structure-property relationship (QSPR) model was developed to extrapolate the KSV prediction to all 210 PCDD/F congeners. Molecular polarizability, molecular size and molecular energy demonstrated leading effects on KSV. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of solid-liquid partition coefficients (Kd) for the herbicides isoproturon and trifluralin in five UK agricultural soils.

Science.gov (United States)

Cooke, Cindy M; Shaw, George; Collins, Chris D

2004-12-01

Isoproturon and trifluralin are herbicides of contrasting chemical characters and modes of action. Standard batch sorption procedures were carried out to investigate the individual sorption behaviour of 14C-isoproturon and 14C-trifluralin in five agricultural soils (1.8-4.2% OC), and the soil solid-liquid partition coefficients (Kd values) were determined. Trifluralin exhibited strong partitioning to the soil solid phase (Kd range 106-294) and low desorption potential, thus should not pose a threat to sensitive waters via leaching, although particle erosion and preferential flow pathways may facilitate transport. For isoproturon, soil adsorption was low (Kd range 1.96-5.75) and desorption was high, suggesting a high leaching potential, consistent with isoproturon being the most frequently found pesticide in UK surface waters. Soil partitioning was directly related to soil organic carbon (OC) content. Accumulation isotherms were modelled using a dual-phase adsorption model to estimate adsorption and desorption rate coefficients. Associations between herbicides and soil humic substances were also shown using gel filtration chromatography.

Apatite/Melt Partitioning Experiments Reveal Redox Sensitivity to Cr, V, Mn, Ni, Eu, W, Th, and U

Science.gov (United States)

Righter, K.; Yang, S.; Humayun, M.

2016-01-01

Apatite is a common mineral in terrestrial, planetary, and asteroidal materials. It is commonly used for geochronology (U-Pb), sensing volatiles (H, F, Cl, S), and can concentrate rare earth elements (REE) during magmatic fractionation and in general. Some recent studies have shown that some kinds of phosphate may fractionate Hf and W and that Mn may be redox sensitive. Experimental studies have focused on REE and other lithophile elements and at simplified or not specified oxygen fugacities. There is a dearth of partitioning data for chalcophile, siderophile and other elements between apatite and melt. Here we carry out several experiments at variable fO2 to study the partitioning of a broad range of trace elements. We compare to existing data and then focus on several elements that exhibit redox dependent partitioning behavior.

Determination of the air/water partition coefficient of groundwater radon using liquid scintillation counter

International Nuclear Information System (INIS)

Lee, K.Y.; Yoon, Y.Y.; Ko, K.S.

2010-01-01

A method was studied for measuring air/water partition coefficient (K air/water ) of groundwater radon by a simple procedure using liquid scintillation counter (LSC). In contrast conventional techniques such as equilibrium partitioning in a closed system or air striping methods, the described method allow for a simple and uncomplicated determination of the coefficient. The (K air/water ) of radon in pure water has been well known quantitatively over a wide range of temperatures. In this work, groundwater samples having high radon concentration instead of distilled water have been used to determine the (K air/water ) of radon in the temperature range of 0-25. Aqueous phase in a closed system was used in this study instead of gaseous phase in conventional methods. Three kinds of groundwater taken from different geologic environments were used to investigate the effect of groundwater properties. With the aim to evaluate the reproducibility of the data an appropriate number of laboratory experiments have been carried out. The results show that tie (K air/water ) of radon in the groundwater is smaller than that in the pure water. However, the temperature effect on the coefficient is similar in the groundwater and the pure water. The method using aqueous phase in a closed system by LSC can be used to determine the (K air/water ) of radon in various groundwaters with a simple procedure. The results will be presented at the NAC-IV conference

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

Science.gov (United States)

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...

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

Science.gov (United States)

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.

Towards the challenging REE exploration in Indonesia

Science.gov (United States)

Setiawan, Iwan

2018-02-01

Rare earth elements (REE) are the seventeen elements, including fifteen from 57La to 71Lu, in addition to 21Sc and 39Y. In rock-forming minerals, rare earth elements typically occur in compounds as trivalent cations in carbonates, oxides, phosphates, and silicates. The REE occur in a wide range of rock types: igneous, sedimentary and metamorphic rocks. REE are one of the critical metals in the world. Their occurrences are important to supply the world needs on high technology materials. Indonesia has a lot of potential sources of REE that are mainly from residual tin mining processes in Bangka islands, which are associated with radioactive minerals e.g. monazite and xenotime. However, the REE from monazite and xenotime are difficult to extract and contain high radioactivity. Granitoids are widely distributed in Sumatra, Sulawesi, Kalimantan and Papua. They also have a very thick weathering crusts. Important REE-bearing minerals are allanite and titanite. Their low susceptibilities during weathering result an economically potential REE concentration. I-/A- type granitoids and their weathered crusts are important REE sources in Indonesia. Unfortunately, their distribution and genesis have not been deeply studied. Future REE explorations challenge are mainly of the granitoids their weathered crusts. Geochemical and mineralogical characterization of type of granitoids and their weathered crusts, the hydrothermally altered rocks, and clear REE regulation will help discover REE deposits in Indonesia.

Novel medium-throughput technique for investigating drug-cyclodextrin complexation by pH-metric titration using the partition coefficient method.

Science.gov (United States)

Dargó, Gergő; Boros, Krisztina; Péter, László; Malanga, Milo; Sohajda, Tamás; Szente, Lajos; Balogh, György T

2018-05-05

The present study was aimed to develop a medium-throughput screening technique for investigation of cyclodextrin (CD)-active pharmaceutical ingredient (API) complexes. Dual-phase potentiometric lipophilicity measurement, as gold standard technique, was combined with the partition coefficient method (plotting the reciprocal of partition coefficients of APIs as a function of CD concentration). A general equation was derived for determination of stability constants of 1:1 CD-API complexes (K 1:1,CD ) based on solely the changes of partition coefficients (logP o/w N -logP app N ), without measurement of the actual API concentrations. Experimentally determined logP value (-1.64) of 6-deoxy-6[(5/6)-fluoresceinylthioureido]-HPBCD (FITC-NH-HPBCD) was used to estimate the logP value (≈ -2.5 to -3) of (2-hydroxypropyl)-ß-cyclodextrin (HPBCD). The results suggested that the amount of HPBCD can be considered to be inconsequential in the octanol phase. The decrease of octanol volume due to the octanol-CD complexation was considered, thus a corrected octanol-water phase ratio was also introduced. The K 1:1,CD values obtained by this developed method showed a good accordance with the results from other orthogonal methods. Copyright © 2018 Elsevier B.V. All rights reserved.

Immiscible silicate liquids at high pressure: the influence of melt structure on elemental partitioning

Energy Technology Data Exchange (ETDEWEB)

Vicenzi, E [Princeton Materials Laboratory, Princeton, NJ (United States); Green, T H [Macquarie Univ., North Ryde, NSW (Australia); Sie, S H [Commonwealth Scientific and Industrial Research Organisation (CSIRO), North Ryde, NSW (Australia). Div. of Exploration Geoscience

1994-12-31

Micro-PIXE analyses have been applied to study partitioning of trace elements between immiscible silicate melts stabilised at 0.5 and 1.0 GPa over a temperature range of 1160-1240 deg C in the system SiO{sub 2}-FeO-Al{sub 2}0{sub 3}-K{sub 2}0 (+P{sub 2}0{sub 5}). The system was doped with a suite of trace elements of geochemical interest: Rb, Ba, Pb, Sr, La, Ce, Sm, Ho, Y, Lu, Th, U, Zr, Hf, Nb and Ta at approximately 200 ppm level for all elements except for the REE`s, Ba and Ta (600-1200 ppm). Trace element partitioning was found to be a complex function of cation field strength (charge/radius{sup 2}). Although field strength is important in determining the nature and degree of partitioning, the authors emphasised that it is only one component of the underlying mechanism for the way in which elements distribute themselves between two silicate liquids. 8 refs., 2 figs.

Immiscible silicate liquids at high pressure: the influence of melt structure on elemental partitioning

Energy Technology Data Exchange (ETDEWEB)

Vicenzi, E. [Princeton Materials Laboratory, Princeton, NJ (United States); Green, T.H. [Macquarie Univ., North Ryde, NSW (Australia); Sie, S.H. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), North Ryde, NSW (Australia). Div. of Exploration Geoscience

1993-12-31

Micro-PIXE analyses have been applied to study partitioning of trace elements between immiscible silicate melts stabilised at 0.5 and 1.0 GPa over a temperature range of 1160-1240 deg C in the system SiO{sub 2}-FeO-Al{sub 2}0{sub 3}-K{sub 2}0 (+P{sub 2}0{sub 5}). The system was doped with a suite of trace elements of geochemical interest: Rb, Ba, Pb, Sr, La, Ce, Sm, Ho, Y, Lu, Th, U, Zr, Hf, Nb and Ta at approximately 200 ppm level for all elements except for the REE`s, Ba and Ta (600-1200 ppm). Trace element partitioning was found to be a complex function of cation field strength (charge/radius{sup 2}). Although field strength is important in determining the nature and degree of partitioning, the authors emphasised that it is only one component of the underlying mechanism for the way in which elements distribute themselves between two silicate liquids. 8 refs., 2 figs.

Determination of solid-liquid partition coefficients (K{sub d}) for the herbicides inspiration and trifluralin in five UK agricultural soils

Energy Technology Data Exchange (ETDEWEB)

Cooke, Cindy M. [Department of Environmental Science and Technology, Faculty of Life Sciences, Imperial College London, Silwood Park Campus, Ascot, Berkshire SL5 7PY (United Kingdom)]. E-mail: cindy.cooke@imperial.ac.uk; Shaw, George [Department of Environmental Science and Technology, Faculty of Life Sciences, Imperial College London, Silwood Park Campus, Ascot, Berkshire SL5 7PY (United Kingdom); Collins, Chris D. [Department of Environmental Science and Technology, Faculty of Life Sciences, Imperial College London, Silwood Park Campus, Ascot, Berkshire SL5 7PY (United Kingdom)

2004-12-01

Isoproturon and trifluralin are herbicides of contrasting chemical characters and modes of action. Standard batch sorption procedures were carried out to investigate the individual sorption behaviour of {sup 14}C-isoproturon and {sup 14}C-trifluralin in five agricultural soils (1.8-4.2% OC), and the soil solid-liquid partition coefficients (K{sub d} values) were determined. Trifluralin exhibited strong partitioning to the soil solid phase (K{sub d} range 106-294) and low desorption potential, thus should not pose a threat to sensitive waters via leaching, although particle erosion and preferential flow pathways may facilitate transport. For isoproturon, soil adsorption was low (K{sub d} range 1.96-5.75) and desorption was high, suggesting a high leaching potential, consistent with isoproturon being the most frequently found pesticide in UK surface waters. Soil partitioning was directly related to soil organic carbon (OC) content. Accumulation isotherms were modelled using a dual-phase adsorption model to estimate adsorption and desorption rate coefficients. Associations between herbicides and soil humic substances were also shown using gel filtration chromatography. - Capsule: Herbicide soil sorption described by a dual-phase adsorption model reflected soil partitioning, as influenced by soil OC and humic substances.

Rapid determination of octanol-water partition coefficient using vortex-assisted liquid-liquid microextraction.

Science.gov (United States)

Román, Iván P; Mastromichali, Anna; Tyrovola, Konstantina; Canals, Antonio; Psillakis, Elefteria

2014-02-21

Vortex-assisted liquid-liquid microextraction (VALLME) coupled with high-performance liquid chromatography (HPLC) is proposed here for the rapid determination of octanol-water partitioning coefficients (Kow). VALLME uses vortex agitation, a mild emulsification procedure, to disperse microvolumes of octanol in the aqueous phase thus increasing the interfacial contact area and ensuring faster partitioning rates. With VALLME, 2min were enough to achieve equilibrium conditions between the octanolic and aqueous phases. Upon equilibration, separation was achieved using centrifugation and the octanolic microdrop was collected and analyzed in a HPLC system. Six model compounds with logKow values ranging between ∼0.5 and 3.5 were used during the present investigations. The proposed method produced logKow values that were consistent with previously published values and the recorded uncertainty was well within the acceptable log unit range. Overall, the key features of the proposed Kow determination procedure comprised speed, reliability, simplicity, low cost and minimal solvent consumption. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

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...

Solvation free energies and partition coefficients with the coarse-grained and hybrid all-atom/coarse-grained MARTINI models.

Science.gov (United States)

Genheden, Samuel

2017-10-01

We present the estimation of solvation free energies of small solutes in water, n-octanol and hexane using molecular dynamics simulations with two MARTINI models at different resolutions, viz. the coarse-grained (CG) and the hybrid all-atom/coarse-grained (AA/CG) models. From these estimates, we also calculate the water/hexane and water/octanol partition coefficients. More than 150 small, organic molecules were selected from the Minnesota solvation database and parameterized in a semi-automatic fashion. Using either the CG or hybrid AA/CG models, we find considerable deviations between the estimated and experimental solvation free energies in all solvents with mean absolute deviations larger than 10 kJ/mol, although the correlation coefficient is between 0.55 and 0.75 and significant. There is also no difference between the results when using the non-polarizable and polarizable water model, although we identify some improvements when using the polarizable model with the AA/CG solutes. In contrast to the estimated solvation energies, the estimated partition coefficients are generally excellent with both the CG and hybrid AA/CG models, giving mean absolute deviations between 0.67 and 0.90 log units and correlation coefficients larger than 0.85. We analyze the error distribution further and suggest avenues for improvements.

Solvation free energies and partition coefficients with the coarse-grained and hybrid all-atom/coarse-grained MARTINI models

Science.gov (United States)

Genheden, Samuel

2017-10-01

We present the estimation of solvation free energies of small solutes in water, n-octanol and hexane using molecular dynamics simulations with two MARTINI models at different resolutions, viz. the coarse-grained (CG) and the hybrid all-atom/coarse-grained (AA/CG) models. From these estimates, we also calculate the water/hexane and water/octanol partition coefficients. More than 150 small, organic molecules were selected from the Minnesota solvation database and parameterized in a semi-automatic fashion. Using either the CG or hybrid AA/CG models, we find considerable deviations between the estimated and experimental solvation free energies in all solvents with mean absolute deviations larger than 10 kJ/mol, although the correlation coefficient is between 0.55 and 0.75 and significant. There is also no difference between the results when using the non-polarizable and polarizable water model, although we identify some improvements when using the polarizable model with the AA/CG solutes. In contrast to the estimated solvation energies, the estimated partition coefficients are generally excellent with both the CG and hybrid AA/CG models, giving mean absolute deviations between 0.67 and 0.90 log units and correlation coefficients larger than 0.85. We analyze the error distribution further and suggest avenues for improvements.

Determining octanol-water partition coefficients for extremely hydrophobic chemicals by combining 'slow stirring' and solid phase micro extraction

NARCIS (Netherlands)

Jonker, Michiel T O

Octanol-water partition coefficients (Kow ) are widely used in fate and effects modelling 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

Correlation of the octanol/water partition coefficient with clearance halftimes of intratracheally instilled aromatic hydrocarbons in rats

International Nuclear Information System (INIS)

Bond, J.A.; Baker, S.M.; Bechtold, W.E.

1985-01-01

Studies on the lung retention of polycyclic aromatic hydrocarbons (PAH) after inhalation have indicated that, in general, the PAH are rapidly cleared from the respiratory tract. Clearance of the PAH from the lungs is best described as bi-phasic, with the long-term component of the clearance curve having a half-time of greater than 24 h. The purpose of this study was to determine whether a relationship exists between the lipophilicity (as measured by the octanol/water partition coefficient, P) of various PAH and the short-term and long-term clearance half-times of PAH in rat lungs. Female F344/Crl rats were administered intratracheally 1 nmol of 14 C-labelled anthracene (AN), benz (a) anthracene (BA), 1-nitropyrene (NP), 6-nitrobenzo (a) pyrene (6-NBP), or dibenzo (c, g) carbazole (DBC). At various times after instillation rats were sacrificed and the amount of 14 C from rat lungs following instillation of the different PAH was biphasic. In all cases, greater than 85% of the initial dose instilled was cleared with a half-time of less than 1 h. The half-times for clearance of the residual 14 C (1-15% of the dose) were 26, 30, 36, 53 and 63 h for AN, NP, 6-NBP, BA and DCB, respectively. The log of the octanol-water partition coefficients for the different PAH examined ranged from 4.1 (AN) to 6.05 (DBC). Plots of the octanol/water coefficients vs. the long-term clearance half-time for the PAH indicated a linear correlation (p 2 =0.96). The results from this study indicate that the greater the lipophilicity of the PAH, the slower the long-term clearance of a small fraction (1-15%) of PAH from rat lungs. These data suggest that predictions of long-term lung clearance can be made for PAH with log octanol-water partition coefficients between 4 and 6. (author)

Evaluation of the ability of arsenic species to traverse cell membranes by simple diffusion using octanol-water and liposome-water partition coefficients.

Science.gov (United States)

Chávez-Capilla, Teresa; Maher, William; Kelly, Tamsin; Foster, Simon

2016-11-01

Arsenic metabolism in living organisms is dependent on the ability of different arsenic species to traverse biological membranes. Simple diffusion provides an alternative influx and efflux route to mediated transport mechanisms that can increase the amount of arsenic available for metabolism in cells. Using octanol-water and liposome-water partition coefficients, the ability of arsenous acid, arsenate, methylarsonate, dimethylarsinate, thio-methylarsonate, thio-dimethylarsinic acid, arsenotriglutathione and monomethylarsonic diglutathione to diffuse through the lipid bilayer of cell membranes was investigated. Molecular modelling of arsenic species was used to explain the results. All arsenic species with the exception of arsenate, methylarsonate and thio-methylarsonate were able to diffuse through the lipid bilayer of liposomes, with liposome-water partition coefficients between 0.04 and 0.13. Trivalent arsenic species and thio-pentavalent arsenic species showed higher partition coefficients, suggesting that they can easily traverse cell membranes by passive simple diffusion. Given the higher toxicity of these species compared to oxo-pentavalent arsenic species, this study provides evidence supporting the risk associated with human exposure to trivalent and thio-arsenic species. Copyright © 2016. Published by Elsevier B.V.

Prediction of air-to-blood partition coefficients of volatile organic compounds using genetic algorithm and artificial neural network

International Nuclear Information System (INIS)

Konoz, Elahe; Golmohammadi, Hassan

2008-01-01

An artificial neural network (ANN) was constructed and trained for the prediction of air-to-blood partition coefficients of volatile organic compounds. The inputs of this neural network are theoretically derived descriptors that were chosen by genetic algorithm (GA) and multiple linear regression (MLR) features selection techniques. These descriptors are: R maximal autocorrelation of lag 1 weighted by atomic Sanderson electronegativities (R1E+), electron density on the most negative atom in molecule (EDNA), maximum partial charge for C atom (MXPCC), surface weighted charge partial surface area (WNSA1), fractional charge partial surface area (FNSA2) and atomic charge weighted partial positive surface area (PPSA3). The standard errors of training, test and validation sets for the ANN model are 0.095, 0.148 and 0.120, respectively. Result obtained showed that nonlinear model can simulate the relationship between structural descriptors and the partition coefficients of the molecules in data set accurately

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

Science.gov (United States)

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...

Application of radial basis function neural network to predict soil sorption partition coefficient using topological descriptors.

Science.gov (United States)

Sabour, Mohammad Reza; Moftakhari Anasori Movahed, Saman

2017-02-01

The soil sorption partition coefficient logK oc is an indispensable parameter that can be used in assessing the environmental risk of organic chemicals. In order to predict soil sorption partition coefficient for different and even unknown compounds in a fast and accurate manner, a radial basis function neural network (RBFNN) model was developed. Eight topological descriptors of 800 organic compounds were used as inputs of the model. These 800 organic compounds were chosen from a large and very diverse data set. Generalized Regression Neural Network (GRNN) was utilized as the function in this neural network model due to its capability to adapt very quickly. Hence, it can be used to predict logK oc for new chemicals, as well. Out of total data set, 560 organic compounds were used for training and 240 to test efficiency of the model. The obtained results indicate that the model performance is very well. The correlation coefficients (R2) for training and test sets were 0.995 and 0.933, respectively. The root-mean square errors (RMSE) were 0.2321 for training set and 0.413 for test set. As the results for both training and test set are extremely satisfactory, the proposed neural network model can be employed not only to predict logK oc of known compounds, but also to be adaptive for prediction of this value precisely for new products that enter the market each year. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation of long-range transport potential of selected brominated flame retardants with measured 1-octanol-air partition coefficients

Energy Technology Data Exchange (ETDEWEB)

Lee, Hyun Jeong; Kwon, Jung Hwan [Div. of Environmental Science and Ecological Engineering, Korea University, Seoul (Korea, Republic of)

2016-10-15

Various alternative flame retardants are used in many countries since polybrominated diphenyl ethers (PBDEs) were classified as persistent organic pollutants (POPs). However, difficulties in the evaluation of the long-range transport potential (LRTP) of the alternatives are related to the lack of information on their physicochemical properties, which govern their environmental fates and transport. Based on the simulation of LRTP using OECD P{sub OV} and LRTP Screening Tool, five alternative brominated flame retardants (BFRs) (hexabromobenzene [HBB], 2,3,4,5,6-pentabromotoluene [PBT], 2,3,4,5,6-pentabromoethylbenzene [PBEB], 2-ethylhexyl 2,3,4,5-tetrabromobenzoate [TBB], and 1,2,4,5-tetrabromo-3,6-dimethylbenzene [TBX]), and 3 PBDEs (BDE-28, BDE-47, and BDE-99) were chosen to perform a refined assessment. This was done using an experimentally measured 1-octanol–air partition coefficient (K{sub OA}) for the calculation of the air–water partition coefficient (K{sub AW}) required for the model. The four selected alternative BFRs (HBB, PBT, PBEB, TBX) have K{sub OA} values close to the in silico estimation used in the screening evaluation. On the other hand, the measured K{sub OA} value for TBB was two orders of magnitude lower than the estimated value used in the screening simulation. The refined simulation showed that characteristic travel distance (CTD) and transfer efficiency (TE) for HBB, PBT, PBEB, and TBX were greater than those for BDE-28, whereas CTD and TE for TBB were lower than those for BDE-28. This suggested that TBB has a lower LRTP than BDE-28, considering the refined partition coefficients.

Determination of partition coefficient and analysis of nitrophenols by three-phase liquid-phase microextraction coupled with capillary electrophoresis.

Science.gov (United States)

Sanagi, Mohd Marsin; Miskam, Mazidatulakmam; Wan Ibrahim, Wan Aini; Hermawan, Dadan; Aboul-Enein, Hassan Y

2010-07-01

A three-phase hollow fiber liquid-phase microextraction method coupled with CE was developed and used for the determination of partition coefficients and analysis of selected nitrophenols in water samples. The selected nitrophenols were extracted from 14 mL of aqueous solution (donor solution) with the pH adjusted to pH 3 into an organic phase (1-octanol) immobilized in the pores of the hollow fiber and finally backextracted into 40.0 microL of the acceptor phase (NaOH) at pH 12.0 located inside the lumen of the hollow fiber. The extractions were carried out under the following optimum conditions: donor solution, 0.05 M H(3)PO(4), pH 3.0; organic solvent, 1-octanol; acceptor solution, 40 microL of 0.1 M NaOH, pH 12.0; agitation rate, 1050 rpm; extraction time, 15 min. Under optimized conditions, the calibration curves for the analytes were linear in the range of 0.05-0.30 mg/L with r(2)>0.9900 and LODs were in the range of 0.01-0.04 mg/L with RSDs of 1.25-2.32%. Excellent enrichment factors of up to 398-folds were obtained. It was found that the partition coefficient (K(a/d)) values were high for 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol and 2,6-dinitrophenol and that the individual partition coefficients (K(org/d) and K(a/org)) promoted efficient simultaneous extraction from the donor through the organic phase and further into the acceptor phase. The developed method was successfully applied for the analysis of water samples.

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

Science.gov (United States)

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

The complex formation-partition and partition-association models of solvent extraction of ions

International Nuclear Information System (INIS)

Siekierski, S.

1976-01-01

Two models of the extraction process have been proposed. In the first model it is assumed that the partitioning neutral species is at first formed in the aqueous phase and then transferred into the organic phase. The second model is based on the assumption that equivalent amounts of cations are at first transferred from the aqueous into the organic phase and then associated to form a neutral molecule. The role of the solubility parameter in extraction and the relation between the solubility of liquid organic substances in water and the partition of complexes have been discussed. The extraction of simple complexes and complexes with organic ligands has been discussed using the first model. Partition coefficients have been calculated theoretically and compared with experimental values in some very simple cases. The extraction of ion pairs has been discussed using the partition-association model and the concept of single-ion partition coefficients. (author)

Partitioning of organochlorine pesticides from water to polyethylene passive samplers

International Nuclear Information System (INIS)

Hale, Sarah E.; Martin, Timothy J.; Goss, Kai-Uwe; Arp, Hans Peter H.; Werner, David

2010-01-01

The mass transfer rates and equilibrium partitioning behaviour of 14 diverse organochlorine pesticides (OCP) between water and polyethylene (PE) passive samplers, cut from custom made PE sheets and commercial polyethylene plastic bags, were quantified. Overall mass transfer coefficients, k O , estimated PE membrane diffusion coefficients, D PE , and PE-water partitioning coefficients, K PE-water, are reported. In addition, the partitioning of three polycyclic aromatic hydrocarbons (PAHs) from water to PE is quantified and compared with literature values. K PE-water values agreed mostly within a factor of two for both passive samplers and also with literature values for the reference PAHs. As PE is expected to exhibit similar sorption behaviour to long-chain alkanes, PE-water partitioning coefficients were compared to hexadecane-water partitioning coefficients estimated with the SPARC online calculator, COSMOtherm and a polyparameter linear free energy relationship based on the Abraham approach. The best correlation for all compounds tested was with COSMOtherm estimated hexadecane-water partitioning coefficients. - The partitioning of organochlorine pesticides between single phase polyethylene passive samplers and water is quantified.

Determination of octanol-water partition coefficients of polar polycyclic aromatic compounds (N-PAC) by high performance liquid chromatography

DEFF Research Database (Denmark)

Helweg, C.; Nielsen, T.; Hansen, P.E.

1997-01-01

Prediction of 1-octanol water partition coefficients for a range of polar N-PAC from HPLC capacity coefficients has been investigated. Two commercially available columns, an ODS column and a Diol column were tested with water-methanol eluents. The best prediction of log K-ow for N-PAC was achieve...... with size and log K-ow for N-PAC was 1.1-1.3 lower than log K-ow for the equivalent PAH. Shielding of the nitrogen atom in the N-PAC compounds caused an increase in log K-ow. (C) 1997 Elsevier Science Ltd....

Rapid analysis of dissolved methane, ethylene, acetylene and ethane using partition coefficients and headspace-gas chromatography.

Science.gov (United States)

Lomond, Jasmine S; Tong, Anthony Z

2011-01-01

Analysis of dissolved methane, ethylene, acetylene, and ethane in water is crucial in evaluating anaerobic activity and investigating the sources of hydrocarbon contamination in aquatic environments. A rapid chromatographic method based on phase equilibrium between water and its headspace is developed for these analytes. The new method requires minimal sample preparation and no special apparatus except those associated with gas chromatography. Instead of Henry's Law used in similar previous studies, partition coefficients are used for the first time to calculate concentrations of dissolved hydrocarbon gases, which considerably simplifies the calculation involved. Partition coefficients are determined to be 128, 27.9, 1.28, and 96.3 at 30°C for methane, ethylene, acetylene, and ethane, respectively. It was discovered that the volume ratio of gas-to-liquid phase is critical to the accuracy of the measurements. The method performance can be readily improved by reducing the volume ratio of the two phases. Method validation shows less than 6% variation in accuracy and precision except at low levels of methane where interferences occur in ambient air. Method detection limits are determined to be in the low ng/L range for all analytes. The performance of the method is further tested using environmental samples collected from various sites in Nova Scotia.

High-pressure (vapour + liquid) equilibria for ternary systems composed by {(E)-2-hexenal or hexanal + carbon dioxide + water}: Partition coefficient measurement

International Nuclear Information System (INIS)

Bejarano, Arturo; López, Pablo I.; Valle, José M. del; Fuente, Juan C. de la

2015-01-01

Highlights: • A new apparatus based on a static–analytic method was assembled in this work. • This work reports high-pressure VLE data of (E)-2-hexenal or hexanal + CO 2 + water. • Data includes (CO 2 + water) partition coefficients of (E)-2-hexenal and hexanal. • High separation factors from water (∼10 4 ) were found especially for (E)-2-hexenal. • The data were obtained at T = (313, 323, and 333) K and pressures from (8 to 19) MPa. - Abstract: A new apparatus based on a static–analytic method assembled in this work was utilised to perform high-pressure (vapour + liquid) equilibria measurements of aqueous ternary systems. This work includes values of isothermal partition coefficients between CO 2 and water of two apple aroma constituents, (E)-2-hexenal and hexanal. Additionally, this work reports new experimental (vapour + liquid) equilibria measurements for the ternary systems (CO 2 + (E)-2-hexenal + water) and (CO 2 + hexanal + water), at fixed liquid phase composition (600 mg · kg −1 ), at temperatures of (313, 323 and 333) K and at pressures from (8 to 19) MPa. Vapour liquid interphase was checked and monitored visually for all the systems studied in this work. No liquid immiscibility was observed at the composition, temperatures and pressures studied. In order to suggest reasonable operation conditions for fractionation of aromas with dense carbon dioxide, partition coefficients of the aroma compounds between CO 2 and water along with their separation factors from water were calculated. Partition coefficients of (E)-2-hexenal between CO 2 and water were in the range of (6 to 91) and where found to be near six times higher than those of hexanal (9 to 17). Very high separation factors from water were observed (∼10 4 ) especially for (E)-2-hexenal. The highest separation factor, for both compounds, was found at a temperature of 313 K and pressures from (12 to 14) MPa

Partition coefficients for Ni, Cu, Pd, Pt, Rh, and Ir between monosulfide solid solution and sulfide liquid and the formation of compositionally zoned Ni-Cu sulfide bodies by fractional crystallization of sulfide liquid

DEFF Research Database (Denmark)

Barnes, S.J.; Makovicky, E.; Makovicky, M.

1996-01-01

of the system. There is a positive correlation between the partition coefficients and sulfur content of the monosulfide solid solution and between the partition coefficients and the sulfur content of the liquid. In sulfur-saturated and sulfur-over-saturated experimental systems, the metals behave in a manner...... (Alexo, Abitibi Greenstone Belt) and a zoned tholeiite-related ore (Oktyabr'sky, Noril'sk region, Siberia). In both cases, the experimental partition coefficients numerically model the composition zones of the actual ores. This supports the model of fractional crystallization of a monosulfide solid...

Effect of Atomic Charges on Octanol–Water Partition Coefficient Using Alchemical Free Energy Calculation

Directory of Open Access Journals (Sweden)

Koji Ogata

2018-02-01

Full Text Available The octanol–water partition coefficient (logPow is an important index for measuring solubility, membrane permeability, and bioavailability in the drug discovery field. In this paper, the logPow values of 58 compounds were predicted by alchemical free energy calculation using molecular dynamics simulation. In free energy calculations, the atomic charges of the compounds are always fixed. However, they must be recalculated for each solvent. Therefore, three different sets of atomic charges were tested using quantum chemical calculations, taking into account vacuum, octanol, and water environments. The calculated atomic charges in the different environments do not necessarily influence the correlation between calculated and experimentally measured ∆Gwater values. The largest correlation coefficient values of the solvation free energy in water and octanol were 0.93 and 0.90, respectively. On the other hand, the correlation coefficient of logPow values calculated from free energies, the largest of which was 0.92, was sensitive to the combination of the solvation free energies calculated from the calculated atomic charges. These results reveal that the solvent assumed in the atomic charge calculation is an important factor determining the accuracy of predicted logPow values.

Estimation of the soil-water partition coefficient normalized to organic carbon for ionizable organic chemicals

DEFF Research Database (Denmark)

Franco, Antonio; Trapp, Stefan

2008-01-01

The sorption of organic electrolytes to soil was investigated. A dataset consisting of 164 electrolytes, composed of 93 acids, 65 bases, and six amphoters, was collected from literature and databases. The partition coefficient log KOW of the neutral molecule and the dissociation constant pKa were...... calculated by the software ACD/Labs®. The Henderson-Hasselbalch equation was applied to calculate dissociation. Regressions were developed to predict separately for the neutral and the ionic molecule species the distribution coefficient (Kd) normalized to organic carbon (KOC) from log KOW and pKa. The log...... KOC of strong acids (pKa correlated to these parameters. The regressions derived for weak acids and bases (undissociated at environmental pH) were similar. The highest sorption was found for strong bases (pKa > 7.5), probably due to electrical interactions. Nonetheless, their log KOC...

Mapping Pesticide Partition Coefficients By Electromagnetic Induction

Science.gov (United States)

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...

A novel method for the determination of adsorption partition coefficients of minor gases in a shale sample by headspace gas chromatography.

Science.gov (United States)

Zhang, Chun-Yun; Hu, Hui-Chao; Chai, Xin-Sheng; Pan, Lei; Xiao, Xian-Ming

2013-10-04

A novel method has been developed for the determination of adsorption partition coefficient (Kd) of minor gases in shale. The method uses samples of two different sizes (masses) of the same material, from which the partition coefficient of the gas can be determined from two independent headspace gas chromatographic (HS-GC) measurements. The equilibrium for the model gas (ethane) was achieved in 5h at 120°C. The method also involves establishing an equation based on the Kd at higher equilibrium temperature, from which the Kd at lower temperature can be calculated. Although the HS-GC method requires some time and effort, it is simpler and quicker than the isothermal adsorption method that is in widespread use today. As a result, the method is simple and practical and can be a valuable tool for shale gas-related research and applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of the partition coefficient between dissolved organic carbon and seawater using differential equilibrium kinetics.

Science.gov (United States)

Kim, Du Yung; Kwon, Jung-Hwan

2018-05-04

Because the freely dissolved fraction of highly hydrophobic organic chemicals is bioavailable, knowing the partition coefficient between dissolved organic carbon and water (K DOCw ) is crucial to estimate the freely dissolved fraction from the total concentration. A kinetic method was developed to obtain K DOCw that required a shorter experimental time than equilibrium methods. The equilibrium partition coefficients of four polychlorinated biphenyls (PCBs) (2,4,4'-trichlorobiphenyl (PCB 28), 2,2',3,5'-tetrachlorobiphenyl (PCB 44), 2,2',4,5,5'-pentachlorobiphenyl (PCB 101), and 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153)) between dissolved organic carbon and seawater (K DOCsw ) were determined using seawater samples from the Korean coast. The log K DOCsw values of PCB 28 were measured by equilibrating PCB 28, the least hydrophobic congener, with seawater samples, and the values ranged from 6.60 to 7.20. For the more hydrophobic PCBs (PCB 44, PCB 101, and PCB 153), kinetic experiments were conducted to determine the sorption rate constants (k 2 ) and their log K DOCsw values were obtained by comparing their k 2 with that of PCB 28. The calculated log K DOCsw values were 6.57-7.35 for PCB 44, 6.23-7.44 for PCB 101, and 6.35-7.73 for PCB 153. The validity of the proposed method was further confirmed using three less hydrophobic polycyclic aromatic hydrocarbons. This kinetic method shortened the experimental time to obtain the K DOCsw values of the more hydrophobic PCBs, which did not reach phase equilibrium. Copyright © 2018 Elsevier Ltd. All rights reserved.

Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater

Science.gov (United States)

Bau, M.; Koschinsky, A.; Dulski, P.; Hein, J.R.

1996-01-01

In order to evaluate details of the partitioning behaviours of Y, rare earth elements (REEs), and Ti between inorganic metal oxide surfaces and seawater, we studied the distribution of these elements in hydrogenetic marine ferromanganese (Fe-Mn) crusts from the Central Pacific Ocean. Nonphosphatized Fe-Mn crusts display shale-normalized rare earths and yttrium (REYSN) patterns (Y inserted between Dy and Ho) that are depleted in light REEs (LREEs) and which show negative anomalies for YSN, and positive anomalies for LaSN, EuSN, GdSN, and in most cases, CeSN. They show considerably smaller Y/ Ho ratios than seawater or common igneous and clastic rocks, indicating that Y and Ho are fractionated in the marine environment. Compared to P-poor crusts, REYSN patterns of phosphatized Fe-Mn crusts are similar, but yield pronounced positive YSN anomalies, stronger positive LaSN anomalies, and enrichment of the HREEs relative to the MREEs. The data suggest modification of REY during phosphatization and indicate that studies requiring primary REY distributions or isotopic ratios should be restricted to nonphosphatized (layers of) Fe-Mn crusts. Apparent bulk coefficients, KMD, describing trace metal partitioning between nonphosphatized hydrogenetic Fe-Mn crusts and seawater, are similar for Pr to Eu and decrease for Eu to Yb. Exceptionally high values of KCeD, which are similar to those of Ti, result from oxidative scavenging of Ce and support previous suggestions that Ce(IV) is a hydroxide-dominated element in seawater. Yttrium and Gd show lower KD values than their respective neighbours in the REY series. Results of modelling the exchange equilibrium between REY dissolved in seawater and REY sorbed on hydrous Fe-Mn oxides corroborate previous studies that suggested the surface complexation of REY can be approximated by their first hydroxide binding constant. Negative "anomalies" occur for stabilities of bulk surface complexes of Gd, La, and particularly Y. The differences in

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

Science.gov (United States)

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. © 2016 SETAC.

Bayesian approach to estimate AUC, partition coefficient and drug targeting index for studies with serial sacrifice design.

Science.gov (United States)

Wang, Tianli; Baron, Kyle; Zhong, Wei; Brundage, Richard; Elmquist, William

2014-03-01

The current study presents a Bayesian approach to non-compartmental analysis (NCA), which provides the accurate and precise estimate of AUC 0 (∞) and any AUC 0 (∞) -based NCA parameter or derivation. In order to assess the performance of the proposed method, 1,000 simulated datasets were generated in different scenarios. A Bayesian method was used to estimate the tissue and plasma AUC 0 (∞) s and the tissue-to-plasma AUC 0 (∞) ratio. The posterior medians and the coverage of 95% credible intervals for the true parameter values were examined. The method was applied to laboratory data from a mice brain distribution study with serial sacrifice design for illustration. Bayesian NCA approach is accurate and precise in point estimation of the AUC 0 (∞) and the partition coefficient under a serial sacrifice design. It also provides a consistently good variance estimate, even considering the variability of the data and the physiological structure of the pharmacokinetic model. The application in the case study obtained a physiologically reasonable posterior distribution of AUC, with a posterior median close to the value estimated by classic Bailer-type methods. This Bayesian NCA approach for sparse data analysis provides statistical inference on the variability of AUC 0 (∞) -based parameters such as partition coefficient and drug targeting index, so that the comparison of these parameters following destructive sampling becomes statistically feasible.

Prediction of octanol-water partition coefficients of organic compounds by multiple linear regression, partial least squares, and artificial neural network.

Science.gov (United States)

Golmohammadi, Hassan

2009-11-30

A quantitative structure-property relationship (QSPR) study was performed to develop models those relate the structure of 141 organic compounds to their octanol-water partition coefficients (log P(o/w)). A genetic algorithm was applied as a variable selection tool. Modeling of log P(o/w) of these compounds as a function of theoretically derived descriptors was established by multiple linear regression (MLR), partial least squares (PLS), and artificial neural network (ANN). The best selected descriptors that appear in the models are: atomic charge weighted partial positively charged surface area (PPSA-3), fractional atomic charge weighted partial positive surface area (FPSA-3), minimum atomic partial charge (Qmin), molecular volume (MV), total dipole moment of molecule (mu), maximum antibonding contribution of a molecule orbital in the molecule (MAC), and maximum free valency of a C atom in the molecule (MFV). The result obtained showed the ability of developed artificial neural network to prediction of partition coefficients of organic compounds. Also, the results revealed the superiority of ANN over the MLR and PLS models. Copyright 2009 Wiley Periodicals, Inc.

Characteristics and genesis of Rare Earth Element (REE) in western Indonesia

Science.gov (United States)

Handoko, A. D.; Sanjaya, E.

2018-02-01

Rare Earth Element (REE) has unique properties that have been used in many hightech applications. The demand of REE increased recently in the world due to its special properties. Although REE concentration in the crust is higher than gold, economically viable deposits are still rare. Reduction of REE exports by China cause increased prices of REE. Due to this condition, exploration of potential REE mines emerged. Indonesia also participates in this phenomenon, and explore the possibility of REE mines in its area. This review will discuss the characteristics and genesis of REE and its occurrence in western Indonesia; focused in Sumatera, Tin Island, and Kalimantan. The review is done based on literature research from several resources about characteristics of rare earth element in general and in the given area. The research shows that the potential REE mines can be found in several different locations in Indonesia, such as Tin Island, Sumatera, and Kalimantan. Most of them are composed of monazite, zircon, and xenotime as rare earth minerals. Monazite iss known for its elevated number of radioactive elements, so study about radioactive content and more environment friendly ore processing becomes compulsory.

Development of polyparameter linear free energy relationship models for octanol-air partition coefficients of diverse chemicals.

Science.gov (United States)

Jin, Xiaochen; Fu, Zhiqiang; Li, Xuehua; Chen, Jingwen

2017-03-22

The octanol-air partition coefficient (K OA ) is a key parameter describing the partition behavior of organic chemicals between air and environmental organic phases. As the experimental determination of K OA is costly, time-consuming and sometimes limited by the availability of authentic chemical standards for the compounds to be determined, it becomes necessary to develop credible predictive models for K OA . In this study, a polyparameter linear free energy relationship (pp-LFER) model for predicting K OA at 298.15 K and a novel model incorporating pp-LFERs with temperature (pp-LFER-T model) were developed from 795 log K OA values for 367 chemicals at different temperatures (263.15-323.15 K), and were evaluated with the OECD guidelines on QSAR model validation and applicability domain description. Statistical results show that both models are well-fitted, robust and have good predictive capabilities. Particularly, the pp-LFER model shows a strong predictive ability for polyfluoroalkyl substances and organosilicon compounds, and the pp-LFER-T model maintains a high predictive accuracy within a wide temperature range (263.15-323.15 K).

Separation of very hydrophobic analytes by micellar electrokinetic chromatography IV. Modeling of the effective electrophoretic mobility from carbon number equivalents and octanol-water partition coefficients.

Science.gov (United States)

Huhn, Carolin; Pyell, Ute

2008-07-11

It is investigated whether those relationships derived within an optimization scheme developed previously to optimize separations in micellar electrokinetic chromatography can be used to model effective electrophoretic mobilities of analytes strongly differing in their properties (polarity and type of interaction with the pseudostationary phase). The modeling is based on two parameter sets: (i) carbon number equivalents or octanol-water partition coefficients as analyte descriptors and (ii) four coefficients describing properties of the separation electrolyte (based on retention data for a homologous series of alkyl phenyl ketones used as reference analytes). The applicability of the proposed model is validated comparing experimental and calculated effective electrophoretic mobilities. The results demonstrate that the model can effectively be used to predict effective electrophoretic mobilities of neutral analytes from the determined carbon number equivalents or from octanol-water partition coefficients provided that the solvation parameters of the analytes of interest are similar to those of the reference analytes.

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

Science.gov (United States)

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. © 2015 SETAC.

Rare earth elements in sedimentary phosphate deposits: Solution to the global REE crisis?

Science.gov (United States)

Emsbo, Poul; McLaughlin, Patrick I.; Breit, George N.; du Bray, Edward A.; Koenig, Alan E.

2015-01-01

The critical role of rare earth elements (REEs), particularly heavy REEs (HREEs), in high-tech industries has created a surge in demand that is quickly outstripping known global supply and has triggered a worldwide scramble to discover new sources. The chemical analysis of 23 sedimentary phosphate deposits (phosphorites) in the United States demonstrates that they are significantly enriched in REEs. Leaching experiments using dilute H2SO4 and HCl, extracted nearly 100% of their total REE content and show that the extraction of REEs from phosphorites is not subject to the many technological and environmental challenges that vex the exploitation of many identified REE deposits. Our data suggest that phosphate rock currently mined in the United States has the potential to produce a significant proportion of the world's REE demand as a byproduct. Importantly, the size and concentration of HREEs in some unmined phosphorites dwarf the world's richest REE deposits. Secular variation in phosphate REE contents identifies geologic time periods favorable for the formation of currently unrecognized high-REE phosphates. The extraordinary endowment, combined with the ease of REE extraction, indicates that such phosphorites might be considered as a primary source of REEs with the potential to resolve the global REE (particularly for HREE) supply shortage.

High-throughput determination of octanol/water partition coefficients using a shake-flask method and novel two-phase solvent system.

Science.gov (United States)

Morikawa, Go; Suzuka, Chihiro; Shoji, Atsushi; Shibusawa, Yoichi; Yanagida, Akio

2016-01-05

A high-throughput method for determining the octanol/water partition coefficient (P(o/w)) of a large variety of compounds exhibiting a wide range in hydrophobicity was established. The method combines a simple shake-flask method with a novel two-phase solvent system comprising an acetonitrile-phosphate buffer (0.1 M, pH 7.4)-1-octanol (25:25:4, v/v/v; AN system). The AN system partition coefficients (K(AN)) of 51 standard compounds for which log P(o/w) (at pH 7.4; log D) values had been reported were determined by single two-phase partitioning in test tubes, followed by measurement of the solute concentration in both phases using an automatic flow injection-ultraviolet detection system. The log K(AN) values were closely related to reported log D values, and the relationship could be expressed by the following linear regression equation: log D=2.8630 log K(AN) -0.1497(n=51). The relationship reveals that log D values (+8 to -8) for a large variety of highly hydrophobic and/or hydrophilic compounds can be estimated indirectly from the narrow range of log K(AN) values (+3 to -3) determined using the present method. Furthermore, log K(AN) values for highly polar compounds for which no log D values have been reported, such as amino acids, peptides, proteins, nucleosides, and nucleotides, can be estimated using the present method. The wide-ranging log D values (+5.9 to -7.5) of these molecules were estimated for the first time from their log K(AN) values and the above regression equation. Copyright © 2015 Elsevier B.V. All rights reserved.

Anion and cation partitioning between olivine, plagioclase phenocrysts and the host magma

International Nuclear Information System (INIS)

Yurimoto, Hisayoshi; Sueno, Shigeho

1984-01-01

Partition coefficients for -1, -2, -3, +1, +2, +3, +4 and +5 valent ions between the groundmass of tholeiite basalt and coexisting olivine and plagioclase phenocrysts from the Mid-Atlantic Ridge have been determined by secondary ion mass spectrometry. The present cation partitioning strongly supports the 'crystal structure control' mechanism. The partition coefficient for an anion is also under control of the crystal structure, so that each of the cation and anion positions in the crystal structure gives rise to a parabola-shaped peak on the partition coefficient vs. ionic radius diagram. (author)

Salinity impacts on water solubility and n-octanol/water partition coefficients of selected pesticides and oil constituents.

Science.gov (United States)

Saranjampour, Parichehr; Vebrosky, Emily N; Armbrust, Kevin L

2017-09-01

Salinity has been reported to influence the water solubility of organic chemicals entering marine ecosystems. However, limited data are available on salinity impacts for chemicals potentially entering seawater. Impacts on water solubility would correspondingly impact chemical sorption as well as overall bioavailability and exposure estimates used in the regulatory assessment. The pesticides atrazine, fipronil, bifenthrin, and cypermethrin, as well as the crude oil constituent dibenzothiophene together with 3 of its alkyl derivatives, all have different polarities and were selected as model compounds to demonstrate the impact of salinity on their solubility and partitioning behavior. The n-octanol/water partition coefficient (K OW ) was measured in both distilled-deionized water and artificial seawater (3.2%). All compounds had diminished solubility and increased K OW values in artificial seawater compared with distilled-deionized water. A linear correlation curve estimated salinity may increase the log K OW value by 2.6%/1 log unit increase in distilled water (R 2  = 0.97). Salinity appears to generally decrease the water solubility and increase the partitioning potential. Environmental fate estimates based on these parameters indicate elevated chemical sorption to sediment, overall bioavailability, and toxicity in artificial seawater. These dramatic differences suggest that salinity should be taken into account when exposure estimates are made for marine organisms. Environ Toxicol Chem 2017;36:2274-2280. © 2017 SETAC. © 2017 SETAC.

Estimating the octanol/water partition coefficient for aliphatic organic compounds using semi-empirical electrotopological index.

Science.gov (United States)

Souza, Erica Silva; Zaramello, Laize; Kuhnen, Carlos Alberto; Junkes, Berenice da Silva; Yunes, Rosendo Augusto; Heinzen, Vilma Edite Fonseca

2011-01-01

A new possibility for estimating the octanol/water coefficient (log P) was investigated using only one descriptor, the semi-empirical electrotopological index (I(SET)). The predictability of four octanol/water partition coefficient (log P) calculation models was compared using a set of 131 aliphatic organic compounds from five different classes. Log P values were calculated employing atomic-contribution methods, as in the Ghose/Crippen approach and its later refinement, AlogP; using fragmental methods through the ClogP method; and employing an approach considering the whole molecule using topological indices with the MlogP method. The efficiency and the applicability of the I(SET) in terms of calculating log P were demonstrated through good statistical quality (r > 0.99; s < 0.18), high internal stability and good predictive ability for an external group of compounds in the same order as the widely used models based on the fragmental method, ClogP, and the atomic contribution method, AlogP, which are among the most used methods of predicting log P.

Limiting partition coefficients of solutes in biphasic trihexyltetradecylphosphonium chloride ionic liquid-supercritical CO2 system: measurement and LSER-based correlation

Czech Academy of Sciences Publication Activity Database

Planeta, Josef; Karásek, Pavel; Roth, Michal

2007-01-01

Roč. 111, č. 26 (2007), s. 7620-7625 ISSN 1520-6106 R&D Projects: GA AV ČR KJB400310504; GA ČR GA203/05/2106; GA ČR GA203/07/0886 Institutional research plan: CEZ:AV0Z40310501 Keywords : phosphonium ionic liquid * supercritical carbon dioxide * solute partition coefficient Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.086, year: 2007

Tissue/blood partition coefficients for xenon in various adipose tissue depots in man

DEFF Research Database (Denmark)

Bülow, J; Jelnes, Rolf; Astrup, A

1987-01-01

Tissue/blood partition coefficients (lambda) for xenon were calculated for subcutaneous adipose tissue from the abdominal wall and the thigh, and for the perirenal adipose tissue after chemical analysis of the tissues for lipid, water and protein content. The lambda in the perirenal tissue...... was found to correlate linearly to the relative body weight (RBW) in per cent with the regression equation lambda = 0.045 . RBW + 0.99. The subcutaneous lambda on the abdomen correlated linearly to the local skinfold thickness (SFT) with the equation lambda = 0.22 SFT + 2.99. Similarly lambda on the thigh...... correlated to SFT with the equation lambda = 0.20 . SFT + 4.63. It is concluded that the previously accepted lambda value of 10 is generally too high in perirenal as well as in subcutaneous tissue. Thus, by application of the present regression equations, it is possible to obtain more exact estimates...

miREE: miRNA recognition elements ensemble

Science.gov (United States)

2011-01-01

Background Computational methods for microRNA target prediction are a fundamental step to understand the miRNA role in gene regulation, a key process in molecular biology. In this paper we present miREE, a novel microRNA target prediction tool. miREE is an ensemble of two parts entailing complementary but integrated roles in the prediction. The Ab-Initio module leverages upon a genetic algorithmic approach to generate a set of candidate sites on the basis of their microRNA-mRNA duplex stability properties. Then, a Support Vector Machine (SVM) learning module evaluates the impact of microRNA recognition elements on the target gene. As a result the prediction takes into account information regarding both miRNA-target structural stability and accessibility. Results The proposed method significantly improves the state-of-the-art prediction tools in terms of accuracy with a better balance between specificity and sensitivity, as demonstrated by the experiments conducted on several large datasets across different species. miREE achieves this result by tackling two of the main challenges of current prediction tools: (1) The reduced number of false positives for the Ab-Initio part thanks to the integration of a machine learning module (2) the specificity of the machine learning part, obtained through an innovative technique for rich and representative negative records generation. The validation was conducted on experimental datasets where the miRNA:mRNA interactions had been obtained through (1) direct validation where even the binding site is provided, or through (2) indirect validation, based on gene expression variations obtained from high-throughput experiments where the specific interaction is not validated in detail and consequently the specific binding site is not provided. Conclusions The coupling of two parts: a sensitive Ab-Initio module and a selective machine learning part capable of recognizing the false positives, leads to an improved balance between

Study on geochemical occurrences of REE in Wangqing oil shale

Energy Technology Data Exchange (ETDEWEB)

Bai, Jing-ru; Wang, Qing; Liu, Tong; Wei, Yan-zhen; Bai, Zhang [Northeast Dianli Univ., Jilin (China). Engineering Research Centre

2013-07-01

Sequential chemical extraction experiment (SCEE) and Float- sink experiment (FSE) have been employed on oil shale research from Wangqing, Jilin province China, in order to determine the binding forms of rare earth elements (REE) in oil shale. The REE contents were determined by the inductively coupled plasma-mass spectrometry (ICP-MS). Wangqing oil shale was screened into specific gravity density level: <1.5g/cm{sup 3}, 1.5-1.6g/cm{sup 3}, 1.6-2.0g/cm{sup 3}, 2.0-2.4g/cm{sup 3}, >2.4g/cm{sup 3}. The mode of occurrences of rare earth elements in Wangqing oil shale was studied by six-step SCEE. FSE results show that REEs in Wangqing oil shale exist mainly in inorganic minerals and more in excluded mineral, while SCEE results show that REEs of Wangqing oil shale is primarily occurred in minerals, including carbonate, Fe-Mn oxide, sulfide, and Si-minerals. FSE and SCEE results fully illustrate excluded mineral is mainly mode of occurrence of REEs in Wangqing oil shale, whereas inorganic minerals and organic matter is not that. The REE distribution pattern curves of FSE density and SCEE fraction products are similar with that of raw oil shale. The REE in different densities products has a close connection with terrigenous clastic rock, and the supply of terrestrial material is stable.

Aeromagnetic expression of rare earth element (REE) deposits in New Mexico, USA

Science.gov (United States)

Li, M.

