Sulphur and oxygen sequestration of n-C37 and n-C38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

USGS Publications Warehouse

Koopmans, M.P.; Schaeffer-Reiss, C.; De Leeuw, J. W.; Lewan, M.D.; Maxwell, J.R.; Schaeffer, P.; Sinninghe, Damste J.S.

1997-01-01

Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature (Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330??C for 72 h to study the diagenetic fate of n-C37 and n-C38 di-and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260??C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S-and O-bound n-C37 and n-C38 skeletons, saturated n-C37 and n-C38 methyl, ethyl, and mid-chain ketones, C37 and C38 mid-chain 2,5-di-n-alkylthiophenes, C37 and C38 1,2-di-n-alkylbenzenes, and C37 and C38 n-alkanes. With increasing thermal maturation, three forms of the n-C37 and n-C38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di-n-alkylbenzenes and saturated ketones), whereas the S-and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C37 and n-C38 skeleton can be expected as well as the corresponding hydrocarbons. Copyright ?? 1997 Elsevier Science Ltd.

Sulphur and oxygen sequestration of n-C 37 and n-C 38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

NASA Astrophysics Data System (ADS)

Koopmans, Martin P.; Schaeffer-Reiss, Christine; de Leeuw, Jan W.; Lewan, Michael D.; Maxwell, James R.; Schaeffer, Philippe; Sinninghe Damsté, Jaap S.

1997-06-01

Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature ( Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330°C for 72 h to study the diagenetic fate of n-C 37 and n-C 38 di- and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260°C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S- and O-bound n-C 37 and n-C 38 skeletons, saturated n-C 37 and n-C38 methyl, ethyl, and mid-chain ketones, C 37 and C 38 mid-chain 2,5-di- n-alkylthiophenes, C 37 and C 38 1,2-di- n-alkylbenzenes, and C 37 and C 38n-alkanes. With increasing thermal maturation, three forms of the n-C 37 and n-C 38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di- n-alkylbenzenes and saturated ketones), whereas the S- and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C 37 and n-C 38 skeleton can be expected as well as the corresponding hydrocarbons.

Uncatalyzed, Regioselective Oxidation of Saturated Hydrocarbons in an Ambient Corona Discharge.

PubMed

Ayrton, Stephen T; Jones, Rhys; Douce, David S; Morris, Mike R; Cooks, R Graham

2018-01-15

Atmospheric pressure chemical ionization (APCI) in air or in nitrogen with just traces of oxygen is shown to yield regioselective oxidation, dehydrogenation, and fragmentation of alkanes. Ozone is produced from ambient oxygen in situ and is responsible for the observed ion chemistry, which includes partial oxidation to ketones and C-C cleavage to give aldehydes. The mechanism of oxidation is explored and relationships between ionic species produced from individual alkanes are established. Unusually, dehydrogenation occurs by water loss. Competitive incorporation into the hydrocarbon chain of nitrogen versus oxygen as a mode of ionization is also demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process for functionalizing alkanes

DOEpatents

Bergman, R.G.; Janowicz, A.H.; Periana, R.A.

1988-05-24

Process for functionalizing saturated hydrocarbons comprises: (a) reacting said saturated hydrocarbons of the formula: R[sub 1]H wherein H represents a hydrogen atom; and R[sub 1] represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRh[P(R[sub 2])[sub 3

One-step hydroprocessing of fatty acids into renewable aromatic hydrocarbons over Ni/HZSM-5: insights into the major reaction pathways.

PubMed

Xing, Shiyou; Lv, Pengmei; Wang, Jiayan; Fu, Junying; Fan, Pei; Yang, Lingmei; Yang, Gaixiu; Yuan, Zhenhong; Chen, Yong

2017-01-25

For high caloricity and stability in bio-aviation fuels, a certain content of aromatic hydrocarbons (AHCs, 8-25 wt%) is crucial. Fatty acids, obtained from waste or inedible oils, are a renewable and economic feedstock for AHC production. Considerable amounts of AHCs, up to 64.61 wt%, were produced through the one-step hydroprocessing of fatty acids over Ni/HZSM-5 catalysts. Hydrogenation, hydrocracking, and aromatization constituted the principal AHC formation processes. At a lower temperature, fatty acids were first hydrosaturated and then hydrodeoxygenated at metal sites to form long-chain hydrocarbons. Alternatively, the unsaturated fatty acids could be directly deoxygenated at acid sites without first being saturated. The long-chain hydrocarbons were cracked into gases such as ethane, propane, and C 6 -C 8 olefins over the catalysts' Brønsted acid sites; these underwent Diels-Alder reactions on the catalysts' Lewis acid sites to form AHCs. C 6 -C 8 olefins were determined as critical intermediates for AHC formation. As the Ni content in the catalyst increased, the Brønsted-acid site density was reduced due to coverage by the metal nanoparticles. Good performance was achieved with a loading of 10 wt% Ni, where the Ni nanoparticles exhibited a polyhedral morphology which exposed more active sites for aromatization.