2016-12-01

With the development of high-tech devices and the expanding demands in industrial production, rare earth elements(REE) has been playing an increasingly important role in the global economy in the past several decades. Different types of REE serve irreplaceable functions in high-tech industry, as well as for developing sustainable energy and catalysis of manufacturing. Given that the global supply of REE has become strained since 2009 and no known substitutes for REE have been found, exploration for new REE deposits is imperative for economic sustainability. Ten main regions have REE deposits in New Mexico, some of which have not been exploited, while some sites such as Gallinas mountains vein deposits are in early exploration stage. Exploration for the reserves and quantization of mineral compositions of New Mexico's REE depositional districts can have economic benefits in general. In this study, high-resolution airborne magnetic and gravity data were used for studying the Gallinas mountains REE deposit. The purposes of this study are to: (1) characterize specific aeromagnetic anomaly and gravity features from the REE deposits, and (2) apply the characterized features to suggest other areas among the ten REE depositional regions for further exploration. All REE deposits in the study area are found associated with alkaline to alkali-calcic volcanic rocks. A quantitative modeling based on aeromagnetic and gravity anomaly mapping was constructed with an assumption of three units: carbonatites, alkaline volcanic intrusions and REE-concentrated minerals (barite, bastnaesite, etc.). The results of this study show that alkaline deposit is characterized by negative magnetic anomalies and carbonatite is associated with gravity anomaly and vertical gravity gradient high. The area with significantly high aeromagnetic anomaly area and also gravity anomaly high supposed to reflect REE-concentrated minerals such as bastnaesite. For further research, hyperspectral information and

Novel matrix for REEs recovery from waste disposal

International Nuclear Information System (INIS)

Hareendran, K.; Singha, Mousumi; Roy, S.B.; Pal, Sangita

2014-01-01

Sorption of lanthanides (98%-99%) onto a novel matrix (polyacrylamide-carboxylate hydroxamate-PAMCHO) not only remove REE's before effluent disposal but also reduces the chance of contamination of potable water, nuclear plant generated shut down or gadolinium containing effluent during controlled fission reaction, in pharmaceutical diagnosis (MRI) and many other useful process effluents. By using such sorbent, 88% of the lanthanides can be recovered using HCl solution less than pH 1 from the laden matrix and can be concentrated more than 5 times. However, sorption into the interlayer's and diffusion of the REE's during leaching depends on the cross-linked structure of the gel matrix and tortuous path of the porous micro-channel (using scanning electron microscope-SEM study). The sequestration of matrix with REE's has been well established by using instrument FT-IR and gadolinium (cation-lanthanide) exchange method. To understand interaction of REE with sorbent, matrix have been prepared with cross-linking amount variation, such as 85:15, 90:10, 95:05 and 98:02 (matrix: cross-linker). A detailed sorption study of cross-linked matrix with gadolinium in feed solution (184 ppm), filtrate, leached and laden sorbent establishes mass balance (using ICP-AES for quantitative determination). This optimized sorbent (PAMCHO) indicates recovery of valuable REEs with elution factor of more than 0.9 when HCl solution of pH1.5 was used. (author)

The impact of aerosol composition on the particle to gas partitioning of reactive mercury.

Science.gov (United States)

Rutter, Andrew P; Schauer, James J

2007-06-01

A laboratory system was developed to study the gas-particle partitioning of reactive mercury (RM) as a function of aerosol composition in synthetic atmospheric particulate matter. The collection of RM was achieved by filter- and sorbent-based methods. Analyses of the RM collected on the filters and sorbents were performed using thermal extraction combined with cold vapor atomic fluorescence spectroscopy (CVAFS), allowing direct measurement of the RM load on the substrates. Laboratory measurements of the gas-particle partitioning coefficients of RM to atmospheric aerosol particles revealed a strong dependence on aerosol composition, with partitioning coefficients that varied by orders of magnitude depending on the composition of the particles. Particles of sodium nitrate and the chlorides of potassium and sodium had high partitioning coefficients, shifting the RM partitioning toward the particle phase, while ammonium sulfate, levoglucosan, and adipic acid caused the RM to partition toward the gas phase and, therefore, had partitioning coefficients that were lower by orders of magnitude.

Study on REE bound water-soluble polysaccharides in plant

International Nuclear Information System (INIS)

Wang Yuqi; Guo Fanqing; Xu Lei; Chen Hongmin; Sun Jingxin; Cao Guoyin

1999-01-01

The binding of REE with water-soluble polysaccharides (PSs) in leaves of fern Dicranopteris Dichotoma (DD) has been studied by molecular activation analysis. The cold-water-soluble and hot-water-soluble PSs in leaves of DD were obtained by using biochemical separation techniques. The PSs of non-deproteinization and deproteinization, were separated on Sephadex G-200 gel permeation chromatography. The absorption curves of elution for the PSs were obtained by colorimetry, and the proteins were detected using Coomassic brilliant G-250. Eight REEs (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in these PSs were determined by instrumental neutron activation analysis. The results obtained show that the REEs are bound firmly with the water-soluble PSs in the plant. A measurement demonstrates that the PSs bound with REEs are mainly of smaller molecular weight (10,000 to 20,000 Dalton)

Partitioning of L-methionine in aqueous two-phase systems containing poly(propylene glycol) and sodium phosphate salts

International Nuclear Information System (INIS)

Salabat, Alireza; Sadeghi, Rahmat; Moghadam, Somayeh Tiani; Jamehbozorg, Bahman

2011-01-01

Highlights: → Thermodynamics parameters for partitioning of L-methionine in ATPS. → Investigation of different effects on partition coefficient of the amino acid. → Propose the best condition for L-methionine partitioning. - Abstract: The partitioning behavior of L-methionine has been studied in aqueous two-phase systems of (poly(propylene glycol) + sodium phosphate salts + H 2 O) at different temperatures. The salts used were sodium di-hydrogen phosphate (NaH 2 PO 4 ), di-sodium hydrogen phosphate (Na 2 HPO 4 ) and tri-sodium phosphate (Na 3 PO 4 ). The effects of tie line length, salt type, and temperature on the partition coefficient of this amino acid have been studied. In addition, thermodynamic parameters (ΔH o , ΔS o and ΔG o ) as a function of temperature were calculated. The results showed that increasing tie line length led to decreasing of the partition coefficient. We also showed that the partition coefficients of the amino acid in the systems containing Na 3 PO 4 are greater than the other two salts. Moreover, it is verified that increasing temperature led to decreasing the partition coefficient. The experimental partition coefficient data are correlated using a modified virial-type model.

A Quantitative Property-Property Relationship for Estimating Packaging-Food Partition Coefficients of Organic Compounds

DEFF Research Database (Denmark)

Huang, L.; Ernstoff, Alexi; Xu, H.

2017-01-01

Organic chemicals encapsulated in beverage and food packaging can migrate to the food and lead to human exposures via ingestion. The packaging-food (Kpf) partition coefficient is a key parameter to estimate the chemical migration from packaging materials. Previous studies have simply set Kpf to 1...... or 1000, or provided separate linear correlations for several discrete values of ethanol equivalencies of food simulants (EtOH-eq). The aim of the present study is to develop a single quantitative property-property relationship (QPPR) valid for different chemical-packaging combinations and for water...... because only two packaging types are included. This preliminary QPPR demonstrates that the Kpf for various chemicalpackaging-food combinations can be estimated by a single linear correlation. Based on more than 1000 collected Kpf in 15 materials, we will present extensive results for other packaging types...

Soil-water partition coefficients for uranium and thorium: a systematic study of Tummalapalle mining site, India

International Nuclear Information System (INIS)

Dalvi, Aditi; Verma, Rakesh; Kumar, Sangita D.; Reddy, A.V.R.

2012-01-01

The simplest and most common parameter for modeling radionuclide mobility in soils is the partition coefficient (K d ). The soil-water partition coefficient for radionuclide is affected by numerous geochemical parameters like pH, sorption to clays, presence of organic matter, iron oxides, other soil constituents and the chemical forms of the radionuclide as well as oxidation/reduction conditions and major ion chemistry. In these studies radionuclides uranium and thorium were systematically assessed for their behaviour in the soils from Tummalapalle mining site. Physico-chemical characteristics such as chemical composition, pH, CaCO 3 content and organic carbon were determined for soils and synthetic groundwater samples. Oven dried soil samples (1g) were taken in polycarbonate tube and washed with synthetic ground water till the pH of the supernatant solution remained unchanged. The soil sample was then equilibrated with 30 mL of synthetic ground water spiked with an element of interest. The pH was adjusted to its initial value by addition of small increments of dilute NaOH/HNO 3 . The tubes containing samples were gently shaken for 72 h at room temperature. On completion of the experiment, it was centrifuged using high-speed centrifugation for 30 min and the aqueous phase was separated and analysed. The blank was processed in the same manner without adding soil. Determination of U and Th in the supernatant was carried out using ICPMS. The K d of thorium was found to be two-three order of magnitude higher than that of uranium for both the soil samples assessed in this study. The presence of carbonates and organic carbon in the groundwater has a significant effect on the K d of uranium. The K d values for uranium were found to be hundred fold lower in the presence of carbonates. (author)

Predicting volume of distribution with decision tree-based regression methods using predicted tissue:plasma partition coefficients.

Science.gov (United States)

Freitas, Alex A; Limbu, Kriti; Ghafourian, Taravat

2015-01-01

Volume of distribution is an important pharmacokinetic property that indicates the extent of a drug's distribution in the body tissues. This paper addresses the problem of how to estimate the apparent volume of distribution at steady state (Vss) of chemical compounds in the human body using decision tree-based regression methods from the area of data mining (or machine learning). Hence, the pros and cons of several different types of decision tree-based regression methods have been discussed. The regression methods predict Vss using, as predictive features, both the compounds' molecular descriptors and the compounds' tissue:plasma partition coefficients (Kt:p) - often used in physiologically-based pharmacokinetics. Therefore, this work has assessed whether the data mining-based prediction of Vss can be made more accurate by using as input not only the compounds' molecular descriptors but also (a subset of) their predicted Kt:p values. Comparison of the models that used only molecular descriptors, in particular, the Bagging decision tree (mean fold error of 2.33), with those employing predicted Kt:p values in addition to the molecular descriptors, such as the Bagging decision tree using adipose Kt:p (mean fold error of 2.29), indicated that the use of predicted Kt:p values as descriptors may be beneficial for accurate prediction of Vss using decision trees if prior feature selection is applied. Decision tree based models presented in this work have an accuracy that is reasonable and similar to the accuracy of reported Vss inter-species extrapolations in the literature. The estimation of Vss for new compounds in drug discovery will benefit from methods that are able to integrate large and varied sources of data and flexible non-linear data mining methods such as decision trees, which can produce interpretable models. Graphical AbstractDecision trees for the prediction of tissue partition coefficient and volume of distribution of drugs.

Partitioning of resveratrol between pentane and DMSO

DEFF Research Database (Denmark)

Shen, Chen; Stein, Paul C.; Klösgen-Buchkremer, Beate Maria

2015-01-01

Partitioning of trans-3,5,4′-trihydroxy-stilbene (resveratrol) between n-pentane and DMSO was investigated as a contribution to understand the interaction between resveratrol and biomembranes. In order to determine the partition coefficient P* of resveratrol between pentane and DMSO, resveratrol ...

Assessment of bioaccumulation of REEs by plant species in a mining area by INAA

International Nuclear Information System (INIS)

Hossain Md Anawar; Maria do Carmo Freitas; Nuno Canha; Isabel Dionisio; Ho Manh Dung; Catarina Galinha; Pacheco, A.M.G.

2012-01-01

Native plant species, lichens and tailings, sampled from a copper-sulphide mining area located in southern-eastern Portugal, were analysed by neutron activation analysis (INAA) for determination of rare earth elements (REEs). Values of ΣREEs and individual REEs concentration of tailing samples are higher than those of natural background concentrations. The higher values of REEs are found in modern slags and the mixture of oxidized gossan and sulphide disseminated country rocks when compared with the alluvial sediments contaminated by mine tailings. The total concentrations of light REEs are higher than those of heavy REEs in all tailing samples. Distribution patterns of PAAS-normalized REEs in mine tailings show slightly LREE enriched and flat HREE pattern with negative Eu anomaly. Lichens accumulated higher concentration of lanthanides than vascular plants. The elevated levels of REEs in lichen, native plant species and tailing samples reflect the contamination of REEs in Sao Domingos mining area. The Carlina corymbosa, Erica australis and Lavandula luisierra accumulated the higher amounts of La, Ce and other REEs than the other plant species grown in this mining area. (author)

Novel approach in k0-NAA for highly concentrated REE Samples.

Science.gov (United States)

Abdollahi Neisiani, M; Latifi, M; Chaouki, J; Chilian, C

2018-04-01

The present paper presents a new approach for k 0 -NAA for accurate quantification with short turnaround analysis times for rare earth elements (REEs) in high content mineral matrices. REE k 0 and Q 0 values, spectral interferences and nuclear interferences were experimentally evaluated and improved with Alfa Aesar Specpure Plasma Standard 1000mgkg -1 mono-rare earth solutions. The new iterative gamma-ray self-attenuation and neutron self-shielding methods were investigated with powder standards prepared from 100mg of 99.9% Alfa Aesar mono rare earth oxide diluted with silica oxide. The overall performance of the new k 0 -NAA method for REEs was validated using a certified reference material (CRM) from Canadian Certified Reference Materials Project (REE-2) with REE content ranging from 7.2mgkg -1 for Yb to 9610mgkg -1 for Ce. The REE concentration was determined with uncertainty below 7% (at 95% confidence level) and proved good consistency with the CRM certified concentrations. Copyright © 2017 Elsevier B.V. All rights reserved.

Partitioning of L-methionine in aqueous two-phase systems containing poly(propylene glycol) and sodium phosphate salts

Energy Technology Data Exchange (ETDEWEB)

Salabat, Alireza, E-mail: a-salabat@araku.ac.ir [Chemistry Department, Arak University, P.O. Box 38156-879, Arak (Iran, Islamic Republic of); Sadeghi, Rahmat [Department of Chemistry, University of Kurdistan, Sanandaj, Kurdistan 66135 (Iran, Islamic Republic of); Moghadam, Somayeh Tiani [Chemistry Department, Arak University, P.O. Box 38156-879, Arak (Iran, Islamic Republic of); Jamehbozorg, Bahman [Department of Chemistry, University of Kurdistan, Sanandaj, Kurdistan 66135 (Iran, Islamic Republic of)

2011-10-15

Highlights: > Thermodynamics parameters for partitioning of L-methionine in ATPS. > Investigation of different effects on partition coefficient of the amino acid. > Propose the best condition for L-methionine partitioning. - Abstract: The partitioning behavior of L-methionine has been studied in aqueous two-phase systems of (poly(propylene glycol) + sodium phosphate salts + H{sub 2}O) at different temperatures. The salts used were sodium di-hydrogen phosphate (NaH{sub 2}PO{sub 4}), di-sodium hydrogen phosphate (Na{sub 2}HPO{sub 4}) and tri-sodium phosphate (Na{sub 3}PO{sub 4}). The effects of tie line length, salt type, and temperature on the partition coefficient of this amino acid have been studied. In addition, thermodynamic parameters ({Delta}H{sup o}, {Delta}S{sup o} and {Delta}G{sup o}) as a function of temperature were calculated. The results showed that increasing tie line length led to decreasing of the partition coefficient. We also showed that the partition coefficients of the amino acid in the systems containing Na{sub 3}PO{sub 4} are greater than the other two salts. Moreover, it is verified that increasing temperature led to decreasing the partition coefficient. The experimental partition coefficient data are correlated using a modified virial-type model.

Effects of rare earth elements and REE-binding proteins on physiological responses in plants.

Science.gov (United States)

Liu, Dongwu; Wang, Xue; Chen, Zhiwei

2012-02-01

Rare earth elements (REEs), which include 17 elements in the periodic table, share chemical properties related to a similar external electronic configuration. REEs enriched fertilizers have been used in China since the 1980s. REEs could enter the cell and cell organelles, influence plant growth, and mainly be bound with the biological macromolecules. REE-binding proteins have been found in some plants. In addition, the chlorophyll activities and photosynthetic rate can be regulated by REEs. REEs could promote the protective function of cell membrane and enhance the plant resistance capability to stress produced by environmental factors, and affect the plant physiological mechanism by regulating the Ca²⁺ level in the plant cells. The focus of present review is to describe how REEs and REE-binding proteins participate in the physiological responses in plants.

Geochemistry of REE in Acid Mine Drainage: Sorption onto Basaluminite and Schwertmannite.

Science.gov (United States)

Lozano Letellier, A.; Ayora, C.; Fernandez-Martinez, A.

2017-12-01

The geochemistry of Rare Earth Elements (REE) has been investigated in natural streams and in mine areas during the last decades. Most of these studies agree that REE are mobile in acidic waters and they transferred to a solid phase when pH increases. However, there is no agreement on the pH range, on which precipitates can retain REE and the mechanisms responsible for the retention. Thus, whereas some authors determined that hydrous ferric oxides (HFOs) scavenge REE from pH 3, other authors observed REE retention by hydrous aluminum oxides (HAOs) from pH 4 to 6.1. A field survey conducted in the Odiel River in the SW Spain showed that pH values higher than 5, REE, Cu, Al and Fe concentrations in the river were lower than expected from a theoretical mixture because they were trapped in the precipitates. For pH below 4, however, only schwertmannite (Fe8O8OH6SO4) and no basaluminite (Al4SO4OH10·5H2O) precipitated. Then, REE, Cu and Al behaved conservatively and Fe does not, indicating that REE are trapped in the Al but not in the Fe solid phase. These observations are perfectly consistent with the REE accumulation in the Al-rich precipitates in the AMD treatment systems. Taking into account these observations, sorption experiments with synthetic basaluminite and schwertmannite at different pH were performed in the laboratory. For Lanthanides and Yttrium, sorption edge took place at pH higher than 5, whereas Sc sorption started at pH 4. A surface complexation model is proposed to explain the retention mechanism onto these two precipitates. Both minerals, schwertmannite and basaluminite showed similar sorption behavior. However, as schwertmannite formation occurs at pH lower than 4, no REE elements are sorbed on it.

REE interactions with hydroxyapatite. Formation of secondary solid phases

International Nuclear Information System (INIS)

Seco, F.; Pablo, J. de; Bruno, J.

2005-01-01

Full text of publication follows: Lighter rare earth elements (REE) commonly occur in nature as the phosphate mineral monazite, while the heavier REE and Yttrium occur as the phosphate mineral xenotime, which has a similar composition, but different coordination environment of the cation. The geochemical behaviour of REE is mainly controlled by their interactions with phosphate minerals such as hydroxyapatite, Ca 5 (PO 4 ) 3 OH, which is a very common phosphate phase in subsurface environments. Furthermore, is a material considered to be used in a High Level Nuclear Waste repository due to its high capacity in the retention of radionuclides. The objective of this work has been to study the reaction mechanisms and thermodynamics of the interaction of La(III) and Yb(III) with hydroxyapatite as a model for general Ln(III) and Ac(III) behaviour. The surface interaction of La(III) and Yb(III) with synthetic hydroxyapatite has been investigated in batch experiments with low REE 3+ initial concentrations in constant 0.1 M NaClO 4 , at room temperature and in N 2 (g) atmosphere to avoid carbonate complex formation. The initial kinetic experiments indicated that a short contact time is needed to reach equilibrium ( 4 .nH 2 O, where a 0.83 4 .nH 2 O with 1.78 4 medium and under N 2 (g) atmosphere. The experimental data indicate that the solubility equilibria is mainly controlled by the aqueous species REE 3+ until approximately pH=5 where the formation of aqueous complexes of the form REEHPO 4 + , REEPO 4 and REE(PO 4 ) 2 3- must be considered. (authors)

REE Comparison Between Muncung Granite Samples and their Weathering Products, Lingga Regency, Riau Islands

Directory of Open Access Journals (Sweden)

Ronaldo Irzon

2016-11-01

Full Text Available DOI:10.17014/ijog.3.3.149-161The increasing demand for Rare Earth Elements (REE is related to the continous development of technology, and these elements are used in modern equipments. REE can occur in igneous and sedimentary rocks in significant amounts as primary deposits, whereas the secondary REE deposit can be produced by intensive lateritic weathering of bedrocks under the tropical or subtropical climate. Lateritic process can increase REE concentration from sub-economic levels in host rocks to be more valuable. Muncung Granite is located in a tropical area of Lingga Regency, Riau Islands Province. REE occurs in the Muncung Granite and in weathered layers (saprolite, laterite, and soil. ICP-MS was applied to measure the REE content in all samples of this study. The average REE content of the Muncung Granite is 265 ppm with Eu anomaly in REE’s spider diagrams. Lateritization process has increased REE content by more than four times compared to that in the Muncung Granite. Ce and Eu anomalies in weathered layers can be associated with weathering process and initial REE contents in the host rock. Ce anomaly in a laterite layer is found to have a negative correlation to REE total enrichment. The REE level in the Muncung Granite is higher than the content in the soil and saprolite layers, but lower than that in the laterite.

Effect of Strain, Region, and Tissue Composition on Glucose Partitioning in Meniscus Fibrocartilage.

Science.gov (United States)

Kleinhans, Kelsey L; Jackson, Alicia R

2017-03-01

A nearly avascular tissue, the knee meniscus relies on diffusive transport for nutritional supply to cells. Nutrient transport depends on solute partitioning in the tissue, which governs the amount of nutrients that can enter a tissue. The purpose of the present study was to investigate the effects of mechanical strain, tissue region, and tissue composition on the partition coefficient of glucose in meniscus fibrocartilage. A simple partitioning experiment was employed to measure glucose partitioning in porcine meniscus tissues from two regions (horn and central), from both meniscal components (medial and lateral), and at three levels of compression (0%, 10%, and 20%). Partition coefficient values were correlated to strain level, water volume fraction, and glycosaminoglycan (GAG) content of tissue specimens. Partition coefficient values ranged from 0.47 to 0.91 (n = 48). Results show that glucose partition coefficient is significantly (p < 0.001) affected by compression, decreasing with increasing strain. Furthermore, we did not find a statistically significant effect of tissue when comparing medial versus lateral (p = 0.181) or when comparing central and horn regions (p = 0.837). There were significant positive correlations between tissue water volume fraction and glucose partitioning for all groups. However, the correlation between GAG content and partitioning was only significant in the lateral horn group. Determining how glucose partitioning is affected by tissue composition and loading is necessary for understanding nutrient availability and related tissue health and/or degeneration. Therefore, this study is important for better understanding the transport and nutrition-related mechanisms of meniscal degeneration.

Topological string partition functions as polynomials

International Nuclear Information System (INIS)

Yamaguchi, Satoshi; Yau Shingtung

2004-01-01

We investigate the structure of the higher genus topological string amplitudes on the quintic hypersurface. It is shown that the partition functions of the higher genus than one can be expressed as polynomials of five generators. We also compute the explicit polynomial forms of the partition functions for genus 2, 3, and 4. Moreover, some coefficients are written down for all genus. (author)

A layer model of ethanol partitioning into lipid membranes.

Science.gov (United States)

Nizza, David T; Gawrisch, Klaus

2009-06-01

The effect of membrane composition on ethanol partitioning into lipid bilayers was assessed by headspace gas chromatography. A series of model membranes with different compositions have been investigated. Membranes were exposed to a physiological ethanol concentration of 20 mmol/l. The concentration of membranes was 20 wt% which roughly corresponds to values found in tissue. Partitioning depended on the chemical nature of polar groups at the lipid/water interface. Compared to phosphatidylcholine, lipids with headgroups containing phosphatidylglycerol, phosphatidylserine, and sphingomyelin showed enhanced partitioning while headgroups containing phosphatidylethanolamine resulted in a lower partition coefficient. The molar partition coefficient was independent of a membrane's hydrophobic volume. This observation is in agreement with our previously published NMR results which showed that ethanol resides almost exclusively within the membrane/water interface. At an ethanol concentration of 20 mmol/l in water, ethanol concentrations at the lipid/water interface are in the range from 30-15 mmol/l, corresponding to one ethanol molecule per 100-200 lipids.

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

Science.gov (United States)

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of the contents and distribution characteristics of REE in natural plants by NAA

International Nuclear Information System (INIS)

Wang, Y.Q.; Sun, J.X.; Chen, H.M.; Guo, F.Q.

1997-01-01

The concentration of 8 REEs (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in 17 species of plants and their host soil, which were collected from a rare earth ore area located in the south of China, have been determined by INAA. The chondritic normalized REE patterns for different parts of plants (e.g., leaf, stem and root) and their host soils were studied. The results showed that the concentration levels of REE for most plants in the sampling area were elevated. Particularly, the leaves of the fern (Dicranopteris dichotoma) contain extremely high concentration of the total REE (675-3358 μg/g). Generally, these REE distribution patterns in every part of plants were very similar and reflected the characteristics of their host soils. However, the chondritic normalized REE patterns in some plants relative to the host soil revealed obvious fractionation, such as the depletion of the heavy REE (for fern, Citrus reticulata and Brassia campestris), the heavy REE enrichment (for Camellia sinensis, Camellia oleifera and Ziziphus) and the Ce positive anomaly (for Gardenia jasminoides). (author)

Stochastic modeling of phosphorus transport in the Three Gorges Reservoir by incorporating variability associated with the phosphorus partition coefficient

Energy Technology Data Exchange (ETDEWEB)

Huang, Lei; Fang, Hongwei; Xu, Xingya; He, Guojian; Zhang, Xuesong; Reible, Danny

2017-08-01

Phosphorus (P) fate and transport plays a crucial role in the ecology of rivers and reservoirs in which eutrophication is limited by P. A key uncertainty in models used to help manage P in such systems is the partitioning of P to suspended and bed sediments. By analyzing data from field and laboratory experiments, we stochastically characterize the variability of the partition coefficient (Kd) and derive spatio-temporal solutions for P transport in the Three Gorges Reservoir (TGR). We formulate a set of stochastic partial different equations (SPDEs) to simulate P transport by randomly sampling Kd from the measured distributions, to obtain statistical descriptions of the P concentration and retention in the TGR. The correspondence between predicted and observed P concentrations and P retention in the TGR combined with the ability to effectively characterize uncertainty suggests that a model that incorporates the observed variability can better describe P dynamics and more effectively serve as a tool for P management in the system. This study highlights the importance of considering parametric uncertainty in estimating uncertainty/variability associated with simulated P transport.

Halogenated methyl-phenyl ethers (anisoles) in the environment: determination of vapor pressures, aqueous solubilities, Henry's law constants, and gas/water- (Kgw), n-octanol/water- (Kow) and gas/n-octanol (Kgo) partition coefficients.

Science.gov (United States)

Pfeifer, O; Lohmann, U; Ballschmiter, K

2001-11-01

Halogenated methyl-phenyl ethers (methoxybenzenes, anisoles) are ubiquitous organics in the environment although they are not produced in industrial quantities. Modelling the fate of organic pollutants such as halogenated anisoles requires a knowledge of the fundamental physico-chemical properties of these compounds. The isomer-specific separation and detection of 60 of the 134 possible congeners allowing an environmental fingerprinting are reported in this study. The vapor pressure p0(L) of more than 60 and further physico-chemical properties of 26 available congeners are given. Vapor pressures p0(L), water solubilities S(L)W, and n-octanol/water partition coefficients Kow were determined by capillary HR-GC (High Resolution Gas Chromatography) on a non-polar phase and by RP-HPLC (Reversed Phase High Performance Liquid Chromatography) on a C18 phase with chlorobenzenes as reference standards. From these experimental data the Henry's law constants H, and the gas/water Kgw and gas/n-octanol Kgo partition coefficients were calculated. We found that vapor pressures, water solubilities, and n-octanol/water partition coefficients of the halogenated anisoles are close to those of the chlorobenzenes. A similar environmental fate of both groups can, therefore, be predicted.

REE potential of the Nordkinn Peninsula, North Norway: A comparison of soil and bedrock composition

International Nuclear Information System (INIS)

Schilling, Julian; Reimann, Clemens; Roberts, David

2014-01-01

Highlights: • Soil geochemistry outlines an extensive REE anomaly on the Nordkinn Peninsula, North Norway. • Soil and bedrock geochemistry are compared with respect to REE and other HFSE. • Petrology of soil and rock samples reveals that the economic potential is limited. • Poor condition of REE minerals causes elevated REE concentrations in AR-digested soil samples. - Abstract: Regional-scale, low-density sampling, geochemical surveys using a variety of different sample materials have repeatedly indicated the Nordkinn Peninsula (northern Norway) as a substantial rare earth element (REE) anomaly. Recently, a more detailed soil geochemical survey, covering about 2000 km 2 at a sample density of 1 site per 2 km 2 , was carried out in the area. The new geochemical survey outlined a large area (several hundred km 2 ) where the soil samples contained several hundred and up to over 2000 mg/kg aqua regia extractable REE. In the surroundings of the highest soil anomalies, bedrock samples were collected for a mineralogical and compositional characterisation of the metasedimentary bedrock with focus on the possible economic potential. The REE concentrations obtained for aliquots of bedrock following aqua regia extraction, 4-Acid digestion and Li-borate fusion/decomposition closely match the results from soil pulps after an aqua regia extraction. Total contents for the REE determined in bedrock using the above methods range between 19 and 429 mg/kg, indicating an overall limited economic REE potential and the predominance of the light REE over the heavy REE. In terms of petrography, essentially all the bedrock samples are characterised by the presence of detrital, altered and locally even decomposed allanite (a LREE-incorporating, epidote-group mineral) and minor xenotime (a HREE-incorporating phosphate) while texturally stable REE phases are scarce. It is the poor condition of the REE minerals that makes them prone towards acidic leaching and, given similar results

Determination of radon partition coefficients between water and different kinds of NAPLs for use in analysis of residual soil NAPLs

Energy Technology Data Exchange (ETDEWEB)

Bonfim, Sarah Andresa; Ferreira, Ângela Fortini Macedo, E-mail: sarah_andresa@hotmail.com [Universidade Federal de Migas Gerais (UFMG), Belo Horizonte, MG (Brazil). Departamento de Engenharia Nuclear; Franklin, Mariza Ramalho; Ferreira, Paulo Roberto Rocha [Instituto de Radioproteção e Dosimetria (IRD/CNEN-RJ), Rio de Janeiro, RJ (Brazil); Rocha, Zildete, E-mail: zildeter7@gmail.com [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

2017-07-01

Different studies indicate the applicability of natural radon as a tracer in the determination of contaminated environments by Non-Aqueous Phase Liquids (NAPLs). Such use being due to the non-homogeneous distribution of this element between water, air and NAPL. Thus, it is known that the concentration of radon in a given soil / aquifer and in a given area may indicate that such site is contaminated by NAPL. However, the simple measurement of radon concentration activity allows only a qualitative evaluation of the area contaminated in study. For a quantitative estimate of the NAPL saturation in the pore space, it is necessary to know the radon partition coefficients between the coexisting phases, considering the kind of NAPL present. The present study, the radon partitioning coefficients between air, water and diverse types of NAPL mixtures, such as gasoline, diesel fuel, alcohol, kerosene and olive oil was measured. In a closed system, was applied an analytical method based on the distribution of the radon between the present phases with the use of a system of Flow Injection Analysis (FIA). The measurement of the specific activity of radon was performed by using an AlphaGUARD monitor. It is observed that, in the presence of NAPL, the concentration of radon in water and air is significantly lower than in its absence, indicating a negative correlation and allowing the evaluation of the contamination of the area by NAPL. (author)

Determination of radon partition coefficients between water and different kinds of NAPLs for use in analysis of residual soil NAPLs

International Nuclear Information System (INIS)

Bonfim, Sarah Andresa; Ferreira, Ângela Fortini Macedo; Rocha, Zildete

2017-01-01

Different studies indicate the applicability of natural radon as a tracer in the determination of contaminated environments by Non-Aqueous Phase Liquids (NAPLs). Such use being due to the non-homogeneous distribution of this element between water, air and NAPL. Thus, it is known that the concentration of radon in a given soil / aquifer and in a given area may indicate that such site is contaminated by NAPL. However, the simple measurement of radon concentration activity allows only a qualitative evaluation of the area contaminated in study. For a quantitative estimate of the NAPL saturation in the pore space, it is necessary to know the radon partition coefficients between the coexisting phases, considering the kind of NAPL present. The present study, the radon partitioning coefficients between air, water and diverse types of NAPL mixtures, such as gasoline, diesel fuel, alcohol, kerosene and olive oil was measured. In a closed system, was applied an analytical method based on the distribution of the radon between the present phases with the use of a system of Flow Injection Analysis (FIA). The measurement of the specific activity of radon was performed by using an AlphaGUARD monitor. It is observed that, in the presence of NAPL, the concentration of radon in water and air is significantly lower than in its absence, indicating a negative correlation and allowing the evaluation of the contamination of the area by NAPL. (author)

Determination and prediction of octanol-air partition coefficients for organophosphate flame retardants.

Science.gov (United States)

Wang, Qingzhi; Zhao, Hongxia; Wang, Yan; Xie, Qing; Chen, Jingwen; Quan, Xie

2017-11-01

Organophosphate flame retardants (OPFRs) have attracted wide concerns due to their toxicities and ubiquitous occurrence in the environment. In this work, Octanol-air partition coefficient (K OA ) for 14 OPFRs including 4 halogenated alkyl-, 5 aryl- and 5 alkyl-OPFRs, were estimated as a function of temperature using a gas chromatographic retention time (GC-RT) method. Their log K OA-GC values and internal energies of phase transfer (Δ OA U/kJmol -1 ) ranged from 8.03 to 13.0 and from 69.7 to 149, respectively. Substitution pattern and molar volume (V M ) were found to be capable of influencing log K OA-GC values of OPFRs. The halogenated alkyl-OPFRs had higher log K OA-GC values than aryl- or alkyl-OPFRs. The bigger the molar volume was, the greater the log K OA-GC values increased. In addition, a predicted model of log K OA-GC versus different relative retention times (RRTs) was developed with a high cross-validated value (Q 2 (cum) ) of 0.951, indicating a good predictive ability and stability. Therefore, the log K OA-GC values of the remaining OPFRs can be predicted by using their RRTs on different GC columns. Copyright © 2017 Elsevier Inc. All rights reserved.

Determination of uranium partition coefficients of a semi-arid soil in Bahia

International Nuclear Information System (INIS)

Fernandes, Heloisa H.F.; Pontedeiro, Elizabeth M.; Su, Jian

2013-01-01

In mining and processing industries, the subsurface is one of the most vulnerable compartments to environmental contamination. Understanding the interactions between soil and contaminants is critical for predicting the possible environmental impacts caused by mining and milling operations. One of the main parameters used for this purpose is the partition (or distribution) coefficient, K d , which allows a relatively simple modeling approach by grouping various sorption phenomena into a single value. However, this parameter is strongly influenced by the physical and chemical characteristics of the medium, such as soil type, pH and solution composition. Thus, this study aims to assess the values of K d for uranium of typical soils from Bahia's semi-arid region using two different types of solute, one being a standard solution of uranyl acetate and one the liquor of uranium generated during processing. To calculate this parameter, batch adsorption experiments were carried out and adsorption isotherms (linear, Langmuir and Freundlich) were constructed using the Mathematica software. Results obtained for a single type of soil showed reduced values of K d for a liquor containing uranium when compared to values obtained with the uranyl acetate solution. This indicates that uranium from liquor is less adsorbed onto soil particles, and hence may move more quickly into the subsurface. (author)

Rees, Prof. Lord Martin (John)

Indian Academy of Sciences (India)

Home; Fellowship. Fellow Profile. Elected: 1991 Honorary. Rees, Prof. Lord Martin (John) FRS. Date of birth: 23 June 1942. Address: Emeritus professor of Cosmology & Astrophysics, Institute of Astronomy, University of Cambridge, Madingley Road, Cambridge CB3 0HA, U.K.. Contact: Office: (+44-1223) 33 7548

Determination of 1-octanol-air partition coefficient using gaseous diffusion in the air boundary layer.

Science.gov (United States)

Ha, Yeonjeong; Kwon, Jung-Hwan

2010-04-15

Exact determination of the partition coefficient between 1-octanol and air (K(OA)) is very important because it is a key descriptor for describing the thermodynamic partitioning between the air and organic phases. In spite of its importance, the number and quality of experimental K(OA) values for hydrophobic organic chemicals are limited because of experimental difficulties. Thus, to measure K(OA) values, a high-throughput method was developed that used liquid-phase extraction with 1-octanol drop at the tip of a microsyringe needle. The concentration in the headspace surrounding the 1 muL octanol drop was equilibrated with liquid octanol containing polycyclic aromatic hydrocarbons (PAHs). The change in concentrations of PAHs in the octanol drop was measured to obtain mass transfer rate constants, and these rate constants were then converted into K(OA) values using a film diffusion model. Thirteen polycyclic aromatic hydrocarbons with log K(OA) between 5 and 12 were chosen for the proof of the principle. Experimental determination of log K(OA) was accomplished in 30 h for PAHs with their log K(OA) less than 11. The measured log K(OA) values were very close to those obtained by various experimental and estimation methods in the literature, suggesting that this new method can provide a fast and easy determination of log K(OA) values for many chemicals of environmental interests. In addition, the applicability of the method can be extended to determine Henry's law constant for compounds with low vapor pressure and to estimate gaseous transfer rate of semivolatile compounds for environmental fate modeling.

Incorporation of REE into leucophanite

DEFF Research Database (Denmark)

Mortensen, Henrik Friis; Balic Zunic, Tonci; Williams, C.T.

2007-01-01

The crystal structures of nine, and the chemical compositions of ten, natural samples of leucophanite, ideally NaCaBeSi2O6F, were investigated. The analysed samples display a large compositional variation with trace-element abundances >50,000 ppm, primarily due to rare earth elements (REE). Fromt...

Aqueous-gas phase partitioning and hydrolysis of organic iodides

International Nuclear Information System (INIS)

Glowa, G.A.; Wren, J.C.

2003-01-01

The volatility and decomposition of organic iodides in a reactor containment building are important parameters to consider when assessing the potential consequences of a nuclear reactor accident. However, there are few experimental data available for the volatilities (often reported as partition coefficients) or few rate constants regarding the decomposition (via hydrolysis) of organic iodides. The partition coefficients and hydrolysis rate constants of eight organic iodides, having a range of molecular structures, have been measured in the current studies. This data, and data accumulated in the literature, have been reviewed and discussed to provide guidelines for appropriate organization of organic iodides for the purpose of modelling iodine behaviour under postulated nuclear reactor accident conditions. After assessment of the partition coefficients and their temperature dependences of many classes of organic compounds, it was found that organic iodides could be divided into two categories based upon their volatility relative to molecular iodine. Similarly, hydrolysis rates and their temperature dependences are assigned to the two categories of organic iodides. (author)

Behaviour of REEs in a tropical estuary and adjacent continental ...

Indian Academy of Sciences (India)

total organic carbon, U/Th ratio, authigenic U, Cu/Zn, V/Cr ratios revealed the oxic environment and thus the ... tions due to depletion by sorption onto particles. .... trace elements (Cr, Ni, Co, Zn) were analysed along ... Results. The concentration of REE and trace elements ..... This effect causes a split of the normalised REE.

The giant Bayan Obo REE-Nb-Fe deposit, China: Controversy and ore genesis

Directory of Open Access Journals (Sweden)

Hong-Rui Fan

2016-05-01

Full Text Available Bayan Obo ore deposit is the largest rare-earth element (REE resource, and the second largest niobium (Nb resource in the world. Due to the complicated element/mineral compositions and involving several geological events, the REE enrichment mechanism and genesis of this giant deposit still remains intense debated. The deposit is hosted in the massive dolomite, and nearly one hundred carbonatite dykes occur in the vicinity of the deposit. The carbonatite dykes can be divided into three types from early to late: dolomite, co-existing dolomite-calcite and calcite type, corresponding to different evolutionary stages of carbonatite magmatism based on the REE and trace element data. The latter always has higher REE content. The origin of the ore-hosting dolomite at Bayan Obo has been addressed in various models, ranging from a normal sedimentary carbonate rocks to volcano-sedimentary sequence, and a large carbonatitic intrusion. More geochemical evidences show that the coarse-grained dolomite represents a Mesoproterozoic carbonatite pluton and the fine-grained dolomite resulted from the extensive REE mineralization and modification of the coarse-grained variety. The ore bodies, distributed along an E–W striking belt, occur as large lenses and underwent more intense fluoritization and fenitization. The first episode mineralization is characterized by disseminated mineralization in the dolomite. The second or main-episode is banded and/or massive mineralization, cut by the third episode consisting of aegirine-rich veins. Various dating methods gave different mineralization ages at Bayan Obo, resulting in long and hot debates. Compilation of available data suggests that the mineralization is rather variable with two peaks at ∼1400 and 440 Ma. The early mineralization peak closes in time to the intrusion of the carbonatite dykes. A significant thermal event at ca. 440 Ma resulted in the formation of late-stage veins with coarse crystals of REE

Superfluid Kubo formulas from partition function

International Nuclear Information System (INIS)

Chapman, Shira; Hoyos, Carlos; Oz, Yaron

2014-01-01

Linear response theory relates hydrodynamic transport coefficients to equilibrium retarded correlation functions of the stress-energy tensor and global symmetry currents in terms of Kubo formulas. Some of these transport coefficients are non-dissipative and affect the fluid dynamics at equilibrium. We present an algebraic framework for deriving Kubo formulas for such thermal transport coefficients by using the equilibrium partition function. We use the framework to derive Kubo formulas for all such transport coefficients of superfluids, as well as to rederive Kubo formulas for various normal fluid systems

The influence of precipitation kinetics on trace element partitioning between solid and liquid solutions: A coupled fluid dynamics/thermodynamics framework to predict distribution coefficients

Science.gov (United States)

Kavner, A.

2017-12-01

In a multicomponent multiphase geochemical system undergoing a chemical reaction such as precipitation and/or dissolution, the partitioning of species between phases is determined by a combination of thermodynamic properties and transport processes. The interpretation of the observed distribution of trace elements requires models integrating coupled chemistry and mechanical transport. Here, a framework is presented that predicts the kinetic effects on the distribution of species between two reacting phases. Based on a perturbation theory combining Navier-Stokes fluid flow and chemical reactivity, the framework predicts rate-dependent partition coefficients in a variety of different systems. We present the theoretical framework, with applications to two systems: 1. species- and isotope-dependent Soret diffusion of species in a multicomponent silicate melt subjected to a temperature gradient, and 2. Elemental partitioning and isotope fractionation during precipitation of a multicomponent solid from a multicomponent liquid phase. Predictions will be compared with results from experimental studies. The approach has applications for understanding chemical exchange in at boundary layers such as the Earth's surface magmatic systems and at the core/mantle boundary.

Use of the Boron partition coefficient ‘K_D’ and B/Ca from planktonic foraminifera in the estimation of past seawater pCO₂

Digital Repository Service at National Institute of Oceanography (India)

Naik, S.S.; Naidu, P.D.

We assess the usefulness of the empirical boron partition coefficient, K_D and B/Ca measured from planktonic foraminifera in estimation of pCO₂ using three different relationships between K_D and temperature derived...

Determination of uranium partition coefficients of a semi-arid soil in Bahia

Energy Technology Data Exchange (ETDEWEB)

Fernandes, Heloisa H.F.; Pontedeiro, Elizabeth M.; Su, Jian, E-mail: heloisa@lasme.coppe.ufrj.br, E-mail: bettinadulley@hotmail.com, E-mail: sujian@lasme.coppe.ufrj.br [Coordenacao dos Cursos de Pos-Graduacao em Engenharia (COPPE/UFRJ), Rio de Janeiro, RJ (Brazil). Lab. de Simulacao e Metodos de Engenharia; Dourado, Eneida R.G., E-mail: eneida@inb.gov.br [Industrias Nucleares do Brasil (INB), Rio de Janeiro, RJ (Brazil)

2013-07-01

In mining and processing industries, the subsurface is one of the most vulnerable compartments to environmental contamination. Understanding the interactions between soil and contaminants is critical for predicting the possible environmental impacts caused by mining and milling operations. One of the main parameters used for this purpose is the partition (or distribution) coefficient, K{sub d}, which allows a relatively simple modeling approach by grouping various sorption phenomena into a single value. However, this parameter is strongly influenced by the physical and chemical characteristics of the medium, such as soil type, pH and solution composition. Thus, this study aims to assess the values of K{sub d} for uranium of typical soils from Bahia's semi-arid region using two different types of solute, one being a standard solution of uranyl acetate and one the liquor of uranium generated during processing. To calculate this parameter, batch adsorption experiments were carried out and adsorption isotherms (linear, Langmuir and Freundlich) were constructed using the Mathematica software. Results obtained for a single type of soil showed reduced values of K{sub d} for a liquor containing uranium when compared to values obtained with the uranyl acetate solution. This indicates that uranium from liquor is less adsorbed onto soil particles, and hence may move more quickly into the subsurface. (author)

REE characteristics and uranium metallogenesis of sandstone-type uranium deposits in northern Sichuan

International Nuclear Information System (INIS)

Zhu Xiyang; Wang Yunliang; Wang Zhichang; Zhang Chengjiang

2004-01-01

On the basis of the analysis of a large number of samples at sandstone-type uranium deposits in northern Sichuan, this paper analyses the REE composition of country rocks, ores, calcite-veins and uranium minerals, and systematically summarizes their REE geochemical characteristics, and discusses variation regularity of REE during depositional and diagenetic processes. By comparing these characteristics with those of typical hydrothermal volcanics-type and metamorphic rock type uranium deposits both at home and abroad, authors suggest that sandstone-type uranium deposits in northern Sichuan are characterized by REE geochemical features of hydrothermal reworking metallogenesis, the uranium mineralization has experienced two stages: the diagenetic preconcentration and the concentration of hydrothermal reworking

Crystallization process of zircon and fergusonite during hydrothermal alteration in Nechalacho REE deposit, Thor Lake, Canada

Science.gov (United States)

Hoshino, M.; Watanabe, Y.; Murakami, H.; Kon, Y.; Tsunematsu, M.

2012-04-01

The core samples of two drill holes, which penetrate sub-horizontal mineralized horizons at Nechalacho REE deposit in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify magmatic and hydrothermal processes that enriched HFSE (e.g. Zr, Nb, Y and REE). Zircon is the most common REE minerals in Nechalacho REE deposit. The zircon is divided into five types as follows: Type-1 zircon occurs as single grain in phlogopite and the chondrite-normalized REE pattern is characterized by a steeply-rising slope from the LREE to the HREE with a positive Ce-anomaly and negative Eu-anomaly. This chemical characteristic is similar to that of igneous zircon. Type-2 zircon consists of HREE-rich magmatic porous core and LREE-Nb-F-rich hydrothermal rim. This type zircon is mostly included in phlogopite and fluorite, and occasionally in microcline. Type-3 zircon is characterized by euhedral to anhedral crystal, occurring in a complex intergrowth with REE fluorocarbonates. Type-3 zircons have high contents of REE, Nb and fluorine. Type-4 zircon consists of porous-core and -rim zones, but their chemical compositions are similar to each other. This type zircon is a subhedral crystal rimmed by fergusonite. Type-5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircons are filled by fergusonite. Type-4 and -5 zircons show low REE and Nb contents. Occurrences of these five types of zircon are different according to the depth and degree of the alteration by hydrothermal solutions rich in F- and CO3 of the two drill holes, which permit a model for evolution of the zircon crystallization in Nechalacho REE deposit as follows: (1) type-1 (single magmatic zircon) is formed in miaskitic syenite. (2) LREE-Nb-F-rich hydrothermal zircon formed around HREE-rich magmatic zircon (type-2 zircon); (3) type-3 zircon crystallized thorough F and CO3-rich hydrothermal alteration of type-2 zircon which formed the complex

Microbial mobilization of rare earth elements (REE from mineral solids—A mini review

Directory of Open Access Journals (Sweden)

Fabienne Barmettler

2016-06-01

Full Text Available In the light of an expected supply shortage of rare earth elements (REE measures have to be undertaken for an efficient use in all kinds of technical, medical, and agricultural applications as well as—in particular—in REE recycling from post-use goods and waste materials. Biologically- based methods might offer an alternative and supplement to physico-chemical techniques for REE recovery and recycling. A wide variety of physiologically distinct microbial groups have the potential to be applied for REE bioleaching form solid matrices. This source is largely untapped until today. Depending of the type of organism, the technical process (including a series of influencing factors, the solid to be treated, and the target element, leaching efficiencies of 80 to 90% can be achieved. Bioleaching of REEs can help in reducing the supply risk and market dependency. Additionally, the application of bioleaching techniques for the treatment of solid wastes might contribute to the conversion towards a more sustainable and environmental friendly economy.

Endoscopy and homogeneous-heterogeneous reactions in MHD radiative peristaltic activity of Ree-Eyring fluid

Science.gov (United States)

Hayat, Tasawar; Akram, Javaria; Alsaedi, Ahmed; Zahir, Hina

2018-03-01

Endoscopic and homogeneous-heterogeneous reactions in MHD peristalsis of Ree-Eyring fluid are addressed. Mathematical modeling and analysis have been performed by utilizing cylindrical coordinates. Nonlinear thermal radiation is present. Impact of slip boundary conditions on temperature and velocity on outer tube are taken into consideration. Lubrication approach is employed. The nonlinear system is executed numerically for solutions of velocity, temperature and concentration. Graphical results are obtained to predict physical interpretation of various embedded parameters. It is noted that homogeneous and heterogeneous reactions affect the concentration alternatively. Moreover Brinkman number rises the temperature and heat transfer coefficient whereas thermal slip drops temperature and heat transfer rate.

Spatially Partitioned Embedded Runge--Kutta Methods

KAUST Repository

Ketcheson, David I.

2013-10-30

We study spatially partitioned embedded Runge--Kutta (SPERK) schemes for partial differential equations (PDEs), in which each of the component schemes is applied over a different part of the spatial domain. Such methods may be convenient for problems in which the smoothness of the solution or the magnitudes of the PDE coefficients vary strongly in space. We focus on embedded partitioned methods as they offer greater efficiency and avoid the order reduction that may occur in nonembedded schemes. We demonstrate that the lack of conservation in partitioned schemes can lead to nonphysical effects and propose conservative additive schemes based on partitioning the fluxes rather than the ordinary differential equations. A variety of SPERK schemes are presented, including an embedded pair suitable for the time evolution of fifth-order weighted nonoscillatory spatial discretizations. Numerical experiments are provided to support the theory.

Spatially Partitioned Embedded Runge--Kutta Methods

KAUST Repository

Ketcheson, David I.; MacDonald, Colin B.; Ruuth, Steven J.

2013-01-01

We study spatially partitioned embedded Runge--Kutta (SPERK) schemes for partial differential equations (PDEs), in which each of the component schemes is applied over a different part of the spatial domain. Such methods may be convenient for problems in which the smoothness of the solution or the magnitudes of the PDE coefficients vary strongly in space. We focus on embedded partitioned methods as they offer greater efficiency and avoid the order reduction that may occur in nonembedded schemes. We demonstrate that the lack of conservation in partitioned schemes can lead to nonphysical effects and propose conservative additive schemes based on partitioning the fluxes rather than the ordinary differential equations. A variety of SPERK schemes are presented, including an embedded pair suitable for the time evolution of fifth-order weighted nonoscillatory spatial discretizations. Numerical experiments are provided to support the theory.

Modeling the geochemical distribution of rare earth elements (REEs using multivariate statistics in the eastern part of Marvast placer, the Yazd province

Directory of Open Access Journals (Sweden)

Amin Hossein Morshedy

2017-07-01

is to maximize both the similarity within each cluster and the difference between clusters, and finally find the structure in the data. Nowadays, cluster analysis is applied in many disciplines: biology, botany, medicine, psychology, geography, marketing, image processing, psychiatry, archaeology, etc. (Everitt et al., 2011. To execute a partitioning algorithm, the principal components analysis (PCA algorithm is applied for feature selection, feature extraction and dimension reduction. Hierarchical clustering can be utilized to provide a nested sequence of partitions with bottom-up or top-down methods based on similarity. The single linkage and complete linkage are the most popular hierarchical algorithms (Jain et al., 1999; Ji et al., 2007. Results and discussion The REE chondrite-normalized pattern for the eastern area in the Marvast placer represents a high match to the standard pattern of monazite. This pattern shows the positive anomaly of Ce and the negative anomaly of Eu. To determine the distribution of REEs concentration, 2D interpolation maps were plotted in three groups of light, middle, and heavy REEs (LREE, MREE, and HREE, which were indicated in the geochemical anomaly at the south and south-west of the area. The relative ratios of (LREE/HREE and (Ce/Eu exposed the high proportion of LREEs to HREEs. In the next section, the hierarchical clustering algorithm was employed to partition the data in the feature and sample levels. The elements portioning demonstrated four separated groups, which can be related to atomic and chemical structures. The studied region was divided into four zones by the clustering approach. The fourth zone confine coincided with the REE anomaly area. Finally, PCA was applied as the multivariate statistical tool to this dataset. Hence three principal components modeled over 90% of the variance. For the first component, the distribution map of load factor has a good agreement with anomaly area. References Alipour-Asll, M., Mirnejad

Determination of partition behavior of organic surrogates between paperboard packaging materials and air.

Science.gov (United States)

Triantafyllou, V I; Akrida-Demertzi, K; Demertzis, P G

2005-06-03

The suitability of recycled paperboard packaging materials for direct food contact applications is a major area of investigation. Chemical contaminants (surrogates) partitioning between recycled paper packaging and foods may affect the safety and health of the consumer. The partition behavior of all possible organic compounds between cardboards and individual foodstuffs is difficult and too time consuming for being fully investigated. Therefore it may be more efficient to determine these partition coefficients indirectly through experimental determination of the partitioning behavior between cardboard samples and air. In this work, the behavior of organic pollutants present in a set of two paper and board samples intended to be in contact with foods was studied. Adsorption isotherms have been plotted and partition coefficients between paper and air have been calculated as a basis for the estimation of their migration potential into food. Values of partition coefficients (Kpaper/air) from 47 to 1207 were obtained at different temperatures. For the less volatile surrogates such as dibutyl phthalate and methyl stearate higher Kpaper/air values were obtained. The adsorption curves showed that the more volatile substances are partitioning mainly in air phase and increasing the temperature from 70 to 100 degrees C their concentrations in air (Cair) have almost doubled. The analysis of surrogates was performed with a method based on solvent extraction and gas chromatographic-flame ionization detection (GC-FID) quantification.

Behaviour of Rare Earth Elements during the Earth's core formation

Science.gov (United States)

Faure, Pierre; Bouhifd, Mohamed Ali; Boyet, Maud; Hammouda, Tahar; Manthilake, Geeth

2017-04-01

Rare Earth Elements (REE) are classified in the refractory group, which means that they have a high temperature condensation and their volatility-controlled fractionation is limited to high-temperature processes. Anomalies have been measured for Eu, Yb and Sm, which are the REE with the lowest condensation temperatures in CAIs and chondrules (e.g. [1]). REE are particularly abundant in the sulfides of enstatite chondrites, 100 to 1000 times the CI value [e.g. 2,3], proving that these elements are not strictly lithophile under extremely reducing conditions. However by investigating experimentally the impact of Earth's core formation on the behavior of Sm and Nd, we have shown the absence of fractionation between Sm and Nd during the segregation of the metallic phase [4]. Recently, Wohlers and Wood [5] proposed that Nd and Sm could be fractionated in presence of a S-rich alloy phase. However, their results were obtained at pressure and temperature conditions below the plausible conditions of the Earth's core formation. Clearly, large pressure range needs to be covered before well-constrained model can be expected. Furthermore, our preliminary metal-silicate partitioning results show that Ce and Eu have higher metal/silicate partition coefficients than their neighboring elements, and that the presence of sulphur enhances the relative difference between partition coefficients. In this presentation, we will present and discuss new metal-silicate partition coefficients of all REE at a deep magma ocean at pressures ranging from those of the uppermost upper mantle ( 5 GPa) to a maximum pressure expected in the range of 20 GPa, temperatures ranging from 2500 to about 3000 K, and oxygen fugacities within IW-1 to IW-5 (1 to 5 orders of magnitude lower than the iron-wüstite buffer). We will discuss the effect of S, as well as the effect of H2O on the behaviour of REE during the Earth's core formation: recent models suggest that contrary to currently accepted beliefs, the

Partitioning and diffusion of PBDEs through an HDPE geomembrane.

Science.gov (United States)

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

Gas/aerosol Partitioning Parameterisation For Global Modelling: A Physical Interpretation of The Relationship Between Activity Coefficients and Relative Humidity

Science.gov (United States)

Metzger, S.; Dentener, F. J.; Lelieveld, J.; Pandis, S. N.

A computationally efficient model (EQSAM) to calculate gas/aerosol partitioning ofsemi-volatile inorganic aerosol components has been developed for use in global- atmospheric chemistry and climate models; presented at the EGS 2001.We introduce and discuss here the physics behind the parameterisation, upon whichthe EQuilib- rium Simplified Aerosol Model EQSAM is based. The parameterisation,which ap- proximates the activity coefficient calculation sufficiently accurately forglobal mod- elling, is based on a method that directly relates aerosol activitycoefficients to the ambient relative humidity, assuming chemical equilibrium.It therefore provides an interesting alternative for the computationally expensiveiterative activity coefficient calculation methods presently used in thermodynamicgas/aerosol equilibrium mod- els (EQMs). The parameterisation can be used,however, also in dynamical models that calculate mass transfer between theliquid/solid aerosol phases and the gas/phase explicitly; dynamical models oftenincorporate an EQM to calculate the aerosol com- position. The gain of theparameterisation is that the entire system of the gas/aerosol equilibrium partitioningcan be solved non-iteratively, a substantial advantage in global modelling.Since we have already demonstrated at the EGS 2001 that EQSAM yields similarresults as current state-of-the-art equilibrium models, we focus here on a dis- cussionof our physical interpretation of the parameterisation; the identification of theparameters needed is crucial. Given the lag of reliable data, the best way tothor- oughly validate the parameterisation for global modelling applications is theimple- mentation in current state-of-the-art gas/aerosol partitioning routines, whichare embe- ded in e.g. a global atmospheric chemistry transport model, by comparingthe results of the parameterisation against the ones based on the widely used activitycoefficient calculation methods (i.e. Bromley, Kussik-Meissner or Pitzer). Then

Seasonal and particle size-dependent variations in gas/particle partitioning of PCDD/Fs

International Nuclear Information System (INIS)

Lee, Se-Jin; Ale, Debaki; Chang, Yoon-Seok; Oh, Jeong-Eun; Shin, Sun Kyoung

2008-01-01

This study monitored particle size-dependent variations in atmospheric polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Two gas/particle partitioning models, the subcooled liquid vapor pressure (P L 0 ) and the octanol-air partition coefficient (K OA ) model, were applied to each particle sizes. The regression coefficients of each fraction against the gas/particle partition coefficient (K P ) were similar for separated particles within the same sample set but differed for particles collected during different periods. Gas/particle partitioning calculated from the integral of fractions was similar to that of size-segregated particles and previously measured bulk values. Despite the different behaviors and production mechanisms of atmospheric particles of different sizes, PCDD/F partitioning of each size range was controlled by meteorological conditions such as atmospheric temperature, O 3 and UV, which reflects no source related with certain particle size ranges but mixed urban sources within this city. Our observations emphasize that when assessing environmental and health effects, the movement of PCDD/Fs in air should be considered in conjunction with particle size in addition to the bulk aerosol. - Gas/particle partitioning of atmospheric PCDD/Fs for different particle sizes reflects the impacts of emitters of different size ranges

Variation of Rare Earth Elements (REEs) in the Sulu and Celebes ...

African Journals Online (AJOL)

This study provides a dataset of rare earth elements (REEs) in the seawater of Sulu and Celebes Seas of Malaysian waters during the PMSE 09' expedition, which was conducted to define the pattern of REEs in both seas. Samples were collected, filtered and pre-concentrated on-board ship then analyzed by using ICP-MS.

The 'Salting Out' Effect: Investigating the Influence of Both the Nature and Concentration of Salt on the Partition Coefficient of Butan-1,4-Dioic Acid

Science.gov (United States)

McCullagh, John

2018-01-01

This sixth-form chemistry activity describes how students can use acid-base titrimetry to investigate how adding salt to the aqueous phase may change the value of the partition coefficient of an organic acid between water and 2-methylpropan-1-ol. While the presence of lithium chloride and sodium chloride increases the value of the partition…

Determination and prediction of octanol-air partition coefficients of hydroxylated and methoxylated polybrominated diphenyl ethers.

Science.gov (United States)

Zhao, Hongxia; Xie, Qing; Tan, Feng; Chen, Jingwen; Quan, Xie; Qu, Baocheng; Zhang, Xin; Li, Xiaona

2010-07-01

The octanol-air partition coefficient (K(OA)) of 19 hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and 10 methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were measured as a function of temperature using a gas chromatographic retention time technique. At room temperature (298.15K), log K(OA) ranged from 8.30 for monobrominated OH/MeO-PBDEs to 13.29 for hexabrominated OH/MeO-PBDEs. The internal energies of phase change from octanol to air (Delta(OA)U) for 29 OH/MeO-PBDE congeners ranged from 72 to 126 kJ mol(-1). Using partial least-squares (PLS) analysis, a statistically quantitative structure-property relationship (QSPR) model for logK(OA) of OH/MeO-PBDE congeners was developed based on the 16 fundamental quantum chemical descriptors computed by PM3 Hamiltonian, for which the Q(cum)(2) was about 0.937. The molecular weight (Mw) and energy of the lowest unoccupied molecular orbital (E(LUMO)) were found to be main factors governing the log K(OA). 2010 Elsevier Ltd. All rights reserved.

QSAR models for predicting octanol/water and organic carbon/water partition coefficients of polychlorinated biphenyls.

Science.gov (United States)

Yu, S; Gao, S; Gan, Y; Zhang, Y; Ruan, X; Wang, Y; Yang, L; Shi, J

2016-04-01

Quantitative structure-property relationship modelling can be a valuable alternative method to replace or reduce experimental testing. In particular, some endpoints such as octanol-water (KOW) and organic carbon-water (KOC) partition coefficients of polychlorinated biphenyls (PCBs) are easier to predict and various models have been already developed. In this paper, two different methods, which are multiple linear regression based on the descriptors generated using Dragon software and hologram quantitative structure-activity relationships, were employed to predict suspended particulate matter (SPM) derived log KOC and generator column, shake flask and slow stirring method derived log KOW values of 209 PCBs. The predictive ability of the derived models was validated using a test set. The performances of all these models were compared with EPI Suite™ software. The results indicated that the proposed models were robust and satisfactory, and could provide feasible and promising tools for the rapid assessment of the SPM derived log KOC and generator column, shake flask and slow stirring method derived log KOW values of PCBs.

The Influence of Oxygen and Sulfur on Uranium Partitioning Into the Core

Science.gov (United States)

Moore, R. D., Jr.; Van Orman, J. A.; Hauck, S. A., II

2017-12-01

Uranium, along with K and Th, may provide substantial long-term heating in planetary cores, depending on the magnitude of their partitioning into the metal during differentiation. In general, non-metallic light elements are known to have a large influence on the partitioning of trace elements, and the presence of sulfur is known to enhance the partitioning of uranium into the metal. Data from the steelmaking literature indicate that oxygen also enhances the solubility of oxygen in liquid iron alloys. Here we present experimental data on the partitioning of U between immiscible liquids in the Fe-S-O system, and use these data along with published metal-silicate partitioning data to calibrate a quantitative activity model for U in the metal. We also determined partition coefficients for Th, K, Nb, Nd, Sm, and Yb, but were unable to fully constrain activity models for these elements with available data. A Monte Carlo fitting routine was used to calculate U-S, U-O, and U-S-O interaction coefficients, and their associated uncertainties. We find that the combined interaction of uranium with sulfur and oxygen is predominant, with S and O together enhancing the solubility of uranium to a far greater degree than either element in isolation. This suggests that uranium complexes with sulfite or sulfate species in the metal. For a model Mars core composition containing 14 at% S and 5 at% O, the metal/silicate partition coefficient for U is predicted to be an order of magnitude larger than for a pure Fe-Ni core.

REE behavior during weathering of basaltic rocks from the Lisbon Volcanic Complex (Portugal)

International Nuclear Information System (INIS)

Prudencio, M.I.; Cabral, J.M.P.; Sequeira Braga, M.A.

1991-01-01

Two weathering profiles developed in alkali basalts from the Lisbon Volcanic Complex were chosen for a REE behavior study. Profile 1 consists of a lava flow with porphyritic texture. Olivine and clinopyroxene are set in a groundmass which mainly comprises plagioclase, clinopyroxene, olivine, biotite, glass and Fe-Ti oxides. X-ray diffraction analysis of the 0 < 2μm fraction revealed: 45-95% smectites and 5-40% halloysite (7.3 angstrom), and Fe and/or Ti oxides. Profile 2 consists of a lava flow with an intergranular texture, where olivine, clinopyroxene and spinel grains are surrounded by large feldspars laths. The 0 < 2μ fraction consists of 80-100% halloysite (7.3 angstrom), < 20% micas and < 10% palygorskite and Fe and/or Ti oxides. The REE were determined by instrumental neutron activation analysis. The clay-sized fractions of the more weathered samples were separated and analyzed too. For the whole samples it was observed that: (1) when halloysites are the dominant clay-minerals (profile 2), REE are more retained in the profile and (2) in general the light REE are less concentrated in the profiles than the intermediate or even the heavy REE. In most weathered samples of profile 1 a significant loss of Ce was found. The REE in the 0 < 2μm fractions are in general enriched relative to the whole samples. In profile 1, where smectites dominate, a significant negative Ce anomaly is also present except for one sample collected at an intermediate level. Among the REE analyzed, Nd is the most enriched compared to the whole samples. In profile 2, where halloysites dominate and micas are present mainly at the bottom of the profile, it was observed that: (a) REE are less fractionated than in profile 1, (b) Ce is depleted at the bottom of the profile but increases upwards, so that at the top the 0 < 2μm fraction reveals a small positive anomaly relative to whole sample

The recovery of rare earth elements (REE) from beach sands

International Nuclear Information System (INIS)

Petrache, Cristina A.; Santos, Gabriel P. Jr.; Fernandez, Lourdes G.; Castillo, Marilyn K.; Tabora, Estrellita U; Intoy, Socorro P.; Reyes, Rolando Y.

2005-01-01

This preliminary study describes a metallurgical process that will extract, recover and produce REE oxides from beach sands obtained from Ombo, San Vicente, northern Palawan. The beach sands contain REE minerals of allanite and small amounts of monazite. Allanite is a sorosilicate mineral containing rare earths, thorium and uranium. Monazite is the anhydrous phosphate of cerium and the lanthanum group of rare earths with thorium commonly present in replacement for cerium and lanthanum. Collected beach sand were first pan-concentrated in-situ to produce heavy mineral concentrates. Screening using a 32 mesh (0.500 mm) sieve was done at the Nuclear Materials Research Laboratory to remove oversize sand particles. The -32 mesh fraction was treated with bromoform (sp. gr. 2.89) to separate the heavy minerals from siliceous gangue. Grinding to -325 mesh size (0.044mm) followed to liberate the minerals prior to leaching. Two acids leachants were used - concentrated HCl for the first trial and a mixture of concentrated HCl and HNO 3 (10:1 volume ratio) for the second trial. Both leaching trials were carried out at 180 o C for 7 hours or until dry. The resulting leached residues were re-dissolved in concentrated HCl and filtered. Ionquest R 801, an organophosphorous extractant, was added to the filtrate to separate the radioactive thorium from REE. Sodium hydroxide was added to the aqueous phase to precipitate the REE. After filtering the precipitate, it was dissolved in HCl. The acid solution was repeatedly extracted three (3) times with Ionquest R 801 to remove iron and other contaminants. Ammonium hydroxide was added to the final solution to precipitate the REE, which was then dried in the oven. The precipitate was calcined/roasted in the furnace at two different temperatures for different periods of time to burn off the organic matter and to form oxides. Results of the XRD analysis showed peaks of the calcined precipitate matching with the peaks of lanthanum oxide

REE enrichment in granite-derived regolith deposits of the southeast United States: Prospective source rocks and accumulation processes

Science.gov (United States)

Foley, Nora K.; Ayuso, Robert A.; Simandl, G.J.; Neetz, M.

2015-01-01

The Southeastern United States contains numerous anorogenic, or A-type, granites, which constitute promising source rocks for REE-enriched ion adsorption clay deposits due to their inherently high concentrations of REE. These granites have undergone a long history of chemical weathering, resulting in thick granite-derived regoliths, akin to those of South China, which supply virtually all heavy REE and Y, and a significant portion of light REE to global markets. Detailed comparisons of granite regolith profiles formed on the Stewartsville and Striped Rock plutons, and the Robertson River batholith (Virginia) indicate that REE are mobile and can attain grades comparable to those of deposits currently mined in China. A REE-enriched parent, either A-type or I-type (highly fractionated igneous type) granite, is thought to be critical for generating the high concentrations of REE in regolith profiles. One prominent feature we recognize in many granites and mineralized regoliths is the tetrad behaviour displayed in REE chondrite-normalized patterns. Tetrad patterns in granite and regolith result from processes that promote the redistribution, enrichment, and fractionation of REE, such as late- to post- magmatic alteration of granite and silicate hydrolysis in the regolith. Thus, REE patterns showing tetrad effects may be a key for discriminating highly prospective source rocks and regoliths with potential for REE ion adsorption clay deposits.

Rare earth element and strontium isotopic study of seamount-type limestones in Mesozoic accretionary complex of Southern Chichibu Terrane, central Japan. Implication for incorporation process of seawater REE into limestones

International Nuclear Information System (INIS)

Tanaka, Kazuya; Miura, Noriko; Asahara, Yoshihiro; Kawabe, Iwao

2003-01-01

Ishimaki and Tahara limestones occur as exotic blocks juxtaposed in the Mesozoic (Jurassic) accretionary complex of Southern Chichibu Terrane in eastern Aichi Prefecture, central Japan. They are supposed to be of the seamount-type limestone, since they have no terrigenous materials and are intimately associated with greenstones. REE (rare earth elements) and Sr isotopic studies for the limestones have been made in order to know their geochemical characteristics, ages and origins. Their 87 Sr/ 86 Sr ratios, when referred to the seawater 87 Sr/ 86 Sr curve and relevant geological data, suggest that Ishimaki and Tahara limestones are the late Permian and the Carboniferous to the Early Permian, respectively. Two greenstone fragments found inside the Ishimaki limestone block and one greenstone sample associated with Tahara limestone block, resemble the Hawaiian alkali basalt in the their REE and Y patterns. This is supporting the idea that the limestone blocks may be parts of reef limestones on ancient volcanic seamounts. All the limestone samples, except three unusual Tahara ones, show seawater REE and Y signatures in their chondrite-normalized patterns. Their REE/Ca ratios, however, are 10 2 -10 4 times as high as those ratios of modern biogenic carbonates like corals and the seawater. Accordingly, seawater REE and Y were incorporated into the limestones, when originally biogenic carbonates transformed into inorganic calcite and its secondary growths occurred in diagenesis in contact with sufficient seawater. This view is favored by the reported REE partition experiment between calcite overgrowths and seawater solution. The seawater Ce anomaly as a function of water depth in the modern ocean is a key to infer the water depth of the REE and Y incorporation. The Ce anomalies given by log (Ce/Ce*) for about a half of Ishimaki samples and most of Tahara ones are between -0.5 and -0.2, which are compatible with the shallow water origin. Another half of Ishimaki samples

Determination of the subcutaneous tissue to blood partition coefficient in patients with severe leg ischaemia by a double isotope washout technique

DEFF Research Database (Denmark)

Bjerre-Jepsen, K; Faris, I; Henriksen, O

1982-01-01

Knowledge of the tissue to blood partition coefficient (lambda) is essential for calculation of the perfusion coefficient in a single tissue based on measurements of the washout of locally injected isotopes. No measurements of lambda for Xenon in subcutaneous tissue in the leg have been done...... in patients with occlusive arterial disease. In 12 patients with occlusive arterial disease in the legs lambda for Xenon was determined in subcutaneous tissue in the calf region and foot as the ratio between the washout rate constant of 131I-Antipyrine and 133Xe. A mixture of the two indicators was injected....... Mean value was 3.7 ml X g-1 (range: 1 X 7-10 X 7) in the calf and 2 X 7 ml X g-1 (range: 1 X 2-4 X 9) in the foot. It is concluded that lambda measurements are necessary for determination of subcutaneous blood flow from 133Xe washout curves in these patients. Determination of lambda is especially...

Ion-adsorption REEs in regolith of the Liberty Hill pluton, South Carolina, USA: An effect of hydrothermal alteration

Science.gov (United States)

Bern, Carleton R.; Yesavage, Tiffany; Foley, Nora K.

2017-01-01

Ion-adsorbed rare earth element (REE) deposits supply the majority of world heavy REE production and substantial light REE production, but relatively little is known of their occurrence outside Southeast Asia. We examined the distribution and forms of REEs on a North American pluton located in the highly weathered and slowly eroding South Carolina Piedmont. The Hercynian Liberty Hill pluton experiences a modern climate that includes ~ 1500 mm annual rainfall and a mean annual temperature of 17 °C. The pluton is medium- to coarse-grained biotite-amphibole granite with minor biotite granite facies. REE-bearing phases are diverse and include monazite, zircon, titanite, allanite, apatite and bastnäsite. Weathered profiles were sampled up to 7 m-deep across the ~ 400 km2 pluton. In one profile, ion-adsorbed REEs plus yttrium (REE + Y) ranged up to 581 mg/kg and accounted for up to 77% of total REE + Y in saprolite. In other profiles, ion-adsorbed REE + Y ranged 12–194 mg/kg and only accounted for 3–37% of totals. The profile most enriched in ion-adsorbed REEs was located along the mapped boundary of two granite facies and contained trioctahedral smectite in the saprolite, evidence suggestive of hydrothermal alteration of biotite at that location. Post-emplacement deuteric alteration can generate easily weathered REE phases, particularly fluorocarbonates. In the case of Liberty Hill, hydrothermal alteration may have converted less soluble to more soluble REE minerals. Additionally, regolith P content was inversely correlated with the fraction ion-adsorbed REEs, and weathering related secondary REE-phosphates were found in some regolith profiles. Both patterns illustrate how low P content aids in the accumulation of ion-adsorbed REEs. The localized occurrence at Liberty Hill sheds light on conditions and processes that generate ion-adsorbed REEs.

Homology and cohomology of Rees semigroup algebras

DEFF Research Database (Denmark)

Grønbæk, Niels; Gourdeau, Frédéric; White, Michael C.

2011-01-01

Let S by a Rees semigroup, and let 1¹(S) be its convolution semigroup algebra. Using Morita equivalence we show that bounded Hochschild homology and cohomology of l¹(S) is isomorphic to those of the underlying discrete group algebra....

Partitioning of naphthalene, methylnaphthalenes and biphenyl between wastewater treatment sludges and water

International Nuclear Information System (INIS)

Southworth, G.R.; Keller, J.L.

1984-01-01

Partition coefficients (K/sub p/) describing the partitioning of naphthalene, methylnaphthalenes and biphenyl between organic-rich wastes and water were determined using 14 C-tracer techniques as well as high performance liquid chromatographic analysis of the wastes and their aqueous extracts. Results of the two procedures were in good agreement. The concentrations of the specific organics in the wastes were not good predictors of concentrations in aqueous extracts, since K/sub p/ varied among the materials tested. Predictions of k/sub p/ based on organic carbon content of the sludges were well below observed values. Oil content of the wastes and oil-water partition coefficients appeared to be important factors in determining K/sub p/. 11 references, 5 tables

Metal partitioning and uptake in central Ontario forests

International Nuclear Information System (INIS)

Watmough, Shaun A.; Dillon, Peter J.; Epova, Ekaterina N.

2005-01-01

Evaluation of the potential environmental risk posed by metals depends to a great extent on modeling the fate and mobility of metals with soil-solution partitioning coefficients (K d ). However, the effect of biological cycling on metal partitioning is rarely considered in standard risk assessments. We determined soil-solution partitioning coefficients for 5 metals (Cd, Zn, Pb, Co and Ni) at 46 forested sites that border the Precambrian Shield in central Ontario, where soil pH aq varied from 3.9 to 8.1. Foliage from the dominant tree species and forest floor samples were also collected from each site to compare their metal levels with K d predictions. Analogous to other studies, log K d values for all metals were predicted by empirical linear regression with soil pH (r 2 = 0.66-0.72), demonstrating that metal partitioning between soil and soil solution can be reliably predicted for relatively unpolluted forest mineral soils by soil pH. In contrast, whereas the so-called bioavailable water-soluble metal fraction could be predicted from soil pH, metal concentrations in foliage and the forest floor at each site were not consistently related to pH. Risk assessment of metals should take into account the role of biota in metal cycling and partitioning in forests, particularly if metal bio-accumulation and chronic toxicity in the food chain, rather than metal mobility in soils, are of primary concern. - Metal cycling by plants should be considered in risk assessment studies

The role of liquid-liquid immiscibility and crystal fractionation in the genesis of carbonatite magmas: insights from Kerimasi melt inclusions

Science.gov (United States)

Guzmics, Tibor; Zajacz, Zoltán; Mitchell, Roger H.; Szabó, Csaba; Wälle, Markus

2015-02-01

We have reconstructed the compositional evolution of the silicate and carbonate melt, and various crystalline phases in the subvolcanic reservoir of Kerimasi Volcano in the East African Rift. Trace element concentrations of silicate and carbonate melt inclusions trapped in nepheline, apatite and magnetite from plutonic afrikandite (clinopyroxene-nepheline-perovskite-magnetite-melilite rock) and calciocarbonatite (calcite-apatite-magnetite-perovskite-monticellite-phlogopite rock) show that liquid immiscibility occurred during the generation of carbonatite magmas from a CO2-rich melilite-nephelinite magma formed at relatively high temperatures (1,100 °C). This carbonatite magma is notably more calcic and less alkaline than that occurring at Oldoinyo Lengai. The CaO-rich (32-41 wt%) nature and alkali-"poor" (at least 7-10 wt% Na2O + K2O) nature of these high-temperature (>1,000 °C) carbonate melts result from strong partitioning of Ca (relative to Mg, Fe and Mn) in the immiscible carbonate and the CaO-rich nature (12-17 wt%) of its silicate parent (e.g., melilite-nephelinite). Evolution of the Kerimasi carbonate magma can result in the formation of natrocarbonatite melts with similar composition to those of Oldoinyo Lengai, but with pronounced depletion in REE and HFSE elements. We suggest that this compositional difference results from the different initial parental magmas, e.g., melilite-nephelinite at Kerimasi and a nephelinite at Oldoinyo Lengai. The difference in parental magma composition led to a significant difference in the fractionating mineral phase assemblage and the element partitioning systematics upon silicate-carbonate melt immiscibility. LA-ICP-MS analysis of coeval silicate and carbonate melt inclusions provides an opportunity to infer carbonate melt/silicate melt partition coefficients for a wide range of elements. These data show that Li, Na, Pb, Ca, Sr, Ba, B, all REE (except Sc), U, V, Nb, Ta, P, Mo, W and S are partitioned into the carbonate

Canonical partition functions: ideal quantum gases, interacting classical gases, and interacting quantum gases

Science.gov (United States)

Zhou, Chi-Chun; Dai, Wu-Sheng

2018-02-01

In statistical mechanics, for a system with a fixed number of particles, e.g. a finite-size system, strictly speaking, the thermodynamic quantity needs to be calculated in the canonical ensemble. Nevertheless, the calculation of the canonical partition function is difficult. In this paper, based on the mathematical theory of the symmetric function, we suggest a method for the calculation of the canonical partition function of ideal quantum gases, including ideal Bose, Fermi, and Gentile gases. Moreover, we express the canonical partition functions of interacting classical and quantum gases given by the classical and quantum cluster expansion methods in terms of the Bell polynomial in mathematics. The virial coefficients of ideal Bose, Fermi, and Gentile gases are calculated from the exact canonical partition function. The virial coefficients of interacting classical and quantum gases are calculated from the canonical partition function by using the expansion of the Bell polynomial, rather than calculated from the grand canonical potential.

Leachability of rare earth elements (REEs) from solid wastes generated during chemical processing of monazite

International Nuclear Information System (INIS)

Radhakrishnan, Sujata; Pillai, P.M.B.

2001-01-01

Studies have been carried out to assess the leachability of REEs from solid wastes generated in monazite processing. Leachability of REEs (La, Ce, Nd, Pr, Sm, Gd) and Y from PbS-Ba(Ra)SO 4 (Mixed cake) and Effluent Treatment Plant cake (calcium hydroxy apatite) has been studied using rain water as the leachant. Studies indicate that 23 -60 % of the REEs gets leached out from the mixed cake in the first 24 hours. From the ETP cake, the percentage of REEs leached out were negligible. The results provide inputs for hazards evaluation in accidental situations resulting in breach of integrity of the waste storages. (author)

Equilibrium partitioning of drug molecules between aqueous and amino acid ester-based ionic liquids

International Nuclear Information System (INIS)

Jing, Jun; Li, Zhiyong; Pei, Yuanchao; Wang, Huiyong; Wang, Jianji

2013-01-01

Highlights: ► Partition coefficients of twelve drug molecules in ILs have been determined. ► The possible mechanism has been investigated from 13 C NMR measurements. ► Hydrophobic π–π interaction is the main driving force for the partitioning of drug molecules. -- Abstract: In this work, a series of novel room temperature ionic liquids (ILs) have been synthesized with cheap, naturally α-amino acid ester as cations and bis(trifluoromethylsulfonyl)imide as anion. The glass transition temperature and thermal decomposition temperature of these ILs, partition coefficients of some coumarins and purine alkaloids between water and the amino acid ester-based ILs at T = 298.15 K, and Gibbs energy, enthalpy and entropy changes for the transfer of caffeine and 6,7-dihydroxycoumarin from water to [LeuC 2 ][Tf 2 N] have been determined. It is shown that these ILs are highly effective materials for the extraction of drug compounds like coumarin, 4-hydroxycoumarin, 7-hydroxycoumarin, 3-aminocoumarin, coumarin-3-carboxylic acid, 6,7-dihydroxycoumarin, 6,7-dihydroxy-4-methylcoumarin, caffeine, theobromine, theophylline, inosine, and 2,6-diaminopurine. The partition process is driven by enthalpy term, and partition coefficients of the drug molecules increase with the increase of hydrophobicity of both the drug molecules and the ILs. Furthermore, the possible partition mechanism has been investigated from 13 C NMR measurements

Uranium and REE recovery from Florida phosphates – Looking back and going forward

International Nuclear Information System (INIS)

Zhang, J.; Birky, B.

2014-01-01

Uranium recovered during the production of phosphoric acid represents a significant source of nuclear fuel as the gap between uranium supply and demand is expected to grow. The phosphate industry in Florida supplied uranium to both the defense and energy sectors in the past, but market conditions ended the recovery process. Currently, the uranium is retained in the phosphoric acid and the granulated fertilizer products, diammonium and monoammonium phosphate, and dispersed on farm fields as a trace element in blended fertilizers. This represents a loss to the nuclear fuel cycle that will never be recovered. In an era of heightened awareness of sustainability and increasing pressure to reduce greenhouse gas emissions, market conditions and social factors may converge to create favorable conditions for uranium recovery to resume. However, the future may not resemble the past as uranium concentrations are lower in the newer mining areas and ion exchange challenges solvent extraction for the extraction technology of choice. New factors will also influence both the economic decision to resume recovery operations, as well as the recovery technology. Rare earth elements (REE) are also present in the processing streams at recoverable levels, and can be co-extracted with uranium using the proven solvent extraction method. REE are vital to the phosphor industry, green energy development, and technology advances in many fields. However, the world has limited REE resources, and the recovery of REE from many of these resources is both economically challenging and environmentally troublesome. Phosphate as a secondary REE resource has a great potential to fill this gap. World annual phosphate rock production has surpassed 200 million tons, representing 60,000 tons of unrecovered REE assuming an average concentration of 300 ppm. In the case of Florida, REE in the phosphate ore reports to four mining and processing streams, with approximately 10% to flotation tailings, 30-40% to

REE bound proteins in natural plant fern Dicranopteris dichitoma by MAA

International Nuclear Information System (INIS)

Guo, F.Q.; Wang, Y.Q.; Sun, J.X.; Chen, H.M.

1996-01-01

Biochemical techniques, including pH variation, outsalting, ultracentrifugation, gel filtration chromatography and electrophoresis, etc., have been employed together with instrumental neutron activation analysis (INAA) to study the rare earth elements (REE) bound proteins in the natural plant fern, Dicranopteris dichitoma. INAA was also used to identify whether the proteins were bound firmly with REE. The results obtained show that two REE bound proteins (RBP-I and RBP-II) have been separated. The molecular weight of RBP-I on Sephadex G-200 gel column is about 8 x 10 5 Daltons and that of RBP-II is less than 12,400 Daltons, respectively. However, SDS-PAGE of the two proteins shows that they mainly have two protein subunits with MW 14,100 and 38,700 Daltons. They are probably conjugated proteins, glycoproteins with different glyco-units. (author). 22 refs., 7 figs., 1 tab

The partitioning of uranium and neptunium onto hydrothermally altered concrete

International Nuclear Information System (INIS)

Zhao, P.; Allen, P.G.; Sylwester, E.R.; Viani, B.E.

2000-01-01

Partition coefficients (K d ) of U(VI) and Np(V) on untreated and hydrothermally altered concrete were measured in 0.01 M NaCl and 0.01 M NaHCO 3 solutions as functions of concentration of the radionuclides, pH, and time. The partition coefficients for both U(VI) and Np(V) on hydrothermally altered concrete are significantly lower than those on untreated concrete. The partition of both U(VI) and Np(V) are pH dependent, although the pH dependence does not appear to reflect precipitation of U and Np-bearing phases. Both sorption and precipitation are likely processes controlling partitioning of U to concrete; sorption is the most likely process controlling the partitioning of Np to concrete. The presence of 0.01 M carbonate species in solution decreases K d of U(VI) for both hydrothermally altered and untreated concrete from ≥ 10 4 mL/g to ∝ 400 to 1000 mL/g indicating a significant impact on U(VI) sorption. In contrast, the presence of carbonate only reduced the K d of Np(V) by one order of magnitude or less. X-ray absorption spectroscopy analysis of U/concrete mixtures at different pHs and times indicate that uranyl ions are partitioned as monomeric species on untreated concrete, but oligomeric species on hydrothermally altered concrete. Similar analysis of Np/concrete mixtures shows that about half of the partitioned Np(V) is reduced to Np(IV) over a period of 6 months. (orig.)

REE-substituted Ca-free zirconolites

International Nuclear Information System (INIS)

Stefanovsky, S.V.; Chernyavskaya, N.E.; Ochkin, A.V.; Yudintsev, S.V.

2002-01-01

Previously we found zirconolite with composition (Gd 0.90 La 0.10 )(Zr 0.91 Ce 0.13 ) (Ti 1.20 Al 0.69 )O 7 in one of the ceramics designed for immobilization of REE-actinide HLW fraction. In this work we studied REEZrTiAlO 7 zirconolites with REE = La, Ce, Pr, Nd, Sm, Gd, Tb, and Y. To obtain the samples, the oxide mixtures were milled, compacted into pellets at 200 MPa and sintered at 1450 deg C or melted at 1550 deg C in air. To convert Ce (IV) to Ce (III), one test was performed in reducing conditions (carbon was introduced in batches). The ceramics were examined by X-ray diffraction (XRD) and by scanning and transmission electron microscopy (SEM, TEM). The XRD data revealed that the La-, Ce-, Pr-, and Nd-bearing samples were not single-phase ceramics. The La-bearing sample was composed of a major perovskite-type phase and a minor baddeleyite. The Ce-bearing samples consisted of major pyrochlore, cerianite-zirconia based cubic solid solution as a second in abundance phase, and minor zirconolite. The Pr-bearing ceramic contained major baddeleyite and a perovskite-type phase, and minor pyrochlore. In the Nd-, Sm-, Gd-, Tb-, and Y-bearing samples, zirconolite was predominant. Rare grains of REE-stabilized zirconia (fianite) were found by SEM in the Nd-, Sm, and Y-bearing ceramics. The Gd- and Tb-bearing samples were single phase. The average zirconolite formulas were Sm 1.06 Zr 1.07 Ti 1.00 Al 0.86 O 7 , Gd 1.01 Zr 1.05 Ti 0.98 Al 0.95 O 7 , Tb 0.93 Zr 1.09 Ti 1.08 Al 0.85 O 7 , and Y 1.05 Zr 1.03 Ti 1.03 Al 0.87 O 7 , hence, close to the specified zirconolite formula within the experimental error. XRD patterns of the Tb- and Y-bearing zirconolites are typical of zirconolite-2M variety. XRD patterns of the Nd-, Sm-, and Gd-bearing zirconolites differ from patterns typical of 2M, 3T, and 3O varieties known from reference data. The TEM study revealed a probable tetragonal symmetry of the zirconolite lattice on electron diffraction pattern

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

Science.gov (United States)

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

Railroad Engineering Education Symposium (REES) 2012 and 2014.

Science.gov (United States)

2016-01-25

Since its initial offering in 2008, the objective of the Railroad Engineering Education Symposium (REES) has been to develop interest among university faculty in railroad transportation engineering, with the goal of facilitating and supporting their ...

Determination of REE in urban park soils from Sao Paulo city for fingerprint of traffic emission contamination

International Nuclear Information System (INIS)

Figueiredo, Ana Maria G.; Camargo, Sonia P.; Sigolo, Joel B.

2009-01-01

The study of rare earth elements (REE) distribution in urban environments has become very interesting in the last years, due to the increasing industrial use of these elements. The REE La, Ce and Nd are used in automobile converter catalysts to stabilize the catalyst support and to enhance the oxidation of pollutants. The honeycomb structure has a typical association of a high Ce (and often also La) concentration combined with high concentrations of Platinum Group Elements. Due to thermal and mechanical wear of catalysts, fine particles enriched in REE are released to the environment. These catalyst particles can accumulate in urban soils, mainly in soils located near high density traffic roads. The aim of this paper was to study the REE distribution and ratios in surface soil samples collected in fourteen urban public parks of Sao Paulo city, to assess the influence of vehicular emissions. Instrumental Neutron Activation Analysis (INAA) was used for the REE analysis. The diagrams normalized to chondrite values showed an enrichment of the light REE (La to Sm), in contrast to the heavy REE (Eu to Lu), with a negative anomaly of Eu. The results obtained indicated that the enrichment in REE is not clearly attributed to vehicular traffic, because of high background values associated to the natural geological composition of the soils. (author)

Direct Measurements of Gas/Particle Partitioning and Mass Accommodation Coefficients in Environmental Chambers.

Science.gov (United States)

Krechmer, Jordan E; Day, Douglas A; Ziemann, Paul J; Jimenez, Jose L

2017-10-17

Secondary organic aerosols (SOA) are a major contributor to fine particulate mass and wield substantial influences on the Earth's climate and human health. Despite extensive research in recent years, many of the fundamental processes of SOA formation and evolution remain poorly understood. Most atmospheric aerosol models use gas/particle equilibrium partitioning theory as a default treatment of gas-aerosol transfer, despite questions about potentially large kinetic effects. We have conducted fundamental SOA formation experiments in a Teflon environmental chamber using a novel method. A simple chemical system produces a very fast burst of low-volatility gas-phase products, which are competitively taken up by liquid organic seed particles and Teflon chamber walls. Clear changes in the species time evolution with differing amounts of seed allow us to quantify the particle uptake processes. We reproduce gas- and aerosol-phase observations using a kinetic box model, from which we quantify the aerosol mass accommodation coefficient (α) as 0.7 on average, with values near unity especially for low volatility species. α appears to decrease as volatility increases. α has historically been a very difficult parameter to measure with reported values varying over 3 orders of magnitude. We use the experimentally constrained model to evaluate the correction factor (Φ) needed for chamber SOA mass yields due to losses of vapors to walls as a function of species volatility and particle condensational sink. Φ ranges from 1-4.

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

Science.gov (United States)

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.

Uncertain Henry's law constants compromise equilibrium partitioning calculations of atmospheric oxidation products

Directory of Open Access Journals (Sweden)

C. Wang

2017-06-01

Full Text Available Gas–particle partitioning governs the distribution, removal, and transport of organic compounds in the atmosphere and the formation of secondary organic aerosol (SOA. The large variety of atmospheric species and their wide range of properties make predicting this partitioning equilibrium challenging. Here we expand on earlier work and predict gas–organic and gas–aqueous phase partitioning coefficients for 3414 atmospherically relevant molecules using COSMOtherm, SPARC Performs Automated Reasoning in Chemistry (SPARC, and poly-parameter linear free-energy relationships. The Master Chemical Mechanism generated the structures by oxidizing primary emitted volatile organic compounds. Predictions for gas–organic phase partitioning coefficients (KWIOM/G by different methods are on average within 1 order of magnitude of each other, irrespective of the numbers of functional groups, except for predictions by COSMOtherm and SPARC for compounds with more than three functional groups, which have a slightly higher discrepancy. Discrepancies between predictions of gas–aqueous partitioning (KW/G are much larger and increase with the number of functional groups in the molecule. In particular, COSMOtherm often predicts much lower KW/G for highly functionalized compounds than the other methods. While the quantum-chemistry-based COSMOtherm accounts for the influence of intra-molecular interactions on conformation, highly functionalized molecules likely fall outside of the applicability domain of the other techniques, which at least in part rely on empirical data for calibration. Further analysis suggests that atmospheric phase distribution calculations are sensitive to the partitioning coefficient estimation method, in particular to the estimated value of KW/G. The large uncertainty in KW/G predictions for highly functionalized organic compounds needs to be resolved to improve the quantitative treatment of SOA formation.

Tinjauan Kemungkinan Sebaran Unsur Tanah Jarang (REE di Lingkungan Panas Bumi

Directory of Open Access Journals (Sweden)

Danny Zulkifli Herman

2014-06-01

Full Text Available http://dx.doi.org/10.17014/ijog.vol4no1.20091Geothermal areas occur mainly in an environment of volcanic/magmatic arc where magma chambers play a role as heat sources. The environment is situated within the convergent plate boundaries. A variety of igneous rocks is associated with this environment ranging from basalt (gabbro to rhyolite (granite but andesite is normally the most abundant igneous rock. The most obvious geothermal indications are exhibited by some surface manifestations comprising hot water seepage, fumaroles, hot spring, geyser, and hydrotermal alteration zones which are being evidences of an active hydrothermal system beneath the surface as a part of volcanism. Despite being a causal factor for alteration of country rocks, most hydrothermal fluids enable to change distribution pattern and content of rare earth elements (REE for instance Ce, Eu, La, Lu, Sm, Nd, and Y particularly during a reaction process. This may have a connection with development of element mobility rates, whilst the characteristics of REE pattern within hydrothermal fluid would have a high variable due to dependency of their original magma source. Considering the important role of hydrothermal fluid in REE mobility development, it is inspired to review the possible relationship of active hydrothermal system and potency of REE distribution pattern in areas of geothermal manifestation.  

Prediction of octanol-air partition coefficients for polychlorinated biphenyls (PCBs) using 3D-QSAR models.

Science.gov (United States)

Chen, Ying; Cai, Xiaoyu; Jiang, Long; Li, Yu

2016-02-01

Based on the experimental data of octanol-air partition coefficients (KOA) for 19 polychlorinated biphenyl (PCB) congeners, two types of QSAR methods, comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA), are used to establish 3D-QSAR models using the structural parameters as independent variables and using logKOA values as the dependent variable with the Sybyl software to predict the KOA values of the remaining 190 PCB congeners. The whole data set (19 compounds) was divided into a training set (15 compounds) for model generation and a test set (4 compounds) for model validation. As a result, the cross-validation correlation coefficient (q(2)) obtained by the CoMFA and CoMSIA models (shuffled 12 times) was in the range of 0.825-0.969 (>0.5), the correlation coefficient (r(2)) obtained was in the range of 0.957-1.000 (>0.9), and the SEP (standard error of prediction) of test set was within the range of 0.070-0.617, indicating that the models were robust and predictive. Randomly selected from a set of models, CoMFA analysis revealed that the corresponding percentages of the variance explained by steric and electrostatic fields were 23.9% and 76.1%, respectively, while CoMSIA analysis by steric, electrostatic and hydrophobic fields were 0.6%, 92.6%, and 6.8%, respectively. The electrostatic field was determined as a primary factor governing the logKOA. The correlation analysis of the relationship between the number of Cl atoms and the average logKOA values of PCBs indicated that logKOA values gradually increased as the number of Cl atoms increased. Simultaneously, related studies on PCB detection in the Arctic and Antarctic areas revealed that higher logKOA values indicate a stronger PCB migration ability. From CoMFA and CoMSIA contour maps, logKOA decreased when substituents possessed electropositive groups at the 2-, 3-, 3'-, 5- and 6- positions, which could reduce the PCB migration ability. These results are

Modular invariant partition functions for toroidally compactified bosonic string

International Nuclear Information System (INIS)

Ardalan, F.; Arfaei, H.

1988-06-01

We systematically find all the modular invariant partition functions for the toroidally compactified closed bosonic string defined on a subset of a simply laced simple Lie algebra lattice, or equivalently for the closed bosonic string moving on a group manifold with the WZW coefficient k=1. We examine the relation between modular invariance of partition function and the possibility of describing it by an even Lorentzian self dual lattice in our context. (author). 23 refs

A selected thermodynamic database for REE to be used in HLNW performance assessment exercises

Energy Technology Data Exchange (ETDEWEB)

Spahiu, K; Bruno, J [MBT Tecnologia Ambiental, Cerdanyola (Spain)

1995-01-01

A selected thermodynamic database for the Rare Earth Elements (REE) to be used in the safety assessment of high-level nuclear waste deposition has been compiled. Thermodynamic data for the aqueous species of the REE with the most important ligands relevant for granitic groundwater conditions have been selected and validated. The dominant soluble species under repository conditions are the carbonate complexes of REE. The solubilities of the oxides, hydroxides, carbonates, hydroxycarbonates, phosphates and other important solids have been selected and validated. Solubilities and solubility limiting solids in repository conditions have been estimated with the selected database. At the initial stages of fuel dissolution, the UO{sub 2} matrix dissolution will determine the concentrations of REE. Later on, solid phosphates, hydroxycarbonates and carbonates may limit their solubility. Recommendations for further studies on important systems in repository conditions have been presented. 136 refs, 13 figs, 16 tabs.

A selected thermodynamic database for REE to be used in HLNW performance assessment exercises

International Nuclear Information System (INIS)

Spahiu, K.; Bruno, J.

1995-01-01

A selected thermodynamic database for the Rare Earth Elements (REE) to be used in the safety assessment of high-level nuclear waste deposition has been compiled. Thermodynamic data for the aqueous species of the REE with the most important ligands relevant for granitic groundwater conditions have been selected and validated. The dominant soluble species under repository conditions are the carbonate complexes of REE. The solubilities of the oxides, hydroxides, carbonates, hydroxycarbonates, phosphates and other important solids have been selected and validated. Solubilities and solubility limiting solids in repository conditions have been estimated with the selected database. At the initial stages of fuel dissolution, the UO 2 matrix dissolution will determine the concentrations of REE. Later on, solid phosphates, hydroxycarbonates and carbonates may limit their solubility. Recommendations for further studies on important systems in repository conditions have been presented. 136 refs, 13 figs, 16 tabs

Using REE tracers to measure sheet erosion changing to rill erosion

International Nuclear Information System (INIS)

Liu Puling; Xue Yazhou; Song Wei; Wang Mingyi; Ju Tongjun

2004-01-01

Rare Earth Elements (REE) tracer method was used to study sheet erosion changing to rill erosion on slope land. By placing different rare earth elements of different soil depth across a slope in an indoor plot, two simulated rainfalls were applied to study the change of erosion type and the rill erosion process. The results indicate that the main erosion type is sheet erosion at the beginning of the rainfalls, and serious erosion happens after rill erosion appears. Accumulated sheet and rill erosion amounts increase with the rainfalls time. The percentage of sheet erosion amount decreases and rill erosion percentage increases with time. At the end of the rainfalls, the total rill erosion amounts are 4-5 times more than sheet erosion. In this paper, a new REE tracer method was used to quantitatively distinguish sheet and rill erosion amounts. The new REE tracer method should be useful to future studying of erosion processes on slope lands. (authors)

High contents of rare earth elements (REEs) in stream waters of a Cu-Pb-Zn mining area.

Science.gov (United States)

Protano, G; Riccobono, F

2002-01-01

Stream waters draining an old mining area present very high rare earth element (REE) contents, reaching 928 microg/l as the maximum total value (sigmaREE). The middle rare earth elements (MREEs) are usually enriched with respect to both the light (LREEs) and heavy (HREEs) elements of this group, producing a characteristic "roof-shaped" pattern of the shale Post-Archean Australian Shales-normalized concentrations. At the Fenice Capanne Mine (FCM), the most important base metal mine of the study area, the REE source coincides with the mine tailings, mostly the oldest ones composed of iron-rich materials. The geochemical history of the REEs released into Noni stream from wastes in the FCM area is strictly determined by the pH, which controls the REE speciation and in-stream processes. The formation of Al-rich and mainly Fe-rich flocs effectively scavenges the REEs, which are readily and drastically removed from the solution when the pH approaches neutrality. Leaching experiments performed on flocs and waste materials demonstrate that Fe-oxides/oxyhydroxides play a key role in the release of lanthanide elements into stream waters. The origin of the "roof-shaped" REE distribution pattern as well as the peculiar geochemical behavior of some lanthanide elements in the aqueous system are discussed.

Experimental determination of trace-element partitioning between pargasite and a synthetic hydrous andesitic melt

Science.gov (United States)

Brenan, J. M.; Shaw, H. F.; Ryerson, F. J.; Phinney, D. L.

1995-10-01

In order to more fully establish a basis for quantifying the role of amphibole in trace-element fractionation processes, we have measured pargasite/silicate melt partitioning of a variety of trace elements (Rb, Ba, Nb, Ta, Hf, Zr, Ce, Nd, Sm, Yb), including the first published values for U, Th and Pb. Experiments conducted at 1000°C and 1.5 GPa yielded large crystals free of compositional zoning. Partition coefficients were found to be constant at total concentrations ranging from ˜ 1 to > 100 ppm, indicating Henry's Law is oparative over this interval. Comparison of partition coefficients measured in this study with previous determinations yields good agreement for similar compositions at comparable pressure and temperature. The compatibility of U, Th and Pb in amphibole decreases in the order Pb > Th > U. Partial melting or fractional crystallization of amphibole-bearing assemblages will therefore result in the generation of excesses in 238U activity relative to 230Th, similar in magnitude to that produced by clinopyroxene. The compatibility of Pb in amphibole relative to U or Th indicates that melt generation in the presence of residual amphibole will result in the long-term enrichment in Pb relative to U or Th in the residue. This process is therefore incapable of producing the depletion in Pb relative to U or Th inferred from the Pb isotopic composition of MORB and OIB. Comparison of partition coefficients measured in this study with previous values for clinopyroxene allows some distinction to be made between expected trace-element fractionations produced during dry (cpx present) and wet (cpx + amphibole present) melting. Rb, Ba, Nb and Ta are dramatically less compatible in clinopyroxene than in amphibole, whereas Th, U, Hf and Zr have similar compatibilities in both phases. Interelement fractionations, such as DNb/DBa are also different for clinopyroxene and amphibole. Changes in certain ratios, such as Ba/Nb, Ba/Th, and Nb/Th within comagmatic suites may

Trace element partitioning between plagioclase and melt: An investigation of the impact of experimental and analytical procedures

Science.gov (United States)

Nielsen, Roger L.; Ustunisik, Gokce; Weinsteiger, Allison B.; Tepley, Frank J.; Johnston, A. Dana; Kent, Adam J. R.

2017-09-01

Quantitative models of petrologic processes require accurate partition coefficients. Our ability to obtain accurate partition coefficients is constrained by their dependence on pressure temperature and composition, and on the experimental and analytical techniques we apply. The source and magnitude of error in experimental studies of trace element partitioning may go unrecognized if one examines only the processed published data. The most important sources of error are relict crystals, and analyses of more than one phase in the analytical volume. Because we have typically published averaged data, identification of compromised data is difficult if not impossible. We addressed this problem by examining unprocessed data from plagioclase/melt partitioning experiments, by comparing models based on that data with existing partitioning models, and evaluated the degree to which the partitioning models are dependent on the calibration data. We found that partitioning models are dependent on the calibration data in ways that result in erroneous model values, and that the error will be systematic and dependent on the value of the partition coefficient. In effect, use of different calibration datasets will result in partitioning models whose results are systematically biased, and that one can arrive at different and conflicting conclusions depending on how a model is calibrated, defeating the purpose of applying the models. Ultimately this is an experimental data problem, which can be solved if we publish individual analyses (not averages) or use a projection method wherein we use an independent compositional constraint to identify and estimate the uncontaminated composition of each phase.

Chromatographic retention prediction and octanol-water partition coefficient determination of monobasic weak acidic compounds in ion-suppression reversed-phase liquid chromatography using acids as ion-suppressors.

Science.gov (United States)

Ming, Xin; Han, Shu-ying; Qi, Zheng-chun; Sheng, Dong; Lian, Hong-zhen

2009-08-15

Although simple acids, replacing buffers, have been widely applied to suppress the ionization of weakly ionizable acidic analytes in reversed-phase liquid chromatography (RPLC), none of the previously reported works focused on the systematic studies about the retention behavior of the acidic solutes in this ion-suppression RPLC mode. The subject of this paper was therefore to investigate the retention behavior of monobasic weak acidic compounds using acetic, perchloric and phosphoric acids as the ion-suppressors. The apparent octanol-water partition coefficient (K" ow) was proposed to calibrate the octanol-water partition coefficient (K(ow)) of these weak acidic compounds, which resulted in a better linear correlation with log k(w), the logarithm of the hypothetical retention factor corresponding to neat aqueous fraction of hydroorganic mobile phase. This log K" ow-log k w linear correlation was successfully validated by the results of monocarboxylic acids and monohydrating phenols, and moreover by the results under diverse experimental conditions for the same solutes. This straightforward relationship not only can be used to effectively predict the retention values of weak acidic solutes combined with Snyder-Soczewinski equation, but also can offer a promising medium for directly measuring K(ow) data of these compounds via Collander equation. In addition, the influence of the different ion-suppressors on the retention of weak acidic compounds was also compared in this RPLC mode.

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

Energy Technology Data Exchange (ETDEWEB)

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.

Metal-silicate Partitioning and Its Role in Core Formation and Composition on Super-Earths

Energy Technology Data Exchange (ETDEWEB)

Schaefer, Laura; Petaev, M. I.; Sasselov, Dimitar D. [Harvard-Smithsonian Center for Astrophysics, 60 Garden St., Cambridge, MA 02138 (United States); Jacobsen, Stein B.; Remo, John L., E-mail: lschaefer@asu.edu [Harvard University, Department of Earth and Planetary Sciences, 20 Oxford St., Cambridge, MA 02138 (United States)

2017-02-01

We use a thermodynamic framework for silicate-metal partitioning to determine the possible compositions of metallic cores on super-Earths. We compare results using literature values of the partition coefficients of Si and Ni, as well as new partition coefficients calculated using results from laser shock-induced melting of powdered metal-dunite targets at pressures up to 276 GPa, which approaches those found within the deep mantles of super-Earths. We find that larger planets may have little to no light elements in their cores because the Si partition coefficient decreases at high pressures. The planet mass at which this occurs will depend on the metal-silicate equilibration depth. We also extrapolate the equations of state (EOS) of FeO and FeSi alloys to high pressures, and present mass–radius diagrams using self-consistent planet compositions assuming equilibrated mantles and cores. We confirm the results of previous studies that the distribution of elements between mantle and core will not be detectable from mass and radius measurements alone. While observations may be insensitive to interior structure, further modeling is sensitive to compositionally dependent properties, such as mantle viscosity and core freeze-out properties. We therefore emphasize the need for additional high pressure measurements of partitioning as well as EOSs, and highlight the utility of the Sandia Z-facilities for this type of work.

Apatite in carbonatitic rocks: Compositional variation, zoning, element partitioning and petrogenetic significance

Science.gov (United States)

Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Zaitsev, Anatoly N.; Couëslan, Christopher; Xu, Cheng; Kynický, Jindřich; Mumin, A. Hamid; Yang, Panseok

2017-03-01

-spectroscopy proved inconclusive for apatites with small P-site deficiencies and other substituent elements in this site. Indicator REE ratios sensitive to redox conditions (δCe, δEu) and hydrothermal overprint (δY) form a fairly tight cluster of values (0.8-1.3, 0.8-1.1 and 0.6-0.9, respectively) and may be used in combination with trace-element abundances for the development of geochemical exploration tools. Hydrothermal apatite forms in carbonatites as the product of replacement of primary apatite, or is deposited in fractures and interstices as euhedral crystals and aggregates associated with typical late-stage minerals (e.g., quartz and chlorite). Hydrothermal apatite is typically depleted in Sr, REE, Mn and Th, but enriched in F (up to 4.8 wt.%) relative to its igneous precursor, and also differs from the latter in at least some of key REE ratios [e.g., shows (La/Yb)cn ≤ 25, or a negative Ce anomaly]. The only significant exception is Sr(± REE,Na)-rich replacement zones and overgrowths on igneous apatite from some dolomite(-bearing) carbonatites. Their crystallization conditions and source fluid appear to be very different from the more common Sr-REE-depleted variety. Based on the new evidence presented in this work, trace-element partitioning between apatite and carbonatitic magmas, phosphate solubility in these magmas, and compositional variation of apatite-group minerals from spatially associated carbonatitic rocks are critically re-evaluated.

Selective electrochemical extraction of REEs from NdFeB magnet waste at room temperature

NARCIS (Netherlands)

Venkatesan, P.; Vander Hoogerstraete, Tom; Hennebel, Tom; Binnemans, Koen; Sietsma, J.; Yang, Y.

2018-01-01

NdFeB magnet waste is one of the important secondary resources from which rare-earth elements (REEs) can be recovered. Herein we present an electrochemical route to selectively extract REEs from the magnet waste at room temperature. First, the magnet waste was partially leached with HCl. The

Control of methanol vapours in a biotrickling filter: performance analysis and experimental determination of partition coefficient.

Science.gov (United States)

Avalos Ramirez, Antonio; Peter Jones, J; Heitz, Michéle

2009-02-01

Methanol vapours were treated in a biotrickling filter (BTF) packed with inert polypropylene spheres. The effects of the nitrogen concentration in the nutrient solution, the empty bed residence time (EBRT) and the methanol inlet concentration, on the BTF performance, were all examined. The elimination capacity (EC), the biomass and the carbon dioxide production rates were all increased with the rising of the nitrogen concentration and the EBRT. The EC also rose with increasing methanol inlet load (IL) when the methanol inlet concentration and the EBRT were varied, from 0.3 to 37.0 g m(-3), and from 20 to 65 s, respectively. The BTF reached its maximum EC level of 2160 g m(-3) h(-1) when it was operated at an IL level of 3700 g m(-3) h(-1). The input methanol was removed through two mechanisms: biodegradation and absorption in the liquid phase. The partition coefficient for the methanol in the BTF was determined at five EBRTs and along the packed bed. It generally followed the Henry model, having an average value of 2.64 x 10(-4)[mol L(-1)](gas)/[mol L(-1)](liquid).

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

Science.gov (United States)

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

2016-06-01

Octanol/water (K(OW)) and octanol/air (K(OA)) partition coefficients are two important physicochemical properties of organic substances. In current practice, K(OW) and K(OA) 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 K(OW) and K(OA). 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 K(OW) and log K(OA) 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 K(OW) and K(OA) of PCBs. Copyright © 2016 Elsevier Inc. All rights reserved.

Hydrothermal mobilization of pegmatite-hosted REE and Zr at Strange Lake, Canada: A reaction path model

Science.gov (United States)

Gysi, Alexander P.; Williams-Jones, Anthony E.

2013-12-01

Petrological and geochemical observations of pegmatites in the Strange Lake pluton, Canada, have been combined with numerical simulations to improve our understanding of fluid-rock interaction in peralkaline granitic systems. In particular, they have made it possible to evaluate reaction paths responsible for hydrothermal mobilization and mineralization of rare earth elements (REE) and Zr. The focus of the study was the B-Zone in the northwest of the pluton, which contains a pegmatite swarm and is the target of exploration for an economically exploitable REE deposit. Many of the pegmatites are mineralogically zoned into a border consisting of variably altered primary K-feldspar, arfvedsonite, quartz, and zirconosilicates, and a core rich in quartz, fluorite and exotic REE minerals. Textural relationships indicate that the primary silicate minerals in the pegmatites were leached and/or replaced during acidic alteration by K-, Fe- and Al-phyllosilicates, aegirine, hematite, fluorite and/or quartz, and that primary zirconosilicates (e.g., elpidite) were replaced by gittinsite and/or zircon. Reaction textures recording coupled dissolution of silicate minerals and crystallization of secondary REE-silicates indicate hydrothermal mobilization of the REE. The mobility of the light (L)REE was limited by the stability of REE-F-(CO2)-minerals (basnäsite-(Ce) and fluocerite-(Ce)), whereas zirconosilicates and secondary gadolinite-group minerals controlled the mobility of Zr and the heavy (H)REE. Hydrothermal fluorite and fluorite-fluocerite-(Ce) solid solutions are interpreted to indicate the former presence of F-bearing saline fluids in the pegmatites. Numerical simulations show that the mobilization of REE and Zr in saline HCl-HF-bearing fluids is controlled by pH, ligand activity and temperature. Mobilization of Zr is significant in both saline HF- and HCl-HF-bearing fluids at low temperature (250 °C). In contrast, the REE are mobilized by saline HCl-bearing fluids

Reaction of seawater with fresh mid-ocean ridge gabbro creates ';atypical' REE pattern and high REE fluid fluxes: Experiments at 425 and 475 °C, 400 and 1000 bar

Science.gov (United States)

Beermann, O.; Garbe-Schönberg, D.; Holzheid, A. D.

2013-12-01

High-temperature MOR hydrothermalism significantly affects ocean chemistry. The Sisters Peak (SP) hydrothermal field at 5°S on the slow-spreading Mid-Atlantic Ridge (MAR) emanates fluids >400°C [1] that have high concentrations of H2, transition metals, and rare earth elements (REE) exhibiting ';atypical' REE pattern characterized by depletions of LREE and HREE relative to MREE and no Eu anomaly [2]. This is in contrast to the ';typical' LREE enrichment and strong positive Eu anomaly known from many MOR vent fluids observed world-wide [e.g., 3]. Besides temperature, the seawater-to-rock ratio (w/r ratio) has significant control on the fluid chemistry [e.g., 4, 5]. To understand how vent fluid REE-signatures are generated during water-rock interaction processes we reacted unaltered gabbro with natural bottom seawater at 425 °C and 400 bar and at 425 and 475 °C at 1000 bar at variable w/r (mass) ratios ranging from 0.5-10 by using cold seal pressure vessels (CSPV). The run durations varied from 3-72 h. Reacted fluids were analysed for major and trace elements by ICP-OES and ICP-MS. In our experiments, ';atypical' REE fluid pattern similar to those of SP fluids were obtained at high w/r ratio (5 and 10) that might be characteristic for focused fluid-flow along e.g., detachment faults at slow-spreading MOR [6]. In contrast, more ';typical'-like REE pattern with elevated LREE and slightly positive Eu anomalies have been reproduced at low w/r ratio (0.5-1). Results of numerical simulations imply that strong positive Eu anomalies of fluids and altered gabbro from high temperature MOR hydrothermal systems can be created by intense rock leaching processes at high w/r ratio (5-10). This suggests that hydrothermal circulation through the ocean crust creates ';typical' REE fluid pattern with strong positive Eu anomalies if seawater reacts with gabbroic host rock that has been already leached in REE at high fluid fluxes. Simulations of the temporal chemical evolution of

REE Distribution in Cultivated and No Cultivated Soils in Two Viticultural Areas of Central Chile: Mineralogical, Pedological and Anthropic Influences

Science.gov (United States)

Castillo, P.; Townley, B.; Aburto, F.

2017-12-01

Within the scope of a Corfo-Innova Project (I+D Wines of Chile-University of Chile) we have recognized remarkable REE patterns in soils of two vineyards located in traditional vinicultural areas: Casablanca and Santa Cruz. Both vineyards have granitic parent rock, with similar petrographic features and REE patterns. We studied REE distribution on twelve cultivated soil profiles at each vineyard, where a full mineralogical, geochemical and pedogenic sampling and characterization was performed. To establish the effect of management no cultivated soil profiles were included from each vineyard location. REE in soil samples were measured by ICP-MS using two digestion methods: lithium metaborate/tetraborate fusion to obtain REE contents in total soil and MMI® partial extraction technique for REE contents on bioavailable phases.Soils display similar signatures of REEs respect to the rock source at both vineyards, but showing relative enrichments in soils of Casablanca and depletion in soils of Santa Cruz. Bioavailable phase data indicates a relative depletion of LREEs compared to HREEs and different anomalies for Ce (positive vs negative) in different areas of the same vineyard. Similar patterns of soils and parent rock suggest that REEs are adequate tracers of lithological source. Enrichments and/or depletions of REE patterns in soils respect to the rock source and Ce anomalies, evidence differential pedogenetic processes occurring at each sampled site. Results of bioavailable phase are coherent with the immobilization and fractionation of LREEs by stable minerals within soils as clays and Fe oxides. Mineralogical results in soil thin sections of Casablanca evidence the occurrence of Ti phases as sphene, ilmenite and rutile, which probably control the relative REE enrichment, since these minerals are considered more stable under pedogenic conditions.Finally, cultivated soils show a depleted but analogous pattern of REE regarding to no cultivated soil, indicating the

SVOC partitioning between the gas phase and settled dust indoors

Science.gov (United States)

Weschler, Charles J.; Nazaroff, William W.

2010-09-01

Semivolatile organic compounds (SVOCs) are a major class of indoor pollutants. Understanding SVOC partitioning between the gas phase and settled dust is important for characterizing the fate of these species indoors and the pathways by which humans are exposed to them. Such knowledge also helps in crafting measurement programs for epidemiological studies designed to probe potential associations between exposure to these compounds and adverse health effects. In this paper, we analyze published data from nineteen studies that cumulatively report measurements of dustborne and airborne SVOCs in more than a thousand buildings, mostly residences, in seven countries. In aggregate, measured median data are reported in these studies for 66 different SVOCs whose octanol-air partition coefficients ( Koa) span more than five orders of magnitude. We use these data to test a simple equilibrium model for estimating the partitioning of an SVOC between the gas phase and settled dust indoors. The results demonstrate, in central tendency, that a compound's octanol-air partition coefficient is a strong predictor of its abundance in settled dust relative to its gas phase concentration. Using median measured results for each SVOC in each study, dustborne mass fractions predicted using Koa and gas-phase concentrations correlate reasonably well with measured dustborne mass fractions ( R2 = 0.76). Combined with theoretical understanding of SVOC partitioning kinetics, the empirical evidence also suggests that for SVOCs with high Koa values, the mass fraction in settled dust may not have sufficient time to equilibrate with the gas phase concentration.

Rare earth elements (REEs in vertebrate microremains from the upper Pridoli Ohesaare beds of Saaremaa Island, Estonia: geochemical clues to palaeoenvironment c

Directory of Open Access Journals (Sweden)

Živilė Žigaitė

2015-02-01

Full Text Available Rare earth element (REE compositions of Nostolepis sp. scales, spines, plates and tesserae from Ohesaare bone beds were measured by in situ microsampling using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS. The obtained REE concentrations, normalized to Post-Archean Australian Shale concentrations, were evaluated using basic geochemical calculations and quantifications. The REE compositions were nearly identical across all the morphotypes and histologies of Nostolepis microremains, showing flat REE patterns with slight depletion in heavy REEs. There was no visible enrichment in middle REEs, indicating good geochemical preservation of bioapatite and absence of any pronounced fractionated REE incorporation during later stages of diagenesis. The shale-normalized (La/YbSN and (La/SmSN REE ratio compilations indicated adsorption as the dominating REE uptake mechanism across all datapoints. The absence of well-defined Ce anomaly suggested oxic palaeoseawater conditions, which agrees with the existing interpretations of the Ohesaare sequence as high-energy shoal and regressive open ocean sedimentary environments.

Study on REE bound proteins in natural plant fern dicranopteris dichotomy by MAA

International Nuclear Information System (INIS)

Guo Fanqing; Wang Yuqi; Sun Jingxing; Chen Hongmin; Xu Lei; Cao Guoyin

1997-01-01

Biochemical techniques, including pH variation, outsalting, ultracentrifugation, gel filtration chromatography and electrophoresis, etc., have been employed together with instrumental neutron activation analysis (INAA) to study the rare earth elements (REE) bound proteins in the natural plant fern, Dicranopteris dichotomy. INAA was also used to identify whether the proteins were bound firmly with REE. The results obtained show that two REE bound proteins (RBP-I and RBP-II) have been separated. The molecular mass (molecular weight, MW) of RBP-I on Sephadex G-200 gel column is about 8 x 10 5 and that of RBP-II is less than 12400, respectively. However, SDS-PAGE of the two proteins shows that they mainly have two protein subunits with MW 14100 and 38700. They are probably conjugated proteins, glycoproteins with different glycol-units

Determination of the pK values of 5-aminosalicylic acid and N-acetylaminosalicylic acid and comparison of the pH dependent lipid-water partition coefficients of sulphasalazine and its metabolites.

Science.gov (United States)

Allgayer, H; Sonnenbichler, J; Kruis, W; Paumgartner, G

1985-01-01

Sulphasalazine (SASP), used in the treatment of inflammatory bowel disease, is split into sulphapyridine (SP) and 5-aminosalicylic acid (5-ASA) in the colon. Lower plasma levels of SASP and 5-ASA as compared to those of SP may be due to different absorption rates from the colon because of different pK values and pH dependent lipid-water partition coefficients. In this study we determined the pK values of 5-ASA and its major metabolite, N-acetyl amino-salicylic acid (AcASA), by 13C-NMR spectroscopy and compared the pH dependent apparent benzene-water partition coefficients (Papp) of SASP, SP and 5-ASA with respect to their different plasma levels. The COOH group of 5-ASA had a pK value of 3.0, the -NH3+ group had 6.0, the -OH group 13.9; the -COOH group of AcASA had 2.7 and the -OH group 12.9; The Papp of SASP (0.042 +/- 0.004) and 5-ASA (0.059 +/- 0.01) were significantly lower than that of SP (0.092 +/- 0.03) (at pH 5.5).

High Pressure/Temperature Metal Silicate Partitioning of Tungsten

Science.gov (United States)

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. 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.

Determination of reversed-phase high performance liquid chromatography based octanol-water partition coefficients for neutral and ionizable compounds: Methodology evaluation.

Science.gov (United States)

Liang, Chao; Qiao, Jun-Qin; Lian, Hong-Zhen

2017-12-15

Reversed-phase liquid chromatography (RPLC) based octanol-water partition coefficient (logP) or distribution coefficient (logD) determination methods were revisited and assessed comprehensively. Classic isocratic and some gradient RPLC methods were conducted and evaluated for neutral, weak acid and basic compounds. Different lipophilicity indexes in logP or logD determination were discussed in detail, including the retention factor logk w corresponding to neat water as mobile phase extrapolated via linear solvent strength (LSS) model from isocratic runs and calculated with software from gradient runs, the chromatographic hydrophobicity index (CHI), apparent gradient capacity factor (k g ') and gradient retention time (t g ). Among the lipophilicity indexes discussed, logk w from whether isocratic or gradient elution methods best correlated with logP or logD. Therefore logk w is recommended as the preferred lipophilicity index for logP or logD determination. logk w easily calculated from methanol gradient runs might be the main candidate to replace logk w calculated from classic isocratic run as the ideal lipophilicity index. These revisited RPLC methods were not applicable for strongly ionized compounds that are hardly ion-suppressed. A previously reported imperfect ion-pair RPLC method was attempted and further explored for studying distribution coefficients (logD) of sulfonic acids that totally ionized in the mobile phase. Notably, experimental logD values of sulfonic acids were given for the first time. The IP-RPLC method provided a distinct way to explore logD values of ionized compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

Age-Dependent Changes in Resting Energy Expenditure (REE): Insights from Detailed Body Composition Analysis in Normal and Overweight Healthy Caucasians.

Science.gov (United States)

Geisler, Corinna; Braun, Wiebke; Pourhassan, Maryam; Schweitzer, Lisa; Glüer, Claus-Christian; Bosy-Westphal, Anja; Müller, Manfred J

2016-06-01

Age-related changes in organ and tissue masses may add to changes in the relationship between resting energy expenditure (REE) and fat free mass (FFM) in normal and overweight healthy Caucasians. Secondary analysis using cross-sectional data of 714 healthy normal and overweight Caucasian subjects (age 18-83 years) with comprehensive information on FFM, organ and tissue masses (as assessed by magnetic resonance imaging (MRI)), body density (as assessed by Air Displacement Plethysmography (ADP)) and hydration (as assessed by deuterium dilution (D₂O)) and REE (as assessed by indirect calorimetry). High metabolic rate organs (HMR) summarized brain, heart, liver and kidney masses. Ratios of HMR organs and muscle mass (MM) in relation to FFM were considered. REE was calculated (REEc) using organ and tissue masses times their specific metabolic rates. REE, FFM, specific metabolic rates, the REE-FFM relationship, HOMA, CRP, and thyroid hormone levels change with age. The age-related decrease in FFM explained 59.7% of decreases in REE. Mean residuals of the REE-FFM association were positive in young adults but became negative in older subjects. When compared to young adults, proportions of MM to FFM decreased with age, whereas contributions of liver and heart did not differ between age groups. HOMA, TSH and inflammation (plasma CRP-levels) explained 4.2%, 2.0% and 1.4% of the variance in the REE-FFM residuals, but age and plasma T3-levels had no effects. HMR to FFM and MM to FFM ratios together added 11.8% on to the variance of REE-FFM residuals. Differences between REE and REEc increased with age, suggesting age-related changes in specific metabolic rates of organs and tissues. This bias was partly explained by plasmaT3-levels. Age-related changes in REE are explained by (i) decreases in fat free mass; (ii) a decrease in the contributions of organ and muscle masses to FFM; and (iii) decreases in specific organ and tissue metabolic rates. Age-dependent changes in the REE

Genesis of iron-apatite ores in Posht-e-Badam Block (Central Iran) using REE geochemistry

Science.gov (United States)

Mokhtari, Mir Ali Asghar; Zadeh, Ghader Hossein; Emami, Mohamad Hashem

2013-06-01

Rare earth elements in apatites of different ore types show characteristic patterns which are related to different modes of formation of the ores. Most of the apatite-bearing iron ores are associated with alkaline magmas with LREE/HREE fractionation varying from moderate to steep. Iron-apatite deposits in Posht-e-Badam Block (Central Iran) have a high concentration of REE (more than 1000 ppm up to 2.5%), and show a strong LREE/HREE ratio with a pronounced negative Eu anomaly. This REE pattern is typical of magmatic apatite and quiet distinct from sedimentary apatites (phosphorites) which have a low REE contents and Ce negative anomalies. On the other hand, they are comparable to the REE patterns of apatites in Kiruna-type iron ores in different parts of the world. The REE patterns of apatites, iron-apatite ores and iron ores are similar and only have different REE contents. This similarity indicates a genetic relation for these rocks. Most of the iron-apatite deposits in Central Iran have similar REE patterns too, which in turn show a genetic relation for all of these deposits. This similarity indicates a similar origin and processes in their genesis. There are some small intrusions around some of the iron-apatite deposits that are petrographically identified as syenite and gabbro. These intrusions also have REE patterns similar to that of iron-apatite ores. This demonstrates a genetic relation between these intrusions and iron-apatite ores. The REE patterns of apatites in different deposits of Posht-e-Badam Block iron-apatite ores show an affinity to alkaline to sub-alkaline magmas and rifting environment. The alkaline host rocks of Central Iran iron-apatite ores are clearly related to an extensional setting where rifting was important (SSE-NNW fault lines). A probable source for this large scale ore forming processes is relatively low partial melting of mantle rocks. The ores have originated by magmatic differentiation as a late phase in the volcanic cycle

Equilibrium partitioning of macromolecules in confining geometries: Improved universality with a new molecular size parameter

DEFF Research Database (Denmark)

Wang, Yanwei; Peters, Günther H.J.; Hansen, Flemming Yssing

2008-01-01

structures (CABS), allows the computation of equilibrium partition coefficients as a function of confinement size solely based on a single sampling of the configuration space of a macromolecule in bulk. Superior in computational speed to previous computational methods, CABS is capable of handling slits...... parameter for characterization of spatial confinement effects on macromolecules. Results for the equilibrium partition coefficient in the weak confinement regime depend only on the ratio ofR-s to the confinement size regardless of molecular details....

Temperature dependencies of Henry's law constants and octanol/water partition coefficients for key plant volatile monoterpenoids.

Science.gov (United States)

Copolovici, Lucian O; Niinemets, Ulo

2005-12-01

To model the emission dynamics and changes in fractional composition of monoterpenoids from plant leaves, temperature dependencies of equilibrium coefficients must be known. Henry's law constants (H(pc), Pa m3 mol(-1) and octanol/water partition coefficients (K(OW), mol mol(-1)) were determined for 10 important plant monoterpenes at physiological temperature ranges (25-50 degrees C for H(pc) and 20-50 degrees C for K(OW)). A standard EPICS procedure was established to determine H(pc) and a shake flask method was used for the measurements of K(OW). The enthalpy of volatilization (deltaH(vol)) varied from 18.0 to 44.3 kJ mol(-1) among the monoterpenes, corresponding to a range of temperature-dependent increase in H(pc) between 1.3- and 1.8-fold per 10 degrees C rise in temperature. The enthalpy of water-octanol phase change varied from -11.0 to -23.8 kJ mol(-1), corresponding to a decrease of K(OW) between 1.15- and 1.32-fold per 10 degrees C increase in temperature. Correlations among physico-chemical characteristics of a wide range of monoterpenes were analyzed to seek the ways of derivation of H(pc) and K(OW) values from other monoterpene physico-chemical characteristics. H(pc) was strongly correlated with monoterpene saturated vapor pressure (P(v)), and for lipophilic monoterpenes, deltaH(vol) scaled positively with the enthalpy of vaporization that characterizes the temperature dependence of P(v) Thus, P(v) versus temperature relations may be employed to derive the temperature relations of H(pc) for these monoterpenes. These data collectively indicate that monoterpene differences in H(pc) and K(OW) temperature relations can importantly modify monoterpene emissions from and deposition on plant leaves.

Sediment-to-Water Partition Coefficients: the Influence of Physicochemical and Seasonal Factors in Eastern Ontario

Energy Technology Data Exchange (ETDEWEB)

Yankovich, Tamara L. [International Atomic Energy Agency, P.O. Box 100, 1400 Vienna (Austria); Shultz, Carmen; Hartwig, Dale; Wills, C. Anne [Atomic Energy of Canada Limited, Chalk River Laboratories, Chalk River, Ontario, K0J 1J0 (Canada); Beresford, Nicholas A. [NERC Centre for Ecology and Hydrology, Lancaster Environment Center, Library Av., Bailrigg, Lancaster, LA1 4AP (United Kingdom); School of Environment and Life Sciences, University of Salford, Manchester, M4 4WT (United Kingdom); Wood, Michael D. [School of Environment and Life Sciences, University of Salford, Manchester, M4 4WT (United Kingdom)

2014-07-01

Sediments often represent an important reservoir for contaminants, such as radionuclides and metals, in aquatic ecosystems. Consequently, lake, stream, and river sediments can potentially act as significant contributors to the total contaminant exposure and radiological doses received by wildlife. Exposure to contaminated sediments is dependent upon several factors. These include net contaminant inputs to a system through time, the physicochemical attributes of the system, the tendency of each contaminant to partition into the sediments relative to water, the spatial distribution of contaminants in the sediments, and the behaviour or life-style of the biota inhabiting a water body. Increased understanding of such factors and their interactions will lead to improved predictions of the radionuclide exposure received by aquatic biota, particularly benthic organisms. Despite the complexity and the dynamic nature of sediments in general, for practical purposes, in environmental impact assessments (EIAs), it is often assumed that radionuclide activity concentrations in various compartments are at steady state with respect to one another. Therefore, ratios can be used to estimate concentrations in one compartment given a known concentration in another. In the case of sediments, sediment-to-water partition coefficients (K{sub d}) are often applied to estimate the contaminant concentration sorbed to particulate matter relative to the concentration measured in the surface water. However, K{sub d} values often range by several orders of magnitude between sampling locations due to site-specific differences in physicochemical conditions in surface waters, seasonal factors, as well as differences in sediment attributes that can affect contaminant partitioning between the dissolved and particulate phases. Consequently, in conducting EIAs, it becomes necessary to either apply generic K{sub d} values that ensure contaminant concentrations in sediments to which biota are exposed are

The effect of melt composition on the partitioning of trace elements between titanite and silicate melt

Science.gov (United States)

Prowatke, S.; Klemme, S.

2003-04-01

The aim of this study is to systematically investigate the influence of melt composition on the partitioning of trace elements between titanite and different silicate melts. Titanite was chosen because of its important role as an accessory mineral, particularly with regard to intermediate to silicic alkaline and calc-alkaline magmas [e.g. 1] and of its relative constant mineral composition over a wide range of bulk compositions. Experiments at atmospheric pressure were performed at temperatures between 1150°C and 1050°C. Bulk compositions were chosen to represent a basaltic andesite (SH3 - 53% SiO2), a dacite (SH2 - 65 SiO2) and a rhyolite (SH1 - 71% SiO2). Furthermore, two additional experimental series were conducted to investigate the effect of Al-Na and the Na-K ratio of melts on partitioning. Starting materials consisted of glasses that were doped with 23 trace elements including some selected rare earth elements (La, Ce, Pr, Sm, Gd, Lu), high field strength elements (Zr, Hf, Nb, Ta) and large ion lithophile elements (Cs, Rb, Ba) and Th and U. The experimental run products were analysed for trace elements using secondary ion mass spectrometry at Heidelberg University. Preliminary results indicate a strong effect of melt composition on trace element partition coefficients. Partition coefficients for rare-earth elements uniformly show a convex-upward shape [2, 3], since titanite accommodates the middle rare-earth elements more readily than the light rare-earth elements or the heavy rare-earth elements. Partition coefficients for the rare-earth elements follow a parabolic trend when plotted against ionic radius. The shape of the parabola is very similar for all studied bulk compositions, the position of the parabola, however, is strongly dependent on bulk composition. For example, isothermal rare-earth element partition coefficients (such as La) are incompatible (D>1) in alkali-poor melt compositions. From our experimental data we present an model that combines

Major, trace and REE geochemistry of recent sediments from lower Catumbela River (Angola)

Science.gov (United States)

Vinha, Manuela; Silva, M. G.; Cabral Pinto, Marina M. S.; Carvalho, Paula Cristina S.

2016-03-01

The mineralogy, texture, major, trace and rare earth elements, from recent sediment samples collected in the lower Catumbela River, were analysed in this study to characterize and discuss the factors controlling its geochemistry and provide data that can be used as tracers of Catumbela River inputs to the Angolan continental shelf. The sediments are mainly sands and silty-sands, but sandy-silt also occurs and the mineralogy is composed of quartz, feldspar, phyllosilicates, magnetite, ilmenite and also carbonates when the river crosses limestones and marls in the downstream sector. The hydraulic sorting originates magnetite-ilmenite and REE-enriched minerals placers. The mineralogy of the sediments is controlled by the source rocks and the degree of chemical weathering is lower than erosion. The texture is mainly controlled by location. There is enrichment in all the analysed trace elements in the fine grained, clay minerals and Fe-oxy-hydroxides rich sediments, compared to the coarse grained and quartz plus feldspar rich ones. The coarse grained sediments (without the placers) are impoverished in ΣREE when compared with UCC and NASC compositions, while the fine grained sediments have ΣREE contents similar to UCC and NASC. The placers have ΣREE contents up to 959.59 mg/kg. The source composition is the dominant factor controlling the REE geochemistry of the analysed sediments as there is no difference in the (La/Yb)N, (La/Sm)N and (Gd/Yb)N ratios in coarse and fine grained sediments. The sorting of magnetite, ilmenite, zircon, throrite, thorianite, rutile and titanite explain the HREE/LREE enriched patterns of the coarse grained sediments.

Uranium and REE potential of the albitite-pyroxenite-microclinite belt of Rajasthan, India

International Nuclear Information System (INIS)

Singh, Govind; Sharma, D.K.; Yadav, O.P.; Jain, Rajan B.; Singh, Rajendra

1998-01-01

A number of radioactive albitite, pyroxenite and microclinite occurrences have been identified in north and central Rajasthan, along or in close proximity to major lineaments, from Dancholi - Mewara in the NE to Tal in the SW. With these new findings the total extent of Albitite belt of Rajasthan now stands at over 320 km. These occurrences have been evaluated on the basis of their U, Th and REE content to identify the potential areas for the second phase of uranium exploration programme. Further, based on the various characteristic features of radioactive host rocks, the Albitite Belt has been divided into five sectors. The U 3 O 8 content of albitites varies from 0.008 to 0.44% and of pyroxenites from 0.022 to 2.0% whereas ThO 2 varies from < 0.005 to 0.83% in albitites and <0.005 to 0.033% in pyroxenities. These albitites, microclinites and pyroxenites are also characterised by anomalous concentration of REEs. Uranium and REE bearing phases are represented by uraninite, brannerite, davidite, fergusonite, monazite, anatase, rutile, zircon, allanite and britholite. The data accrued so far suggest that U and REE potential of the Mewara-Maonda and Hurra Ki Dhani-Rohil sectors are very high and hence needs further detailed integrated exploration. (author)

[Application of reversed-phase ion-pair chromatography for universal estimation of octanol-water partition coefficients of acid, basic and amphoteric drugs].

Science.gov (United States)

Zhu, Hui; Yang, Ri-Fang; Yun, Liu-Hong; Jiang, Yu; Li, Jin

2009-09-01

This paper is to establish a reversed-phase ion-pair chromatography (RP-IPC) method for universal estimation of the octanol/water partition coefficients (logP) of a wide range of structurally diverse compounds including acidic, basic, neutral and amphoteric species. The retention factors corresponding to 100% water (logk(w)) were derived from the linear part of the logk'/phi relationship, using at least four isocratic logk' values containing different organic compositions. The logk(w) parameters obtained were close to the corresponding logP values obtained with the standard "shake flask" methods. The mean deviation for test drugs is 0.31. RP-IPC with trifluoroacetic acid as non classic ion-pair agents can be applicable to determine the logP values for a variety of drug-like molecules with increased accuracy.

Uranium, thorium and REE partitioning into sulfide liquids at high pressure and high temperature: Implications for reduced, S-rich planetary bodies

Science.gov (United States)

Wohlers, A.; Wood, B. J.

2017-12-01

Based on models of the young solar nebula it is likely that the inner planets went through an early reduced phase of accretion with high metal/silicate ratio and low volatile element contents. Mercury is an existing example of a large planetary embryo with these characteristics but also with a very high S content. In order to investigate the geochemical evolution of Mercury-like bodies we experimentally determined the partitioning of lithophile elements (U, Th, Eu, Sm, Nd, Zr, La, Ce, Yb) between sulfide liquid, low-S metals and silicate melt at 1.5 GPa and 1400-2100˚C. Our results, when combined with those of Wohlers and Wood (2015) show that under highly reducing conditions (FeOsilicatemetal and FeO contents of the silicate may be understood in terms of exchange reactions: UO2 + 2FeS = 2FeO + US2silicate sulfide silicate sulfideHigh concentrations of FeSmetal and low FeO contents of the silicate melts drive the reaction to the right, yielding high US2 in the sulfide and high DU. A second effect which raises DU (and other lithophile D's) is the S content of the silicate melt. The latter increases rapidly at low FeO contents and reaches 11wt %. This greatly reduces the activity coefficient of FeO, displacing the reaction further to the right. At 1.5GPa and 1400˚C we obtain sulfide-silicate partitioning with DNd/DSm 1.4 and DTh 0.1DU. As temperature increases to 2100˚C, DNd/DSm declines to 1.0 and DTh/DU increases to 0.3. We estimated the effects of accreting a reduced sulfur-rich component (with FeS core) added to early Earth. The results at 1400˚C imply the possibility of a significant ( 11ppm) 142Nd anomaly in silicate Earth and the addition of >8 ppb U to the core, but require an unreasonably high Th/U of silicate Earth (4.54). Results at 2100˚C lead to a 142Nd anomaly of 0 but addition of such a reduced sulfur-rich body could add up to 10 ppb of U to the core, together with 21 ppb Th. This combination would generate 3 TW of the energy required for the

Radionuclide partitioning in environmental systems: a critical analysis

International Nuclear Information System (INIS)

Cremers, A.; Maes, A.

1986-01-01

A survey is given of some of the important processes involved in the solid-liquid distribution behaviour of radionuclides in both well-defined adsorbents and multicomponent natural systems. The thermodynamic significance of distribution coefficients is analyzed and the various parameters affecting partition behaviour are discussed in relation to possible retention mechanisms. Attention is being given to factors such as solid/liquid ratio, pH-Eh, reversibility, liquid phase composition and speciation effects. Various processes are discussed such as ion exchange and complex formation involving clays, oxides, humic acids. It is shown that, only in rare cases, Ksub(D) values can be rationalized in terms of process mechanistics. In addition, it is indicated that, in general, radionuclide distribution coefficients cannot be considered as constants unless the conditions are restricted to very small loading intervals. It is furthermore suggested that, in order to produce meaningful data on radionuclide partitioning behaviour, efforts should be made to operate under conditions which are representative for the 'in situ' situation. (author)

Approximation methods for the partition functions of anharmonic systems

International Nuclear Information System (INIS)

Lew, P.; Ishida, T.

1979-07-01

The analytical approximations for the classical, quantum mechanical and reduced partition functions of the diatomic molecule oscillating internally under the influence of the Morse potential have been derived and their convergences have been tested numerically. This successful analytical method is used in the treatment of anharmonic systems. Using Schwinger perturbation method in the framework of second quantization formulism, the reduced partition function of polyatomic systems can be put into an expression which consists separately of contributions from the harmonic terms, Morse potential correction terms and interaction terms due to the off-diagonal potential coefficients. The calculated results of the reduced partition function from the approximation method on the 2-D and 3-D model systems agree well with the numerical exact calculations

The Influence of Basaltic Islands on the Oceanic REE Distribution: A Case Study From the Tropical South Pacific

Directory of Open Access Journals (Sweden)

Mario Molina-Kescher

2018-03-01

Full Text Available The Rare Earth Elements (REEs have been widely used to investigate marine biogeochemical processes as well as the sources and mixing of water masses. However, there are still important uncertainties about the global aqueous REE cycle with respect to the contributions of highly reactive basaltic minerals originating from volcanic islands and the role of Submarine Groundwater Discharge (SGD. Here we present dissolved REE concentrations obtained from waters at the island-ocean interface (including SGD, river, lagoon and coastal waters from the island of Tahiti and from three detailed open ocean profiles on the Manihiki Plateau (including neodymium (Nd isotope compositions, which are located in ocean currents downstream of Tahiti. Tahitian fresh waters have highly variable REE concentrations that likely result from variable water–rock interaction and removal by secondary minerals. In contrast to studies on other islands, the SGD samples do not exhibit elevated REE concentrations but have distinctive REE distributions and Y/Ho ratios. The basaltic Tahitian rocks impart a REE pattern to the waters characterized by a middle REE enrichment, with a peak at europium similar to groundwaters and coastal waters of other volcanic islands in the Pacific. However, the basaltic island REE characteristics (with the exception of elevated Y/Ho ratios are lost during transport to the Manihiki Plateau within surface waters that also exhibit highly radiogenic Nd isotope signatures. Our new data demonstrate that REE concentrations are enriched in Tahitian coastal water, but without multidimensional sampling, basaltic island Nd flux estimates range over orders of magnitude from relatively small to globally significant. Antarctic Intermediate Water (AAIW loses its characteristic Nd isotopic signature (−6 to −9 around the Manihiki Plateau as a consequence of mixing with South Equatorial Pacific Intermediate Water (SEqPIW, which shows more positive values (−1 to �

Determination of solid-liquid partition coefficients (Kd) for diazinon, propetamphos and cis-permethrin: implications for sheep dip disposal

International Nuclear Information System (INIS)

Cooke, Cindy M.; Shaw, George; Lester, John N.; Collins, Chris D.

2004-01-01

Two groups of chemicals are currently licensed for use in sheep dip products in the UK. These are organophosphate (OP) insecticides and synthetic pyrethroid (SP) insecticides. SPs are deemed to be less toxic to human health than OPs, although they are approximately 100 times more toxic to some elements of the aquatic environment. Three insecticides were selected for experimental investigation: diazinon, propetamphos (OPs) and cis-permethrin (SP), representative of the active ingredients used in sheep dip formulations, with additional uses in insect control in crops, and for domestic control of flies, mosquitoes, cockroaches, lice, ticks and spiders. The UK Government has recently reviewed agricultural practices relating to the disposal of used sheep dip, because the constituent insecticides are frequently detected in UK watercourses and the presence of these compounds is a severe hazard to the aquatic environment. Standard batch sorption experiments were carried out to investigate insecticide partitioning from water to soil, and the relationship between sorption and soil organic carbon content is discussed. Sorption isotherms and K d values showed that cis-permethrin adsorption was fastest on all five soils investigated, exhibiting the greatest total partitioning to the soil phase (83.8-94.8%) and high resistance to desorption. In comparison, the OP insecticides exhibited moderately strong soil adsorption as evidenced by their K d coefficients (diazinon K d 12-35 and propetamphos K d 9-60), with low sorption reversibility (<15%). Calculation of a hydrological retardation factor in a scenario representative of a typical UK environment suggested that SP insecticides such as cis-permethrin will not migrate in the soil profile due to their virtual immobility and strong soil retention, and thus waste sheep dip disposal to agricultural land should not pose a risk to aquatic life if applied with appropriate controls

Effects of chain length, chlorination degree, and structure on the octanol-water partition coefficients of polychlorinated n-alkanes.

Science.gov (United States)

Hilger, Bettina; Fromme, Hermann; Völkel, Wolfgang; Coelhan, Mehmet

2011-04-01

Log octanol-water partition coefficients (log Kow) of 40 synthesized polychlorinated n-alkanes (PCAs) with different chlorination degrees were determined using reversed-phase high performance liquid chromatography (RP-HPLC). In addition, log Kow values of a technical mixture namely Cereclor 63L as well as 15 individual in house synthesized C10, C11, and C12 chloroalkanes with known chlorine positions were estimated. Based on these results, the effects of chain length, chlorination degree, and structure were explored. The estimated log Kow values ranged from 4.10 (polychlorinated n-decanes with 50.2% chlorine content) to 11.34 (polychlorinated n-octacosanes with 54.8% chlorine content) for PCAs and from 3.82 (1,2,5,6,9,10-hexachlorodecane) to 7.75 (1,1,1,3,9,11,11,11-octachlorododecane) for the individual chloroalkanes studied. The results showed that log Kow value was influenced linearly at a given chlorine content by chain length, while a polynominal effect was observed in dependence on the chlorination degree of an alkane chain. Chlorine substitution pattern influenced markedly the log Kow value of chloroalkanes.

Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: A Monte Carlo simulation study

Energy Technology Data Exchange (ETDEWEB)

Quesada-Pérez, Manuel; Maroto-Centeno, José Alberto [Departamento de Física, Escuela Politécnica Superior de Linares, Universidad de Jaén, 23700 Linares, Jaén (Spain); Adroher-Benítez, Irene [Grupo de Física de Fluidos y Biocoloides, Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Granada, 18071 Granada (Spain)

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.

Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: A Monte Carlo simulation study

International Nuclear Information System (INIS)

Quesada-Pérez, Manuel; Maroto-Centeno, José Alberto; Adroher-Benítez, Irene

2014-01-01

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

U-TH-REE mobility and diffusion in granitic environments during alteration of accessory minerals and U-ores

International Nuclear Information System (INIS)

Cathelineau, M.; Vergneaud, M.

1989-01-01

U, Th and REE concentrations and distributions have been studied in granitic rocks, using a multidisciplinary approach involving micromapping of cracks in oriented samples, together with mineralogical and geochemical studies of the different U-Th-REE bearing phases. The behavior of U, Th and Nd, considered as chemical analogue elements of the radiotoxic nuclides, was investigated either in the vicinity of microsites (accessory mineral enviornment) or along plurimetric sections around U-ore bodies. The different granite minerals, especially the accessory minerals (uraninite, monazite, thorite, apatite, xeonotime), as well as U-ores, present different initial concentrations of U, Th and REE. Limitations to the analogy between these U-Th-REE concentrations and the radwastes is discussed as a function of their mineralogical features, chemical compostion, size and solubilities. These primary concentrations present different behavior when subjected to hydrothermal alteration, such as propylitization, phyllite type alteration, or clay alteration. Results show that in reduced media, in the temperature range 80-2000 0 C, the rate of mobilization of U, Th, REE is relatively moderate. However, fluids enriched in flourides, phosphates or carbonates may significantly solubilize and transport U and REE under specific conditions. In addition, the degree of opening of the microcracks and faults, as well as the oxidation-reduction processes, are critical parameters for the efficiency of the granitic geological barrier

How lithology and climate affect REE mobility and fractionation along a shale weathering transect of the Susquehanna Shale Hills Critical Zone Observatory

Science.gov (United States)

Ma, L.; Jin, L.; Dere, A. L.; White, T.; Mathur, R.; Brantley, S. L.

2012-12-01

Shale weathering is an important process in global elemental cycles. Accompanied by the transformation of bedrock into regolith, many elements including rare earth elements (REE) are mobilized primarily by chemical weathering in the Critical Zone. Then, REE are subsequently transported from the vadose zone to streams, with eventual deposition in the oceans. REE have been identified as crucial and strategic natural resources; and discovery of new REE deposits will be facilitated by understanding global REE cycles. At present, the mechanisms and environmental factors controlling release, transport, and deposition of REE - the sources and sinks - at Earth's surface remain unclear. Here, we present a systematic study of soils, stream sediments, stream waters, soil water and bedrock in six small watersheds that are developed on shale bedrock in the eastern USA to constrain the mobility and fractionation of REE during early stages of chemical weathering. The selected watersheds are part of the shale transect established by the Susquehanna Shale Hills Observatory (SSHO) and are well suited to investigate weathering on shales of different compositions or within different climate regimes but on the same shale unit. Our REE study from SSHO, a small gray shale watershed in central Pennsylvania, shows that up to 65% of the REE (relative to parent bedrock) is depleted in the acidic and organic-rich soils due to chemical leaching. Both weathering soil profiles and natural waters show a preferential removal of middle REE (MREE: Sm to Dy) relative to light REE (La to Nd) and heavy REE (Ho to Lu) during shale weathering, due to preferential release of MREE from a phosphate phase (rhabdophane). Strong positive Ce anomalies observed in the regolith and stream sediments point to the fractionation and preferential precipitation of Ce as compared to other REE, in the generally oxidizing conditions of the surface environments. One watershed developed on the Marcellus black shale in

REE geochemistry and genesis of Daxin uranium deposit

International Nuclear Information System (INIS)

Li Zhixing; Qi Fucheng; He Zhongbo; Zhang Zilong

2011-01-01

Through the analysis on typical REE parameters,chondrite-normalized REE patterns and hierarchical cluster analysis of rocks in the structural-geochemical zonation in Daxin uranium deposit, the paper discusses the uranium source and genesis. The study shows that the uranium source mainly came from Cambrian System. The Devonian System is maily as the favorable room for saving ores in addition to pre-concentrated room for uranium. Underground water resulted from early and late Yanshanian movement and the heating of volcanic rock was turned into geothermal water and it was moved upward by the force of tectonic movement. The geothermal water mainly extracted active uranium from the Cambrian rocks, then moved upward along main regional fault (F2) connecting the Cambrian rocks and the Devonian rocks until it arrived in structural fracture zone which was controlled by secondary faults (F13, F23, F33). At last, the uranium element in geothermal water was precipitated and concentrated into the uranium deposit in reducing environment of enriched organic material and pyrite. (authors)

Equilibrium thermodynamics of the partitioning of non-steroidal anti-inflammatory drugs into human erythrocyte ghost membranes

International Nuclear Information System (INIS)

Omran, Ahmed A.

2013-01-01

Graphical abstract: Bar diagram representing thermodynamic parameters obtained for the partitioning of NSAIDs into human erythrocyte ghost membranes at physiological pH; 7.4. Highlights: • Partition coefficients of NSAIDs into HEG membranes were determined. • Thermodynamic parameters were evaluated and successfully analyzed. • Partitioning of NSAIDs into HEG membranes was exothermic. • Partitioning of NSAIDs into HEG is spontaneous with negative free energy values. • Identical partitioning enthalpy–entropy driven compensation mechanism was shown. -- Abstract: In this work,second derivative spectrophotometry was applied for determining the partition coefficients (K p s) of four non-steroidal anti-inflammatory drugs (NSAIDs; flufenamic, meclofenamic, mefenamic and niflumic acids) into human erythrocyte ghost (HEG) membranes over a temperature range from (283.2 to 313.2) K. The proposed method allowed the evaluation and direct analyses of thermodynamic parameters; enthalpy (ΔH W→M ), Gibbs energy (ΔG W→M ) and entropy (ΔS W→M ) changes of the partitioning of NSAIDs into HEG membranes. The partitioning of NSAIDs between polar aqueous phase and non-polar lipid bilayer HEG membrane phase was exothermic with negative (ΔH W→M ) which compensated for the changes in (ΔS W→M ). The negative values of (ΔG W→M ) revealed that the partitioning of NSAIDs into HEG, owing to their transfer from polar aqueous phase and non-polar HEG phase is spontaneous. The enthalpy–entropy correlation analysis resulted in a good linearity that suggests an identical partitioning enthalpy–entropy driven compensation mechanism for the studied NSAIDs

Exactly soluble models for surface partition of large clusters

International Nuclear Information System (INIS)

Bugaev, K.A.; Bugaev, K.A.; Elliott, J.B.

2007-01-01

The surface partition of large clusters is studied analytically within a framework of the 'Hills and Dales Model'. Three formulations are solved exactly by using the Laplace-Fourier transformation method. In the limit of small amplitude deformations, the 'Hills and Dales Model' gives the upper and lower bounds for the surface entropy coefficient of large clusters. The found surface entropy coefficients are compared with those of large clusters within the 2- and 3-dimensional Ising models

Partition functions. I. Improved partition functions and thermodynamic quantities for normal, equilibrium, and ortho and para molecular hydrogen

Science.gov (United States)

Popovas, A.; Jørgensen, U. G.

2016-11-01

Context. Hydrogen is the most abundant molecule in the Universe. Its thermodynamic quantities dominate the physical conditions in molecular clouds, protoplanetary disks, etc. It is also of high interest in plasma physics. Therefore thermodynamic data for molecular hydrogen have to be as accurate as possible in a wide temperature range. Aims: We here rigorously show the shortcomings of various simplifications that are used to calculate the total internal partition function. These shortcomings can lead to errors of up to 40 percent or more in the estimated partition function. These errors carry on to calculations of thermodynamic quantities. Therefore a more complicated approach has to be taken. Methods: Seven possible simplifications of various complexity are described, together with advantages and disadvantages of direct summation of experimental values. These were compared to what we consider the most accurate and most complete treatment (case 8). Dunham coefficients were determined from experimental and theoretical energy levels of a number of electronically excited states of H2. Both equilibrium and normal hydrogen was taken into consideration. Results: Various shortcomings in existing calculations are demonstrated, and the reasons for them are explained. New partition functions for equilibrium, normal, and ortho and para hydrogen are calculated and thermodynamic quantities are reported for the temperature range 1-20 000 K. Our results are compared to previous estimates in the literature. The calculations are not limited to the ground electronic state, but include all bound and quasi-bound levels of excited electronic states. Dunham coefficients of these states of H2 are also reported. Conclusions: For most of the relevant astrophysical cases it is strongly advised to avoid using simplifications, such as a harmonic oscillator and rigid rotor or ad hoc summation limits of the eigenstates to estimate accurate partition functions and to be particularly careful when

Fractionation of chemical elements including the REEs and 226Ra in stream contaminated with coal-mine effluent

International Nuclear Information System (INIS)

Centeno, L.M.; Faure, G.; Lee, G.; Talnagi, J.

2004-01-01

Water draining from abandoned open-pit coal mines in southeastern Ohio typically has a low pH and high concentrations of Fe, Al and Mn, as well as of trace metals (Pb, Cu, Zn, Ni, Co, etc.) and of the rare earth elements (REEs). The cations of different elements are sorbed selectively by Fe and Al hydroxide precipitates which form with increasing pH. As a result, the trace elements are separated from each other when the hydroxide precipitates are deposited in the channel of a flowing stream. Therefore, the low-energy environment of a stream contaminated by mine effluent is a favorable site for the chemical fractionation of the REEs and of other groups of elements with similar chemical properties. The interpretation of chemical analyses of water collected along a 30-km-stretch of Rush Creek near the town of New Lexington, Perry County, Ohio, indicates that the abundances of the REEs in the water appear to change downstream when they are normalized to the REE concentrations of the mine effluent. In addition, the Ce/La ratios (and those of all REEs) in the water decrease consistently downstream. The evidence indicates that the REEs which remain in solution are enriched La and Ce because the other REEs are sorbed more efficiently. The solid Fe(OH) 3 precipitates in the channel of Rush Creek upstream of New Lexington also contain radioactive 226 Ra that was sorbed from the water. This isotope of Ra is a decay product of 238 U which occurs in the Middle Pennsylvanian (Upper Carboniferous) coal and in the associated shale of southeastern Ohio. The activity of 226 Ra of the Fe(OH) 3 precipitates increases with rising pH, but then declines farther downstream as the concentration of Ra remaining in the water decreases

Rare earth elements (REEs): effects on germination and growth of selected crop and native plant species.

Science.gov (United States)

Thomas, Philippe J; Carpenter, David; Boutin, Céline; Allison, Jane E

2014-02-01

The phytotoxicity of rare earth elements (REEs) is still poorly understood. The exposure-response relationships of three native Canadian plant species (common milkweed, Asclepias syriaca L., showy ticktrefoil, Desmodium canadense (L.) DC. and switchgrass, Panicum virgatum L.) and two commonly used crop species (radish, Raphanus sativus L., and tomato, Solanum lycopersicum L.) to the REEs lanthanum (La), yttrium (Y) and cerium (Ce) were tested. In separate experiments, seven to eight doses of each element were added to the soil prior to sowing seeds. Effects of REE dose on germination were established through measures of total percent germination and speed of germination; effects on growth were established through determination of above ground biomass. Ce was also tested at two pH levels and plant tissue analysis was conducted on pooled samples. Effects on germination were mostly observed with Ce at low pH. However, effects on growth were more pronounced, with detectable inhibition concentrations causing 10% and 25% reductions in biomass for the two native forb species (A. syriaca and D. canadense) with all REEs and on all species tested with Ce in both soil pH treatments. Concentration of Ce in aboveground biomass was lower than root Ce content, and followed the dose-response trend. From values measured in natural soils around the world, our results continue to support the notion that REEs are of limited toxicity and not considered extremely hazardous to the environment. However, in areas where REE contamination is likely, the slow accumulation of these elements in the environment could become problematic. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

Nature of parent rocks, mineralization styles and ore genesis of regolith-hosted REE deposits in South China: An integrated genetic model

Science.gov (United States)

Li, Yan Hei Martin; Zhao, Wen Winston; Zhou, Mei-Fu

2017-10-01

Regolith-hosted rare earth element (REE) deposits, also called ion-adsorption or weathered crust elution-deposited REE deposits are distributed over Jiangxi, Guangdong, Fujian, Hunan, Guangxi and Yunnan provinces in South China. In general, these deposits can be categorized into the HREE-dominated type, for example the famous Zudong deposit in southern Jiangxi province and the LREE-dominated type, such as the Heling and Dingnan deposits in southern Jiangxi province. Most of these deposits form from weathering of biotite and muscovite granites, syenites, monzogranites, granodiorites, granite porphyries, and rhyolitic tuffs. The parent rocks are generally peraluminous, siliceous, alkaline and contain a variety of REE-bearing minerals. Mostly, REE patterns of regolith are inherited from the parent rocks, and therefore, characteristics of the parent rocks impose a significant control on the ore formation. Data compilation shows that autometasomatism during the latest stage of granite crystallization is likely essential in forming the HREE-enriched granites, whereas LREE-enriched granites could form through magmatic differentiation. These deposits are normally two- to three-fold, but could be up to ten-fold enrichment in REE compared to the parent granites, where the maximum enrichment usually occurs from the lower B to the upper C horizon. Ce shows different behavior with the other REEs. Strongly positive Ce anomalies commonly occur at the upper part of weathering profiles, likely due to oxidation of Ce3+ to Ce4+ and removal of Ce from soil solutions through precipitation of cerianite. Vertical pH and redox gradients in weathering crusts facilitate dissolution of REE-bearing minerals at shallow level and fixation of REE at depth through either adsorption on clay minerals or precipitation of secondary minerals. At the same time, mass removal of major elements plays an important role in concentrating REE in regolith. Combination of mass removal and eluviation

Th, U, REE Backgrounds and Phytoavailability in Soils of the Padanian Plain (Northern Italy

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Dario Di Giuseppe

2014-12-01

Full Text Available In this contribution we present ICP-MS analyses carried out on agricultural soils from the eastern-most part of the Padanian plain (Ferrara Province and on the related crop products. The aim is to provide, for the first time, backgrounds for some trace elements such as rare earth elements (REE, thorium (Th, uranium (U and to understand the related phytoavailability. In particular, detailed analyses have been done on Sorghum Vulgare plants, analyzing distinct plant parts in different vegetative periods. Results indicate that a REE concentration in plant tissues is always lower than in the related soils, precluding the occurrence of bioaccumulation and b no preferential elemental uptake and REE fractionation. In this light, the observed soil/plant relationships could be used in the definition of markers of territoriality (provenance fingerprint for agricultural products.

Analysis of polyethoxylated surfactants in microemulsion-oil-water systems III. Fractionation and partitioning of polyethoxylated alcohol surfactants

International Nuclear Information System (INIS)

Marquez, N.; Bravo, B.; Ysambertt, F.; Chavez, G.; Subero, N.; Salager, J.L.

2002-01-01

Oligomer distribution of polyethoxylated alcohol and polyethoxylated nonylphenol surfactants is studied by normal and reverse-phase high performance liquid chromatography (HPLC). A RP8 column is able to efficiently separate these surfactants according to their alkyl chain (lipophilic) group, while silica and amino columns separate them according to their polyether chain length (hydrophilic group). Polyethoxylated alcohol and polyethoxylated nonylphenol oligomers selectively partition between the microemulsion-oil-water phases of a Winsor III system. Partitioning of these oligomers was analyzed by HPLC with RI detection. The logarithm of the partition coefficient between the water and oil linearly increases with the number of ethylene oxide groups per molecule of oligomer. For a same ethoxylation degree, the partition coefficient of a polyethoxylated tridecanol is found to be higher than the one of the corresponding nonylphenol specie. On the other hand, a polyethoxylated nonylphenol exhibits a higher solubilization than the matching polyethoxylated alcohol

Uptake and Effects of Six Rare Earth Elements (REEs on Selected Native and Crop Species Growing in Contaminated Soils.

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David Carpenter

Full Text Available Rare earth elements (REEs have become increasingly important metals used in modern technology. Processes including mining, oil refining, discarding of obsolete equipment containing REEs, and the use of REE-containing phosphate fertilizers may increase the likelihood of environmental contamination. However, there is a scarcity of information on the toxicity and accumulation of these metals to terrestrial primary producers in contaminated soils. The objective of this work was to assess the phytotoxicity and uptake from contaminated soil of six REEs (chloride forms of praseodymium, neodymium, samarium, terbium, dysprosium, and erbium on three native plants (Asclepias syriaca L., Desmodium canadense (L. DC., Panicum virgatum L. and two crop species (Raphanus sativus L., Solanum lycopersicum L. in separate dose-response experiments under growth chamber conditions. Limited effects of REEs were found on seed germination and speed of germination. Effects on aboveground and belowground biomass were more pronounced, especially for the three native species, which were always more sensitive than the crop species tested. Inhibition concentrations (IC25 and IC50 causing 25 or 50% reductions in plant biomass respectively, were measured. For the native species, the majority of aboveground biomass IC25s (11 out of 18 fell within 100 to 300 mg REE/kg dry soil. In comparison to the native species, IC25s for the crops were always greater than 400 mg REE/kg, with the majority of results (seven out of 12 falling above 700 mg REE/kg. IC50s were often not detected for the crops. Root biomass of native species was also affected at lower doses than in crops. REE uptake by plants was higher in the belowground parts than in the above-ground plant tissues. Results also revealed that chloride may have contributed to the sensitivity of the native species, Desmodium canadense, one of the most sensitive species studied. Nevertheless, these results demonstrated that

Trace element and REE composition of five samples of the Yucca Mountain calcite-silica deposits. Special report No. 8

International Nuclear Information System (INIS)

Livingston, D.

1993-07-01

The attached materials document the results of part of a recent effort of geochemical sampling and analysis at Yucca Mountain and nearby regions. The efforts come as a result of interest in comprehensive analyses of rare earth elements (REE), lanthanum (La) through lutecium (Lu). Several additional, non-REE analyses were obtained as well. Commercially available REE analyses have proved to be insufficiently sensitive for geochemical purposes. Dr. Roman Schmitt at the Radiation Center at Oregon State University in Corvallis was sent five samples as a trial effort. The results are very encouraging. The purpose of compiling Dr. Schmitt's report and the other materials is to inform the sponsor of his independent observations of these results and other information that sent to him. To provide a more complete appreciation of the utility of REE analyses a copy of Dave Vaniman's recent article is included in which he notes that REE analyses from Yucca Mountain indicate the occurrence of two distinctly different REE patterns as do several other chemical parameters of the calcite-silica deposits. Our four samples with high equivalent CaCO 3 were collected from sites we believe to be spring deposits. One sample, 24D, is from southern Crater Flat which is acknowledged by U.S.G.S. investigators to be a spring deposit. All four of these samples have REE patterns similar to those from the saturated zone reported by Vaniman

Partitioning of fluorotelomer alcohols to octanol and different sources of dissolved organic carbon.

Science.gov (United States)

Carmosini, Nadia; Lee, Linda S

2008-09-01

Interest in the environmental fate of fluorotelomer alcohols (FTOHs) has spurred efforts to understand their equilibrium partitioning behavior. Experimentally determined partition coefficients for FTOHs between soil/water and air/water have been reported, but direct measurements of partition coefficients for dissolved organic carbon (DOC)/water (K(doc)) and octanol/ water(K(ow)) have been lacking. Here we measured the partitioning of 8:2 and 6:2 FTOH between one or more types of DOC and water using enhanced solubility or dialysis bag techniques, and also quantified K(ow) values for 4:2 to 8:2 FTOH using a batch equilibration method. The range in measured log K(doc) values for 8:2 FTOH using the enhanced solubility technique with DOC derived from two soils, two biosolids, and three reference humic acids is 2.00-3.97 with the lowest values obtained for the biosolids and an average across all other DOC sources (biosolid DOC excluded) of 3.54 +/- 0.29. For 6:2 FTOH and Aldrich humic acid, a log K(doc) value of 1.96 +/- 0.45 was measured using the dialysis technique. These average values are approximately 1 to 2 log units lower than previously indirectly estimated K(doc) values. Overall, the affinity for DOC tends to be slightly lower than that for particulate soil organic carbon. Measured log K(ow) values for 4:2 (3.30 +/- 0.04), 6:2 (4.54 +/- 0.01), and 8:2 FTOH (5.58 +/- 0.06) were in good agreement with previously reported estimates. Using relationships between experimentally measured partition coefficients and C-atom chain length, we estimated K(doc) and K(ow) values for shorter and longer chain FTOHs, respectively, that we were unable to measure experimentally.

Geochemical and mineralogical characteristics of REE in granite-derived regolith: a model for the Southeast United States

Science.gov (United States)

Foley, Nora K.; Bern, Carleton R.; Ayuso, Robert A.; Hubbard, Bernard E.; Shah, Anjana K.

2015-01-01

Rare earth element (REE) ion-adsorption clay deposits are of global economic importance because they currently supply a significant portion of the world’s annual production of both light (LREE) and heavy REE (HREE). There is considerable ambiguity regarding the origin of

Restoring canonical partition functions from imaginary chemical potential

Science.gov (United States)

Bornyakov, V. G.; Boyda, D.; Goy, V.; Molochkov, A.; Nakamura, A.; Nikolaev, A.; Zakharov, V. I.

2018-03-01

Using GPGPU techniques and multi-precision calculation we developed the code to study QCD phase transition line in the canonical approach. The canonical approach is a powerful tool to investigate sign problem in Lattice QCD. The central part of the canonical approach is the fugacity expansion of the grand canonical partition functions. Canonical partition functions Zn(T) are coefficients of this expansion. Using various methods we study properties of Zn(T). At the last step we perform cubic spline for temperature dependence of Zn(T) at fixed n and compute baryon number susceptibility χB/T2 as function of temperature. After that we compute numerically ∂χ/∂T and restore crossover line in QCD phase diagram. We use improved Wilson fermions and Iwasaki gauge action on the 163 × 4 lattice with mπ/mρ = 0.8 as a sandbox to check the canonical approach. In this framework we obtain coefficient in parametrization of crossover line Tc(µ2B) = Tc(C-ĸµ2B/T2c) with ĸ = -0.0453 ± 0.0099.

Coding Partitions

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Fabio Burderi

2007-05-01

Full Text Available Motivated by the study of decipherability conditions for codes weaker than Unique Decipherability (UD, we introduce the notion of coding partition. Such a notion generalizes that of UD code and, for codes that are not UD, allows to recover the ``unique decipherability" at the level of the classes of the partition. By tacking into account the natural order between the partitions, we define the characteristic partition of a code X as the finest coding partition of X. This leads to introduce the canonical decomposition of a code in at most one unambiguouscomponent and other (if any totally ambiguouscomponents. In the case the code is finite, we give an algorithm for computing its canonical partition. This, in particular, allows to decide whether a given partition of a finite code X is a coding partition. This last problem is then approached in the case the code is a rational set. We prove its decidability under the hypothesis that the partition contains a finite number of classes and each class is a rational set. Moreover we conjecture that the canonical partition satisfies such a hypothesis. Finally we consider also some relationships between coding partitions and varieties of codes.

Solubilities of some hydrous REE phosphates with implications for diagenesis and sea water concentrations

International Nuclear Information System (INIS)

Jonasson, R.G.; Bancroft, G.M.; Nesbitt, H.W.

1985-01-01

Solubility product determinations suggest that the hydrous phosphates of the rare earths, REPO 4 .xH 2 O, are important in controlling the sea water REE concentrations. Two of these solids, rhabdophane, (P6 2 22) and 'hydrous xenotime', (I4 1 /amd), have been synthesized at 100 C via the acid hydrolysis of the respective REE pyrophosphate. The solubility products at infinite dilution were determined to be pK 0 = 24.5, (La at 25 C); 26.0, (Pr at 100 C); 25.7, (Nd at 100 C); and 25.5, (Er at 100 C). On the basis of calculations involving the reaction of Re 3+ with apatite to form the hydrous phosphate, the lanthanum concentration in sea water is predicted to be about 140 pmol/L. Laboratory experiments support the hypothesis that apatite is a substrate for reactions with dissolved REE. (author)

Atmospheric concentrations and phase partitioning of polycyclic aromatic hydrocarbons in Izmir, Turkey

Energy Technology Data Exchange (ETDEWEB)

Demircioglu, Eylem; Odabasi, Mustafa [Faculty of Engineering, Department of Environmental Engineering, Dokuz Eylul University, Izmir (Turkey); Sofuoglu, Aysun [Faculty of Engineering, Department of Chemical Engineering, Izmir Institute of Technology, Gulbahce-Urla (Turkey)

2011-04-15

Ambient air polycyclic aromatic hydrocarbon (PAH) samples were collected at a suburban (n = 63) and at an urban site (n = 14) in Izmir, Turkey. Average gas-phase total PAH (sum {sub 14}PAH) concentrations were 23.5 ng m{sup -3} for suburban and 109.7 ng m{sup -3} for urban sites while average particle-phase total PAH concentrations were 12.3 and 34.5 ng m{sup -3} for suburban and urban sites, respectively. Higher ambient PAH concentrations were measured in the gas-phase and sum {sub 14}PAH concentrations were dominated by lower molecular weight PAHs. Multiple linear regression analysis indicated that the meteorological parameters were effective on ambient PAH concentrations. Emission sources of particle-phase PAHs were investigated using a diagnostic plot of fluorene (FLN)/(fluorine + pyrene; PY) versus indeno[1,2,3-cd]PY/(indeno[1,2,3-cd]PY + benzo[g,h,i]perylene) and several diagnostic ratios. These approaches have indicated that traffic emissions (petroleum combustion) were the dominant PAH sources at both sites for summer and winter seasons. Experimental gas-particle partition coefficients (K{sub P}) were compared to the predictions of octanol-air (K{sub OA}) and soot-air (K{sub SA}) partition coefficient models. The correlations between experimental and modeled K{sub P} values were significant (r{sup 2} = 0.79 and 0.94 for suburban and urban sites, respectively, p < 0.01). Octanol-based absorptive partitioning model predicted lower partition coefficients especially for relatively volatile PAHs. However, overall there was a relatively good agreement between the measured K{sub P} and soot-based model predictions. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

What concentration of actinides can be packed into calcite? Hints from rare earth element (REE) composition

International Nuclear Information System (INIS)

Christiansen, J.; Stipp, S.L.S.; Waight, T.; Baker, J.A.

2005-01-01

Full text of publication follows: For reliable modelling of actinide mobility in the event of spent fuel repository failure, we need data describing the uptake capacity of the minerals likely to find themselves in the transport path. Calcite (CaCO 3 ) is a common secondary mineral in fractures and pore fillings, especially downstream from degrading concrete facilities, so it is a likely candidate for incorporation. Investigations made under ACTAF, a 5. Framework EURATOM integrated project, as well as some other research studies, have shown that actinides are successfully incorporated as substituting ions within the calcite mineral structure. The question remaining, is how much can calcite take up. Geologists routinely use relative concentrations of rare Earth elements (REE's), the lanthanides, for interpreting rock genesis and history. One can also adopt them as analogues for the radioactive elements because their f-orbital electron configuration makes them behave very much like actinides. We collected and analysed a suite of 70 calcite samples from a great number of possible formation environments, geological ages and geographical locations, for the purpose of finding the range and maximum of total f-orbital substitution possible in calcite, under natural conditions. We analysed them using Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). The maximum concentration found was about 5 x 10 -3 mole/kg total REE in a sample that had a geological history of formation where REE fluids played a role. Over the whole suite, total REE ranged from less than 10 -4 moles/kg for limestone samples formed from biogenic calcite where REE-enriched fluids would have played a negligible role. Thus, in natural calcite, REE's are present and all evidence points to a structural incorporation within the mineral rather than as a separate REE-rich phase. These data compare favourably with mole fractions from calcite grown synthetically, where as much as 6 x 10 -3

Quantitative structure-property relationship study of n-octanol-water partition coefficients of some of diverse drugs using multiple linear regression

International Nuclear Information System (INIS)

Ghasemi, Jahanbakhsh; Saaidpour, Saadi

2007-01-01

A quantitative structure-property relationship (QSPR) study was performed to develop models those relate the structures of 150 drug organic compounds to their n-octanol-water partition coefficients (log P o/w ). Molecular descriptors derived solely from 3D structures of the molecular drugs. A genetic algorithm was also applied as a variable selection tool in QSPR analysis. The models were constructed using 110 molecules as training set, and predictive ability tested using 40 compounds. Modeling of log P o/w of these compounds as a function of the theoretically derived descriptors was established by multiple linear regression (MLR). Four descriptors for these compounds molecular volume (MV) (geometrical), hydrophilic-lipophilic balance (HLB) (constitutional), hydrogen bond forming ability (HB) (electronic) and polar surface area (PSA) (electrostatic) are taken as inputs for the model. The use of descriptors calculated only from molecular structure eliminates the need for experimental determination of properties for use in the correlation and allows for the estimation of log P o/w for molecules not yet synthesized. Application of the developed model to a testing set of 40 drug organic compounds demonstrates that the model is reliable with good predictive accuracy and simple formulation. The prediction results are in good agreement with the experimental value. The root mean square error of prediction (RMSEP) and square correlation coefficient (R 2 ) for MLR model were 0.22 and 0.99 for the prediction set log P o/w

Modification of REE distribution of ordinary chondrites from Atacama (Chile) and Lut (Iran) hot deserts: Insights into the chemical weathering of meteorites

Science.gov (United States)

Pourkhorsandi, Hamed; D'Orazio, Massimo; Rochette, Pierre; Valenzuela, Millarca; Gattacceca, Jérôme; Mirnejad, Hassan; Sutter, Brad; Hutzler, Aurore; Aboulahris, Maria

2017-09-01

The behavior of rare earth elements (REEs) during hot desert weathering of meteorites is investigated. Ordinary chondrites (OCs) from Atacama (Chile) and Lut (Iran) deserts show different variations in REE composition during this process. Inductively coupled plasma-mass spectrometry (ICP-MS) data reveal that hot desert OCs tend to show elevated light REE concentrations, relative to OC falls. Chondrites from Atacama are by far the most enriched in REEs and this enrichment is not necessarily related to their degree of weathering. Positive Ce anomaly of fresh chondrites from Atacama and the successive formation of a negative Ce anomaly with the addition of trivalent REEs are similar to the process reported from Antarctic eucrites. In addition to REEs, Sr and Ba also show different concentrations when comparing OCs from different hot deserts. The stability of Atacama surfaces and the associated old terrestrial ages of meteorites from this region give the samples the necessary time to interact with the terrestrial environment and to be chemically modified. Higher REE contents and LREE-enriched composition are evidence of contamination by terrestrial soil. Despite their low degrees of weathering, special care must be taken into account while working on the REE composition of Atacama meteorites for cosmochemistry applications. In contrast, chondrites from the Lut desert show lower degrees of REE modification, despite significant weathering signed by Sr content. This is explained by the relatively rapid weathering rate of the meteorites occurring in the Lut desert, which hampers the penetration of terrestrial material by forming voluminous Fe oxide/oxyhydroxides shortly after the meteorite fall.

The evaluation of the equilibrium partitioning method using sensitivity distributions of species in water and soil or sediment

NARCIS (Netherlands)

Beelen P van; Verbruggen EMJ; Peijnenburg WJGM; ECO

2002-01-01

The equilibrium partitioning method (EqP-method) can be used to derive environmental quality standards (like the Maximum Permissible Concentration or the intervention value) for soil or sediment, from aquatic toxicity data and a soil/water or sediment/water partitioning coefficient. The validity of

Environmental impact assessment on the radioactive of a REE separation project

International Nuclear Information System (INIS)

Li Nana; Zhu Yucheng; Cai Minqi

2011-01-01

Based on the investigation of field actual environment and analysis of radioactive sources, and industrial process techniques, environmental impact of the radioactive from a REE separation project has been analyzed, assessed and forecasted. The investigation and monitoring of actual radioactive in the environment indicated that value of assessment factors remained within the range of natural background level as a whole. The maximum annual individual effective dose for occupational worker and the public were forecasted and were found to be 1.622 mSv/a and 0.029 mSv/a respectively. Both of the values are lower than annual dose limit respectively. The radioactive impact of this project on the environment will comply with the standard limit of law and requirements after the reservation measures are carried out to REE. (authors)

Quantitative structure-property relationships for octanol-water partition coefficients of polybrominated diphenyl ethers.

Science.gov (United States)

Li, Linnan; Xie, Shaodong; Cai, Hao; Bai, Xuetao; Xue, Zhao

2008-08-01

Theoretical molecular descriptors were tested against logK(OW) values for polybrominated diphenyl ethers (PBDEs) using the Partial Least-Squares Regression method which can be used to analyze data with many variables and few observations. A quantitative structure-property relationship (QSPR) model was successfully developed with a high cross-validated value (Q(cum)(2)) of 0.961, indicating a good predictive ability and stability of the model. The predictive power of the QSPR model was further cross-validated. The values of logK(OW) for PBDEs are mainly governed by molecular surface area, energy of the lowest unoccupied molecular orbital and the net atomic charges on the oxygen atom. All these descriptors have been discussed to interpret the partitioning mechanism of PBDE chemicals. The bulk property of the molecules represented by molecular surface area is the leading factor, and K(OW) values increase with the increase of molecular surface area. Higher energy of the lowest unoccupied molecular orbital and higher net atomic charge on the oxygen atom of PBDEs result in smaller K(OW). The energy of the lowest unoccupied molecular orbital and the net atomic charge on PBDEs oxygen also play important roles in affecting the partition of PBDEs between octanol and water by influencing the interactions between PBDEs and solvent molecules.

Desorption modeling of hydrophobic organic chemicals from plastic sheets using experimentally determined diffusion coefficients in plastics.

Science.gov (United States)

Lee, Hwang; Byun, Da-Eun; Kim, Ju Min; Kwon, Jung-Hwan

2018-01-01

To evaluate rate of migration from plastic debris, desorption of model hydrophobic organic chemicals (HOCs) from polyethylene (PE)/polypropylene (PP) films to water was measured using PE/PP films homogeneously loaded with the HOCs. The HOCs fractions remaining in the PE/PP films were compared with those predicted using a model characterized by the mass transfer Biot number. The experimental data agreed with the model simulation, indicating that HOCs desorption from plastic particles can generally be described by the model. For hexachlorocyclohexanes with lower plastic-water partition coefficients, desorption was dominated by diffusion in the plastic film, whereas desorption of chlorinated benzenes with higher partition coefficients was determined by diffusion in the aqueous boundary layer. Evaluation of the fraction of HOCs remaining in plastic films with respect to film thickness and desorption time showed that the partition coefficient between plastic and water is the most important parameter influencing the desorption half-life. Copyright © 2017 Elsevier Ltd. All rights reserved.

Stability of coefficients in the Kronecker product of a hook and a rectangle

International Nuclear Information System (INIS)

Ballantine, Cristina M; Hallahan, William T

2016-01-01

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). (paper)

Partition of selected food preservatives in fish oil-water systems

DEFF Research Database (Denmark)

Cheng, Hongyuan; Friis, Alan; Leth, Torben

2010-01-01

The partition coefficients (Kow) of benzoic acid and sorbic acid in systems of fish oil (sand eel)–water, fish oil–buffer solution, rape oil–water and olive oil–water were experimentally determined in a temperature range from 5 to 43 °C and pH from 4.5 to 6.5 °C. The dimerization of benzoic acid...... in fish oil–water system was observed at 25 °C. Two modifications have been made to the Nordic Food Analysis Standard for the determination of sorbic acid by HPLC. The experimental results show that the Kow of benzoic acid and sorbic acid in fish oil–buffer system is ca. 100 times lower than that in fish...... oil–water system. The Kow values of benzoic acid and sorbic acid in fish oil and water system decrease with increasing system pH values. The partition coefficients of plant origin and fish origin oils are in the same order of magnitude even though their molecular structures are very different....

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

Science.gov (United States)

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.

Determination of solid-liquid partition coefficients (K{sub d}) for diazinon, propetamphos and cis-permethrin: implications for sheep dip disposal

Energy Technology Data Exchange (ETDEWEB)

Cooke, Cindy M.; Shaw, George; Lester, John N.; Collins, Chris D

2004-08-15

Two groups of chemicals are currently licensed for use in sheep dip products in the UK. These are organophosphate (OP) insecticides and synthetic pyrethroid (SP) insecticides. SPs are deemed to be less toxic to human health than OPs, although they are approximately 100 times more toxic to some elements of the aquatic environment. Three insecticides were selected for experimental investigation: diazinon, propetamphos (OPs) and cis-permethrin (SP), representative of the active ingredients used in sheep dip formulations, with additional uses in insect control in crops, and for domestic control of flies, mosquitoes, cockroaches, lice, ticks and spiders. The UK Government has recently reviewed agricultural practices relating to the disposal of used sheep dip, because the constituent insecticides are frequently detected in UK watercourses and the presence of these compounds is a severe hazard to the aquatic environment. Standard batch sorption experiments were carried out to investigate insecticide partitioning from water to soil, and the relationship between sorption and soil organic carbon content is discussed. Sorption isotherms and K{sub d} values showed that cis-permethrin adsorption was fastest on all five soils investigated, exhibiting the greatest total partitioning to the soil phase (83.8-94.8%) and high resistance to desorption. In comparison, the OP insecticides exhibited moderately strong soil adsorption as evidenced by their K{sub d} coefficients (diazinon K{sub d} 12-35 and propetamphos K{sub d} 9-60), with low sorption reversibility (<15%). Calculation of a hydrological retardation factor in a scenario representative of a typical UK environment suggested that SP insecticides such as cis-permethrin will not migrate in the soil profile due to their virtual immobility and strong soil retention, and thus waste sheep dip disposal to agricultural land should not pose a risk to aquatic life if applied with appropriate controls.

Adaptive Neuro-Fuzzy Computing Technique for Determining Turbulent Flow Friction Coefficient

Directory of Open Access Journals (Sweden)

Mohammad Givehchi

2013-08-01

Full Text Available Estimation of the friction coefficient in pipes is very important in many water and wastewater engineering issues, such as distribution of velocity and shear stress, erosion, sediment transport and head loss. In analyzing these problems, knowing the friction coefficient, can obtain estimates that are more accurate. In this study in order to estimate the friction coefficient in pipes, using adaptive neuro-fuzzy inference systems (ANFIS, grid partition method was used. For training and testing of neuro-fuzzy model, the data derived from the Colebrook’s equation was used. In the neuro-fuzzy approach, pipe relative roughness and Reynolds number are considered as input variables and friction coefficient as output variable is considered. Performance of the proposed approach was evaluated by using of the data obtained from the Colebrook’s equation and based on statistical indicators such as coefficient determination (R2, root mean squared error (RMSE and mean absolute error (MAE. The results showed that the adaptive nerou-fuzzy inference system with grid partition method and gauss model as an input membership function and linear as an output function could estimate friction coefficient more accurately than other conditions. The new proposed approach in this paper has capability of application in the practical design issues and can be combined with mathematical and numerical models of sediment transfer or real-time updating of these models.

Palaeoenvironmental signatures revealed from rare earth element (REE compositions of vertebrate microremains of the Vesiku Bone Bed (Homerian, Wenlock, Saaremaa Island, Estonia

Directory of Open Access Journals (Sweden)

Alexandre Fadel

2015-02-01

Full Text Available Rare earth elements (REEs have been analysed from fossil vertebrate microremains (thelodont scales from the Vesiku Bone Bed, Saaremaa, Estonia, using in situ microsampling by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS. Well-preserved scales of three species of the genus Thelodus (T. carinatus, T. laevis and Thelodus sp. show very uniform REE patterns with slightly lower overall REE concentrations in enameloid than in dentine, with enrichment in middle REEs, depletion in heavy REEs and pronounced negative europium anomaly, but no cerium anomaly. The results of this study suggest a similar diagenetic history and possibly contemporaneous habitats for all three Thelodus species, as well as possible suboxic to anoxic conditions of the bottom and pore waters during the formation of the Vesiku Bone Bed.

Influence of biochar on isoproturon partitioning and bioaccessibility in soil.

Science.gov (United States)

Reid, B J; Pickering, F L; Freddo, A; Whelan, M J; Coulon, F

2013-10-01

The influence of biochar (5%) on the loss, partitioning and bioaccessibility of (14)C-isoproturon ((14)C-IPU) was evaluated. Results indicated that biochar had a dramatic effect upon (14)C-IPU partitioning: (14)C-IPU extractability (0.01 M CaCl2) in biochar-amended treatments was reduced to <2% while, (14)C-IPU extractability in biochar free treatments decreased with ageing from 90% to 40%. A partitioning model was constructed to derive an effective partition coefficient for biochar:water (KBW of 7.82 × 10(4) L kg(-1)). This was two orders of magnitude greater than the apparent Kfoc value of the soil organic carbon:water (631 L kg(-1)). (14)C-radiorespirometry assays indicated high competence of microorganisms to mineralise (14)C-IPU in the absence of biochar (40.3 ± 0.9%). Where biochar was present (14)C-IPU mineralisation never exceeded 2%. These results indicate reduced herbicide bioaccessibility. Increasing IPU application to ×10 its recommended dose was ineffective at redressing IPU sequestration and its low bioaccessibility. Copyright © 2013 Elsevier Ltd. All rights reserved.

QSPR models of n-octanol/water partition coefficients and aqueous solubility of halogenated methyl-phenyl ethers by DFT method.

Science.gov (United States)

Zeng, Xiao-Lan; Wang, Hong-Jun; Wang, Yan

2012-02-01

The possible molecular geometries of 134 halogenated methyl-phenyl ethers were optimized at B3LYP/6-31G(*) level with Gaussian 98 program. The calculated structural parameters were taken as theoretical descriptors to establish two new novel QSPR models for predicting aqueous solubility (-lgS(w,l)) and n-octanol/water partition coefficient (lgK(ow)) of halogenated methyl-phenyl ethers. The two models achieved in this work both contain three variables: energy of the lowest unoccupied molecular orbital (E(LUMO)), most positive atomic partial charge in molecule (q(+)), and quadrupole moment (Q(yy) or Q(zz)), of which R values are 0.992 and 0.970 respectively, their standard errors of estimate in modeling (SD) are 0.132 and 0.178, respectively. The results of leave-one-out (LOO) cross-validation for training set and validation with external test sets both show that the models obtained exhibited optimum stability and good predictive power. We suggests that two QSPR models derived here can be used to predict S(w,l) and K(ow) accurately for non-tested halogenated methyl-phenyl ethers congeners. Copyright © 2011 Elsevier Ltd. All rights reserved.

Visualising the equilibrium distribution and mobility of organic contaminants in soil using the chemical partitioning space.

Science.gov (United States)

Wong, Fiona; Wania, Frank

2011-06-01

Assessing the behaviour of organic chemicals in soil is a complex task as it is governed by the physical chemical properties of the chemicals, the characteristics of the soil as well as the ambient conditions of the environment. The chemical partitioning space, defined by the air-water partition coefficient (K(AW)) and the soil organic carbon-water partition coefficient (K(OC)), was employed to visualize the equilibrium distribution of organic contaminants between the air-filled pores, the pore water and the solid phases of the bulk soil and the relative importance of the three transport processes removing contaminants from soil (evaporation, leaching and particle erosion). The partitioning properties of twenty neutral organic chemicals (i.e. herbicides, pharmaceuticals, polychlorinated biphenyls and volatile chemicals) were estimated using poly-parameter linear free energy relationships and superimposed onto these maps. This allows instantaneous estimation of the equilibrium phase distribution and mobility of neutral organic chemicals in soil. Although there is a link between the major phase and the dominant transport process, such that chemicals found in air-filled pore space are subject to evaporation, those in water-filled pore space undergo leaching and those in the sorbed phase are associated with particle erosion, the partitioning coefficient thresholds for distribution and mobility can often deviate by many orders of magnitude. In particular, even a small fraction of chemical in pore water or pore air allows for evaporation and leaching to dominate over solid phase transport. Multiple maps that represent soils that differ in the amount and type of soil organic matter, water saturation, temperature, depth of surface soil horizon, and mineral matters were evaluated.

Petrology and geochemistry of REE-rich Mafé banded iron formations (Bafia group, Cameroon)

Science.gov (United States)

Nkoumbou, Charles; Gentry, Fuh Calistus; Tchakounte Numbem, Jacqueline; Belle Ekwe Lobé, Yolande Vanessa; Nwagoum Keyamfé, Christin Steve

2017-07-01

Archaean-Paleoproterozoic foliated amphibole-gneisses and migmatites interstratified with amphibolites, pyroxeno-amphibolites and REE-rich banded-iron formations outcrop at Mafé, Ndikinimeki area. The foliation is nearly vertical due to tight folds. Flat-lying quartz-rich mica schists and quartzites, likely of Pan-African age, partly cover the formations. Among the Mafé BIFs, the oxide BIF facies shows white layers of quartz and black layers of magnetite and accessory hematite, whereas the silicate BIF facies is made up of thin discontinuous quartz layers alternating with larger garnet (almandine-spessartine) + chamosite + ilmenite ± Fe-talc layers. REE-rich oxide BIFs compositions are close to the East Pacific Rise (EPR) hydrothermal deposit; silicate BIFs plot midway between EPR and the associated amphibolite, accounting for a contamination by volcanic materials, in addition to the hydrothermal influence during their oceanic deposition. The association of an oceanic setting with alkaline and tholeiitic magmatism is typical of the Algoma-type BIF deposit. The REE-rich BIFs indices recorded at Mafé are interpreted as resulting from an Archaean-Paleoproterozoic mineralization.

The role of pegmatites and acid fluids for REE/HFSE mobilization in the Strange Lake peralkaline granitic pluton, Canada

Science.gov (United States)

Gysi, A. P.; Williams-Jones, A.

2012-12-01

The Strange Lake pluton in Canada is a mid-Proterozoic peralkaline granitic intrusion that is host to a world-class rare earth element (REE), yttrium (Y) and high-field strength element (HFSE) deposit containing more than 50 Mt ore at >1.5 wt.% REE and >3 wt.% Zr. The highest REE/HFSE concentrations are found in pegmatite-rich zones characterized by intense alteration. Previous studies of Strange Lake and other peralkaline and alkaline intrusions, such as Khan Bogd (Mongolia) and Tamazeght (Morocco) plutons have shown that hydrothermal alteration may play an important role in the mobility of the REE/HFSE. However, the fluid chemistry and conditions of alteration (i.e., P, T, pH, fO2, ligand activity) in these systems still need to be constrained to evaluate the importance and scale of such hydrothermal mobilization. We present new data from the B-zone, a pegmatite-rich zone located in NW Strange Lake. The pegmatites are generally zoned and form two main types. The border-type pegmatites consist of quartz, K-feldspar and hematized aegirine, whereas volatile-rich pegmatites consist of hydrothermal quartz and fluorite. Transitions between both types were also observed, with the K-feldspar being partly altered and replaced by Al-Si-rich phyllosilicates. The heavy (H)REE and Zr were primarily concentrated in zirconosilicates such as elpidite, now pseudomorphed by zircon or gittinsite, whereas light (L)REE and Y were concentrated in REE-F-(CO2)-minerals such as fluocerite and bastnäsite. Textural and mineralogical observations indicate that these minerals are primary and were partly to completely leached upon fluid-rock interaction in the pegmatites. Secondary phases include Ca-F-Y-rich minerals, mainly hydrothermal fluorite, that fill vugs and replaced primary REEHFSE minerals. The presence of hydrothermal fluorite veins, micro-veins, vugs and micro-breccia in the most altered parts of the B-zone are interpreted to reflect interaction of the rocks with a F-rich fluid

Determination of Th and REE in columbite - tantalite samples by ICP-OES

International Nuclear Information System (INIS)

Hanuman, V.V.; Khorge, C.R.; Radhamai, R.; Nair, Sajitha; Srivastava, P.K.

2007-01-01

A simple method of decomposition and separation of Th and REE in columbite- tantalite is developed for determination by ICP- OES. The sample is decomposed with hydrofluoric and hydrochloric acid in presence of little sulphuric acid to avoid drying on water bath. Th and rare earths are separated as fluoride together with undecomposed sample. The residue is fused with a 1: 1 mixture of sodium di hydrogen orthophosphate and sodium pyrophosphate. The melt is dissolved in water for measurement. Nitric acid is found unsuitable due to loss in Ce in some of the samples. Matrix elements (more than 97.5) are removed in single step by both the treatments. The free cassiterite present in samples is not attacked during acid digestion. However, the same is easily decomposed in fusion. U (IV) is also precipitated along with Th and REE when hydrochloric acid is used. As expected uranium is lost when nitric acid is used. The results are compared with existing well-established procedure involving peroxide fusion for decomposition; hydroxide and fluoride precipitation separation. Both the methods yielded comparable result. The method is simple, comparatively rapid and suitable for routine application for determination of REE , Th and U(IV) content. The RSD of the method was found to be in the range of 1- 1.5% for various elements. (author)

Discrete event simulation of NASA's Remote Exploration and Experimentation Project (REE)

Science.gov (United States)

Dunphy, J.; Rogstad, S.

2001-01-01

The Remote Exploration and Experimentation Project (REE) is a new initiative at JPL to be able to place a supercomputer on board a spacecraft and allow large amounts of data reduction and compression to be done before science results are returned to Earth.

The effect of the water-to-rock ratio on REE distribution in hydrothermal fluids: An experimental study

Science.gov (United States)

Beermann, Oliver; Garbe-Schönberg, Dieter; Holzheid, Astrid

2013-04-01

High-temperature submarine MOR hydrothermalism creates high elemental fluxes into, and out of, oceanic lithosphere significantly affecting ocean chemistry. The Turtle Pits hydrothermal system discovered at 5° S on the slow-spreading Mid-Atlantic Ridge (MAR) in water depths of ~3000 m (~300 bar) emanates 'ultrahot' fluids > 400 ° C [1] with high concentrations of dissolved gases (e.g., H2), transition metals, and rare earth elements (REE). The normalised REE patterns of these 'ultrahot' fluids are uncommon as they exhibit depletions of LREE and no Eu-anomaly ('special' REE-signature in [2]), which is in contrast to the "typical" LREE enrichment and pronounced positive Eu-anomaly known from many MOR vent fluids observed world-wide [e.g., 3]. Although hydrothermal fluid REE-signatures may play a key role in understanding processes during water-rock interaction, only few experimental data have been published on REE distribution in seawater-like fluids reacted with rocks from the ocean crust [e.g., 4, 5]. Besides temperature, the seawater-to-rock ratio (w/r ratio) strongly affects water-rock reaction processes and, thus, has significant control on the fluid chemistry [e.g., 6, 7]. To understand how vent fluid REE-signatures are generated during water-rock interaction processes we designed a series of experiments reacting different fluid types with mineral assemblages from fresh, unaltered gabbro at 425 ° C and 400 bar using cold seal pressure vessels (CSPV). Mixtures of 125-500 μm-sized hand-picked plagioclase and clinopyroxene grains separated from unaltered gabbro reacted in gold capsules with 3.2 wt.% NaCl(aq) fluid (similar to seawater salinity), or with natural seawater. The w/r (mass) ratio ranged from 1 to 100 and the run durations were varied from 3 to 30 d in the NaCl(aq) experiments, and was 3 d in the seawater experiments. The reacted fluids were extracted after quenching and analysed by ICP-OES and ICP-MS. Only in the seawater experiments, the gabbro

Partitioning of Nanoparticles into Organic Phases and Model Cells

Energy Technology Data Exchange (ETDEWEB)

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

Experimental determination and thermodynamic modeling of phase equilibrium and protein partitioning in aqueous two-phase systems containing biodegradable salts

International Nuclear Information System (INIS)

Perez, Brenda; Malpiedi, Luciana Pellegrini; Tubío, Gisela; Nerli, Bibiana; Alcântara Pessôa Filho, Pedro de

2013-01-01

Highlights: ► Binodal data of systems (water + polyethyleneglycol + sodium) succinate are reported. ► Pitzer model describes the phase equilibrium of systems formed by polyethyleneglycol and biodegradable salts satisfactorily. ► This simple thermodynamic framework was able to predict the partitioning behaviour of model proteins acceptably well. - Abstract: Phase diagrams of sustainable aqueous two-phase systems (ATPSs) formed by polyethyleneglycols (PEGs) of different average molar masses (4000, 6000, and 8000) and sodium succinate are reported in this work. Partition coefficients (Kps) of seven model proteins: bovine serum albumin, catalase, beta-lactoglobulin, alpha-amylase, lysozyme, pepsin, urease and trypsin were experimentally determined in these systems and in ATPSs formed by the former PEGs and other biodegradable sodium salts: citrate and tartrate. An extension of Pitzer model comprising long and short-range term contributions to the excess Gibbs free energy was used to describe the (liquid + liquid) equilibrium. Comparison between experimental and calculated tie line data showed mean deviations always lower than 3%, thus indicating a good correlation. The partition coefficients were modeled by using the same thermodynamic approach. Predicted and experimental partition coefficients correlated quite successfully. Mean deviations were found to be lower than the experimental uncertainty for most of the assayed proteins.

Mineralogy and geochemistry of REE-Zr-Nb mineralised nepheline syenites in the peralkaline Ilímaussaq complex, South Greenland

DEFF Research Database (Denmark)

Borst, Anouk Margaretha

Summary: The rare earth elements (REE) share unique physical, chemical and light-emitting properties that are of great importance to the high-tech industry. Among the many rocks containing appreciable amounts of REE, alkaline igneous rocks and carbonatites provide important resources for these el...

Deciphering human-climate interactions in an ombrotrophic peat record: REE, Nd and Pb isotope signatures of dust supplies over the last 2500 years (Misten bog, Belgium)

Science.gov (United States)

Fagel, N.; Allan, M.; Le Roux, G.; Mattielli, N.; Piotrowska, N.; Sikorski, J.

2014-06-01

A high-resolution peat record from Eastern Belgium reveals the chronology of dust deposition for the last 2500 years. REE and lithogenic elements in addition to Nd and Pb isotopes were measured in a 173 cm age-dated peat profile and provide a continuous chronology of dust source and intensity. Calculated dust flux show pronounced increases c. 300 BC, 600 AD, 1000 AD, 1200 AD and from 1700 AD, corresponding to local and regional human activities combined with climate change. The Industrial Revolution samples (1700-1950 AD) are characterised by a significant enrichment in Sc-normalised REE abundance (sum REE/Sc > 25) due to intensive coal combustion. For the pre-Industrial Revolution samples, the Sc-normalised REE abundance (10 climate. Combining REE abundance, fractionation between Light REE and Heavy REE and Nd isotope data in ombrotrophic peat allows one to distinguish between dust flux changes related to human and climate forcings.

REE compositions in fossil vertebrate dental tissues indicate biomineral preservation

Science.gov (United States)

Žigaite, Ž.; Kear, B.; Pérez-Huerta, A.; Jeffries, T.; Blom, H.

2012-04-01

Rare earth element (REE) abundances have been measured in a number of Palaeozoic and Mesozoic dental tissues using Laser Ablation Inductively Coupled Plasma Mass-spectrometry (LA-ICP-MS). Fossil vertebrates analysed comprise scales and tesserae of Silurian and Devonian acanthodians, chondrichthyans, galeaspids, mongolepids, thelodonts, as well as teeth of Cretaceous lungfish and marine reptiles. The evaluation of fossil preservation level has been made by semi-quantitative spot geochemistry analyses on fine polished teeth and scale thin sections, using Energy Dispersive X-ray Spectroscopy (EDS). Fossil teeth and scales with significant structure and colour alteration have shown elevated heavy element concentrations, and the silicification of bioapatite has been common in their tissues. Stable oxygen isotope measurements (δ18O) of bulk biomineral have been conducted in parallel, and showed comparatively lower heavy oxygen values in the same fossil tissues with stronger visible alteration. Significant difference in REE concentrations has been observed between the dentine and enamel of Cretaceous plesiosaurs, suggesting the enamel to be more geochemically resistant to diagenetic overprint.

Atmospheric concentration characteristics and gas-particle partitioning of PCBs in a rural area of eastern Germany

International Nuclear Information System (INIS)

Mandalakis, Manolis; Stephanou, Euripides G.

2007-01-01

Atmospheric concentrations of polychlorinated biphenyls (PCBs) were measured in 14 successive daytime and nighttime air samples collected from Melpitz, a rural site in eastern Germany. The average total concentration of PCBs was 110+/-80pgm -3 and they were predominately present in the gas phase (∼95%). Composition of individual congeners closely resembled those of Clophen A30 and Aroclor 1232. Partial vapor pressures of PCBs were well correlated with temperature and the steep slopes obtained from Clausius-Clapeyron plots (-4500 to -8000) indicated that evaporation from adjacent land surfaces still controls the atmospheric levels of these pollutants. Particle-gas partitioning coefficients (K P ) of PCBs were well correlated with the respective sub-cooled vapor pressures (P L o ), but the slopes obtained from logK P versus logP L o plots (-0.16 to -0.59) deviated significantly from the expected value of -1. Overall, gas-particle partitioning of PCBs was better simulated by Junge-Pankow than octanol/air partition coefficient-based model

Absorption dynamics of organic chemical transport across trout gills as related to octanol-water partition coefficient

International Nuclear Information System (INIS)

McKim, J.; Schmieder, P.; Veith, G.

1985-01-01

An in vivo fish preparation was used that allowed a direct measure of the transport rates of 14 different organic chemicals across the gills of rainbow trout (Salmo gairdneri). The chemicals, all C14 labeled, were selected from five classes, encompassing a range of octanol-water partition coefficient (log P) values, from 0.23 (ethyl formate) to 7.5 (mirex). The uptake efficiency (extraction efficiency) of each chemical was determined by monitoring the inspired and expired water of trout exposed to each chemical over an exposure period of 1 to 6 hr. The mean gill extraction efficiency for all chemicals tested varied from a low of 7% to a high of 60%, extracted in a single pall of the chemical across the gills. The extraction efficiency of chemicals with log P or 1 or less were low and showed no relationship to log P. These low extraction efficiencies seen at log P of 1 and below with molecular weights below 100 were indicative of aqueous pore transport. The mean extraction efficiency for chemicals with log P values of 1 to 3 seemed to vary directly with log P, to a maximum of slightly greater than 60%, suggesting that uptake was controlled by the lipid membrane. The mean extraction efficiency for chemicals with log P of 3 to 6 was independent of log P and remained at 60%, which suggested that gill uptake was controlled by aqueous diffusion rates rather than gill membrane permeability. The mean extraction efficiency with mirex (log P . 7.5) decreased to 20%

Study and modeling of the evolution of gas-liquid partitioning of hydrogen sulfide in model solutions simulating winemaking fermentations.

Science.gov (United States)

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%.

Magmatic evolution and REE mineralization in the early Cambrian Jbel Boho igneous complex in the Bou Azzer inlier (Anti-Atlas/Morocco)

OpenAIRE

Benaouda, Rachid

2015-01-01

The igneous rocks of Jbel Boho emerged in three phases: an initial phase with alkaline volcanism followed by the intrusion of a syenitic pluton and later the emplacement of a dyke swarm. The Jbel Boho alkaline complex shows some interesting aspects of hydrothermal REE mineralization in the late differentiation stage. REE mineralization is found in a rhyolitic dyke and some late hydrothermal veins. Synchysite-(Ce), which was identified by EPMA analysis, is the main REE mineral.

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

Science.gov (United States)

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.

Atmospheric occurrence, transport and gas-particle partitioning of polychlorinated biphenyls over the northwestern Pacific Ocean

Science.gov (United States)

Wu, Zilan; Lin, Tian; Li, Zhongxia; Li, Yuanyuan; Guo, Tianfeng; Guo, Zhigang

2017-10-01

Ship-board air samples were collected during March to May 2015 from the East China Sea (ECS) to the northwestern Pacific Ocean (NWP) to explore the atmospheric occurrence and gas-particle partitioning of polychlorinated biphenyls (PCBs) when the westerly East Asian Monsoon prevailed. Total PCB concentrations in the atmosphere ranged from 56.8 to 261 pg m-3. Higher PCB levels were observed off the coast and minor temperature-induced changes showed that continuous emissions from East Asia remain as an important source to the regional atmosphere. A significant relationship between Koa (octanol-air partition coefficient) and KP (gas-particle partition coefficient) for PCBs was observed under continental air masses, suggesting that land-derived organic aerosols affected the PCB gas-particle partitioning after long-range transport, while an absence of this correlation was identified in marine air masses. The PCB partitioning cannot be fully explained by the absorptive mechanism as the predicted KP were found to be 2-3 orders of magnitude lower than the measured Kp, while the prediction was closely matched when soot adsorption was considered. The results suggested the importance of soot carbon as a transport medium for PCBs during their long-range transport and considerable impacts of continental outflows on PCBs across the downwind area. The estimated transport mass of particulate PCBs into the ECS and NWP totals 2333 kg during the spring, constituting ca. 17% of annual emission inventories of unintentionally produced PCB in China.

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

Science.gov (United States)

Eganhouse, Robert P.

2016-01-01

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.

Experimental Study of the Partitioning of Siderophile Elements in a Crystallizing Lunar Magma Ocean

Science.gov (United States)

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.

Confocal Raman Microscopy for in Situ Measurement of Phospholipid-Water Partitioning into Model Phospholipid Bilayers within Individual Chromatographic Particles.

Science.gov (United States)

Kitt, Jay P; Bryce, David A; Minteer, Shelley D; Harris, Joel M

2018-06-05

The phospholipid-water partition coefficient is a commonly measured parameter that correlates with drug efficacy, small-molecule toxicity, and accumulation of molecules in biological systems in the environment. Despite the utility of this parameter, methods for measuring phospholipid-water partition coefficients are limited. This is due to the difficulty of making quantitative measurements in vesicle membranes or supported phospholipid bilayers, both of which are small-volume phases that challenge the sensitivity of many analytical techniques. In this work, we employ in situ confocal Raman microscopy to probe the partitioning of a model membrane-active compound, 2-(4-isobutylphenyl) propionic acid or ibuprofen, into both hybrid- and supported-phospholipid bilayers deposited on the pore walls of individual chromatographic particles. The large surface-area-to-volume ratio of chromatographic silica allows interrogation of a significant lipid bilayer area within a very small volume. The local phospholipid concentration within a confocal probe volume inside the particle can be as high as 0.5 M, which overcomes the sensitivity limitations of making measurements in the limited membrane areas of single vesicles or planar supported bilayers. Quantitative determination of ibuprofen partitioning is achieved by using the phospholipid acyl-chains of the within-particle bilayer as an internal standard. This approach is tested for measurements of pH-dependent partitioning of ibuprofen into both hybrid-lipid and supported-lipid bilayers within silica particles, and the results are compared with octanol-water partitioning and with partitioning into individual optically trapped phospholipid vesicle membranes. Additionally, the impact of ibuprofen partitioning on bilayer structure is evaluated for both within-particle model membranes and compared with the structural impacts of partitioning into vesicle lipid bilayers.

Unique Path Partitions

DEFF Research Database (Denmark)

Bessenrodt, Christine; Olsson, Jørn Børling; Sellers, James A.

2013-01-01

We give a complete classification of the unique path partitions and study congruence properties of the function which enumerates such partitions.......We give a complete classification of the unique path partitions and study congruence properties of the function which enumerates such partitions....

The criteria for the Cohen-Macaulayness and Gorensteiness of Rees algebras of ideals having positive analytic deviation

International Nuclear Information System (INIS)

Duong Quoc Viet.

1994-06-01

This paper investigates the relationships between the maximal reduction number and q-invariant of a graded ring in the case of Rees ring being a Cohen-Macaulay or Gorenstein ring. From these relationships we give the criteria for Rees algebra of the ideal I having arbitrary analytic deviation to be Cohen-Macaulay and Gorenstein in terms of associated graded ring and maximal reduction number of I. (author). 16 refs

Rare earth elements (REE) as natural and applied tracers in the catchment area of Gessental valley, former uranium mining area of Eastern Thuringia, Germany

Science.gov (United States)

Buechel, G.; Merten, D.; Geletneky, J. W.; Kothe, E.

2003-04-01

Between 1947 and 1990 about 113.000 t of uranium were excavated at the former uranium mining site of Ronneburg (Eastern Thuringia, Germany). The legacy consists of more than 200 million m^3 of metasedimentary rocks rich in organic matter, sulfides and heavy metals originally deposited in mining heaps at the surface. The metasedimentary rocks formed under anoxic conditions about a 400 Mio. years ago are now exposed to oxic conditions. The oxidation of markasite and pyrite results in the formation of H_2SO_4. The formation of acid mine drainage (AMD) leads to high concentrations of uranium, rare earth elements (REE) and other heavy metals in surface water, seepage water and groundwater. This mobilization is due to alteration enhanced by high microbial activity and low pH. The tolerance mechanisms towards heavy metal pollution of soil substrate and surface/groundwater has allowed the selection of microbes which have, e.g. specific transporter genes and which are associated to plants in symbiotic interactions like mycorrhiza. In order to follow the processes linking alteration of metasedimentary rocks to biological systems the use of tracers is needed. One group of such tracers occuring in high concentrations in the water phase at the Ronneburg mining site are the REE (La-Lu) which are featured by very similar chemical behaviour. They show smooth but continuous variations of their chemical behaviour as a function of atomic number. For seepage water of the waste rock dump Nordhalde - sampled over a period of two years - the shale normalized REE patterns show enrichment of heavy REE and only minor variations, although the concentration differs. At sampling points in the surface water and in groundwater rather similar REE patterns were observed. Thus, REE can be used as tracers to identify diffuse inflow of REE-rich acid mine drainage of the dumps into the creek and the sediments. The absolute concentrations of REE in the creek and in ground water are up to 1000 times

Review of the partitioning of chemicals into different plastics: Consequences for the risk assessment of marine plastic debris

International Nuclear Information System (INIS)

O'Connor, Isabel A.; Golsteijn, Laura; Hendriks, A. Jan

2016-01-01

Marine plastic debris are found worldwide in oceans and coastal areas. They degrade only slowly and contain chemicals added during manufacture or absorbed from the seawater. Therefore, they can pose a long-lasting contaminant source and potentially transfer chemicals to marine organisms when ingested. In order to assess their risk, the contaminant concentration in the plastics needs to be estimated and differences understood. We collected from literature plastic water partition coefficients of various organic chemicals for seven plastic types: polydimethylsiloxane (PDMS), high-density, low-density and ultra-high molecular weight polyethylene (LDPE, HDPE, UHMWPE), polystyrene (PS), polypropylene (PP), and polyvinyl chloride (PVC). Most data was available for PDMS (1060) and LDPE (220), but much less for the remaining plastics (73). Where possible, regression models were developed and the partitioning was compared between the different plastic types. The partitioning of chemicals follows the order of LDPE ≈ HDPE ≥ PP > PVC ≈ PS. Data describing the impact of weathering are urgently needed. - Highlights: • Comparison of organic chemicals partitioning into seven plastic types • Linear correlation between plastic-water partition coefficient K pw and K ow • More data is needed for polypropylene, polystyrene and polyvinyl chloride. • In all plastic types, most K pw were similar to/smaller than the corresponding K ow .

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

Science.gov (United States)

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.

Solid/liquid partition coefficients (Kd) for selected soils and sediments at Forsmark and Laxemar-Simpevarp

Energy Technology Data Exchange (ETDEWEB)

Sheppard, Steve; Long, Jeff; Sanipelli, Barb [ECOMatters Inc., Pinawa (Canada); Sohlenius, Gustav [Geological Survey of Sweden (SGU), Uppsala (Sweden)

2009-03-15

Soil and sediment solid/liquid partition coefficients (Kd) are used to indicate the relative mobility of radionuclides and elements of concern from nuclear fuel waste, as well as from other sources. The Kd data are inherently extremely variable, but also vary systematically with key environmental attributes. For soil Kd, the key variables are pH, clay content and organic carbon content. For sediment Kd, water type (freshwater versus marine) and sediment type (benthic versus suspended) are important. This report summarized Kd data for soils and sediments computed from indigenous stable element concentrations measured at the Forsmark and Laxemar-Simpevarp sites. These were then compared to several literature sources of Kd data for Ce, Cl, Co, Cr, Cs, Fe, Ho, I, La, Mn, Mo, Nb, Nd, Ni, Np, Pa, Pb, Pu, Ra, Sb, Se, Sm, Sn, Sr, Tc, Th, Tm, U and Yb. The Kd data computed from indigenous stable element concentrations may be especially relevant for assessment of long-lived radionuclides from deep disposal of waste, because the long time frame for the potential releases is more consistent with the steady state measured using indigenous stable elements. For almost every one of these elements in soils, a statistically meaningful regression equation was developed to allow estimation of Kd for any soil given a modest amount of information about the soil. Nonetheless, the median residual geometric standard deviation (GSD) was 4.3-fold, implying confidence bounds of about 18-fold above and below the best estimate Kd. For sediment, the values are categorised simply by water type and sediment type. The median GSD for sediment Kd as measured at the Forsmark and Laxemar-Simpevarp sites was 2.5-fold, but the median GSD among literature values was as high as 8.6-fold. Clearly, there remains considerable uncertainty in Kd values, and it is important to account for this in assessment applications

Solid/liquid partition coefficients (Kd) for selected soils and sediments at Forsmark and Laxemar-Simpevarp

International Nuclear Information System (INIS)

Sheppard, Steve; Long, Jeff; Sanipelli, Barb; Sohlenius, Gustav

2009-03-01

Soil and sediment solid/liquid partition coefficients (Kd) are used to indicate the relative mobility of radionuclides and elements of concern from nuclear fuel waste, as well as from other sources. The Kd data are inherently extremely variable, but also vary systematically with key environmental attributes. For soil Kd, the key variables are pH, clay content and organic carbon content. For sediment Kd, water type (freshwater versus marine) and sediment type (benthic versus suspended) are important. This report summarized Kd data for soils and sediments computed from indigenous stable element concentrations measured at the Forsmark and Laxemar-Simpevarp sites. These were then compared to several literature sources of Kd data for Ce, Cl, Co, Cr, Cs, Fe, Ho, I, La, Mn, Mo, Nb, Nd, Ni, Np, Pa, Pb, Pu, Ra, Sb, Se, Sm, Sn, Sr, Tc, Th, Tm, U and Yb. The Kd data computed from indigenous stable element concentrations may be especially relevant for assessment of long-lived radionuclides from deep disposal of waste, because the long time frame for the potential releases is more consistent with the steady state measured using indigenous stable elements. For almost every one of these elements in soils, a statistically meaningful regression equation was developed to allow estimation of Kd for any soil given a modest amount of information about the soil. Nonetheless, the median residual geometric standard deviation (GSD) was 4.3-fold, implying confidence bounds of about 18-fold above and below the best estimate Kd. For sediment, the values are categorised simply by water type and sediment type. The median GSD for sediment Kd as measured at the Forsmark and Laxemar-Simpevarp sites was 2.5-fold, but the median GSD among literature values was as high as 8.6-fold. Clearly, there remains considerable uncertainty in Kd values, and it is important to account for this in assessment applications

Determination of the REE in environmental samples near a coal power station based on k0-standardized NAA with counting in a LEPD

International Nuclear Information System (INIS)

Freitas, M.C.; Gouveia, M.A.; Prudencio, M.I.; Cabral, J.M.P.; Corte, F. de

1993-01-01

The REE contents in lichens and plants determined by k 0 -standardized NAA with LEPD and HPGe are compared. Similar values were obtained for Sm, Eu, Tb and Yb and better values for Ce and Nd by using LEPD Besides, LEPD allows the determination of Gd, Tm and Lu. The study of REE concentrations in the neighbourhood of two coal power stations show that in the station under construction (C.T. Pego), the index of accumulation of each REE by the lichens and olive tree leaves is identical in two sampling loci where the soils have different REE concentrations; and in the station in operation (C.T. Sines), the REE contents in the soils is identical and the differences observed in the lichens and wild terrestrial plants are most probably due to the fly-ashes emission from the station. (author) 9 refs.; 4 figs.; 6 tabs

Trace element mobility in mine waters from granitic pegmatite U–Th–REE deposits, Bancroft area, Ontario

International Nuclear Information System (INIS)

Desbarats, A.J.; Percival, J.B.; Venance, K.E.

2016-01-01

Small, low-grade, granitic pegmatite U–Th–REE deposits are found throughout the Grenville geological province of eastern Canada. Groundwater quality at historical mining properties in the Bancroft area was investigated in order to better understand the mobility of trace elements that may pose health risks if there is renewed development of this class of mineral deposit. Groundwater samples were obtained from diamond drill holes, flowing adits and flooded mine shafts. Uranium occurs almost entirely in the dissolved (<0.45 μm) phase and is found at concentrations reaching 2579 μg/L. The Canadian maximum acceptable concentration for U in drinking water (0.02 mg/L) was exceeded in 70% of samples. Regulatory limits for 226 Ra (0.5 Bq/L) and for 210 Pb (0.2 Bq/L) were generally exceeded in these samples as well. Speciation modeling indicates that over 98% of dissolved U is in the form of highly mobile uranyl-Ca–carbonate complexes known to inhibit U adsorption. Uranium concentrations in groundwater appear to be correlated with the uranothorite content of the deposits rather than with their U grade. Uranothorite may be more soluble than uraninite, the other ore mineral, because of its non-ideal composition and metamict structure. Thorium, released concomitantly with U during the dissolution of uranothorite and thorian uraninite, exhibits median and maximum total concentrations of only 0.1 and 11 μg/L, respectively. Mass balance and stoichiometric considerations indicate that almost all Th is immobilized very close to its source. The sums of total light REE (La–Gd) concentrations have median and maximum values of 6 and 117 μg/L, respectively. The sums of total heavy REE (Tb–Lu) concentrations have median and maximum values of 0.8 and 21 μg/L, respectively. Light REE are derived mainly from the dissolution of metamict allanite whereas the sources of heavy REE are widely dispersed among accessory minerals. Fractionation patterns of REE in the dissolved

Measured and numerically partitioned phytoplankton spectral absorption coefficients in inland waters

NARCIS (Netherlands)

Zhang, Y.; Liu, M.; Van Dijk, M.A.; Zhu, G.; Gong, Z.; Li, Y.M.; Qin, B.

2009-01-01

Total particulate, tripton and phytoplankton absorption coefficients were measured for eutrophic (Lake Taihu), meso-eutrophic (Lake Tianmuhu) and mesotrophic waters (the Three Gorges Reservoir) in China using the quantitative filter technique. Meanwhile, tripton and phytoplankton absorption

Distribution of REEs and yttrium among major geochemical phases of marine Fe–Mn-oxides: Comparative study between hydrogenous and hydrothermal deposits

Digital Repository Service at National Institute of Oceanography (India)

SuryaPrakash, L.; Ray, D.; Paropkari, A.L.; Mudholkar, A.V.; Satyanarayanan, M.; Sreenivas, B.; Chandrasekharam, D.; Kota, D.; KameshRaju, K.A.; Kaisary, S.; Balaram, V.; Gurav, T.

REEs. Thermodynamic calculations (Hass et al., 1995) as well as laboratory experiments (Lewis et al., 1998; Douville et al., 1999) show that dissolved REEs in geothermal fluid mostly occur as fluoride, chloride, sulfate complexes or free...

Release of U, Th, and REE from granitic rock: A mineralogical approach

International Nuclear Information System (INIS)

Markovaara-Koivisto, M.

2006-01-01

Finland plans to dispose of its spent nuclear fuel deep in the bedrock, and comprehensive assessment of the potential risks is required. One risk is glaciations induced by climate change, which might eventually cause malfunction of the engineered barrier system and breakdown of the copper-iron canisters containing the spent fuel. The fuel might then come into contact with groundwater. This groundwater might be acidic rain water, or oxygenated glacial melt water, which intrudes into the bedrock with hydrostatic pressure under the ice sheet. In this study, behaviour of uranium and rare earth elements was investigated in the Palmottu uranium deposit. Studies in the Palmottu deposit provide an indication of how uranium and other harmful elements could migrate from the repository to the surrounding bedrock in the event the canisters were breached. The spent fuel contains uranium and other actinides. The possible release of these elements and their behaviour after release in bedrock and groundwater were studied by means of chemical analogues occurring in nature, namely uranium (U), thorium (Th) and rare earth elements (REE). The study was focused on the mode of occurrence of these elements in granitic rocks. The chemistry of the mineral phases was explored by scanning electron microscopy and wavelength dispersive spectrometry, while the release of the elements was investigated with leaching experiments. In the first phase the samples were leached with artificial groundwater. In the second phase a HNO 3 solution of pH 5 was used, and in the final step a solution of pH 3. The U, Th and REE phases after each leaching were studied by fieldemission scanning electron microscopy and energy dispersive XRay microanalysis (EDAX), and the leachates were analysed by mass spectrometry (ICPMS and ICPAES). The aim of this study was to clarify how U, Th and REEs behave in the leaching processes associated with solutions simulating possible natural water conditions in the bedrock and to

Summer-winter concentrations and gas-particle partitioning of short chain chlorinated paraffins in the atmosphere of an urban setting.

Science.gov (United States)

Wang, Thanh; Han, Shanlong; Yuan, Bo; Zeng, Lixi; Li, Yingming; Wang, Yawei; Jiang, Guibin

2012-12-01

Short chain chlorinated paraffins (SCCPs) are semi-volatile chemicals that are considered persistent in the environment, potential toxic and subject to long-range transport. This study investigates the concentrations and gas-particle partitioning of SCCPs at an urban site in Beijing during summer and wintertime. The total atmospheric SCCP levels ranged 1.9-33.0 ng/m(3) during wintertime. Significantly higher levels were found during the summer (range 112-332 ng/m(3)). The average fraction of total SCCPs in the particle phase (ϕ) was 0.67 during wintertime but decreased significantly during the summer (ϕ = 0.06). The ten and eleven carbon chain homologues with five to eight chlorine atoms were the predominant SCCP formula groups in air. Significant linear correlations were found between the gas-particle partition coefficients and the predicted subcooled vapor pressures and octanol-air partition coefficients. The gas-particle partitioning of SCCPs was further investigated and compared with both the Junge-Pankow adsorption and K(oa)-based absorption models. Copyright © 2012 Elsevier Ltd. All rights reserved.

Calculation of site affinity constants and cooperativity coefficients for binding of ligands and/or protons to macromolecules. II. Relationships between chemical model and partition function algorithm.

Science.gov (United States)

Fisicaro, E; Braibanti, A; Lamb, J D; Oscarson, J L

1990-05-01

The relationships between the chemical properties of a system and the partition function algorithm as applied to the description of multiple equilibria in solution are explained. The partition functions ZM, ZA, and ZH are obtained from powers of the binary generating functions Jj = (1 + kappa j gamma j,i[Y])i tau j, where i tau j = p tau j, q tau j, or r tau j represent the maximum number of sites in sites in class j, for Y = M, A, or H, respectively. Each term of the generating function can be considered an element (ij) of a vector Jj and each power of the cooperativity factor gamma ij,i can be considered an element of a diagonal cooperativity matrix gamma j. The vectors Jj are combined in tensor product matrices L tau = (J1) [J2]...[Jj]..., thus representing different receptor-ligand combinations. The partition functions are obtained by summing elements of the tensor matrices. The relationship of the partition functions with the total chemical amounts TM, TA, and TH has been found. The aim is to describe the total chemical amounts TM, TA, and TH as functions of the site affinity constants kappa j and cooperativity coefficients bj. The total amounts are calculated from the sum of elements of tensor matrices Ll. Each set of indices (pj..., qj..., rj...) represents one element of a tensor matrix L tau and defines each term of the summation. Each term corresponds to the concentration of a chemical microspecies. The distinction between microspecies MpjAqjHrj with ligands bound on specific sites and macrospecies MpAqHR corresponding to a chemical stoichiometric composition is shown. The translation of the properties of chemical model schemes into the algorithms for the generation of partition functions is illustrated with reference to a series of examples of gradually increasing complexity. The equilibria examined concern: (1) a unique class of sites; (2) the protonation of a base with two classes of sites; (3) the simultaneous binding of ligand A and proton H to a

Sediment pore water distribution coefficients of PCB congeners in enriched black carbon sediment

International Nuclear Information System (INIS)

Martinez, Andres; O'Sullivan, Colin; Reible, Danny; Hornbuckle, Keri C.

2013-01-01

More than 2300 sediment pore water distribution coefficients (K PCBids ) of 93 polychlorinated biphenyls (PCBs) were measured and modeled from sediments from Indiana Harbor and Ship Canal. K PCBids were calculated from previously reported bulk sediment values and newly analyzed pore water. PCBs in pore waters were measured using SPME PDMS-fiber and ∑PCB ranged from 41 to 1500 ng L −1 . The resulting K PCBids were ∼1 log unit lower in comparison to other reported values. A simple model for the K PCBid consisted of the product of the organic carbon fraction and the octanol–water partition coefficient and provided an excellent prediction for the measured values, with a mean square error of 0.09 ± 0.06. Although black carbon content is very high in these sediments and was expected to play an important role in the distribution of PCBs, no improvement was obtained when a two-carbon model was used. -- Highlights: •PCB sediment-pore water distribution coefficients were measured and modeled. •Distribution coefficients were lower in comparison to other reported values. •Organic carbon fraction times the K OW yielded the best prediction model. •The incorporation of black carbon into a model did not improve the results. -- The organic carbon fraction times the octanol–water partition coefficient yielded the best prediction model for the sediment pore water distribution coefficient of PCBs

Partitioning of organophosphorus pesticides into phosphatidylcholine small unilamellar vesicles studied by second-derivative spectrophotometry.

Science.gov (United States)

Takegami, Shigehiko; Kitamura, Keisuke; Ohsugi, Mayuko; Ito, Aya; Kitade, Tatsuya

2015-06-15

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 (R(2)=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. Copyright © 2015 Elsevier B.V. All rights reserved.

General geochemical properties and abundances of the rare earth elements

International Nuclear Information System (INIS)

Henderson, P.

1984-01-01

This chapter reviews some of the fundamental aspects of rare earth elements (REE) geochemistry and gives data on abundances in the solar system, the bulk Earth and the Earth's crust. It describes the state of knowledge on the partitioning of the REE, especially in igneous rock systems, and cites reference works concerned with the REE. Several chemical properties of REE are discussed (oxidation states; redox conditions; element coordination and ionic radii; element substitution). (Auth.)

Development of long-lived radionuclides partitioning technology - Experimental/theoretical study of phase equilibria for multicomponent multiphase systems

Energy Technology Data Exchange (ETDEWEB)

Lee, Chul Soo; Lee, Se Il; Sim, Yeon Sik; Park, Sung Bin; Yang, Sung Oh; Park, Ji Yong [Korea University, Seoul (Korea, Republic of)

1995-08-01

In various partitioning processes, rare earth elements and actinide elements are separated from other elements in the first stage. They are then separated into rare earth groups and actinde groups. The first stage is accomplished by solvent extraction using DEHPA, by precipitation using oxalic= acid, or by cation exchange. The second stage is carried out by selective back-extraction or by selective elution using DTPA. In these processes the equilibria is governed by the concentrations of nitric acid, of solvents, and of precipitants among others. In this study various distribution coefficients in partitioning processes were experimentally determined. And thermodynamic models were proposed to calculate distribution coefficients with experimentally determined equilibrium constants. 32 refs., 11 tabs., 23 figs. (author)

Prediction of gas/particle partitioning of polybrominated diphenyl ethers (PBDEs) in global air: A theoretical study

Science.gov (United States)

Li, Y.-F.; Ma, W.-L.; Yang, M.

2015-02-01

Gas/particle (G/P) partitioning of semi-volatile organic compounds (SVOCs) is an important process that primarily governs their atmospheric fate, long-range atmospheric transport, and their routes of entering the human body. All previous studies on this issue are hypothetically based on equilibrium conditions, the results of which do not predict results from monitoring studies well in most cases. In this study, a steady-state model instead of an equilibrium-state model for the investigation of the G/P partitioning behavior of polybrominated diphenyl ethers (PBDEs) was established, and an equation for calculating the partition coefficients under steady state (KPS) of PBDEs (log KPS = log KPE + logα) was developed in which an equilibrium term (log KPE = log KOA + logfOM -11.91 where fOM is organic matter content of the particles) and a non-equilibrium term (log α, caused by dry and wet depositions of particles), both being functions of log KOA (octanol-air partition coefficient), are included. It was found that the equilibrium is a special case of steady state when the non-equilibrium term equals zero. A criterion to classify the equilibrium and non-equilibrium status of PBDEs was also established using two threshold values of log KOA, log KOA1, and log KOA2, which divide the range of log KOA into three domains: equilibrium, non-equilibrium, and maximum partition domain. Accordingly, two threshold values of temperature t, tTH1 when log KOA = log KOA1 and tTH2 when log KOA = log KOA2, were identified, which divide the range of temperature also into the same three domains for each PBDE congener. We predicted the existence of the maximum partition domain (the values of log KPS reach a maximum constant of -1.53) that every PBDE congener can reach when log KOA ≥ log KOA2, or t ≤ tTH2. The novel equation developed in this study was applied to predict the G/P partition coefficients of PBDEs for our Chinese persistent organic pollutants (POPs) Soil and Air Monitoring

Bioconcentration factors and plant-water partition coefficients of munitions compounds in barley.

Science.gov (United States)

Torralba-Sanchez, Tifany L; Kuo, Dave T F; Allen, Herbert E; Di Toro, Dominic M

2017-12-01

Plants growing in the soils at military ranges and surrounding locations are exposed, and potentially able to uptake, munitions compounds (MCs). The extent to which a compound is transferred from the environment into organisms such as plants, referred to as bioconcentration, is conventionally measured through uptake experiments with field/synthetic soils. Multiple components/phases that vary among different soil types and affect the bioavailability of the MC, however, hinder the ability to separate the effects of soil characteristics from the MC chemical properties on the resulting plant bioconcentration. To circumvent the problem, this work presents a protocol to measure steady state bioconcentration factors (BCFs) for MCs in barley (Hordeum vulgare L.) using inert laboratory sand rather than field/synthetic soils. Three MCs: 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (2,4-DNT), and 2,4-dinitroanisole (2,4-DNAN), and two munition-like compounds (MLCs): 4-nitroanisole (4-NAN) and 2-methoxy-5-nitropyridine (2-M-5-NPYNE) were evaluated. Approximately constant plant biomass and exposure concentrations were achieved within a one-month period that produced steady state log BCF values: 0.62 ± 0.02, 0.70 ± 0.03, 1.30 ± 0.06, 0.52 ± 0.03, and 0.40 ± 0.05 L kg plant dwt -1 for TNT, 2,4-DNT, 2,4-DNAN, 4-NAN, and 2-M-5-NPYNE, respectively. Furthermore, results suggest that the upper-bounds of the BCFs can be estimated within an order of magnitude by measuring the partitioning of the compounds between barley biomass and water. This highlights the importance of partition equilibrium as a mechanism for the uptake of MCs and MLCs by barley from interstitial water. The results from this work provide chemically meaningful data for prediction models able to estimate the bioconcentration of these contaminants in plants. Copyright © 2017 Elsevier Ltd. All rights reserved.

A rapid sample decomposition procedure for bromo-heavies containing ferruginous material: determination of REEs and thorium by ICP-AES

International Nuclear Information System (INIS)

Khorge, C.R.; Murugesan, P.; Chakrapani, G.

2013-01-01

A rapid method of sample decomposition and dissolution for bromoform heavies is described for the determination of REEs and thorium by inductively coupled plasma- optical emission spectrometry. For application to geochemical exploration to achieve the high sample throughput; a simple and rapid analytical procedure is a prerequisite. In order to speed-up the existing methodology, phosphate fusion was introduced for decomposition of samples. In the proposed method, bromoform-heavies material are fused with 1:1 mixture of sodium dihydrogen orthophosphate and tetra-sodium pyrophosphate and dissolved in distilled water. After disintegration of melt, the solution was subjected to oxalate precipitation followed by R 2 O 3 separation for separating the REEs from major matrix interfering elements. The rare earth elements and thorium in the resultant solution were determined by ICP-OES. The results are compared with the results obtained by well-established existing dissolution procedures involving HF-HCl-HClO 4 acid treatment and NaF/KHF 2 fusion followed by H 2 SO 4 acid fuming. The accuracy of the method was evaluated by doping the phosphate blank with known amount of REEs and comparing the recoveries obtained using the present method. The method is simple, rapid and is suitable for the routine determination of REEs and Th in bromoform-heavies. The RSD of the method was found to be within 1-3% for Th and REEs by ICP-AES. (author)

Spectral response of REE3+ doped LaAlO3

International Nuclear Information System (INIS)

Boronat, C.; Correcher, V.; Garcia G, J.; Morales, A.; Zarate, J.; Rivera, T.

2016-10-01

This paper reports on the preliminary results obtained from the cathodoluminescence (Cl) and thermoluminescence (Tl) properties of undoped LaAlO 3 (LAO) and LaAlO 3 : REE (REE=Dy 3+ , Pr 3+ and Eu 3+ ) to be potentially employed for dosimetric purposes. The samples were synthesized by a sol-gel process based on the Pechini 's method with a spray-drying technique and, subsequently, characterized by environmental scanning electron microscopy and energy dispersive X-ray analysis spectrometry. Cl spectra display sharp and narrow wavebands that could specifically be associated with structural (in the range of 300-450 nm) and point defects (from 450 to 800 nm). The observed wavebands could be assigned as follows: (i) 480 and 570 from the Dy-doped LAO should corresponding respectively to 4 F 9/2 → 6 H 15/2 and 4 F 9/2 → 6 H 13/2 transitions, (II) 490-638 from the Pr-doped LAO is linked to 3 P 0 → 3 H 4 , 1 D 2 → 3 H 4 transitions and (III) 590 and 620 where the dopant Eu 3+ gives rise to 5 D 0 → 7 F 1 and 5 D 0 → 7 F 2 transitions and (IV) a UV-blue broad band is associated with NBOHC in undoped LAO. Such emissions are due to the presence of the 4f electrons of rare earth ions that are shielded by the outer 5s and 5p electrons, the intra-4f emission spectra of REE. Furthermore, the study performed on the Tl emission of LaAlO 3 :Dy 3+ displays (i) two maxima centred at 150 and 240 degrees Celsius (ratio 1:2) similarly to the Pr 3+ doped sample but with 7:5 of ratio. And (II) the highest radiation sensitivity, allowing us to think on the potential use of this material for dosimetric purposes, however further works are necessary to confirm such assertion. (Author)

PREDICTING SOIL SORPTION COEFFICIENTS OF ORGANIC CHEMICALS USING A NEURAL NETWORK MODEL

Science.gov (United States)

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 ...

Effects of organic ligands on fractionation of rare earth elements (REEs) in hydroponic plants: an application to the determination of binding capacities by humic acid for modeling.

Science.gov (United States)

Ding, ShiMing; Liang, Tao; Zhang, ChaoSheng; Yan, JunCai; Zhang, ZiLi

2006-12-01

Previous studies have revealed the fractionation processes of rare earth elements (REEs) in hydroponic plants, with a heavy REE (HREE, the elements from Gd to Lu) enrichment in leaves. In this study, effects on the HREE enrichment in soybean leaves with additions of carboxylic acids (acetate, malate, citrate, NTA, EDTA and DTPA) and two soil humic acids (HAs) were investigated. REE speciation in carboxylic acid and HA solutions was simulated using Visual MINTEQ and Model V, respectively. The results showed that the effects caused by carboxylic acids were strongly dependent on the differences between their binding strengths for light REEs (LREEs, the elements from La to Eu) and those for HREEs. A good correlation existed between these effects and the changes of free REE ions in solutions. This relationship was also observed for the HA treatments, provided that the intrinsic equilibrium constants of REEs for cation-proton exchange with HA (i.e., pK(MHA)) in Model V were estimated using a free-energy relationship with the stability constants for REE complexation with lactic acid. It is suggested that this set of pK(MHA) values is more suitable for use in Model V for the simulation of REE complexation with HA.

REE in some tertiary volcanic complexes in the Republic of Macedonia

International Nuclear Information System (INIS)

Tasev, Goran; Serafimovski, Todor

2009-01-01

Petrological and geochemical features of the Tertiary magmatic rocks from the Republic of Macedonia were subject of study in this paper. The latest K-Ar, 87 Sr/ 86 Sr, and REE data for samples from Kratovo- Zletovo, Sasa-Toranica and Damjan-Buchim ore districts are presented. Whole rock XRF analyses confirmed host rock composition as dacites, quartz-latites, trachyandesites, rhyolites and rhyodacites. Absolute age determinations by the K-Ar dating method have shown ages range from 31 to 14 Ma confirming Oligocene-Miocene age as previously determined by relative methods. Determinations of 87 Sr/ 86 Sr ratios (0.70504 to 0.71126) suggest material is sourced from the contact zone between the lower crust and upper mantle where contamination of primary melt occurred. New REE data including negative Eu anomalies along with previously determined La/Yb ratios ranging from 13.3 to 43.0 (Serafimovski 1990) confirm inferred material source. These new data reconfirm previous results, provide insight into the Tertiary magmatic history of the district, and suggest the exact origin of the material that produced the Tertiary magmatic rocks.

Partitioning of etofenprox under simulated California rice-growing conditions.

Science.gov (United States)

Vasquez, Martice E; Gunasekara, Amrith S; Cahill, Thomas M; Tjeerdema, Ronald S

2010-01-01

The pyrethroid insecticide etofenprox is of current interest to rice farmers in the Sacramento Valley owing to its effectiveness against the rice water weevil, Lissorhoptrus oryzophilus Kuschel. This study aimed to describe the partitioning of etofenprox under simulated rice field conditions by determining its Henry's law constant (H) (an estimate of volatilization) and organic carbon-normalized soil-water distribution coefficient (K(oc)) at representative field temperatures. A comparison of etofenprox and lambda-cyhalothrin is presented using a level-1 fugacity model. Experimental determination of H revealed that etofenprox partitioned onto the apparatus walls and did not significantly volatilize; the maximum value of H was estimated to be 6.81 x 10(-1) Pa m(3) mol(-1) at 25 degrees C, based on its air and water method detection limits. Calculated values for H ranged from 5.6 x 10(-3) Pa m(3) mol(-1) at 5 degrees C to 2.9 x 10(-1) Pa m(3) mol(-1) at 40 degrees C, based on estimated solubility and vapor pressure values at various temperatures. Log K(oc) values (at 25 degrees C) were experimentally determined to be 6.0 and 6.4 for Princeton and Richvale rice field soils, respectively, and were very similar to the values for other pyrethroids. Finally, temperature appears to have little influence on etofenprox sorption, as the log K(oc) for the Princeton soil at 35 degrees C was 6.1. High sorption coefficients and relatively insignificant desorption and volatilization of etofenprox suggest that its insolubility drives it to partition from water by sorbing to soils with high affinity. Offsite movement is unlikely unless transported in a bound state on suspended sediments.

Metal/silicate partitioning of Pt and the origin of the "late veneer"

Science.gov (United States)

Ertel, W.; Walter, M. J.; Drake, M. J.; Sylvester, P. J.

2002-12-01

the melting point of the 1 atm, AnDi system and the melting point of the Pt capsule material. Over 150 piston cylinder and 12 multi anvil experiments have been performed. Pt solubility is only slightly dependent on temperature, decreasing between 1800 and 1400°C by less than an order of magnitude. In consequence, the partitioning behavior of Pt is mostly determined by its oxygen fugacity dependence, which has only been determined in 1 atm experiments. At 10 kbar, metal/silicate partition coefficients (D's) decrease by about 3 orders of magnitude. The reason for this is not understood, but might be attributed to a first order phase transition as found for, e.g., SiO2 or H2O. Above 10 kbar any increase in pressure does not lead to any further significant decrease in partition coefficients. Solubilities stay roughly constant up to 140 kbar. Abundances of moderately siderophile elements were possibly established by metal/silicate equilibrium in a magma ocean. These results for Pt suggest that the abundances of HSEs were most probably established by the accretion of a chondritic veneer following core formation, as metal/silicate partition coefficients are too high to be consistent with metal/silicate equilibrium in a magma ocean.

Summer–winter concentrations and gas-particle partitioning of short chain chlorinated paraffins in the atmosphere of an urban setting

International Nuclear Information System (INIS)

Wang Thanh; Han Shanlong; Yuan Bo; Zeng Lixi; Li Yingming; Wang Yawei; Jiang Guibin

2012-01-01

Short chain chlorinated paraffins (SCCPs) are semi-volatile chemicals that are considered persistent in the environment, potential toxic and subject to long-range transport. This study investigates the concentrations and gas-particle partitioning of SCCPs at an urban site in Beijing during summer and wintertime. The total atmospheric SCCP levels ranged 1.9–33.0 ng/m 3 during wintertime. Significantly higher levels were found during the summer (range 112–332 ng/m 3 ). The average fraction of total SCCPs in the particle phase (φ) was 0.67 during wintertime but decreased significantly during the summer (φ = 0.06). The ten and eleven carbon chain homologues with five to eight chlorine atoms were the predominant SCCP formula groups in air. Significant linear correlations were found between the gas-particle partition coefficients and the predicted subcooled vapor pressures and octanol–air partition coefficients. The gas-particle partitioning of SCCPs was further investigated and compared with both the Junge–Pankow adsorption and K oa -based absorption models. - Highlights: ► Short chain chlorinated paraffins were investigated in air samples from Beijing. ► Higher levels of SCCPs were found in air during summertime than wintertime. ► Relevant physical–chemical properties were estimated by SPARC and EPI Suite. ► Obtained data were used to model the gas-particle partitioning of SCCPs. - Atmospheric levels and gas-particle partitioning of SCCPs in Beijing, China.

Data and uncertainty assessment for radionuclide Kd partitioning coefficients in granitic rock for use in SR-Can calculations

International Nuclear Information System (INIS)

Crawford, James; Neretnieks, Ivars; Malmstroem, Maria

2006-10-01

SKB is currently preparing licence applications related to the proposed deep repository for spent nuclear fuel as well as the encapsulation plant required for canister fabrication. The present report is one of several specific data reports that form the data input to an interim safety report (SR-Can) for the encapsulation plant licence application. This report concerns the derivation and recommendation of generic K d data (i.e. linear partitioning coefficients) for safety assessment modelling of far-field radionuclide transport in fractured granitic rock. The data are derived for typical Swedish groundwater conditions and rock types distinctive of those found on the Simpevarp peninsula and Forsmark. Data have been derived for 8 main elements (Cs, Sr, Ra, Ni, Th, U, Np, Am) and various oxidation states. The data have also been supplied with tentative correction factors to account for artefacts that have not been previously considered in detail in previous compilations. For the main reviewed solutes the data are given in terms of a best estimate K d value assumed to be the median of the aggregate set of selected data. A range corresponding to the 25-75% inter-quartile range is also specified and probable ranges of uncertainty are estimated in the form of an upper and lower limit to the expected variability. Data for an additional 19 elements that have not been reviewed are taken from a previous compilation by Carbol and Engkvist

Validade da equação de Henry e Rees que estima a taxa metabólica de repouso em adolescentes masculinos Validez de la ecuación de Henry y Rees que estima la tasa metabólica de reposo en adolescentes masculinos Validity of the equation of Henry and Rees that estimates the resting metabolic rate in male adolescents

Directory of Open Access Journals (Sweden)

Paulo Henrique S. Fonseca

2011-06-01

Full Text Available OBJETIVO: Analisar a validade da equação de predição da taxa metabólica de repouso proposta por Henry e Rees (1991 em adolescentes do sexo masculino. MÉTODOS: Estudo transversal, com amostra de conveniência constituída de 52 meninos, entre dez e 17 anos, sendo mensuradas a massa corporal e a calorimetria indireta. A massa corporal foi substituída na equação de Henry e Rees para determinar a taxa metabólica de repouso predita. A calorimetria indireta foi determinada pelos valores do consumo de O2 e produção de CO2, e usada na equação de Weir (1949, considerada método padrão para o cálculo da taxa metabólica de repouso. Todas as medidas foram realizadas pela manhã, com o indivíduo em jejum de seis horas, em posição supina e em repouso muscular. Realizaram-se os seguintes procedimentos estatísticos: teste t pareado; erro constante (com diferença aceita entre as médias OBJETIVO: Analizar la validez de la ecuación de predicción de la tasa metabólica de reposo (TMR propuesta por Henry y Rees (1991 en adolescentes del sexo masculino. MÉTODOS: Estudio transversal, con muestra de conveniencia constituida por 52 niños, entre 10 y 17 años, siendo medidas las variables a continuación: masa corporal y calorimetría indirecta (CI. La masa corporal fue sustituida en la ecuación de Henry y Rees (1991 para determinar la TMR predicha. La CI fue determinada por los valores del consumo de O2 y producción de CO2 y usada en la ecuación de Weir (1949, considerada como método estándar de la TMR. Todas las medidas fueron realizadas por la mañana, con el individuo en ayuno de 6 horas, en posición supina y en reposo muscular. Se realizaron los siguientes procedimientos estadísticos: prueba “t” pareada; error constante (EC - con diferencia aceptada entre los promedios menor que 5% y, para análisis de la concordancia entre los dos métodos, el procedimiento gráfico de Bland y Altman. RESULTADOS: La ecuación propuesta por

Estudo QSPR sobre os coeficientes de partição: descritores mecânico-quânticos e análise multivariada QSPR study on partition coefficients: quantum-mechanical descriptors and multivariate analysis

Directory of Open Access Journals (Sweden)

Edilson Grünheidt Borges

2002-12-01

Full Text Available Quantum chemistry and multivariate analysis were used to estimate the partition coefficients between n-octanol and water for a serie of 188 compounds, with the values of the q 2 until 0.86 for crossvalidation test. The quantum-mechanical descriptors are obtained with ab initio calculation, using the solvation effects of the Polarizable Continuum Method. Two different Hartree-Fock bases were used, and two different ways for simulating solvent cavity formation. The results for each of the cases were analised, and each methodology proposed is indicated for particular case.

Partitioning of polar and non-polar neutral organic chemicals into human and cow milk.

Science.gov (United States)

Geisler, Anett; Endo, Satoshi; Goss, Kai-Uwe

2011-10-01

The aim of this work was to develop a predictive model for milk/water partition coefficients of neutral organic compounds. Batch experiments were performed for 119 diverse organic chemicals in human milk and raw and processed cow milk at 37°C. No differences (milk were observed. The polyparameter linear free energy relationship model fit the calibration data well (SD=0.22 log units). An experimental validation data set including hormones and hormone active compounds was predicted satisfactorily by the model. An alternative modelling approach based on log K(ow) revealed a poorer performance. The model presented here provides a significant improvement in predicting enrichment of potentially hazardous chemicals in milk. In combination with physiologically based pharmacokinetic modelling this improvement in the estimation of milk/water partitioning coefficients may allow a better risk assessment for a wide range of neutral organic chemicals. Copyright © 2011 Elsevier Ltd. All rights reserved.

Determination of n-octanol/water partition coefficient for DDT-related compounds by RP-HPLC with a novel dual-point retention time correction.

Science.gov (United States)

Han, Shu-ying; Qiao, Jun-qin; Zhang, Yun-yang; Yang, Li-li; Lian, Hong-zhen; Ge, Xin; Chen, Hong-yuan

2011-03-01

n-Octanol/water partition coefficients (P) for DDTs and dicofol were determined by reversed-phase high performance liquid chromatography (RP-HPLC) on a C(18) column using methanol-water mixture as mobile phase. A dual-point retention time correction (DP-RTC) was proposed to rectify chromatographic retention time (t(R)) shift resulted from stationary phase aging. Based on this correction, the relationship between logP and logk(w), the logarithm of the retention factor extrapolated to pure water, was investigated for a set of 12 benzene homologues and DDT-related compounds with reliable experimental P as model compounds. A linear regression logP=(1.10±0.04) logk(w) - (0.60±0.17) was established with correlation coefficient R(2) of 0.988, cross-validated correlation coefficient R(cv)(2) of 0.983 and standard deviation (SD) of 0.156. This model was further validated using four verification compounds, naphthalene, biphenyl, 2,2-bis(4-chlorophenyl)-1,1-dichloroethane (p,p'-DDD) and 2,2-bis(4-chlorophenyl)-1,1-dichloroethene (p,p'-DDE) with similar structure to DDT. The RP-HPLC-determined P values showed good consistency with shake-flask (SFM) or slow-stirring (SSM) results, especially for highly hydrophobic compounds with logP in the range of 4-7. Then, the P values for five DDT-related compounds, 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1,1-trichloroethane (o,p'-DDT), 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1-dichloroethane (o,p'-DDD), 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1-dichloroethene (o,p'-DDE), and 2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (dicofol) and its main degradation product 4,4'-dichlorobenzophenone (p,p'-DBP) were evaluated by the improved RP-HPLC method for the first time. The excellent precision with SD less than 0.03 proved that the novel DP-RTC protocol can significantly increases the determination accuracy and reliability of P by RP-HPLC. Copyright © 2011 Elsevier Ltd. All rights reserved.

Computational estimation of logarithm of octanol/air partition coefficients and subcooled vapour pressures for each of 75 chloronaphtalene congeners

Energy Technology Data Exchange (ETDEWEB)

Puzyn, T.; Falandysz, J.; Rostkowski, P.; Piliszek, S.; Wilczyniska, A. [Univ. of Gdansk (Poland)

2004-09-15

Polychlorinated naphthalenes (PCNs, CNs) are known persistent organic pollutants, contaminating natural ecosystems in effect of technical human activity. Toxic effects induced by individual congers of PCNs are reported elsewhere. Great risk of these chemical compounds is additionally connected with theirs excellent ability to be transported via atmosphere from a source to the remote regions on the Glob. Chloronaphthalene congeners had been found in Arctic regions at significant level in spite of the fact, that they had never been synthesized there, and also thermal processes like municipal waste incineration or domestic heating (other possible sources of PCNs in the environment) were not so intensive there. In 1996 F. Wania and D. Mackay have formulated some empirical rules, which have been very useful in estimation and modeling of environmental transport processes of persistent organic pollutants like PCNs. Two very important physico-chemical parameters in the theory of global distillation and cold condensation are: logarithm of n-octanol/air partition coefficient (log K{sub OA}) and logarithm of subcooled vapour pressure (log P{sub L}). Values of log K{sub OA} and log P{sub L} in standard procedures are determined by means of chromatographic methods. In order to reduce costs and number of experiments, we have proposed simple computational method of estimation log K{sub OA} and log P{sub L}.

Size distribution of rare earth elements in coal ash

Science.gov (United States)

Scott, Clinton T.; Deonarine, Amrika; Kolker, Allan; Adams, Monique; Holland, James F.

2015-01-01

Rare earth elements (REEs) are utilized in various applications that are vital to the automotive, petrochemical, medical, and information technology industries. As world demand for REEs increases, critical shortages are expected. Due to the retention of REEs during coal combustion, coal fly ash is increasingly considered a potential resource. Previous studies have demonstrated that coal fly ash is variably enriched in REEs relative to feed coal (e.g, Seredin and Dai, 2012) and that enrichment increases with decreasing size fractions (Blissett et al., 2014). In order to further explore the REE resource potential of coal ash, and determine the partitioning behavior of REE as a function of grain size, we studied whole coal and fly ash size-fractions collected from three U.S commercial-scale coal-fired generating stations burning Appalachian or Powder River Basin coal. Whole fly ash was separated into , 5 um, to 5 to 10 um and 10 to 100 um particle size fractions by mechanical shaking using trace-metal clean procedures. In these samples REE enrichments in whole fly ash ranges 5.6 to 18.5 times that of feedcoals. Partitioning results for size separates relative to whole coal and whole fly ash will also be reported. 

Environmental Characteristics of Carbonatite and Alkaline Intrusion-related Rare Earth Element (REE) Deposits

Science.gov (United States)

Seal, R. R., II; Piatak, N. M.

2017-12-01

Carbonatites and alkaline intrusions are important sources of REEs. Environmental risks related to these deposit types have been assessed through literature review and evaluation of the geochemical properties of representative samples of mill tailings and their leachates. The main ore mineral in carbonatite deposits is bastnasite [(Ce,La)(CO3)F], which is found with dolomite and calcite ( 65 %), barite (20 - 25 %), plus a number of minor accessory minerals including sulfides such as galena and pyrite. Generally, alkaline intrusion-related REE deposits either occur in layered complexes or with dikes and veins cutting alkaline intrusions. Such intrusions have a more diverse group of REE ore minerals that include fluorcarbonates, oxides, silicates, and phosphates. Ore also can include minor calcite and iron (Fe), lead (Pb), and zinc (Zn) sulfides. The acid-generating potential of both deposit types is low because of a predominance of carbonate minerals in the carbonatite deposits, the presence of feldspars and minor calcite in alkaline intrusion-related deposits, and to only minor to trace occurrence of potentially acid-generating sulfide minerals. Both deposit types, however, are produced by igneous and hydrothermal processes that enrich high-field strength, incompatible elements, which typically are excluded from common rock-forming minerals. Elements such as yttrium (Y), niobium Nb), zirconium (Zr), hafnium (Hf), tungsten (W), titanium (Ti), tantalum (Ta), scandium (Sc), thorium (Th), and uranium (U) can be characteristic of these deposits and may be of environmental concern. Most of these elements, including the REEs, but with the exception of U, have low solubilities in water at the near-neutral pH values expected around these deposits. Mill tailings from carbonatite deposits can exceed residential soil and sediment criteria for Pb, and leachates from mill tailings can exceed drinking water guidelines for Pb. The greatest environmental challenges, however, are

Assessing the combined influence of TOC and black carbon in soil–air partitioning of PBDEs and DPs from the Indus River Basin, Pakistan

International Nuclear Information System (INIS)

Ali, Usman; Mahmood, Adeel; Syed, Jabir Hussain; Li, Jun; Zhang, Gan; Katsoyiannis, Athanasios; Jones, Kevin C.; Malik, Riffat Naseem

2015-01-01

Levels of polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DPs) were investigated in the Indus River Basin from Pakistan. Concentrations of ∑PBDEs and ∑DPs were ranged between 0.05 and 2.38 and 0.002–0.53 ng g −1 in the surface soils while 1.43–22.1 and 0.19–7.59 pg m −3 in the passive air samples, respectively. Black carbon (f BC ) and total organic carbon (f TOC ) fractions were also measured and ranged between 0.73 and 1.75 and 0.04–0.2%, respectively. The statistical analysis revealed strong influence of f BC than f TOC on the distribution of PBDEs and DPs in the Indus River Basin soils. BDE's congener profile suggested the input of penta–bromodiphenylether (DE-71) commercial formulation in the study area. Soil–air partitioning of PBDEs were investigated by employing octanol-air partition coefficients (K OA ) and black carbon-air partition coefficients (K BC−A ). The results of both models suggested the combined influence of total organic carbon (absorption) and black carbon (adsorption) in the studied area. - Highlights: • Model based calculations of black carbon-air partition coefficients for PBDEs. • Soil and air levels of PBDEs and DPs reported first time for ecologically important sites of the Indus River Basin, Pakistan. • Both, f BC and f TOC showed combined influence on soil–air partitioning of PBDEs in the Indus River Basin, Pakistan. - BC and TOC showed combined influence on soil–air partitioning of POPs i-e., PBDEs in the Indus River Basin, Pakistan

Influence of biochar on isoproturon partitioning and bioaccessibility in soil

International Nuclear Information System (INIS)

Reid, B.J.; Pickering, F.L.; Freddo, A.; Whelan, M.J.; Coulon, F.

2013-01-01

The influence of biochar (5%) on the loss, partitioning and bioaccessibility of 14 C-isoproturon ( 14 C-IPU) was evaluated. Results indicated that biochar had a dramatic effect upon 14 C-IPU partitioning: 14 C-IPU extractability (0.01 M CaCl 2 ) in biochar-amended treatments was reduced to 14 C-IPU extractability in biochar free treatments decreased with ageing from 90% to 40%. A partitioning model was constructed to derive an effective partition coefficient for biochar:water (K BW of 7.82 × 10 4 L kg −1 ). This was two orders of magnitude greater than the apparent K foc value of the soil organic carbon:water (631 L kg −1 ). 14 C-radiorespirometry assays indicated high competence of microorganisms to mineralise 14 C-IPU in the absence of biochar (40.3 ± 0.9%). Where biochar was present 14 C-IPU mineralisation never exceeded 2%. These results indicate reduced herbicide bioaccessibility. Increasing IPU application to ×10 its recommended dose was ineffective at redressing IPU sequestration and its low bioaccessibility. Highlights: •Biochar had a dramatic effect on IPU partitioning. •IPU extractability was reduced to BW ) was 7.82 × 10 4 L kg −1 . •K BW was 124 times greater than the apparent K foc value of the control. •Biochar precluded microbial bioaccessibility – no catabolic response was observed. -- Biochar dramatically reduced 14 C-IPU extractability ( BW being ×123 greater than the apparent K foc . Correspondingly, microbial bioaccessibility of IPU was negligible

Is the gas-particle partitioning in alpha-pinene secondary organic aerosol reversible?

Science.gov (United States)

Grieshop, Andrew P.; Donahue, Neil M.; Robinson, Allen L.

2007-07-01

This paper discusses the reversibility of gas-particle partitioning in secondary organic aerosol (SOA) formed from α-pinene ozonolysis in a smog chamber. Previously, phase partitioning has been studied quantitatively via SOA production experiments and qualitatively by perturbing temperature and observing particle evaporation. In this work, two methods were used to isothermally dilute the SOA: an external dilution sampler and an in-chamber technique. Dilution caused some evaporation of SOA, but repartitioning took place on a time scale of tens of minutes to hours-consistent with an uptake coefficient on the order of 0.001-0.01. However, given sufficient time, α-pinene SOA repartitions reversibly based on comparisons with data from conventional SOA yield experiments. Further, aerosol mass spectrometer (AMS) data indicate that the composition of SOA varies with partitioning. These results suggest that oligomerization observed in high-concentration laboratory experiments may be a reversible process and underscore the complexity of the kinetics of formation and evaporation of SOA.

A flow-through aqueous standard generation system for thin film microextraction investigations of UV filters and biocides partitioning to different environmental compartments

International Nuclear Information System (INIS)

Ahmadi, Fardin; Sparham, Chris; Pawliszyn, Janusz

2017-01-01

In this paper problems associated with preparation of aqueous standard of highly hydrophobic compounds such as partial precipitation, being lost on the surfaces, low solubility in water and limited sample volume for accurate determination of their distribution coefficients are addressed. The following work presents two approaches that utilize blade thin film microextraction (TFME) to investigate partitioning of UV filters and biocides to humic acid (dissolved organic carbon) and sediment. A steady-state concentration of target analytes in water was generated using a flow-through aqueous standard generation (ASG) system. Dialysis membranes, a polytetrafluoroethylene permeation tube, and a frit porous (0.5 μm) coated by epoxy glue were basic elements used for preparation of the ASG system. In the currently presented study, negligible depletion TFME using hydrophilic-lipophilic balance (HLB) and octadecyl silica-based (C18) sorbents was employed towards the attainment of free concentration values of target analytes in the studied matrices. Thin film geometry provided a large volume of extraction phase, which improved the sensitivity of the method towards highly matrix-bound analytes. Extractions were performed in the equilibrium regime so as to prevent matrix effects and with aims to reach maximum method sensitivity for all analytes under study. Partitioning of analytes on dissolved organic carbon (DOC) was investigated in ASG to facilitate large sample volume conditions. Binding percentages and DOC distribution coefficients (Log K DOC ) ranged from 20 to 98% and 3.71–6.72, respectively. Furthermore, sediment-water partition coefficients (K d ), organic-carbon normalized partition coefficients (Log K OC ), and DOC distribution coefficients (Log K DOC ) were investigated in slurry sediment, and ranged from 33 to 2860, 3.31–5.24 and 4.52–5.75 Lkg -1 , respectively. The obtained results demonstrated that investigations utilizing ASG and TFME can yield reliable

Partition thermodynamics of ionic surfactants between phosphatidylcholine vesicle and water phases

Science.gov (United States)

Chu, Shin-Chi; Hung, Chia-Hui; Wang, Shun-Cheng; Tsao, Heng-Kwong

2003-08-01

The partition of ionic surfactants (sodium alkyl sulfate and alkyl trimethyl ammonium bromide) between phosphatidylcholine vesicles and aqueous phase is investigated by simple conductometry under different temperatures. The experimental results can be well represented by the proposed regular solution theory and the thermodynamic parameters satisfy the thermodynamic consistency. The deviation from ideal partition is manifested through the effective interaction energy between lipid and surfactant wb, which is O(kT) large. It is found that wb rises as the alkyl chain is decreased for a specified head group. This is attributed to significant mismatch of chain lengths between surfactant and lipid molecules. The partition coefficient K declines with increasing temperature. The energy barrier from bilayer to aqueous phase, Δμ/kT∝ln K, is in the range of 16-26 kJ/mol. As the alkyl chain length is decreased for a given head group, Δμ is lowered by 1.3-1.5 kJ/mol per methylene group. Two independent analyses are employed to confirm this result. Using the thermodynamic parameters determined from experiments, the internal energy, entropy, and free energy of the partition process can be derived. Partition is essentially driven by the internal energy gain. The solubilizing ability, which is represented by the maximum surfactant-lipid ratio in the bilayer, Reb also decreases in accord with the K parameter. It is because the change in temperature influences the surfactant incorporation into the bilayer more than the formation of micelles.

Distribution and origin of major and trace elements (particularly REE, U and Th) into labile and residual phases in an acid soil profile (Vosges Mountains, France)

Science.gov (United States)

Aubert, D.; Probst, A.; Stille, P.

2003-04-01

Physical and chemical weathering of rocks and minerals lead to soil formation and allow the removal of chemical elements from these systems to ground- or surface waters. But most of the time the determination of element concentrations in soils is not sufficient to estimate whether they are being accumulated or what is their ability to be released in the environment. Thus, the distribution and chemical binding for a given element is very important because it determines its mobility and potential bioavailability throughout a soil profile. Heavy metals and REE (Rare Earth Elements) are particularly of environmental concern because of their potential toxicity. For most of them, their chemical form strongly depends on the evolution of physico-chemical parameters like pH or redox conditions that will induce adsorption-desorption, complexation or co-precipitation phenomena in the material. The purpose of this study is to determine the distribution of several major and trace elements (especially REE, Th and U) in an acidic forested podzolic soil profile from the Vosges Mountains (France). To achieve this goal we use a 7 step sequential extraction procedure that allows determining precisely the origin and the behaviour of particular elements in the environment (Leleyter et al., 1999). In addition we performed leaching experiments using very dilute acetic and hydrochloric acid in order to establish the origin of REE in this soil. The results of the sequential extraction indicate that most of the metals, Th and U are mainly bound to Fe oxides. Organic matter appears also to be a great carrier of P, Ca, Fe and REE even if its content is very low in the deep horizons of the soil. Moreover, we show that in each soil horizon, middle REE (MREE) to heavy REE (HREE) are more labile than light REE (LREE). Leaching experiments using dilute acid solution further suggest that in the shallowest horizons REE largely derive from atmospheric deposition whereas at greater depth, weathering

U-Pb, Nd isotope and REE geochemistry in eclogites from the Cabo Ortegal Complex, Galicia, Spain: an example of REE immobility conserving MORB-like patterns during high-grade metamorphism

International Nuclear Information System (INIS)

Bernard-Griffiths, J.; Peucat, J.-J.; Cornichet, J.; Iglesias Ponce de Leon, M.; Gil Ibarguchi, J.I.

1985-01-01

REE abundances and Nd isotopic compositions were determined on representative samples of eclogite from the Cabo Ortegal Complex of northern Spain. Zircons were also separated from a whole-rock eclogite and analysed by the U-Pb radiometric method. Results indicate that eclogite facies metamorphism occurred between 480 and 420 Ma ago, but no precise constraint can be placed on the protolith age. The REE patterns observed suggest that there has been no significant alteration of the protolith whole-rock systems and that high-grade metamorphism has had little effect on the more mobile LREE. The eclogite protoliths were probably derived from ancient mantle sources with geochemical characteristics very similar to present-day MORB sources. This implies that LREE-depleted (N-type) tholeiites have been erupted at constructive plate margins since at least the early Palaeozoic and possibly long before. The Cabo Ortegal eclogites are allochthonous. They have been thrust up on to the continent and thus they can be compared to other eclogites which also show MORB-like characteristics (e.g., 90% of the eclogites of Vendee area of western France). (orig.)

A comparison of the analysis of REE-bearing phosphates by standardless EDS and standardised EDS and WDS

International Nuclear Information System (INIS)

Griffin, B.J.; Hancock, R.C.; Trautman, R.L.

2002-01-01

Full text: Current generation energy dispersive X-ray analysis systems EDS on SEM are user-friendly with 'simple' software interfaces. Minimal training is considered necessary for operation. One aim of this study was to test this hypothesis. The second aim, as a part of other studies, was to compare the results of the x-ray microanalysis of a suite of rare earth element (REE) bearing standard glasses and also a suite of rare earth element (REE) bearing phosphate mineral grains using different analytical systems. Our results from the same sample mounts have been obtained using three analytical systems: an Oxford Instruments ISIS EDS on a JEOL 6400 SEM, a Noran Voyager EDS on a JEOL 6400 SEM and a Moran Scientific WDS package on a JEOL 6400 SEM. A total of forty nine natural mineral grains have been analysed for twenty-two elements, including the REE, Ca, P and F (where possible) by each analytical system. Additional analyses were obtained from simple REE-bearing glass standards, each containing only one REE at around 11 wt %. The natural mineral grain results obtained from the different analytical systems show a number of significant variations. The two EDS datasets are comparable in terms of total REE but generally are a factor of two less than the WDS dataset. Internally the EDS datasets differ in that one set shows consistently a strong negative yttrium oxide result (typically -1 wt %) due to an excessive correction for a strong phosphorus overlap (Ka on La) whereas the second dataset shows the reverse with typically 1 wt % yttrium oxide reported, as a result of inadequate correction of the phosphorus overlap. Major elements are comparable between the standard-based datasets but not with the standardless dataset although all show similar reproducibility. The standard glass results are more coherent and consistent, as would be expected from the simpler composition and higher abundances. One clear outcome from these data is that complex compositions where

Retention of bile salts in micellar electrokinetic chromatography: relation of capacity factor to octanol-water partition coefficient and critical micellar concentration.

Science.gov (United States)

Lucangioli, S E; Carducci, C N; Tripodi, V P; Kenndler, E

2001-12-25

The capacity factors of 16 anionic cholates (from six bile salts, including their glyco- and tauro-conjugates) were determined in a micellar electrokinetic chromatography (MEKC) system consisting of buffer, pH 7.5 (phosphate-boric acid; 20 mmol/l) with 50 mmol/l sodium dodecyl sulfate (SDS) as micelle former and 10% acetonitrile as organic modifier. The capacity factors of the fully dissociated, negatively charged analytes (ranging between 0.2 and 60) were calculated from their mobilities, with a reference background electrolyte (BGE) without SDS representing "free" solution. For comparison, the capacity factors were derived for a second reference BGE where the SDS concentration (5 mmol/l) is close to the critical micellar concentration (CMC). The capacity factors are compared with the logarithm of the octanol-water partition coefficient, log Pow, as measure for lipophilicity. Clear disagreement between these two parameters is found especially for epimeric cholates with the hydroxy group in position 7. In contrast, fair relation between the capacity factor of the analytes and their CMC is observed both depending strongly on the orientation of the OH groups, and tauro-conjugation as well. In this respect the retention behaviour of the bile salts in MEKC seems to reflect their role as detergents in living systems, and might serve as model parameter beyond lipophilicity.

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

Science.gov (United States)

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. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Uranium partitioning under acidic conditions in a sandy soil aquifer

International Nuclear Information System (INIS)

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

1995-01-01

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 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

Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

Directory of Open Access Journals (Sweden)

R. M. Healy

2008-06-01

Full Text Available A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NO_x and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl-hydroxylamine (PFBHA to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively.

Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.

Leaching kinetics of neodymium in sulfuric acid of rare earth elements (REE) slag concentrated by pyrometallurgy from magnetite ore

Energy Technology Data Exchange (ETDEWEB)

Yoon, Ho-Sung; Kim, Chul-Joo; Chung, Kyung Woo; Lee, Jin-Young; Shin, Shun Myung [Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon (Korea, Republic of); Lee, Su-Jeong; Joe, A-Ram; Lee, Se-Il; Yoo, Seung-Joon [Seonam University, Asan (Korea, Republic of)

2014-10-15

We studied the leaching kinetics of recovering neodymium in sulfuric acid from the rare earth elements (REE) slag concentrated by smelting reduction from a magnetite ore containing monazite. The leaching kinetics on neodymium was conducted at a reactant concentration of 1.5 g REE slag per L of 0.3M H{sub 2}SO{sub 4}, agitation of 750 rpm and temperature ranging from 30 to 80 .deg. C. Neodymium oxide included in the REE slag was completely converted into neodymium sulfate phase (Nd{sub 2}(SO{sub 4}){sub 3}) in H{sub 2}SO{sub 4} after the leaching of 5 h, 80 .deg. C. As a result, the leaching mechanism was determined in a two-stage model based on the shrinking core model with spherical particles. The first step was determined by chemical reaction, and the second step was determined by ash layer diffusion because the leaching of REEs by the first chemical reaction increases the formation of the ash layer affecting as a resistance against the leaching. By using the Arrhenius expression, the apparent activation energy of the first chemical reaction step was found to be 9 kJmol{sup -1}. After the first chemical reaction, leaching reaction rate was determined by the ash layer diffusion. The apparent activation energy of ash layer diffusion was found to be 32 kJmol{sup -1}.

Leaching kinetics of neodymium in sulfuric acid of rare earth elements (REE) slag concentrated by pyrometallurgy from magnetite ore

International Nuclear Information System (INIS)

Yoon, Ho-Sung; Kim, Chul-Joo; Chung, Kyung Woo; Lee, Jin-Young; Shin, Shun Myung; Lee, Su-Jeong; Joe, A-Ram; Lee, Se-Il; Yoo, Seung-Joon

2014-01-01

We studied the leaching kinetics of recovering neodymium in sulfuric acid from the rare earth elements (REE) slag concentrated by smelting reduction from a magnetite ore containing monazite. The leaching kinetics on neodymium was conducted at a reactant concentration of 1.5 g REE slag per L of 0.3M H 2 SO 4 , agitation of 750 rpm and temperature ranging from 30 to 80 .deg. C. Neodymium oxide included in the REE slag was completely converted into neodymium sulfate phase (Nd 2 (SO 4 ) 3 ) in H 2 SO 4 after the leaching of 5 h, 80 .deg. C. As a result, the leaching mechanism was determined in a two-stage model based on the shrinking core model with spherical particles. The first step was determined by chemical reaction, and the second step was determined by ash layer diffusion because the leaching of REEs by the first chemical reaction increases the formation of the ash layer affecting as a resistance against the leaching. By using the Arrhenius expression, the apparent activation energy of the first chemical reaction step was found to be 9 kJmol -1 . After the first chemical reaction, leaching reaction rate was determined by the ash layer diffusion. The apparent activation energy of ash layer diffusion was found to be 32 kJmol -1

Mineralogy and REE geochemistry at Gomish-Tappeh Zn-Pb-Cu (Ag deposit, southwest of Zanjan

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Tooba Salehi

2010-11-01

Full Text Available Gomish-Tappeh Zn-Pb-Cu (Ag deposit is located 90 km southwest of Zanjan, in northwestern part of Urumieh-Dokhtar volcano-plutonic zone. Exposed rocks at the area include Oligo-Miocene volcano-sedimentary and sedimentary sequences as well as Pliocene volcano-plutonic sequence (andesite porphyry dykes, dacitic subvolcanic dome and rhyodacitic volcanics. Alteration in the deposit developed as silicic, silicic-sulfidic, sericitic, carbonate, argillic and propylitic. Main mineralization at the Gomish-Tappeh deposit is observed as veins occurring in a steeply-deeping normal fault defined by an NE-SW trend in host rocks such as dacitic crystal litic tuff, dacitic subvolcanic dome, specifically the rhyolitic tuff. Paragenetic minerals in the ore veins consist of pyrite, arsenopyrite, chalcopyrite, bornite, low-Fe sphalerite, galena, tetrahedrite and specularite. Gangue minerals accompanying the ores include quartz, calcite, chlorite, sericite and clay minerals. Based on geochemical data, average grades for samples from the ore veins at the Gomish-Tappeh deposit are: 4% Pb, 6% Zn, 2% Cu and 88 ppm Ag. Moreover, REE distribution patterns for altered samples of the dacitic subvolcanic dome and acidic tuff when compared with fresh samples, show enrichment in LREE, while HREE demonstrate various bahaviours. The negative Eu anomaly in chondrite-normalized REE patterns for these rocks is related to the increase in fluid/rock ratio and destruction of those grains of plagioclase enriched in Eu. REE distribution patterns for the silty tuff (footwall to the ore compared with acidic tuff represent enrichment in all REE as well as positive Eu anomalies. However, the ore samples indicate more enrichment in LREE/HREE ratios and higher Eu contents when compared with wallrock of the ore veins (silty tuff. This is due to the influence of chloric magmatic-hydrothermal fluids that caused alteration along the ore zone, releasing LREE and Eu from the host rocks and finally

Origin of dolomites in a downslope biostrome, Jefferson Formation (Frasnian), central Idaho: evidence from REE patterns, stable isotopes, and petrography

Energy Technology Data Exchange (ETDEWEB)

Dorobek, S.L.

1987-08-01

A completely dolomitized coral-stromatoporoid biostrome occurs at the top of the Dark Dolomite member of the Jefferson Formation (Frasnian) at Grandview Canyon, Lost River Range, central Idaho. The biostrome overlies a thick sequence of dolostones that were deposited in slope to deep ramp settings. The biostrome, therefore, formed in an open marine setting after shallowing of deep water environments. Zoned dolospar cement fills dissolution vugs and tectonic fractures. Stable isotopes for zoned dolospar are -13.1 to -6.5 per thousand delta/sup 18/O (average - 11.5) and -1.5 to -0.1 per thousand delta/sup 13/C (average -0.4). REE patterns for zoned dolospar have positive Ce anomalies, but total REE abundance is similar to REE abundance for replacive dolomites. Stratigraphic occurrence in an open marine setting, stable isotopes, and REE patterns suggest replacive dolomite phases formed during shallow burial diagenesis with significant involvement of nonevaporated sea water. More negative Ce anomalies near the top of the biostrome suggest a diagenetic overprint by oxidizing meteoric waters. Zoned dolospar probably formed from warmer, reducing burial fluids. Carbon for zoned dolospar probably was recycled from preexisting dolomite. These data may be useful for interpreting the origin of other anomalous platform dolostones.

Effect of vehicles and sodium lauryl sulphate on xenobiotic permeability and stratum corneum partitioning in porcine skin

International Nuclear Information System (INIS)

Merwe, Deon van der; Riviere, Jim E.

2005-01-01

Dermal contact with potentially toxic agricultural and industrial chemicals is a common hazard encountered in occupational, accidental spill and environmental contamination scenarios. Different solvents and chemical mixtures may influence dermal absorption. The effects of sodium lauryl sulphate (SLS) on the stratum corneum partitioning and permeability in porcine skin of 10 agricultural and industrial chemicals in water, ethanol and propylene glycol were investigated. The chemicals were phenol, p-nitrophenol, pentachlorophenol, methyl parathion, ethyl parathion, chlorpyrifos, fenthion, simazine, atrazine and propazine. SLS decreased partitioning into stratum corneum from water for lipophilic compounds, decreased partitioning from propylene glycol and did not alter partitioning from ethanol. SLS effects on permeability were less consistent, but generally decreased permeability from water, increased permeability from ethanol and had an inconsistent effect on permeability from propylene glycol. It was concluded that, for the compounds tested, partitioning into the stratum corneum was determined by the relative solubility of the solute in the donor solvent and the stratum corneum lipids. Permeability, however, reflected the result of successive, complex processes and was not predictable from stratum corneum partitioning alone. Addition of SLS to solvents altered partitioning and absorption characteristics across a range of compounds, which indicates that partition coefficients or skin permeability from neat chemical exposure should be used with caution in risk assessment procedures for chemical mixtures

Ab Initio Predictions of K, He and Ar Partitioning Between Silicate Melt and Liquid Iron Under High Pressure

Science.gov (United States)

Xiong, Z.; Tsuchiya, T.

2017-12-01

Element partitioning is an important property in recording geochemical processes during the core-mantle differentiation. However, experimental measurements of element partitioning coefficients under extreme temperature and pressure condition are still challenging. Theoretical modeling is also not easy, because it requires estimation of high temperature Gibbs free energy, which is not directly accessible by the standard molecular dynamics method. We recently developed an original technique to simulate Gibbs free energy based on the thermodynamics integration method[1]. We apply it to element partitioning of geochemical intriguing trace elements between molten silicate and liquid iron such as potassium, helium and argon as starting examples. Radiogenic potassium in the core can provide energy for Earth's magnetic field, convection in the mantle and outer core[2]. However, its partitioning behavior between silicate and iron remains unclear under high pressure[3,4]. Our calculations suggest that a clear positive temperature dependence of the partitioning coefficient but an insignificant pressure effect. Unlike sulfur and silicon, oxygen dissolved in the metals considerably enhances potassium solubility. Calculated electronic structures reveal alkali-metallic feature of potassium in liquid iron, favoring oxygen with strong electron affinity. Our results suggest that 40K could serve as a potential radiogenic heat source in the outer core if oxygen is the major light element therein.­­ We now further extend our technique to partitioning behaviors of other elements, helium and argon, to get insides into the `helium paradox' and `missing argon' problems. References [1] T. Taniuchi, and T. Tsuchiya, Phys.Rev.B. In press [2] B.A. Buffett, H.E. Huppert, J.R. Lister, and A.W. Woods, Geophys.Res.Lett. 29 (1996) 7989-8006. [3] V.R. Murthy, W. Westrenen, and Y. Fei, Nature. 426 (2003) 163-165. [4] A. Corgne, S.Keshav, Y. Fei, and W.F. McDonough, Earth.Planet.Sci.Lett. 256 (2007

Partitioning of polychlorinated biphenyls into human cells and adipose tissues: evaluation of octanol, triolein, and liposomes as surrogates.

Science.gov (United States)

Quinn, Cristina L; van der Heijden, Stephan A; Wania, Frank; Jonker, Michiel T O

2014-05-20

Whereas octanol, triacylglycerides, and liposomes have all been proposed as surrogates for measuring the affinity of hydrophobic organic contaminants to human lipids, no comparative evaluation of their suitability exists. Here we conducted batch sorption experiments with polyoxymethylene passive samplers to determine the partition coefficients at 37 °C of 18 polychlorinated biphenyls (PCBs) from water into (i) triolein (Ktriolein/water), (ii) eight types of liposomes (Kliposome/water), (iii) human abdominal fat tissues (KAFT/water) from seven individuals, and (iv) human MCF-7 cells cultured in vitro (Kcell/water). Differences between KAFT/water among individuals and between Kliposome/water among liposome types were very small and not correlated to structural attributes of the PCBs. Similarly, the length and degree of saturation of the phospholipid carbon chains, the headgroup, and the composition of the liposome did not affect the partitioning of PCBs into the studied liposomes. Whereas Kliposome/water values were similar to literature values of Koctanol/water adjusted to 37 °C, they both were lower than KAFT/water and Kcell/water by a factor of 3 on average. Partitioning of PCBs into triolein on the other hand closely mimicked that into human lipids, for which triolein is thus a better surrogate than either octanol or liposomes. Previously published polyparameter linear free energy relationships for partitioning from water into storage lipids and liposomes predicted the measured partition coefficients with a root-mean-square error of less than 0.15 log units, if the chosen equations and solute descriptors do not allow chlorine substitution in the ortho-position to influence the prediction. By guiding the selection of (i) a surrogate for the experimental determination and (ii) a method for the prediction of partitioning into human lipids, this study contributes to a better assessment of hydrophobic organic contaminant bioaccumulation in humans.

Unravelling the sulphur isotope systematics of an alkaline magmatic province: implications for REE mineralization and exploration

Science.gov (United States)

Hutchison, W.; Finch, A.; Boyce, A.; Friis, H.; Borst, A. M.; Horsburgh, N. J.

2017-12-01

Some of the world's best alkaline rare earth element (REE) deposits are formed in magmatic systems that are sealed (i.e., those that are autometasomatised and maintain reducing conditions). Conversely, in open systems where oxidizing fluids infiltrate, it is commonly assumed that REE are redistributed over a wider (less concentrated) zone. Sulphur isotope fractionation is sensitive to variations in temperature and redox, and, although sulphide minerals are relatively abundant in alkaline systems, there have been few attempts to test these hypotheses and develop a sulphur isotope proxy for alkaline metasomatism and formation of associated REE deposits. The Gardar Rift Province in southern Greenland was volcanically active in two periods between 1300 and 1100 Ma and is an ideal natural laboratory to explore sulphur isotope systematics because a near-complete alkaline magmatic lineage is exposed. We present new δ34S from across the province with a particular focus on three alkaline systems (Ilímaussaq, Motzfeldt and Ivigtût) that also host major REE deposits. Primitive mafic rocks from regional Gardar dykes and lavas have a restricted range of δ34S between 0 and 3 ‰ and fractional crystallization imparts no observable change in δ34S. In a few cases high-δ34S rocks (>15 ‰) occur when intrusive units have assimilated local sedimentary crust (δ34S = 25 ‰). Most δ34S variation takes place in the roof zones of alkaline intrusions during late-magmatic and hydrothermal stages, and we identify clear differences between the complexes. At Ilímaussaq, where the magmatic series is exceptionally reduced (below QFM buffer), roof zone δ34S remains narrow (0-3 ‰). At Motzfeldt, a more open oxidizing roof zone (MH buffer), δ34S ranges from -12 ‰ in late-stage fluorite veins to +12 ‰ where local crust has been assimilated. Ivigtût is intermediate between these end-members varying between -5 to +5 ‰. The δ34S variations primarily relate to temperature and

Brominated flame retardants in the urban atmosphere of Northeast China: Concentrations, temperature dependence and gas-particle partitioning

Energy Technology Data Exchange (ETDEWEB)

Qi, Hong; Li, Wen-Long; Liu, Li-Yan; Song, Wei-Wei; Ma, Wan-Li, E-mail: mawanli002@163.com; Li, Yi-Fan, E-mail: ijrc_pts_paper@yahoo.com

2014-09-01

57 pairs of air samples (gas and particle phases) were collected using a high volume air sampler in a typical city of Northeast China. Brominated flame retardants (BFRs) including 13 polybrominated diphenyl ethers (PBDEs, including BDEs 17, 28, 47, 49, 66, 85, 99, 100, 138, 153, 154, 183, and 209) and 9 alternative BFRs (p-TBX, PBBZ, PBT, PBEB, DPTE, HBBZ, γ-HBCD, BTBPE, and DBDPE) were analyzed. The annual average total concentrations of the 13 PBDEs and the 9 alternative BFRs were 69 pg/m{sup 3} and 180 pg/m{sup 3}, respectively. BDE 209 and γ-HBCD were the dominant congeners, according to the one-year study. The partial pressure of BFRs in the gas phase was significantly correlated with the ambient temperature, except for BDE 85, γ-HBCD and DBDPE, indicating the important influence of ambient temperature on the behavior of BFRs in the atmosphere. It was found that the gas–particle partitioning coefficients (logK{sub p}) for most low molecular weight BFRs were highly temperature dependent as well. Gas–particle partitioning coefficients (logK{sub p}) also correlated with the sub-cooled liquid vapor pressure (logP{sub L}{sup o}). Our results indicated that absorption into organic matter is the main control mechanism for the gas–particle partitioning of atmospheric PBDEs. - Highlights: • Both PBDEs and alternative BFRs were analyzed in the atmosphere of Northeast China. • Partial pressure of BFRs was significantly correlated with the ambient temperature. • A strong temperature dependence of gas-particle partitioning was found. • Absorption into organic matter was the control mechanism for G-P partitioning.

Improved calculation of the third virial coefficient of a free anyon gas

International Nuclear Information System (INIS)

Law, J.; Khare, A.; Bhaduri, R.K.; Suzuki, A.

1994-01-01

For three anyons confined in a harmonic oscillator, only the class of states that interpolates nonlinearly with the statistical parameter contributes to the third virial coefficient of a free anyon gas. Rather than evaluating the full three-body partition function as was done in an earlier publication [J. Law, A. Suzuki, and R. Bhaduri, Phys. Rev. A 46, 4693 (1992)], here only the nonlinear contribution is calculated, thus avoiding delicate cancellations between the irrelevant linear part and the two-body partition function. Our numerical results are consistent with the simple analytical form suggested recently by Myrheim and Olaussen [Phys. Lett. B 299, 267 (1993)

Normalized rare earth elements in water, sediments, and wine: identifying sources and environmental redox conditions

Science.gov (United States)

Piper, David Z.; Bau, Michael

2013-01-01

The concentrations of the rare earth elements (REE) in surface waters and sediments, when normalized on an element-by-element basis to one of several rock standards and plotted versus atomic number, yield curves that reveal their partitioning between different sediment fractions and the sources of those fractions, for example, between terrestrial-derived lithogenous debris and seawater-derived biogenous detritus and hydrogenous metal oxides. The REE of ancient sediments support their partitioning into these same fractions and further contribute to the identification of the redox geochemistry of the sea water in which the sediments accumulated. The normalized curves of the REE that have been examined in several South American wine varietals can be interpreted to reflect the lithology of the bedrock on which the vines may have been grown, suggesting limited fractionation during soil development.

Condensation and fractionation of rare earths in the solar nebula

International Nuclear Information System (INIS)

Davis, A.M.; Grossman, L.

1979-01-01

Using the most recent thermodynamic data, the condensation behaviour of REE was calculated and several models were investigated to explain group II REE patterns in Allende inclusions. All models involve removal of large fractions of the more refractory heavy REE in an early condensate, probably perovskite, followed by condensation of the remainder at lower temperature. Previous workers found that the pattern of one such inclusion could not be fit by that of the gas remaining after ideal solution of REE in perovskite and, assuming the presence of only one REE component, calculated relative activity coefficients for REE in perovskite that would be needed to produce a match. In attempting to fit 20 group II patterns with this type of model, it was found that these activity coefficients could not be used for most inclusions and that the relationship between ionic radius and required activity coefficients had to change rapidly and irregularly over a narrow range of perovskite removal temperature. Because this feature and the high degree of non-ideality needed are most unreasonable, a different model is proposed in which two REE components control the patterns: (1) the gas remaining after removal of perovskite in which REE dissolve in ideal solution; (2) a material uniformly enriched in all REE. Two-component models in which solid solution of REE in perovskite is slightly non-ideal and activity coefficients vary negligibly over a narrow temperature range cannot be ruled out. By varying perovskite removal temperatures and the relative proportions of the two components, all 20 REE patterns can be satisfactorily explained. (author)

A linear solvation energy relationship model of organic chemical partitioning to dissolved organic carbon.

Science.gov (United States)

Kipka, Undine; Di Toro, Dominic M

2011-09-01

Predicting the association of contaminants with both particulate and dissolved organic matter is critical in determining the fate and bioavailability of chemicals in environmental risk assessment. To date, the association of a contaminant to particulate organic matter is considered in many multimedia transport models, but the effect of dissolved organic matter is typically ignored due to a lack of either reliable models or experimental data. The partition coefficient to dissolved organic carbon (K(DOC)) may be used to estimate the fraction of a contaminant that is associated with dissolved organic matter. Models relating K(DOC) to the octanol-water partition coefficient (K(OW)) have not been successful for many types of dissolved organic carbon in the environment. Instead, linear solvation energy relationships are proposed to model the association of chemicals with dissolved organic matter. However, more chemically diverse K(DOC) data are needed to produce a more robust model. For humic acid dissolved organic carbon, the linear solvation energy relationship predicts log K(DOC) with a root mean square error of 0.43. Copyright © 2011 SETAC.

A flow-through aqueous standard generation system for thin film microextraction investigations of UV filters and biocides partitioning to different environmental compartments.

Science.gov (United States)

Ahmadi, Fardin; Sparham, Chris; Pawliszyn, Janusz

2017-11-01

In this paper problems associated with preparation of aqueous standard of highly hydrophobic compounds such as partial precipitation, being lost on the surfaces, low solubility in water and limited sample volume for accurate determination of their distribution coefficients are addressed. The following work presents two approaches that utilize blade thin film microextraction (TFME) to investigate partitioning of UV filters and biocides to humic acid (dissolved organic carbon) and sediment. A steady-state concentration of target analytes in water was generated using a flow-through aqueous standard generation (ASG) system. Dialysis membranes, a polytetrafluoroethylene permeation tube, and a frit porous (0.5 μm) coated by epoxy glue were basic elements used for preparation of the ASG system. In the currently presented study, negligible depletion TFME using hydrophilic-lipophilic balance (HLB) and octadecyl silica-based (C18) sorbents was employed towards the attainment of free concentration values of target analytes in the studied matrices. Thin film geometry provided a large volume of extraction phase, which improved the sensitivity of the method towards highly matrix-bound analytes. Extractions were performed in the equilibrium regime so as to prevent matrix effects and with aims to reach maximum method sensitivity for all analytes under study. Partitioning of analytes on dissolved organic carbon (DOC) was investigated in ASG to facilitate large sample volume conditions. Binding percentages and DOC distribution coefficients (Log K DOC ) ranged from 20 to 98% and 3.71-6.72, respectively. Furthermore, sediment-water partition coefficients (K d ), organic-carbon normalized partition coefficients (Log K OC ), and DOC distribution coefficients (Log K DOC ) were investigated in slurry sediment, and ranged from 33 to 2860, 3.31-5.24 and 4.52-5.75 Lkg -1 , respectively. The obtained results demonstrated that investigations utilizing ASG and TFME can yield reliable binding

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

Science.gov (United States)

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

Heavy metal partitioning of suspended particulate matter-water and sediment-water in the Yangtze Estuary.

Science.gov (United States)

Feng, Chenghong; Guo, Xiaoyu; Yin, Su; Tian, Chenhao; Li, Yangyang; Shen, Zhenyao

2017-10-01

The partitioning of ten heavy metals (As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, and Zn) between the water, suspended particulate matter (SPM), and sediments in seven channel sections during three hydrologic seasons in the Yangtze Estuary was comprehensively investigated. Special attention was paid to the role of tides, influential factors (concentrations of SPM and dissolved organic carbon, and particle size), and heavy metal speciation. The SPM-water and sediment-water partition coefficients (K p ) of the heavy metals exhibited similar changes along the channel sections, though the former were larger throughout the estuary. Because of the higher salinity, the K p values of most of the metals were higher in the north branch than in the south branch. The K p values of Cd, Co, and As generally decreased from the wet season to the dry season. Both the diagonal line method and paired samples t-test showed that no specific phase transfer of heavy metals existed during the flood and ebb tides, but the sediment-water K p was more concentrated for the diagonal line method, owing to the relatively smaller tidal influences on the sediment. The partition coefficients (especially the K p for SPM-water) had negative correlations with the dissolved organic carbon (DOC) but positive correlations were noted with the particle size for most of the heavy metals in sediment. Two types of significant correlations were observed between K p and metal speciation (i.e., exchangeable, carbonate, reducible, organic, and residual fractions), which can be used to identify the dominant phase-partition mechanisms (e.g., adsorption or desorption) of heavy metals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Measurement of polyurethane foam - air partition coefficients for semivolatile organic compounds as a function of temperature: Application to passive air sampler monitoring.

Science.gov (United States)

Francisco, Ana Paula; Harner, Tom; Eng, Anita

2017-05-01

Polyurethane foam - air partition coefficients (K PUF-air ) for 9 polycyclic aromatic hydrocarbons (PAHs), 10 alkyl-substituted PAHs, 4 organochlorine pesticides (OCPs) and dibenzothiophene were measured as a function of temperature over the range 5 °C-35 °C, using a generator column approach. Enthalpies of PUF-to-air transfer (ΔH PUF-air , kJ/mol) were determined from the slopes of log K PUF-air versus 1000/T (K), and have an average value of 81.2 ± 7.03 kJ/mol. The log K PUF-air values at 22 °C ranged from 4.99 to 7.25. A relationship for log K PUF-air versus log K OA was shown to agree with a previous relationship based on only polychlorinated biphenyls (PCBs) and derived from long-term indoor uptake study experiments. The results also confirm that the existing K OA -based model for predicting log K PUF-air values is accurate. This new information is important in the derivation of uptake profiles and effective air sampling volumes for PUF disk samplers so that results can be reported in units of concentration in air. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

Alkylarylnitrosoureas--stability in aqueous solution, partition coefficient, alkylating activity and its relationship to SCE induction in Chinese hamster V 79-E cells.

Science.gov (United States)

Mendel, J; Thust, R; Schwarz, H

1982-01-01

The alkylating activity, chemical stability in aqueous solution (pH 7.0; 37 degrees C), and partition coefficient (octanol/water) of the following compounds were determined: 1-methyl-3-phenyl-1-nitrosourea (MPNU), 1-ethyl-3-phenyl-1-nitrosourea (EPNU), 1-isopropyl-3-phenyl-1-nitrosourea (i-PrPNU), 1-methyl-3-(p-fluorophenyl)-1-nitrosourea (F-MPNU), 1-methyl-3-(p-chlorophenyl)-1-nitrosourea (Cl-MPNU), 1-methyl-3-(p-bromophenyl)-1-nitrosourea (Br-MPNU), 1,3-dimethyl-3-phenyl-1-nitrosourea (DMPNU), and 1-methyl-3-naphthyl-1-nitrosocarbamate (NCA). 1-Methyl-1-nitrosourea (MNU) and 1-ethyl-1-nitrosourea (ENU) were used for the comparison. THe rate of decomposition in aqueous solution is discussed concerning the influences of the substituents at the 1- and 3-N-atom. The mono- and disubstituted N-nitrosoureas showed a coarse correlation between alkylating activity and SCE induction in Chinese hamster V 79-E cells. On the other hand, this correlation is missing in the case of NCA, which is a potent SCE inducer despite relatively low alkylating activity. DMPNU is the strongest SCE inducer, but this compound shows a high stability in aqueous solution and, consequently, we were not able to detect an alkylating activity.

Safety-Critical Partitioned Software Architecture: A Partitioned Software Architecture for Robotic

Science.gov (United States)

Horvath, Greg; Chung, Seung H.; Cilloniz-Bicchi, Ferner

2011-01-01

The flight software on virtually every mission currently managed by JPL has several major flaws that make it vulnerable to potentially fatal software defects. Many of these problems can be addressed by recently developed partitioned operating systems (OS). JPL has avoided adopting a partitioned operating system on its flight missions, primarily because doing so would require significant changes in flight software design, and the risks associated with changes of that magnitude cannot be accepted by an active flight project. The choice of a partitioned OS can have a dramatic effect on the overall system and software architecture, allowing for realization of benefits far beyond the concerns typically associated with the choice of OS. Specifically, we believe that a partitioned operating system, when coupled with an appropriate architecture, can provide a strong infrastructure for developing systems for which reusability, modifiability, testability, and reliability are essential qualities. By adopting a partitioned OS, projects can gain benefits throughout the entire development lifecycle, from requirements and design, all the way to implementation, testing, and operations.

Mineralogy, geochemistry and origin of Zafarabad iron deposit based on REE and trace elements of magnetite

Directory of Open Access Journals (Sweden)

Mehrdad Barati

2013-10-01

Full Text Available Zafarabad iron deposit is located northwest of Divandareh, in the northern margin of Sanandaj-Sirjan plutonic-metamorphic zone. The deposit is in lentoid to tubular shape, within a shear zone and occrrued in host rocks of calc-schist and limestone. Magnetite with massive, cataclastic and replacement textures are the main phases, while pyrite and other sulfide minerals are found. Major and trace elements are measured by ICP-MS and ICP-AES methods. Based on some ratios of trace elements in the ore samples and (Ti+V vs. Cal+Al+Mn and Ti+V vs. Ni/(Cr+Mn diagrams which are used for classification of iron deposit types, Zafarabad iron deposit fall in the range of skarn deposits. Spider diagrams show a steady decline from LREE to HREE elements with Eu (mean value of 0.06 ppm and Ce (mean value of 0.94 ppm negative anomalies. Comparing the distribution patterns of REE for the Zafarabad magnetites with those of various types of iron deposits shows that the REE pattern for Zafarabad is similar to these deposits. Analysis of calculated parameters for REE shows that the hydrothermal fluids responsible for mineralization are mainly of magmatic origin through fractionation and crystallization processes of a deep iron rich fluid phase and its emplacement within the carbonate rocks, forming iron skarn.

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

Science.gov (United States)

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...

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

Science.gov (United States)

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.

Data and uncertainty assessment for radionuclide K{sub d} partitioning coefficients in granitic rock for use in SR-Can calculations

Energy Technology Data Exchange (ETDEWEB)

Crawford, James; Neretnieks, Ivars; Malmstroem, Maria [Royal Inst. of Technology, Stockholm (Sweden). Dept. of Chemical Engineering and Technology

2006-10-15

SKB is currently preparing licence applications related to the proposed deep repository for spent nuclear fuel as well as the encapsulation plant required for canister fabrication. The present report is one of several specific data reports that form the data input to an interim safety report (SR-Can) for the encapsulation plant licence application. This report concerns the derivation and recommendation of generic K{sub d} data (i.e. linear partitioning coefficients) for safety assessment modelling of far-field radionuclide transport in fractured granitic rock. The data are derived for typical Swedish groundwater conditions and rock types distinctive of those found on the Simpevarp peninsula and Forsmark. Data have been derived for 8 main elements (Cs, Sr, Ra, Ni, Th, U, Np, Am) and various oxidation states. The data have also been supplied with tentative correction factors to account for artefacts that have not been previously considered in detail in previous compilations. For the main reviewed solutes the data are given in terms of a best estimate K{sub d} value assumed to be the median of the aggregate set of selected data. A range corresponding to the 25-75% inter-quartile range is also specified and probable ranges of uncertainty are estimated in the form of an upper and lower limit to the expected variability. Data for an additional 19 elements that have not been reviewed are taken from a previous compilation by Carbol and Engkvist.

Limiting partition coefficients of sulfur-containing aromatics in a biphasic [bmim][MeSO4]-supercritical CO(2) system

Czech Academy of Sciences Publication Activity Database

Planeta, Josef; Šťavíková, Lenka; Karásek, Pavel; Roth, Michal

2011-01-01

Roč. 56, č. 3 (2011), s. 527-531 ISSN 0021-9568 R&D Projects: GA ČR GA203/08/1465 Institutional research plan: CEZ:AV0Z40310501 Keywords : ionic liquid * supercritical carbon dioxide * solute partitioning Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.693, year: 2011

Uranium-thorium disequilibria and partitioning on melting of garnet peridotite

International Nuclear Information System (INIS)

Beattie, P.

1993-01-01

The abundances of isotopes in the 238 U decay series can be used as both tracers and chronometers of magmatic processes. In the subsolidus asthenosphere, the activity of each daughter isotope (defined as the product of its concentration and decay constant, and denoted by parentheses) is assumed to be equal to that of its parent. By contrast, ( 230 Th/ 238 U) is greater than unity in most recent mid-ocean-ridge and ocean-island basalts, implying that thorium is more incompatible (that is, it is partitioned into the melt phase more strongly) than uranium. Melting of spinel peridotite cannot produce the ( 230 Th) excesses, because measured partition coefficients for pyroxenes and olivine demonstrate that uranium is more incompatible than thorium for this rock. Here I report garnet-melt partitioning data which show that for this mineral-melt pair thorium does behave more incompatibility than uranium, thus supporting the suggestion that mid-ocean-ridge basalts (MORB) are produced by melting initiated at depths where garnet is stable. Using these data, I show that the observed ( 230 Th/ 238 U) ratios of MORB and most ocean-island basalts can be explained by slow, near-fractional melting initiated in the garnet stability field. (author)

Partitioning of phthalates among the gas phase, airborne particles and settled dust in indoor environments

DEFF Research Database (Denmark)

Weschler, Charles J.; Salthammer, Tunga; Fromme, Hermann

2008-01-01

(s)) or the octanol/air partition coefficient (K-OA). For each phthalate in each apartment, the ratio of its particle concentration to its dust concentration (C-particle/C-Dust) was calculated, The median values of this ratio were within an order of magnitude of one another for five of the phthalate esters despite...

Carbonatites in China: A review for genesis and mineralization

Directory of Open Access Journals (Sweden)

Cheng Xu

2010-10-01

Full Text Available Carbonatites are commonly related to the accumulation of economically valuable substances such as REE, Cu, and P. The debate over the origin of carbonatites and their relationship to associated silicate rocks has been ongoing for about 45 years. Worldwide, the rocks characteristically display more geochemical enrichments in Ba, Sr and REE than sedimentary carbonate rocks. However, carbonatite’s geochemical features are disputed because of secondary mineral effects. Rock-forming carbonates from carbonatites at Qinling, Panxi region, and Bayan Obo in China show REE distribution patterns ranging from LREE enrichment to flat patterns. They are characterized by a Sr content more than 10 times higher than that of secondary carbonates. The coarse- and fine-grained dolomites from Bayan Obo H8 dolomite marbles also show similar high Sr abundance, indicating that they are of igneous origin. Some carbonates in Chinese carbonatites show REE (especially HREE contents and distribution patterns similar to those of the whole rocks. These intrusive carbonatites display lower platinum group elements and stronger fractionation between Pt and Ir relative to high-Si extrusive carbonatite. This indicates that most intrusive carbonatites may be carbonate cumulates. Maoniuping and Daluxiang in Panxi region are large REE deposits. Hydrothermal fluorite ore veins occur outside of the carbonatite bodies and are emplaced in wallrock syenite. The fluorite in Maoniuping has Sr and Nd isotopes similar to carbonatite. The Daluxiang fluorite shows Sr and REE compositions different from those in Maoniuping. The difference is reflected by both the carbonatites and rock-forming carbonates, indicating that REE mineralization is related to carbonatites. The cumulate processes of carbonate minerals make fractionated fluids rich in volatiles and LREE as a result of low partition coefficients for REE between carbonate and carbonatite melt and an increase from LREE to HREE. The

Selective Recovery of Yttrium and Ytterbium Oxides from Abu Rusheid REEs Concentrate via Alkaline Leaching and Solvent Extraction

International Nuclear Information System (INIS)

El-Sheikh, E.M.

2017-01-01

The REEs concentrate prepared from Abu Rusheid lamprophyre ore material is found to assay 44.65% Y_2O_3 and 13.87% Yb_2O_3 together with less amounts of 10 other REEs. This concentrate has been subjected to alkaline leaching process using seven different alkali reagents (single or mixed). From the obtained results, the mixed Na_2CO_3/(NH_4)HCO_3 reagent has been able to leach up to 87.32 % of Yb and 98.73% of Y together with a minor amount of Eu( 1.44)%. Finally, TBP extractant has been used to separate highly pure Yb and Y concentrate oxides from the nitrate solution

Leaching Kinetics of Praseodymium in Sulfuric Acid of Rare Earth Elements (REE) Slag Concentrated by Pyrometallurgy from Magnetite Ore

International Nuclear Information System (INIS)

Kim, Chul-Joo; Yoon, Ho-Sung; Chung, Kyung Woo; Lee, Jin-Young; Kim, Sung-Don; Shin, Shun Myung; Kim, Hyung-Seop; Cho, Jong-Tae; Kim, Ji-Hye; Lee, Eun-Ji; Lee, Se-Il; Yoo, Seung-Joon

2015-01-01

A leaching kinetics was conducted for the purpose of recovery of praseodymium in sulfuric acid (H 2 SO 4 ) from REE slag concentrated by the smelting reduction process in an arc furnace as a reactant. The concentration of H 2 SO 4 was fixed at an excess ratio under the condition of slurry density of 1.500 g slag/L, 0.3 mol H 2 SO 4 , and the effect of temperatures was investigated under the condition of 30 to 80 .deg. C. As a result, praseodymium oxide (Pr 6 O 1 1) existing in the slag was completely converted into praseodymium sulfate (Pr 2 (SO 4 ) 3 ·8H 2 O) after the leaching of 5 h. On the basis of the shrinking core model with a shape of sphere, the first leaching reaction was determined by chemical reaction mechanism. Generally, the solubility of pure REEs decreases with the increase of leaching temperatures in sulfuric acid, but REE slag was oppositely increased with increasing temperatures. It occurs because the ash layer included in the slag is affected as a resistance against the leaching. By using the Arrhenius expression, the apparent activation energy of the first chemical reaction was determined to be 9.195 kJmol -1 . In the second stage, the leaching rate is determined by the ash layer diffusion mechanism. The apparent activation energy of the second ash layer diffusion was determined to be 19.106 kJmol -1 . These relative low activation energy values were obtained by the existence of unreacted ash layer in the REE slag

Polyacrylate–water partitioning of biocidal compounds: Enhancing the understanding of biocide partitioning between render and water

DEFF Research Database (Denmark)

Bollmann, Ulla E.; Ou, Yi; Mayer, Philipp

2014-01-01

-N-octylisothiazolinone). The correlation of the polyacrylate-water partition constants with the octanol-water partition constants is significant, but the polyacrylate-water partition constants were predominantly below octanol-water partition constants (Kow). The comparison with render-water distribution constants showed that estimating...

Determination of Unbound Partition Coefficient and in Vitro-in Vivo Extrapolation for SLC13A Transporter-Mediated Uptake.

Science.gov (United States)

Riccardi, Keith; Li, Zhenhong; Brown, Janice A; Gorgoglione, Matthew F; Niosi, Mark; Gosset, James; Huard, Kim; Erion, Derek M; Di, Li

2016-10-01

Unbound partition coefficient (Kpuu) is important to an understanding of the asymmetric free drug distribution of a compound between cells and medium in vitro, as well as between tissue and plasma in vivo, especially for transporter-mediated processes. Kpuu was determined for a set of compounds from the SLC13A family that are inhibitors and substrates of transporters in hepatocytes and transporter-transfected cell lines. Enantioselectivity was observed, with (R)-enantiomers achieving much higher Kpuu (>4) than the (S)-enantiomers (<1) in human hepatocytes and SLC13A5-transfected human embryonic 293 cells. The intracellular free drug concentration correlated directly with in vitro pharmacological activity rather than the nominal concentration in the assay because of the high Kpuu mediated by SLC13A5 transporter uptake. Delivery of the diacid PF-06649298 directly or via hydrolysis of the ethyl ester prodrug PF-06757303 resulted in quite different Kpuu values in human hepatocytes (Kpuu of 3 for diacid versus 59 for prodrug), which was successfully modeled on the basis of passive diffusion, active uptake, and conversion rate from ester to diacid using a compartmental model. Kpuu values changed with drug concentrations; lower values were observed at higher concentrations possibly owing to a saturation of transporters. Michaelis-Menten constant (Km) of SLC13A5 was estimated to be 24 μM for PF-06649298 in human hepatocytes. In vitro Kpuu obtained from rat suspension hepatocytes supplemented with 4% fatty acid free bovine serum albumin showed good correlation with in vivo Kpuu of liver-to-plasma, illustrating the potential of this approach to predict in vivo Kpuu from in vitro systems. Copyright © 2016 by The American Society for Pharmacology and Experimental Therapeutics.

Linking biosensor responses to Cd, Cu and Zn partitioning in soils

International Nuclear Information System (INIS)

Dawson, J.J.C.; Campbell, C.D.; Towers, W.; Cameron, C.M.; Paton, G.I.

2006-01-01

Soils bind heavy metals according to fundamental physico-chemical parameters. Bioassays, using bacterial biosensors, were performed in pore waters extracted from 19 contrasting soils individually amended with Cd, Cu and Zn concentrations related to the EU Sewage Sludge Directive. The biosensors were responsive to pore waters extracted from Zn amended soils but less so to those of Cu and showed no toxicity to pore water Cd at these environmentally relevant amended concentrations. Across the range of soils, the solid-solution heavy metal partitioning coefficient (K d ) decreased (p d values. Gompertz functions of Cu and Zn, K d values against luminescence explained the relationship between heavy metals and biosensors. Consequently, biosensors provide a link between biologically defined hazard assessments of metals and standard soil-metal physico-chemical parameters for determining critical metal loadings in soils. - Biosensors link biological hazard assessments of metals in soils with physico-chemical partitioning

Laboratory actinide partitioning: Whitlockite/liquid and influence of actinide concentration levels

International Nuclear Information System (INIS)

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

1983-01-01

Fission and alpha track radiography techniques have been used to measure partition coefficients (D) at trace (ppm) concentration levels for the actinide elements Th, U, and Pu between synthetic whitlockite and coexisting 'haplobasaltic' silicate liquid at 1 bar pressure and 1250 deg C at oxygen fugacities from 10 sup(-8.5) and 10sup(-0.7) bars. Pu is much more readily incorporated into crystalline phases than is U or Th under reducing conditions, because Pu is primarily trivalent, whereas U and Th are tetravalent. Definitive valence state assignments cannot be made, but our best estimates of corrected partition coefficients for Pu +3 , Pu +4 , Th +4 , U +4 , and U +6 are given for whitlockites. The effect of changing pressure and liquidus temperature is relatively small, which probably reflects a weak temperature dependence for D (whitlockite) but possibly could be due to cancellation of opposing temperature and pressure effects. Comparison of experiments at trace U levels with those containing percent concentrations of UO 2 indicate that Si is involved in the substitution of U in whitlockite with U + 2Si Ca + 2P being the most likely mechanism. Dsub(U) is lower, 0.3 vs 0.5, at percent levels compared to 20 ppm. This is best explained by the effect of U on melt structure or by a decrease in the fraction of tetravalent U at high concentrations. (author)

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

Science.gov (United States)

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

Solid/liquid partition coefficients (Kd) and plant/soil concentration ratios (CR) for selected soils, tills and sediments at Forsmark

International Nuclear Information System (INIS)

Sheppard, Steve; Sohlenius, Gustav; Omberg, Lars-Gunnar; Borgiel, Mikael; Grolander, Sara; Norden, Sara

2011-11-01

Solid/liquid partition coefficients (K d ) are used to indicate the relative mobility of radionuclides and elements of concern from nuclear fuel waste, as well as from other sources. To indicate the uptake of radionuclides in biota concentration ratios (CR) between soil and biota are used. This report summarized K d data for regolith and marine sediments based on concentrations of 69 indigenous stable elements measured from samples collected at the Forsmark site and CR data concerning cereals growing on these soils. The samples included 50 regolith samples from agricultural land and wetlands, 8 samples of till collected at different depths, and two marine sediment samples. In addition, cereal grains, stems and roots were collected from 4 sites for calculation of CRs. The regolith samples represented the major 5 deposits, which can be used as arable land, at the site (clayey till, glacial clay, clay gyttja and peat (cultivated and undisturbed)). K d values were generally lower for peat compared to clay soils. There were also clear differences in K d resulting from differences in soil chemistry within each regolith type. Soil pH was the most important factor, and K d values for many elements were lower in acidic clay soils compared to basic clay soils. Although there were only a few samples of sandy till and marine sediment, the K d values were generally consistent with the corresponding regolith K d values. Of the different cereal parts the grain always had the lowest CR. In most cases, the root CR was significantly higher than the grain CR, whereas only for a few elements were the grain and stem CR values different

Sediment-porewater partition of polycyclic aromatic hydrocarbons (PAHs) from Lanzhou Reach of Yellow River, China

Energy Technology Data Exchange (ETDEWEB)

Yu Yong [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Xu Jian, E-mail: xujian@nankai.edu.cn [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Wang Ping; Sun Hongwen; Dai Shugui [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

2009-06-15

Pollution of polycyclic aromatic hydrocarbons (PAHs) in the aquatic environment has drawn much attention around the world. The occurrence of 16 priority PAHs in the sediments and corresponding porewaters in Lanzhou Reach of Yellow River, China, and their partitioning behavior between the two phases were investigated. The results demonstrated that the total PAH levels in the sediments were positively correlated with the sediment clay contents (R{sup 2} = 0.756). Concentrations of total PAHs in porewaters ranged from 48.2 to 206 {mu}g/L, and indeno[1,2,3-cd]pyrene (InP) was the most abundant compound measured in the porewater samples with a mean value of 42.9 {mu}g/L. The compositions of PAHs in porewaters were dominated by their compositions in the sediment samples. The in situ organic carbon normalized partition coefficients (logK{sub oc}{sup '}) of the PAHs between sediments and porewaters were significantly correlated with their octanol-water partition coefficients (log K{sub ow}) when log K{sub ow} values were less than 5.5 (naphthalene (Nap) excluded). logK{sub oc}{sup '} values of 14 PAHs were lower than those predicted by the Karickhoff relationship. This discrepancy was largest for InP, dibenzo[a,h]anthracene (DBA), and benzo[ghi]perylene (BgP). The results in present study showed the tendency of PAHs release from sediment to porewater, indicating that PAHs sequestered in the sediments may be a pollution source to aquatic ecosystem.

COMPUTING VERTICES OF INTEGER PARTITION POLYTOPES

Directory of Open Access Journals (Sweden)

A. S. Vroublevski

2015-01-01

Full Text Available The paper describes a method of generating vertices of the polytopes of integer partitions that was used by the authors to calculate all vertices and support vertices of the partition polytopes for all n ≤ 105 and all knapsack partitions of n ≤ 165. The method avoids generating all partitions of n. The vertices are determined with the help of sufficient and necessary conditions; in the hard cases, the well-known program Polymake is used. Some computational aspects are exposed in more detail. These are the algorithm for checking the criterion that characterizes partitions that are convex combinations of two other partitions; the way of using two combinatorial operations that transform the known vertices to the new ones; and employing the Polymake to recognize a limited number (for small n of partitions that need three or more other partitions for being convexly expressed. We discuss the computational results on the numbers of vertices and support vertices of the partition polytopes and some appealing problems these results give rise to.

Leaching Kinetics of Praseodymium in Sulfuric Acid of Rare Earth Elements (REE) Slag Concentrated by Pyrometallurgy from Magnetite Ore

Energy Technology Data Exchange (ETDEWEB)

Kim, Chul-Joo; Yoon, Ho-Sung; Chung, Kyung Woo; Lee, Jin-Young; Kim, Sung-Don; Shin, Shun Myung [Korea Institute of Geoscience and Mineral Resources, Daejeon (Korea, Republic of); Kim, Hyung-Seop; Cho, Jong-Tae; Kim, Ji-Hye; Lee, Eun-Ji; Lee, Se-Il; Yoo, Seung-Joon [Seonam University, Asan (Korea, Republic of)

2015-02-15

A leaching kinetics was conducted for the purpose of recovery of praseodymium in sulfuric acid (H{sub 2}SO{sub 4}) from REE slag concentrated by the smelting reduction process in an arc furnace as a reactant. The concentration of H{sub 2}SO{sub 4} was fixed at an excess ratio under the condition of slurry density of 1.500 g slag/L, 0.3 mol H{sub 2}SO{sub 4}, and the effect of temperatures was investigated under the condition of 30 to 80 .deg. C. As a result, praseodymium oxide (Pr{sub 6}O{sub 1}1) existing in the slag was completely converted into praseodymium sulfate (Pr{sub 2}(SO{sub 4}){sub 3}·8H{sub 2}O) after the leaching of 5 h. On the basis of the shrinking core model with a shape of sphere, the first leaching reaction was determined by chemical reaction mechanism. Generally, the solubility of pure REEs decreases with the increase of leaching temperatures in sulfuric acid, but REE slag was oppositely increased with increasing temperatures. It occurs because the ash layer included in the slag is affected as a resistance against the leaching. By using the Arrhenius expression, the apparent activation energy of the first chemical reaction was determined to be 9.195 kJmol{sup -1}. In the second stage, the leaching rate is determined by the ash layer diffusion mechanism. The apparent activation energy of the second ash layer diffusion was determined to be 19.106 kJmol{sup -1}. These relative low activation energy values were obtained by the existence of unreacted ash layer in the REE slag.

Grow your own REE deposits: Novel observations from the soils of Southern Portugal

Science.gov (United States)

Hardy, Liam; Smith, Martin; Boyce, Adrian; McDonald, Alison; Heller, Shaun; Bamberger, Axel; Blum, Astrid; Hood, Leo

2017-04-01

Industrialised eucalyptus farming in Serra de Monchique has been well documented for its regional impacts on water flow, for its destructive centralisation of local economics (Jenkins, 1979) and for its derogatory impacts on local ecology (Brito, 1999) (Matias & Lamberts, 2011), it is another story of cash cropping for short term gain in an area of sensitive environmental balance which had previously been suitably subsistence farmed for some 700 years with no outside influence until the early 1950s (Jenkins, 1979). The farming has irreversibly changed local customs, soil and water systems, but formed new and intricate relationships between the troposol, oxisol and latosol formations and plants which have not previously been studied in this region in terms of soil geochemistry. During research in the region (as part of the SoS Rare/NERC-UK program) into metal and clay interactions in the troposol formations of Monchique, it was noted that rare earth elements (REEs) and other soluble ions were being mobilised in the upper half of the profiles by some seasonal cycle other than the natural meteoric input/leaching expected during classical lateritisation (Tardy, 1997). It was observed that some 40% of Fe and some 30% of Y were leaving the profile during wet season and concentrating at specific depths during dry seasons to a grade of some 160ppm Y and were thus, potentially viable as an economic resource of Heavy REEs. This PICO presentation discusses the proposed anthropogenic/biogenic mechanism for this concentration and how you too could potentially grow an economically viable REE enriched garden. References: Brito, J. G. (1999). Management strategies for conservation of the lizard Lacerta schreiberi in Portugal. Biological conservation, 311-319. Jenkins, R. (1979). The Road to Alto: An account of peasants, capitalists and their soil in the mountains of Southern Portugal. London: Pluto, ISBN: 0861040767. Matias, M., & Lamberts, P. (2011, May 26). Parliamentary

Spectral response of REE{sup 3+} doped LaAlO{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Boronat, C.; Correcher, V. [CIEMAT, Av. Complutense 40, 28040 Madrid (Spain); Garcia G, J. [Museo Nacional de Ciencias Naturales - Consejo Superior de Investigaciones Cientificas, 28006 Madrid (Spain); Morales, A.; Zarate, J. [Universidad Michoacana de San Nicolas de Hidaldo, Instituto de Investigacion en Metalurgia y Materiales, Ciudad Universitaria, Morelia, Michoacan (Mexico); Rivera, T., E-mail: Cecilia.Boronat@ciemat.es [IPN, Ciudad de Mexico (Mexico)

2016-10-15

This paper reports on the preliminary results obtained from the cathodoluminescence (Cl) and thermoluminescence (Tl) properties of undoped LaAlO{sub 3} (LAO) and LaAlO{sub 3}: REE (REE=Dy{sup 3+}, Pr{sup 3+} and Eu{sup 3+}) to be potentially employed for dosimetric purposes. The samples were synthesized by a sol-gel process based on the Pechini 's method with a spray-drying technique and, subsequently, characterized by environmental scanning electron microscopy and energy dispersive X-ray analysis spectrometry. Cl spectra display sharp and narrow wavebands that could specifically be associated with structural (in the range of 300-450 nm) and point defects (from 450 to 800 nm). The observed wavebands could be assigned as follows: (i) 480 and 570 from the Dy-doped LAO should corresponding respectively to {sup 4}F{sub 9/2}→{sup 6}H{sub 15/2} and {sup 4}F{sub 9/2}→{sup 6}H{sub 13/2} transitions, (II) 490-638 from the Pr-doped LAO is linked to {sup 3}P{sub 0}→{sup 3}H{sub 4}, {sup 1}D{sub 2}→{sup 3}H{sub 4} transitions and (III) 590 and 620 where the dopant Eu{sup 3+} gives rise to {sup 5}D{sub 0}→{sup 7}F{sub 1} and {sup 5}D{sub 0}→{sup 7}F{sub 2} transitions and (IV) a UV-blue broad band is associated with NBOHC in undoped LAO. Such emissions are due to the presence of the 4f electrons of rare earth ions that are shielded by the outer 5s and 5p electrons, the intra-4f emission spectra of REE. Furthermore, the study performed on the Tl emission of LaAlO{sub 3}:Dy{sup 3+} displays (i) two maxima centred at 150 and 240 degrees Celsius (ratio 1:2) similarly to the Pr{sup 3+} doped sample but with 7:5 of ratio. And (II) the highest radiation sensitivity, allowing us to think on the potential use of this material for dosimetric purposes, however further works are necessary to confirm such assertion. (Author)

Alternative measures of lipophilicity: from octanol-water partitioning to IAM retention.

Science.gov (United States)

Giaginis, Costas; Tsantili-Kakoulidou, Anna

2008-08-01

This review describes lipophilicity parameters currently used in drug design and QSAR studies. After a short historical overview, the complex nature of lipophilicity as the outcome of polar/nonpolar inter- and intramolecular interactions is analysed and considered as the background for the discussion of the different lipophilicity descriptors. The first part focuses on octanol-water partitioning of neutral and ionisable compounds, evaluates the efficiency of predictions and provides a short description of the experimental methods for the determination of distribution coefficients. A next part is dedicated to reversed-phase chromatographic techniques, HPLC and TLC in lipophilicity assessment. The two methods are evaluated for their efficiency to simulate octanol-water and the progress achieved in the refinement of suitable chromatographic conditions, in particular in the field of HPLC, is outlined. Liposomes as direct models of biological membranes are examined and phospolipophilicity is compared to the traditional lipophilicity concept. Difficulties associated with liposome-water partitioning are discussed. The last part focuses on Immobilised Artificial Membrane (IAM) chromatography as an alternative which combines membrane simulation with rapid measurements. IAM chromatographic retention is compared to octanol-water and liposome-water partitioning as well as to reversed-phase retention and its potential to predict biopartitioning and biological activities is discussed.

Characterization of bovine serum albumin partitioning behaviors in polymer-salt aqueous two-phase systems.

Science.gov (United States)

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. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Rare Earth Elements (REE Deposits Associated with Great Plain Margin Deposits (Alkaline-Related, Southwestern United States and Eastern Mexico

Directory of Open Access Journals (Sweden)

Virginia T. McLemore

2018-01-01

Full Text Available W.G. Lindgren in 1933 first noted that a belt of alkaline-igneous rocks extends along the eastern edge of the Rocky Mountains and Basin and Range provinces from Alaska and British Columbia southward into New Mexico, Trans-Pecos Texas, and eastern Mexico and that these rocks contain relatively large quantities of important commodities such as, gold, fluorine, zirconium, rare earth elements (REE, tellurium, gallium, and other critical elements. In New Mexico, these deposits were called Great Plain Margin (GPM deposits, because this north-south belt of alkaline-igneous rocks roughly coincides with crustal thickening along the margin between the Great Plains physiographic province with the Basin and Range (including the Rio Grande rift and Rocky Mountains physiographic provinces, which extends into Trans-Pecos Texas and eastern Mexico. Since 1996, only minor exploration and development of these deposits in New Mexico, Texas, and eastern Mexico has occurred because of low commodity prices, permitting issues, and environmental concerns. However, as the current demand for gold and critical elements, such as REE and tellurium has increased, new exploration programs have encouraged additional research on the geology of these deposits. The lack of abundant quartz in these systems results in these deposits being less resistant to erosion, being covered, and not as well exposed as other types of quartz-rich deposits, therefore additional undiscovered alkaline-related gold and REE deposits are likely in these areas. Deposits of Th-REE-fluorite (±U, Nb epithermal veins and breccias are found in the several GPM districts, but typically do not contain significant gold, although trace amounts of gold are found in most GPM districts. Gold-rich deposits in these districts tend to have moderate to low REE and anomalously high tungsten and sporadic amounts of tellurium. Carbonatites are only found in New Mexico and Mexico. The diversity of igneous rocks, including

Environmental concentration and atmospheric deposition of halogenated flame retardants in soil from Nepal: Source apportionment and soil-air partitioning.

Science.gov (United States)

Yadav, Ishwar Chandra; Devi, Ningombam Linthoingambi; Li, Jun; Zhang, Gan

2018-02-01

While various investigations have been driven on polybrominated diphenyl ethers (PBDEs) and other flame retardants (FRs) in different framework around the world, information about contamination and fate of PBDEs and other FRs in developing countries especially in the Indian subcontinent is uncommon. Nepal being located in the Indian subcontinent, very little is known about contamination level of semi-volatile organic pollutants discharged into the environment. This motivated us to investigate the environmental fate of halogenated flame retardant (HFRs) in Nepalese condition. In this study, we investigated the concentration, fate, and sources of 9 PBDEs, 2 dechlorane plus isomers (DPs), and 6 novel brominated flame retardants (NBFRs). Moreover, air-soil exchange and soil-air partitioning were also evaluated to characterize the pattern of air-soil exchange and environmental fate. In general, the concentrations of NBFRs in soil were more prevalent than PBDEs and DPs, and accounted 95% of ∑HFRs. By and large, the concentrations of NBFRs and DPs were measured high in Kathmandu, while PBDEs level exceeded in Pokhara. Principal component analysis (PCA) study suggested contributions from commercial penta-, octa-, and deca-BDEs products and de-bromination of highly brominated PBDEs as the significant source of PBDEs. Likewise, low f anti ratio suggested DPs in soil might have originated from long-range atmospheric transport from remote areas, while high levels of decabromodiphenyl ethane (DBDPE) in soil were linked with the use of wide varieties of consumer products. The estimated fugacity fraction (ff) for individual HFR was quite lower (soil is overwhelming. Soil-air partitioning study revealed neither octanol-air partition coefficient (K OA ) nor black carbon partition coefficient (K BC-A ) is an appropriate surrogate for soil organic matter (SOM), subsequently, absorption by SOM has no or little role in the partitioning of HFRs. Copyright © 2017 Elsevier Ltd. All

Space-partition method for the variance-based sensitivity analysis: Optimal partition scheme and comparative study

International Nuclear Information System (INIS)

Zhai, Qingqing; Yang, Jun; Zhao, Yu

2014-01-01

Variance-based sensitivity analysis has been widely studied and asserted itself among practitioners. Monte Carlo simulation methods are well developed in the calculation of variance-based sensitivity indices but they do not make full use of each model run. Recently, several works mentioned a scatter-plot partitioning method to estimate the variance-based sensitivity indices from given data, where a single bunch of samples is sufficient to estimate all the sensitivity indices. This paper focuses on the space-partition method in the estimation of variance-based sensitivity indices, and its convergence and other performances are investigated. Since the method heavily depends on the partition scheme, the influence of the partition scheme is discussed and the optimal partition scheme is proposed based on the minimized estimator's variance. A decomposition and integration procedure is proposed to improve the estimation quality for higher order sensitivity indices. The proposed space-partition method is compared with the more traditional method and test cases show that it outperforms the traditional one

Are predictive equations for estimating resting energy expenditure accurate in Asian Indian male weightlifters?

Directory of Open Access Journals (Sweden)

Mini Joseph

2017-01-01

Full Text Available Background: The accuracy of existing predictive equations to determine the resting energy expenditure (REE of professional weightlifters remains scarcely studied. Our study aimed at assessing the REE of male Asian Indian weightlifters with indirect calorimetry and to compare the measured REE (mREE with published equations. A new equation using potential anthropometric variables to predict REE was also evaluated. Materials and Methods: REE was measured on 30 male professional weightlifters aged between 17 and 28 years using indirect calorimetry and compared with the eight formulas predicted by Harris–Benedicts, Mifflin-St. Jeor, FAO/WHO/UNU, ICMR, Cunninghams, Owen, Katch-McArdle, and Nelson. Pearson correlation coefficient, intraclass correlation coefficient, and multiple linear regression analysis were carried out to study the agreement between the different methods, association with anthropometric variables, and to formulate a new prediction equation for this population. Results: Pearson correlation coefficients between mREE and the anthropometric variables showed positive significance with suprailiac skinfold thickness, lean body mass (LBM, waist circumference, hip circumference, bone mineral mass, and body mass. All eight predictive equations underestimated the REE of the weightlifters when compared with the mREE. The highest mean difference was 636 kcal/day (Owen, 1986 and the lowest difference was 375 kcal/day (Cunninghams, 1980. Multiple linear regression done stepwise showed that LBM was the only significant determinant of REE in this group of sportspersons. A new equation using LBM as the independent variable for calculating REE was computed. REE for weightlifters = −164.065 + 0.039 (LBM (confidence interval −1122.984, 794.854]. This new equation reduced the mean difference with mREE by 2.36 + 369.15 kcal/day (standard error = 67.40. Conclusion: The significant finding of this study was that all the prediction equations

The prediction of blood-tissue partitions, water-skin partitions and skin permeation for agrochemicals.

Science.gov (United States)

Abraham, Michael H; Gola, Joelle M R; Ibrahim, Adam; Acree, William E; Liu, Xiangli

2014-07-01

There is considerable interest in the blood-tissue distribution of agrochemicals, and a number of researchers have developed experimental methods for in vitro distribution. These methods involve the determination of saline-blood and saline-tissue partitions; not only are they indirect, but they do not yield the required in vivo distribution. The authors set out equations for gas-tissue and blood-tissue distribution, for partition from water into skin and for permeation from water through human skin. Together with Abraham descriptors for the agrochemicals, these equations can be used to predict values for all of these processes. The present predictions compare favourably with experimental in vivo blood-tissue distribution where available. The predictions require no more than simple arithmetic. The present method represents a much easier and much more economic way of estimating blood-tissue partitions than the method that uses saline-blood and saline-tissue partitions. It has the added advantages of yielding the required in vivo partitions and being easily extended to the prediction of partition of agrochemicals from water into skin and permeation from water through skin. © 2013 Society of Chemical Industry.

Influences of binding to dissolved organic matter on hydrophobic organic compounds in a multi-contaminant system: Coefficients, mechanisms and ecological risks.

Science.gov (United States)

Li, Yi-Long; He, Wei; Liu, Wen-Xiu; Kong, Xiang-Zhen; Yang, Bin; Yang, Chen; Xu, Fu-Liu

2015-11-01

The complexation flocculation (CF) method was successfully employed to identify binding coefficients (Kdoc) of specific organic contaminants to dissolved organic matter (DOM, often indicated by dissolved organic carbon, DOC) in a multi-contaminant hydrophobic organic contaminant (HOC) system. Kdoc values were obtained for most of the evaluated 33 HOCs, indicating the feasibility and applicability of the CF method in a multi-contaminant system. Significant positive correlations were observed between binding coefficients and octanol-water partition coefficients (Kow) for organic halogen compounds, such as polybrominated diphenyl ethers (PBDEs) (R(2) = 0.95, p mechanisms between PAHs and organic halogen compounds exist. These differences further result in discriminative competition partitions of HOCs between DOM and organisms. Assuming that only freely dissolved HOCs are bioconcentrative, the results of DOM-influenced bioconcentration factor (BCFDOM) and DOM-influenced lowest observed effect level (LOELDOM) indicate that the ecological risk of HOCs is decreased by DOM. Copyright © 2015 Elsevier Ltd. All rights reserved.

Development of partitioning method: confirmation of behavior of technetium in 4-Group Partitioning Process by a small scale experiment

International Nuclear Information System (INIS)

Morita, Yasuji; Yamaguchi, Isoo; Fujiwara, Takeshi; Kubota, Masumitsu; Mizoguchi, Kenichi

1998-08-01

The separation behavior of Tc in the whole of 4-Group Partitioning Process was examined by a flask-scale experiment using simulated high-level liquid waste containing a macro amount of Tc, in order to confirm the reproducibility of the results obtained in previous studies on the Tc behavior at each step of the process. The 4-Group Partitioning Process consists of pre-treatment step, extraction step with diisodecylphosphoric acid (DIDPA), adsorption step with active carbon or precipitation step by denitration for the separation of Tc and platinum group metals (PGM), and adsorption step with inorganic ion exchangers. The present study deals with the behavior of Tc and other elements at all the above steps and additional step for Tc dissolution from the precipitate formed by the denitration. At the pre-treatment step, the ratio of Tc precipitated was very low (about 0.2%) at both operations of heating-denitration and colloid removal. Tc was not extracted with DIDPA and was contained quantitatively in the raffinate from the extraction step. Batch adsorption with active carbon directly from the raffinate showed that distribution coefficient of Tc was more than 100ml/g, which is high enough for the separation. It also revealed much effect of coexisting Mo on the Tc adsorption. At the precipitation step by denitration, 98.2% of Tc were precipitated. At the Tc dissolution from the precipitate with H 2 O 2 , 84.2% of Tc were selectively dissolved in a single operation. Tc was not adsorbed with inorganic ion exchangers. From these results, composition of Tc product from the partitioning process was estimated. The weight ratio of Tc in the Tc product can be increased to about 50% at least. Main contaminating elements are Cr, Ni, Sr, Ba, Mo and Pd. Process optimization to decrease their contamination should be performed in a next study. (J.P.N.)

Generalized finite polynomial approximation (WINIMAX) to the reduced partition function of isotopic molecules

International Nuclear Information System (INIS)

Lee, M.W.; Bigeleisen, J.

1978-01-01

The MINIMAX finite polynomial approximation to an arbitrary function has been generalized to include a weighting function (WINIMAX). It is suggested that an exponential is a reasonable weighting function for the logarithm of the reduced partition function of a harmonic oscillator. Comparison of the error function for finite orthogonal polynomial (FOP), MINIMAX, and WINIMAX expansions of the logarithm of the reduced vibrational partition function show WINIMAX to be the best of the three approximations. A condensed table of WINIMAX coefficients is presented. The FOP, MINIMAX, and WINIMAX approximations are compared with exact calculations of the logarithm of the reduced partition function ratios for isotopic substitution in H 2 O, CH 4 , CH 2 O, C 2 H 4 , and C 2 H 6 at 300 0 K. Both deuterium and heavy atom isotope substitution are studied. Except for a third order expansion involving deuterium substitution, the WINIMAX method is superior to FOP and MINIMAX. At the level of a second order expansion WINIMAX approximations to ln(s/s')f are good to 2.5% and 6.5% for deuterium and heavy atom substitution, respectively

Audre's daughter: Black lesbian steganography in Dee Rees' Pariah and Audre Lorde's Zami: A New Spelling of My Name.

Science.gov (United States)

Kang, Nancy

2016-01-01

This article argues that African-American director Dee Rees' critically acclaimed debut Pariah (2011) is a rewriting of lesbian poet-activist Audre Lorde's iconic "bio-mythography" Zami: A New Spelling of My Name (1982). The article examines how Rees' work creatively and subtly re-envisions Lorde's Zami by way of deeply rooted and often cleverly camouflaged patterns, resonances, and contrasts. Shared topics include naming, mother-daughter bonds, the role of clothing in identity formation, domestic abuse, queer time, and lesbian, gay, bisexual, and transgender legacy discourse construction. What emerges between the visual and written texts is a hidden language of connection--what may be termed Black lesbian steganography--which proves thought-provoking to viewers and readers alike.

Nitrogen partitioning during Earth's accretion and core-mantle differentiation

Science.gov (United States)

Speelmanns, I. M.; Schmidt, M. W.; Liebske, C.

2017-12-01

On present day Earth, N is one of the key constituents of our atmosphere and forms the basis of life. However, the deep Earth geochemistry of N, i.e. its distribution and isotopic fractionation between Earth's deep reservoirs is not well constrained. This study investigates nitrogen partitioning between metal and silicate melts as relevant for core segregation during the accretion of planetesimals into the Earth. We have determined N-partitioning coefficients over a wide range of temperatures (1250-2000 °C), pressures (15-35 kbar) and oxygen fugacity's, the latter in the relevant range of core segregation (IW-5 to IW). Centrifuging piston cylinders were used to equilibrate and then gravitationally separate metal-silicate melt pairs. Separation of the two melts is necessary to avoid micro nugget contamination in the silicate melt at reducing conditions double capsule technique in all experiments, using an outer metallic (Pt) and inner non-metallic capsule (graphite or Al2O3), minimizes N-loss over the course of the experiments compared to single non-metallic capsules. The two quenched melts were cut apart mechanically, cleaned at the outside, their N concentrations were then analysed on bulk samples by an elemental analyser, the low abslute masses requiring careful development of analytical routines. Despite these difficulties, we were able to determine a DNmetal/silicate of 13±0.3 at IW-1 decreasing to 2.0±0.2 at IW-5.5, at 1250°C and 15 kbar, N partitioning into the core forming metal. Increasing temperature dramatically lowers the DNmetal/silicate to e.g. 0.5±0.15 at IW-4, during early core formation N was hence mildly incompatible in the metal. The results suggest that under magma ocean conditions (> 2000 oC and fO2 IW-2.5), N-partition coefficents were within a factor of 2 of unity. Hence, N did not partition into the core, which should contain negliligible quantities of N. The few available literature data [1],[2],[3] support N changing compatibility with

Partitioning in P-T concept

International Nuclear Information System (INIS)

Zhang Peilu; Qi Zhanshun; Zhu Zhixuan

2000-01-01

Comparison of dry- and water-method for partitioning fission products and minor actinides from the spent fuels, and description of advance of dry-method were done. Partitioning process, some typical concept and some results of dry-method were described. The problems fond in dry-method up to now were pointed out. The partitioning study program was suggested

REE in suspended particulate matter and sediment of the Zuari estuary and adjacent shelf, western India: Influence of mining and estuarine turbidity

Digital Repository Service at National Institute of Oceanography (India)

Shynu, R.; Rao, V.P.; Parthiban, G.; Balakrishnan, S.; Narvekar, T.; Kessarkar, P.M.

in the development of ETM in the lower estuary (Rao et al., 2011). As a consequence bottom sediment may have been re-suspended, thereby increasing SPM and REE in the water column and mixed up with the sediment brought by the river. In other words, the REE.... Seminar Volume on Earth Resources for Goa’s Development. Geological Survey of India, pp. 1-13. Goldstein, S.J., Jacobsen, S.B., 1988. Rare earth elements in river waters. Earth Planetary Science Letters 89, 35-47. Govindaraju, K., 1994. Compilation...

Partition coefficients of organics between water and carbon dioxide revisited: Correlation with solute molecular descriptors and solvent cohesive properties

Czech Academy of Sciences Publication Activity Database

Roth, Michal

2016-01-01

Roč. 50, č. 23 (2016), s. 12857-12863 ISSN 0013-936X R&D Projects: GA ČR(CZ) GA16-03749S Institutional support: RVO:68081715 Keywords : partitioning between water and supercritical CO2 * organic solutes * K-factor modeling * linear solvation energy relationship Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 6.198, year: 2016

Partitioning planning studies: Preliminary evaluation of metal and radionuclide partitioning the high-temperature thermal treatment systems

International Nuclear Information System (INIS)

Liekhus, K.; Grandy, J.; Chambers, A.

1997-03-01

A preliminary study of toxic metals and radionuclide partitioning during high-temperature processing of mixed waste has been conducted during Fiscal Year 1996 within the Environmental Management Technology Evaluation Project. The study included: (a) identification of relevant partitioning mechanisms that cause feed material to be distributed between the solid, molten, and gas phases within a thermal treatment system; (b) evaluations of existing test data from applicable demonstration test programs as a means to identify and understand elemental and species partitioning; and, (c) evaluation of theoretical or empirical partitioning models for use in predicting elemental or species partitioning in a thermal treatment system. This preliminary study was conducted to identify the need for and the viability of developing the tools capable of describing and predicting toxic metals and radionuclide partitioning in the most applicable mixed waste thermal treatment processes. This document presents the results and recommendations resulting from this study that may serve as an impetus for developing and implementing these predictive tools

Partitioning planning studies: Preliminary evaluation of metal and radionuclide partitioning the high-temperature thermal treatment systems

Energy Technology Data Exchange (ETDEWEB)

Liekhus, K.; Grandy, J.; Chambers, A. [and others

1997-03-01

A preliminary study of toxic metals and radionuclide partitioning during high-temperature processing of mixed waste has been conducted during Fiscal Year 1996 within the Environmental Management Technology Evaluation Project. The study included: (a) identification of relevant partitioning mechanisms that cause feed material to be distributed between the solid, molten, and gas phases within a thermal treatment system; (b) evaluations of existing test data from applicable demonstration test programs as a means to identify and understand elemental and species partitioning; and, (c) evaluation of theoretical or empirical partitioning models for use in predicting elemental or species partitioning in a thermal treatment system. This preliminary study was conducted to identify the need for and the viability of developing the tools capable of describing and predicting toxic metals and radionuclide partitioning in the most applicable mixed waste thermal treatment processes. This document presents the results and recommendations resulting from this study that may serve as an impetus for developing and implementing these predictive tools.

Partitioning and desorption behavior of polycyclic aromatic hydrocarbons from disparate sources

International Nuclear Information System (INIS)

Reeves, W.R.; McDonald, T.J.; Cizmas, L.; Donnelly, K.C.

2004-01-01

Contaminated sediments pose a unique challenge for risk assessment or remediation because the overlying water column may transport contaminants offsite or to ecological receptors. This research compares the behavior of polycyclic aromatic hydrocarbons (PAHs) on marine sediments from two sites. The first site was affected by shipping activities and the second was impacted by a creosote seep. Organic carbon:water partitioning coefficients (K oc values) were measured with three solutions. Desorption was measured using Tenax beads. PAHs from the ship channel had lower K oc values than those from the creosote facility. For example, the average log K oc value of ship channel pyrene was significantly lower than that of creosote facility pyrene (4.39±0.35 and 5.29±0.09, respectively, when tested in 5 mM calcium chloride). These results were consistent with the greater desorption of pyrene, phenanthrene and benzo(a)pyrene from the ship channel than from the creosote facility sediments. Organic compound desorption from sediments can be considered to be a two-stage process, with a labile fraction that desorbs quickly and a refractory fraction that desorbs much more slowly. In both sediments, more than 75% of the benzo(a)pyrene was found to have partitioned into the refractory phase. The amounts of phenanthrene and pyrene that partitioned into the refractory phase were lower. Linear correlations of log K oc with log (C R /C L ) (where C R and C L are the fractions of the compound in the refractory and labile phases, respectively, at time zero) showed that partitioning measurements made with the US EPA's Toxicity Characteristic Leaching Procedure fluid (US EPA, 1996) most closely matched predictions of desorption behavior. The data imply that with a larger data set, it may be possible to relate simple partitioning measurements to desorption behavior. Partitioning measurements were used to predict water concentrations. Despite having higher concentrations of carcinogenic PAHs

Formation of fast-spreading lower oceanic crust as revealed by a new Mg-REE coupled geospeedometer

Science.gov (United States)

Sun, Chenguang; Lissenberg, C. Johan

2018-04-01

A new geospeedometer is developed based on the differential closures of Mg and rare earth element (REE) bulk-diffusion between coexisting plagioclase and clinopyroxene. By coupling the two elements with distinct bulk closure temperatures, this speedometer can numerically solve the initial temperatures and cooling rates for individual rock samples. As the existing Mg-exchange thermometer was calibrated for a narrow temperature range and strongly relies on model-dependent silica activities, a new thermometer is developed using literature experimental data. When the bulk closure temperatures of Mg and REE are determined, respectively, using this new Mg-exchange thermometer and the existing REE-exchange thermometer, this speedometer can be implemented for a wide range of compositions, mineral modes, and grain sizes. Applications of this new geospeedometer to oceanic gabbros from the fast-spreading East Pacific Rise at Hess Deep reveal that the lower oceanic crust crystallized at temperatures of 998-1353 °C with cooling rates of 0.003-10.2 °C/yr. Stratigraphic variations of the cooling rates and crystallization temperatures support deep hydrothermal circulations and in situ solidification of various replenished magma bodies. Together with existing petrological, geochemical and geophysical evidence, results from this new speedometry suggest that the lower crust formation at fast-spreading mid-ocean ridges involves emplacement of primary mantle melts in the deep section of the crystal mush zone coupled with efficient heat removal by crustal-scale hydrothermal circulations. The replenished melts become chemically and thermally evolved, accumulate as small magma bodies at various depths, feed the shallow axial magma chamber, and may also escape from the mush zone to generate off-axial magma lenses.

Na, Rb and Cs partitioning between metal, silicate and sulfide: Implications for volatile depletion in terrestrial planets

Science.gov (United States)

Boujibar, A.; Fei, Y.; Du, Z.; Righter, K.; Bullock, E. S.

2017-12-01

Inner Solar System materials are known for their depletion in volatile elements, including the moderately volatile alkalis: Na, K, Rb, and Cs. The origin of this depletion is still uncertain, as several processes could have been involved, during the nebular condensation or planetary accretion. Volatile depletion is commonly estimated through comparison of alkali concentrations relatively to those of chondrites, assuming they remain in planetary mantles during core segregation. However, experimental studies show that substantial K can partition into metals that are enriched in sulfur and oxygen. Several models have also suggested that sulfides may have played an important role during episodes of sulfide segregation from a crystallizing magma ocean (sulfide matte) or accretion of S-rich planetary embryos. For Mercury, a sulfide layer could be present between core and mantle, due to immiscibility between Si-rich and S-rich metals. Therefore, here we investigate whether alkali elements (Na, Cs and Rb) could be partly sequestered in planetary cores during their differentiation. We conducted experiments at high pressure and temperature (1 to 5 GPa and up to 1900 °C) to determine partition coefficients of Na, Rb and Cs between metal and silicate. Our results show that pressure, temperature, sulfur and oxygen in metals enhance the partitioning of Na, Rb and Cs into metals, as previously found for K. For all three investigated alkalis (Na, Rb and Cs), we found a maximum partition coefficient of 1 between sulfides containing 13 wt% O and silicate melt. Therefore, S-rich cores or sulfide layers formed due to immiscibility in Fe-S-O systems could have acted as important geochemical reservoirs for alkali elements. Using our experimental data and different assumptions on initial bulk abundances, we evaluate volatile depletion in terrestrial planets, by comparing resulting mantle alkali concentrations after core segregation, with actual concentrations in the Earth's mantle.

Native oxy-PAHs, N-PACs, and PAHs in historically contaminated soils from Sweden, Belgium, and France: their soil-porewater partitioning behavior, bioaccumulation in Enchytraeus crypticus, and bioavailability.

Science.gov (United States)

Arp, Hans Peter H; Lundstedt, Staffan; Josefsson, Sarah; Cornelissen, Gerard; Enell, Anja; Allard, Ann-Sofie; Kleja, Dan Berggren

2014-10-07

Soil quality standards are based on partitioning and toxicity data for laboratory-spiked reference soils, instead of real world, historically contaminated soils, which would be more representative. Here 21 diverse historically contaminated soils from Sweden, Belgium, and France were obtained, and the soil-porewater partitioning along with the bioaccumulation in exposed worms (Enchytraeus crypticus) of native polycyclic aromatic compounds (PACs) were quantified. The native PACs investigated were polycyclic aromatic hydrocarbons (PAHs) and, for the first time to be included in such a study, oxygenated-PAHs (oxy-PAHs) and nitrogen containing heterocyclic PACs (N-PACs). The passive sampler polyoxymethylene (POM) was used to measure the equilibrium freely dissolved porewater concentration, Cpw, of all PACs. The obtained organic carbon normalized partitioning coefficients, KTOC, show that sorption of these native PACs is much stronger than observed in laboratory-spiked soils (typically by factors 10 to 100), which has been reported previously for PAHs but here for the first time for oxy-PAHs and N-PACs. A recently developed KTOC model for historically contaminated sediments predicted the 597 unique, native KTOC values in this study within a factor 30 for 100% of the data and a factor 3 for 58% of the data, without calibration. This model assumes that TOC in pyrogenic-impacted areas sorbs similarly to coal tar, rather than octanol as typically assumed. Black carbon (BC) inclusive partitioning models exhibited substantially poorer performance. Regarding bioaccumulation, Cpw combined with liposome-water partition coefficients corresponded better with measured worm lipid concentrations, Clipid (within a factor 10 for 85% of all PACs and soils), than Cpw combined with octanol-water partition coefficients (within a factor 10 for 76% of all PACs and soils). E. crypticus mortality and reproducibility were also quantified. No enhanced mortality was observed in the 21 historically

The Euler–Riemann gases, and partition identities

International Nuclear Information System (INIS)

Chair, Noureddine

2013-01-01

The Euler theorem in partition theory and its generalization are derived from a non-interacting quantum field theory in which each bosonic mode with a given frequency is equivalent to a sum of bosonic mode whose frequency is twice (s-times) as much, and a fermionic (parafermionic) mode with the same frequency. Explicit formulas for the graded parafermionic partition functions are obtained, and the inverse of the graded partition function (IGPPF), turns out to be bosonic (fermionic) partition function depending on the parity of the order s of the parafermions. It is also shown that these partition functions are generating functions of partitions of integers with restrictions, the Euler generating function is identified with the inverse of the graded parafermionic partition function of order 2. As a result we obtain new sequences of partitions of integers with given restrictions. If the parity of the order s is even, then mixing a system of parafermions with a system whose partition function is (IGPPF), results in a system of fermions and bosons. On the other hand, if the parity of s is odd, then, the system we obtain is still a mixture of fermions and bosons but the corresponding Fock space of states is truncated. It turns out that these partition functions are given in terms of the Jacobi theta function θ 4 , and generate sequences in partition theory. Our partition functions coincide with the overpartitions of Corteel and Lovejoy, and jagged partitions in conformal field theory. Also, the partition functions obtained are related to the Ramond characters of the superconformal minimal models, and in the counting of the Moore–Read edge spectra that appear in the fractional quantum Hall effect. The different partition functions for the Riemann gas that are the counter parts of the Euler gas are obtained by a simple change of variables. In particular the counter part of the Jacobi theta function is (ζ(2t))/(ζ(t) 2 ) . Finally, we propose two formulas which brings

Hawk: A Runtime System for Partitioned Objects

NARCIS (Netherlands)

Ben Hassen, S.; Bal, H.E.; Tanenbaum, A.S.

1997-01-01

Hawk is a language-independent runtime system for writing data-parallel programs using partitioned objects. A partitioned object is a multidimensional array of elements that can be partitioned and distributed by the programmer. The Hawk runtime system uses the user-defined partitioning of objects

[On the partition of acupuncture academic schools].

Science.gov (United States)

Yang, Pengyan; Luo, Xi; Xia, Youbing

2016-05-01

Nowadays extensive attention has been paid on the research of acupuncture academic schools, however, a widely accepted method of partition of acupuncture academic schools is still in need. In this paper, the methods of partition of acupuncture academic schools in the history have been arranged, and three typical methods of"partition of five schools" "partition of eighteen schools" and "two-stage based partition" are summarized. After adeep analysis on the disadvantages and advantages of these three methods, a new method of partition of acupuncture academic schools that is called "three-stage based partition" is proposed. In this method, after the overall acupuncture academic schools are divided into an ancient stage, a modern stage and a contemporary stage, each schoolis divided into its sub-school category. It is believed that this method of partition can remedy the weaknesses ofcurrent methods, but also explore a new model of inheritance and development under a different aspect through thedifferentiation and interaction of acupuncture academic schools at three stages.

Temporal–spatial variation and partitioning prediction of antibiotics in surface water and sediments from the intertidal zones of the Yellow River Delta, China

International Nuclear Information System (INIS)

Zhao, Shengnan; Liu, Xinhui; Cheng, Dengmiao; Liu, Guannan; Liang, Baocui; Cui, Baoshan; Bai, Junhong

2016-01-01

As special zones, the intertidal zones of the Yellow River Delta (YRD) are highly variable along with time and space. Fluvial–marine and land–ocean interactions which frequently occur in these areas have a great impact on the fate of pollutants. Antibiotics, which contribute to antibiotic-resistant genes (ARGs), are widely detected in wastewater, natural water, soil, sediments, and even drinking water. Therefore, it is meaningful to investigate the occurrence and fate of antibiotics in these special zones. In this study, eight antibiotics belonging to tetracyclines (TCs), fluoroquinolones (FQs), and macrolides (MLs) were detected in the surface water and sediments from the intertidal zones of YRD during two seasons. Two models were established to predict the partitioning coefficients of norfloxacin (NOR) and erythromycin (ETM) using physicochemical properties of sediments, respectively. The total concentrations of these antibiotics were 82.94–230.96 ng·L"− "1 and 40.97–207.44 ng·g"− "1, respectively, in the surface water and sediments. Seasonal variation was mainly influenced by the frequency of antibiotics use and environment factors. The regions with river supply exhibited the highest concentrations of antibiotics in surface water and sediments. Meanwhile, particle-size fractions, cation exchange capability (CEC), and metal ions content played dominant roles in the partitioning behaviors of NOR and ETM between the surface water and sediments. Both models established in this study featured accuracy and feasibility, which provided the methods for predicting the partitioning coefficients of emerging contaminants similar in structures to NOR and ETM in the intertidal zones. - Highlights: • The intertidal zones of YRD were polluted by antibiotics to some extent. • The river supply was a major pathway for the antibiotic pollution of the intertidal zones of YRD. • The partitioning coefficients of NOR and ETM can be predicted using the physicochemical

Determination of infinite dilution activity coefficients using HS-SPME/GC/FID for hydrocarbons in furfural at temperatures of (298.15, 308.15, and 318.15) K

International Nuclear Information System (INIS)

Arantes Furtado, Filipe; Vieira Coelho, Gerson Luiz

2012-01-01

Highlights: ► Two approaches were proposed using SPME on determination of infinite dilution activity coefficients. ► Infinite dilution activity coefficients of nine solutes in solvent furfural at T = (298.15, 308.15, and 318.15) K. ► Fiber–gas partition coefficients of nine solutes on PDMS at T = (298.15, 308.15, and 318.15) K. ► Optical microscopy analysis and statistical tests to measure possible damages on fiber coating. ► Advantages and limitations of methodology proposed were discussed. - Abstract: A new methodology using the headspace solid phase microextraction (HS-SPME) technique has been used to evaluate the infinite dilution activity coefficient (γ 12 ∞ ) of nine hydrocarbons (alkanes, cycloalkanes, and aromatics) in furfural solvent. The main objective of this study was to validate a faster and lower cost methodology expanding the use of HS-SPME to determine infinite dilution activity of solutes in organic solvents. Two approaches were proposed for the determination of γ 12 ∞ in order to use this technique (HS-SPME). In addition, the fiber–gas partition coefficients (K fg ) for each analyte at each of the studied temperatures were determined. The activity and partition coefficients have been reported at temperatures of (298.15, 308.15, and 318.15) K. The data were compared with the literature infinite dilution data determined by other methods such as liquid–gas chromatography (GLC) and gas stripping. Partial molar excess enthalpies of mixing at infinite dilution for each solute have been determined. The fibers were tested before and after each experiment, using statistical methods to ensure that their properties do not change during the experiments. The fibers were also analyzed by optical microscopy to evaluate possible surface damage by comparing them with new fibers. The activity coefficient values correlated well with the data in the literature and showed average deviations less than 10%.

Analysis of load balance in hybrid partitioning | Talib | Botswana ...

African Journals Online (AJOL)

In information retrieval systems, there are three types of index partitioning schemes - term partitioning, document partitioning, and hybrid partitioning. The hybrid-partitioning scheme combines both term and document partitioning schemes. Term partitioning provides high concurrency, which means that queries can be ...

Study of REE behaviors, fluid inclusions, and O, S stable Isotopes in Zafar-abad iron skarn deposit, NW Divandarreh, Kordestan province

Directory of Open Access Journals (Sweden)

Mehrdad Barati

2014-10-01

Full Text Available Introduction The Zafar-abad iron ore deposit, situated in the NW part of Divandarreh (lat. 36°01'14" and long. 46°58'22". The ore body is located on the northern margin of the Sanandaj-Sirjan igneous metamorphic zone. The Zafar-abad Fe-skarn deposit is one of the important, medium- size mineral deposits in western Iran. REE patterns of skarn magnetite were among others studied in Skarn deposit by (Taylor, 1979 Hydrothermal alteration and fluid-rock interaction significantly affect total contents of REE and their patterns in fluids. Moreover, fractionation of REE by chemical complication, adsorption effects and redox reactions are characteristic processes determining REE behavior during crystallization. Stable isotope data for oxygen and sulfur have been widely used with great success to trace the origin and evolution history of paleo-hydrothermal fluids of meteoric, magmatic, and metamorphic. Materials and methods The present study investigates REE and stable Isotope geochemistry of magnetite and pyrite in Zafar-abad deposit and temperature of trapped fluid inclusions based on geothermometry analysis. In order to study the major, trace and REE compositions of Zafar-abad magnetite, twelve samples were collected from surface of ore exposures. The emphasis during sampling was on ores with primary textures. Discussion The Zafar-abad district is situated in Mesozoic and Cenozoic sedimentary, meta-sedimentary and meta-igneous rocks in Sanandaj-Sirjan igneous metamorphic zone. Sedimentary sequences dominantly composed of calcareous and conglomerate rocks. Various meta-sedimentary rocks are intercalated with the sedimentary rocks, and comprise biotite and muscovite-rich schist, calc-schist, calc-silicate rock. Several distinct ductile tectonic fabrics have been identified around the Zafar-abad deposit. The main ore body at Zafar-abad is in the form of a roughly horizontal, discordant, lens to tabular-shaped body plunging 10° NW, where it appears to

Multilevel Methods for Elliptic Problems with Highly Varying Coefficients on Nonaligned Coarse Grids

Energy Technology Data Exchange (ETDEWEB)

Scheichl, Robert [Univ. of Bath (United Kingdom). Dept. of Mathematical Sciences; Vassilevski, Panayot S. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Zikatanov, Ludmil T. [Pennsylvania State Univ., University Park, PA (United States). Dept. of Mathematics

2012-06-21

We generalize the analysis of classical multigrid and two-level overlapping Schwarz methods for 2nd order elliptic boundary value problems to problems with large discontinuities in the coefficients that are not resolved by the coarse grids or the subdomain partition. The theoretical results provide a recipe for designing hierarchies of standard piecewise linear coarse spaces such that the multigrid convergence rate and the condition number of the Schwarz preconditioned system do not depend on the coefficient variation or on any mesh parameters. One assumption we have to make is that the coarse grids are sufficiently fine in the vicinity of cross points or where regions with large diffusion coefficients are separated by a narrow region where the coefficient is small. We do not need to align them with possible discontinuities in the coefficients. The proofs make use of novel stable splittings based on weighted quasi-interpolants and weighted Poincaré-type inequalities. Finally, numerical experiments are included that illustrate the sharpness of the theoretical bounds and the necessity of the technical assumptions.

Determination of REE and U in agricultural soils from Jaguari River basin, Sao Paulo, by neutron activation analysis

International Nuclear Information System (INIS)

Ruby, E.C.; Modesto, R.P.; Lemos, M.M.G.

2009-01-01

Uranium has the highest atomic weight of the naturally occurring elements. It is weakly radioactive and occurs naturally in low concentrations (a few parts per million) in soil, rock and water. The rare earth elements (REE) form the largest chemically coherent group in the periodic table. The versatility and specificity of the REE have given them a level of technological, environmental, and economic importance considerably greater than might be expected. The objective of this work was to determine the concentration of the lanthanides (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu), and U, considering the soil use and occupation from the Jaguari river basin, Sao Paulo. Instrumental Neutron Activation Analysis (INAA) was used for the REE and U analysis The study area is located in a traditional agricultural area which is nowadays one of the main industrial regions of Brazil. In order to evaluate the quality of these soils in relation to lanthanides and U levels, the obtained concentrations were compared to guiding values reported by environmental protection agencies. The 75th percentile for U in agricultural soils (2.76 mg kg- 1 ) was higher than in the control areas (1.61 mg kg -1 ), but much lower than the maximum allowed concentration for soils in The Netherlands (28.3 mg kg -1 ). The lanthanides presented concentration levels higher than the guiding values of the RIVM - -National Institute for Public Health and the Environment guidelines. (author)

Partitioning sparse rectangular matrices for parallel processing

Energy Technology Data Exchange (ETDEWEB)

Kolda, T.G.

1998-05-01

The authors are interested in partitioning sparse rectangular matrices for parallel processing. The partitioning problem has been well-studied in the square symmetric case, but the rectangular problem has received very little attention. They will formalize the rectangular matrix partitioning problem and discuss several methods for solving it. They will extend the spectral partitioning method for symmetric matrices to the rectangular case and compare this method to three new methods -- the alternating partitioning method and two hybrid methods. The hybrid methods will be shown to be best.

A brief history of partitions of numbers, partition functions and their modern applications

Science.gov (United States)

Debnath, Lokenath

2016-04-01

'Number rules the universe.' The Pythagoras 'If you wish to forsee the future of mathematics our course is to study the history and present conditions of the science.' Henri Poincaré 'The primary source (Urqell) of all mathematics are integers.' Hermann Minkowski This paper is written to commemorate the centennial anniversary of the Mathematical Association of America. It deals with a short history of different kinds of natural numbers including triangular, square, pentagonal, hexagonal and k-gonal numbers, and their simple properties and their geometrical representations. Included are Euclid's and Pythagorean's main contributions to elementary number theory with the main contents of the Euclid Elements of the 13-volume masterpiece of mathematical work. This is followed by Euler's new discovery of the additive number theory based on partitions of numbers. Special attention is given to many examples, Euler's theorems on partitions of numbers with geometrical representations of Ferrers' graphs, Young's diagrams, Lagrange's four-square theorem and the celebrated Waring problem. Included are Euler's generating functions for the partitions of numbers, Euler's pentagonal number theorem, Gauss' triangular and square number theorems and the Jacobi triple product identity. Applications of the theory of partitions of numbers to different statistics such as the Bose- Einstein, Fermi- Dirac, Gentile, and Maxwell- Boltzmann statistics are briefly discussed. Special attention is given to pedagogical information through historical approach to number theory so that students and teachers at the school, college and university levels can become familiar with the basic concepts of partitions of numbers, partition functions and their modern applications, and can pursue advanced study and research in analytical and computational number theory.

Derivation of the chemical-equilibrium rate coefficient using scattering theory

Science.gov (United States)

Mickens, R. E.

1977-01-01

Scattering theory is applied to derive the equilibrium rate coefficient for a general homogeneous chemical reaction involving ideal gases. The reaction rate is expressed in terms of the product of a number of normalized momentum distribution functions, the product of the number of molecules with a given internal energy state, and the spin-averaged T-matrix elements. An expression for momentum distribution at equilibrium for an arbitrary molecule is presented, and the number of molecules with a given internal-energy state is represented by an expression which includes the partition function.

Correlations for the partition behavior of proteins in aqueous two-phase systems

DEFF Research Database (Denmark)

Schmidt, A.S.; Andrews, B.A.; Asenjo, J.A.

1996-01-01

to its high hydrophilicity. In the case of subtilisin and trypsin inhibitor, their high concentrations in the top phase were due to their hydrophobic nature (hydrophobic interaction with PEG) and small size (negligible steric exclusion). The maximum concentration in the bottom phase for trypsin inhibitor...... of the overall protein concentration, by the ratio between the ''saturation'' equations of the two individual phases. Better correlations were obtained when an empirical sigmoidal Boltzmann equation was fitted to the data, since in virtually all cases the partition coefficient is constant at low protein...

Determination of the n-octanol/water partition coefficients of weakly ionizable basic compounds by reversed-phase high-performance liquid chromatography with neutral model compounds.

Science.gov (United States)

Liang, Chao; Han, Shu-ying; Qiao, Jun-qin; Lian, Hong-zhen; Ge, Xin

2014-11-01

A strategy to utilize neutral model compounds for lipophilicity measurement of ionizable basic compounds by reversed-phase high-performance liquid chromatography is proposed in this paper. The applicability of the novel protocol was justified by theoretical derivation. Meanwhile, the linear relationships between logarithm of apparent n-octanol/water partition coefficients (logKow '') and logarithm of retention factors corresponding to the 100% aqueous fraction of mobile phase (logkw ) were established for a basic training set, a neutral training set and a mixed training set of these two. As proved in theory, the good linearity and external validation results indicated that the logKow ''-logkw relationships obtained from a neutral model training set were always reliable regardless of mobile phase pH. Afterwards, the above relationships were adopted to determine the logKow of harmaline, a weakly dissociable alkaloid. As far as we know, this is the first report on experimental logKow data for harmaline (logKow = 2.28 ± 0.08). Introducing neutral compounds into a basic model training set or using neutral model compounds alone is recommended to measure the lipophilicity of weakly ionizable basic compounds especially those with high hydrophobicity for the advantages of more suitable model compound choices and convenient mobile phase pH control. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of melt composition on metal-silicate partitioning of siderophile elements and constraints on core formation in the angrite parent body

Science.gov (United States)

Steenstra, E. S.; Sitabi, A. B.; Lin, Y. H.; Rai, N.; Knibbe, J. S.; Berndt, J.; Matveev, S.; van Westrenen, W.

2017-09-01

We present 275 new metal-silicate partition coefficients for P, S, V, Cr, Mn, Co, Ni, Ge, Mo, and W obtained at moderate P (1.5 GPa) and high T (1683-1883 K). We investigate the effect of silicate melt composition using four end member silicate melt compositions. We identify possible silicate melt dependencies of the metal-silicate partitioning of lower valence elements Ni, Ge and V, elements that are usually assumed to remain unaffected by changes in silicate melt composition. Results for the other elements are consistent with the dependence of their metal-silicate partition coefficients on the individual major oxide components of the silicate melt composition suggested by recently reported parameterizations and theoretical considerations. Using multiple linear regression, we parameterize compiled metal-silicate partitioning results including our new data and report revised expressions that predict their metal-silicate partitioning behavior as a function of P-T-X-fO2. We apply these results to constrain the conditions that prevailed during core formation in the angrite parent body (APB). Our results suggest the siderophile element depletions in angrite meteorites are consistent with a CV bulk composition and constrain APB core formation to have occurred at mildly reducing conditions of 1.4 ± 0.5 log units below the iron-wüstite buffer (ΔIW), corresponding to a APB core mass of 18 ± 11%. The core mass range is constrained to 21 ± 8 mass% if light elements (S and/or C) are assumed to reside in the APB core. Incorporation of light elements in the APB core does not yield significantly different redox states for APB core-mantle differentiation. The inferred redox state is in excellent agreement with independent fO2 estimates recorded by pyroxene and olivine in angrites.

Development of partitioning method : cold experiment with partitioning test facility in NUCEF (I)

International Nuclear Information System (INIS)

Yamaguchi, Isoo; Morita, Yasuji; Kondo, Yasuo

1996-03-01

A test facility in which about 1.85 x 10 14 Bq of high-level liquid waste can be treated has been completed in 1994 at Nuclear Fuel Cycle Safety Engineering Research Facility (NUCEF) for research and development of Partitioning Method. The outline of the partitioning test facility and support equipments for it which were design terms, constructions, arrangements, functions and inspections were given in JAERI-Tech 94-030. The present report describes the results of the water transfer test and partitioning tests, which are methods of precipitation by denitration, oxalate precipitation, solvent extraction, and adsorption with inorganic ion exchanger, using nitric acid to master operation method of the test facility. As often as issues related to equipments occurred during the tests, they were improved. As to issues related to processes such as being stopped up of columns, their measures of solution were found by testing in laboratories. They were reflected in operation of the Partitioning Test Facility. Their particulars and improving points were described in this report. (author)

Purification of biomaterials by phase partitioning

Science.gov (United States)

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.

Quantitative relationship between the octanol/water partition coefficient and the diffusion limitation of the exchange between adipose and blood.

Science.gov (United States)

Levitt, David G

2010-01-07

The goal of physiologically based pharmacokinetics (PBPK) is to predict drug kinetics from an understanding of the organ/blood exchange. The standard approach is to assume that the organ is "flow limited" which means that the venous blood leaving the organ equilibrates with the well-stirred tissue compartment. Although this assumption is valid for most solutes, it has been shown to be incorrect for several very highly fat soluble compounds which appear to be "diffusion limited". This paper describes the physical basis of this adipose diffusion limitation and its quantitative dependence on the blood/water (Kbld-wat) and octanol/water (Kow) partition coefficient. Experimental measurements of the time dependent rat blood and adipose concentration following either intravenous or oral input were used to estimate the "apparent" adipose perfusion rate (FA) assuming that the tissue is flow limited. It is shown that the ratio of FA to the anatomic perfusion rate (F) provides a measure of the diffusion limitation. A quantitative relationship between this diffusion limitation and Kbld-wat and Kow is derived. This analysis was applied to previously published data, including the Oberg et. al. measurements of the rat plasma and adipose tissue concentration following an oral dose of a mixture of 13 different polychlorinated biphenyls. Solutes become diffusion limited at values of log Kow greater than about 5.6, with the adipose-blood exchange rate reduced by a factor of about 30 for a solute with a log Kow of 7.36. Quantitatively, a plot of FA/F versus Kow is well described assuming an adipose permeability-surface area product (PS) of 750/min. This PS corresponds to a 0.14 micron aqueous layer separating the well-stirred blood from the adipose lipid. This is approximately equal to the thickness of the rat adipose capillary endothelium. These results can be used to quantitate the adipose-blood diffusion limitation as a function of Kow. This is especially important for the highly

Betweenness-based algorithm for a partition scale-free graph

International Nuclear Information System (INIS)

Zhang Bai-Da; Wu Jun-Jie; Zhou Jing; Tang Yu-Hua

2011-01-01

Many real-world networks are found to be scale-free. However, graph partition technology, as a technology capable of parallel computing, performs poorly when scale-free graphs are provided. The reason for this is that traditional partitioning algorithms are designed for random networks and regular networks, rather than for scale-free networks. Multilevel graph-partitioning algorithms are currently considered to be the state of the art and are used extensively. In this paper, we analyse the reasons why traditional multilevel graph-partitioning algorithms perform poorly and present a new multilevel graph-partitioning paradigm, top down partitioning, which derives its name from the comparison with the traditional bottom—up partitioning. A new multilevel partitioning algorithm, named betweenness-based partitioning algorithm, is also presented as an implementation of top—down partitioning paradigm. An experimental evaluation of seven different real-world scale-free networks shows that the betweenness-based partitioning algorithm significantly outperforms the existing state-of-the-art approaches. (interdisciplinary physics and related areas of science and technology)

Plane partition vesicles

International Nuclear Information System (INIS)

Rensburg, E J Janse van; Ma, J

2006-01-01

We examine partitions and their natural three-dimensional generalizations, plane partitions, as models of vesicles undergoing an inflation-deflation transition. The phase diagrams of these models include a critical point corresponding to an inflation-deflation transition, and exhibits multicritical scaling in the vicinity of a multicritical point located elsewhere on the critical curve. We determine the locations of the multicritical points by analysing the generating functions using analytic and numerical means. In addition, we determine the numerical values of the multicritical scaling exponents associated with the multicritical scaling regimes in these models

Hf and Nd Isotopic and REE Investigations of Magnetite in a Proterozoic IOCG system: Fingerprinting Sources and Timing of Mineralisation

Science.gov (United States)

Schaefer, B. F.

2016-12-01

The Stuart Shelf on the margin of the Gawler Craton, South Australia, contains numerous economic and sub-econmic IOCG mineralised systems, including the giant Olympic Dam Cu-Au-U deposit. Hematite and magnetite have played a critical in the genesis of all of these deposits, and increasingly it appears that magnetite has been in equilibrium with either the final mineralised assemblage or was critical in transporting metals during the ore forming event. 14 magnetites and one hematite from three separate styles of iron oxide mineralisation associated with the Prominent Hill Cu-Au deposit were selected for detailed analysis. The REE and isotopic separations were all conducted by low blank wet chemistry and isotopes determined by TIMS (Nd) and MC-ICPMS (Hf). Magnetites associated with skarn style mineralsiation proximal to the ore body are unformly depleted in REE, whereas hematite within the ore and magmatic magmatites and whole rock gabbros from the nearby 1590Ma White Hill Gabbro intrusion are all relatively LREE enriched and display a comparable range in REE. Significantly however, magnetite separates almost invariably display more evolved Hf isotopic signatures than the host lithologies adjacent the economic mineralisation (dacites and metasediments at Prominent Hill mine) implying that the magnetites were sourcing their REE inventory dominantly from the local crust rather than a mantle derived source. In contrast, the magmatic magnetites from the White Hill Complex display Nd and Hf isotopes which are slightly more primitive, recording a greater relative mantle component, however still requiring a significant crustal input. Significantly, the hematite which contains the Au mineralisation preserves ɛNd (1590) = -4.04 and ɛHf (1590) = -6.05 essentially identical to the magmatic magnetites and their host gabbros in the White Hill complex and the basalts and dacites of the host Gawler Range Volcanics (ɛNd (1590) = -7.10 - -3.72 and ɛHf (1590) = -7.69 - -1

Experimental Partitioning of Chalcophile Elements between Mantle Silicate Minerals and Basaltic Melt at High Pressures and Temperatures - Implications for Sulfur Geochemistry of Mantle and Crust

Science.gov (United States)

Dasgupta, R.; Jego, S.; Ding, S.; Li, Y.; Lee, C. T.

2015-12-01

The behavior of chalcophile elements during mantle melting, melt extraction, and basalt differentiation is critical for formation of ore deposits and geochemical model and evolution of crust-mantle system. While chalcophile elements are strongly partitioned into sulfides, their behavior with different extent of melting, in particular, in the absence of sulfides, can only be modeled with complete knowledge of the partitioning behavior of these elements between dominant mantle minerals and basaltic melt with or without dissolved sulfide (S2-). However, experimental data on mineral-melt partitioning are lacking for many chalcophile elements. Crystallization experiments were conducted at 3 GPa and 1450-1600 °C using a piston cylinder and synthetic silicate melt compositions similar to low-degree partial melt of peridotite. Starting silicate mixes doped with 100-300 ppm of each of various chalcophile elements were loaded into Pt/graphite double capsules. To test the effect of dissolved sulfur in silicate melt on mineral-melt partitioning of chalcophile elements, experiments were conducted on both sulfur-free and sulfur-bearing (1100-1400 ppm S in melt) systems. Experimental phases were analyzed by EPMA (for major elements and S) and LA-ICP-MS (for trace elements). All experiments produced an assemblage of cpx + melt ± garnet ± olivine ± spinel and yielded new partition coefficients (D) for Sn, Zn, Mo, Sb, Bi, Pb, and Se for cpx/melt, olivine/melt, and garnet/melt pairs. Derived Ds (mineral/basalt) reveal little effect of S2- in the melt on mineral-melt partition coefficients of the measured chalcophile elements, with Ds for Zn, Mo, Bi, Pb decreasing by less than a factor of 2 from S-free to S-bearing melt systems or remaining similar, within error, between S-free and S-bearing melt systems. By combining our data with existing partitioning data between sulfide phases and silicate melt we model the fractionation of these elements during mantle melting and basalt

The importance of applying an appropriate data partitioning

CERN Document Server

Dimitrov, Gancho; The ATLAS collaboration

2015-01-01

In this presentation are described specific technical solutions put in place in various database applications of the ATLAS experiment at LHC where we make use of several partitioning techniques available in Oracle 11g. With the broadly used range partitioning and its option of automatic interval partitioning we add our own logic in PLSQL procedures and scheduler jobs to sustain data sliding windows in order to enforce various data retention policies. We also make use of the new Oracle 11g reference partitioning in the ATLAS Nightly Build System to achieve uniform data segmentation. However the most challenging was to segment the data of the new ATLAS Distributed Data Management system, which resulted in tens of thousands list type partitions and sub-partitions. Partition and sub-partition management, index strategy, statistics gathering and queries execution plan stability are important factors when choosing an appropriate physical model for the application data management. The so-far accumulated knowledge wi...

Effect of Silicon on Activity Coefficients of Platinum in Liquid Fe-Si, With Application to Core Formation

Science.gov (United States)

Righter, K.; Pando, K.; Danielson, L. R.; Humayun, M.

2017-01-01

Earth's core contains approximately 10% of a light element that is likely a combination of S, C, Si, and O, with Si possibly being the most abundant light element. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE) in Fe liquids, and thus the partitioning behavior of those elements between core and mantle. The effect of Si can be small such as for Ni and Co, or large such as for Mo, Ge, Sb, As. The effect of Si on many siderophile elements is unknown yet could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of Pt (with Re and Ru in progress or planned) between metal and silicate melt. The results will be applied to Earth, for which we have excellent constraints on the mantle Pt concentrations.

Present status of partitioning developments

International Nuclear Information System (INIS)

Nakamura, Haruto; Kubota, Masumitsu; Tachimori, Shoichi

1978-09-01

Evolution and development of the concept of partitioning of high-level liquid wastes (HLLW) in nuclear fuel reprocessing are reviewed historically from the early phase of separating useful radioisotopes from HLLW to the recent phase of eliminating hazardous nuclides such as transuranium elements for safe waste disposal. Since the criteria in determining the nuclides for elimination and the respective decontamination factors are important in the strategy of partitioning, current views on the criteria are summarized. As elimination of the transuranium is most significant in the partitioning, various methods available of separating them from fission products are evaluated. (auth.)

Classification algorithms using adaptive partitioning

KAUST Repository

Binev, Peter; Cohen, Albert; Dahmen, Wolfgang; DeVore, Ronald

2014-01-01

© 2014 Institute of Mathematical Statistics. Algorithms for binary classification based on adaptive tree partitioning are formulated and analyzed for both their risk performance and their friendliness to numerical implementation. The algorithms can be viewed as generating a set approximation to the Bayes set and thus fall into the general category of set estimators. In contrast with the most studied tree-based algorithms, which utilize piecewise constant approximation on the generated partition [IEEE Trans. Inform. Theory 52 (2006) 1335.1353; Mach. Learn. 66 (2007) 209.242], we consider decorated trees, which allow us to derive higher order methods. Convergence rates for these methods are derived in terms the parameter - of margin conditions and a rate s of best approximation of the Bayes set by decorated adaptive partitions. They can also be expressed in terms of the Besov smoothness β of the regression function that governs its approximability by piecewise polynomials on adaptive partition. The execution of the algorithms does not require knowledge of the smoothness or margin conditions. Besov smoothness conditions are weaker than the commonly used Holder conditions, which govern approximation by nonadaptive partitions, and therefore for a given regression function can result in a higher rate of convergence. This in turn mitigates the compatibility conflict between smoothness and margin parameters.

Classification algorithms using adaptive partitioning

KAUST Repository

Binev, Peter

2014-12-01

© 2014 Institute of Mathematical Statistics. Algorithms for binary classification based on adaptive tree partitioning are formulated and analyzed for both their risk performance and their friendliness to numerical implementation. The algorithms can be viewed as generating a set approximation to the Bayes set and thus fall into the general category of set estimators. In contrast with the most studied tree-based algorithms, which utilize piecewise constant approximation on the generated partition [IEEE Trans. Inform. Theory 52 (2006) 1335.1353; Mach. Learn. 66 (2007) 209.242], we consider decorated trees, which allow us to derive higher order methods. Convergence rates for these methods are derived in terms the parameter - of margin conditions and a rate s of best approximation of the Bayes set by decorated adaptive partitions. They can also be expressed in terms of the Besov smoothness β of the regression function that governs its approximability by piecewise polynomials on adaptive partition. The execution of the algorithms does not require knowledge of the smoothness or margin conditions. Besov smoothness conditions are weaker than the commonly used Holder conditions, which govern approximation by nonadaptive partitions, and therefore for a given regression function can result in a higher rate of convergence. This in turn mitigates the compatibility conflict between smoothness and margin parameters.

Combinatorial interpretations of binomial coefficient analogues related to Lucas sequences

OpenAIRE

Sagan, Bruce; Savage, Carla

2009-01-01

Let s and t be variables. Define polynomials {n} in s, t by {0}=0, {1}=1, and {n}=s{n-1}+t{n-2} for n >= 2. If s, t are integers then the corresponding sequence of integers is called a Lucas sequence. Define an analogue of the binomial coefficients by C{n,k}={n}!/({k}!{n-k}!) where {n}!={1}{2}...{n}. It is easy to see that C{n,k} is a polynomial in s and t. The purpose of this note is to give two combinatorial interpretations for this polynomial in terms of statistics on integer partitions in...

Solid/liquid partition coefficients (K{sub d}) and plant/soil concentration ratios (CR) for selected soils, tills and sediments at Forsmark