Wave Velocities in Hydrocarbons and Hydrocarbon Saturated - Applications to Eor Monitoring.

NASA Astrophysics Data System (ADS)

Wang, Zhijing

In order to effectively utilize many new seismic technologies and interpret the results, acoustic properties of both reservoir fluids and rocks must be well understood. It is the main purpose of this dissertation to investigate acoustic wave velocities in different hydrocarbons and hydrocarbon saturated rocks under various reservoir conditions. The investigation consists of six laboratory experiments, followed by a series of theoretical and application analyses. All the experiments involve acoustic velocity measurements in hydrocarbons and rocks with different hydrocarbons, using the ultrasonic pulse-transmission methods, at elevated temperatures and pressures. In the experiments, wave velocities are measured versus both temperature and pressure in 50 hydrocarbons. The relations among the acoustic velocity, temperature, pressure, API gravity, and the molecular weight of the hydrocarbons are studied, and empirical equations are established which allow one to calculate the acoustic velocities in hydrocarbons with known API gravities. Wave velocities in hydrocarbon mixtures are related to the composition and the velocities in the components. The experimental results are also analyzed in terms of various existing theories and models of the liquid state. Wave velocities are also measured in various rocks saturated with different hydrocarbons. The compressional wave velocities in rocks saturated with pure hydrocarbons increase with increasing the carbon number of the hydrocarbons. They decrease markedly in all the heavy hydrocarbon saturated rocks as temperature increases. Such velocity decreases set the petrophysical basis for in-situ seismic monitoring thermal enhanced oil recovery processes. The effects of carbon dioxide flooding and different pore fluids on wave velocities in rocks are also investigated. It is highly possible that there exist reflections of seismic waves at the light-heavy oil saturation interfaces in-situ. It is also possible to use seismic methods to monitor carbon dioxide flooding processes. Velocity dispersions are analyzed theoretically in rocks saturated with different pore fluids. The results are discussed in terms of the Biot theory and the "local flow" mechanism. Applications of the results and the applicability of using seismic methods to monitor various enhanced oil recovery and production processes are also discussed.

Formation of hydrocarbon compounds during the hydrocracking of non-edible vegetable oils with cobalt-nickel supported on hierarchical HZSM-5 catalyst

NASA Astrophysics Data System (ADS)

Marlinda, L.; Al-Muttaqii, M.; Roesyadi, A.; Prajitno, D. H.

2017-05-01

The hierarchical Co-Ni/HZSM-5 catalyst with hierarchical pore structure was prepared by desilication and incipient wetness impregnation. Hydrocracking of non-edible vegetable oils at temperature of 400 °C, 20±5 bar for 2 h was performed in the presence of this type of catalyst under hydrogen initial pressure in pressured batch reactor. Non-edible vegetable oils, such as Reutealis trisperma (Blanco) airy shaw (sunan candlenut) and Hevea brasiliensis (rubber seed) were chosen to study the effect of the degree of saturation and lateral chain length on hydrocarbon compounds obtained through hydrocracking. Cerbera manghas oil was also tested for comparison because the composition of fatty acid was different with the other oils The hydrocracking test indicated that liquid product produced has a similar hydrocarbon compounds with petroleum diesel. The most abundant hydrocarbon is pentadecane (n-C15) and heptadecane (n-C17). The high aromatic compounds were found in liquid product produced in hydrocracking of Sunan candlenut oil.

Structure of gel phase saturated lecithin bilayers: temperature and chain length dependence.

PubMed Central

Sun, W J; Tristram-Nagle, S; Suter, R M; Nagle, J F

1996-01-01

Systematic low-angle and wide-angle x-ray scattering studies have been performed on fully hydrated unoriented multilamamellar vesicles of saturated lecithins with even chain lengths N = 16, 18, 20, 22, and 24 as a function of temperature T in the normal gel (L beta') phase. For all N, the area per chain Ac increases linearly with T with an average slope dAc/dT = 0.027 A2/degree C, and the lamellar D-spacings also increase linearly with an average slope dD/dT = 0.040 A/degree C. At the same T, longer chain length lecithins have more densely packed chains, i.e., smaller Ac's, than shorter chain lengths. The chain packing of longer chain lengths is found to be more distorted from hexagonal packing than that of smaller N, and the distortion epsilon of all N approaches the same value at the respective transition temperatures. The thermal volume expansion of these lipids is accounted for by the expansion in the hydrocarbon chain region. Electron density profiles are constructed using four orders of low-angle lamellar peaks. These show that most of the increase in D with increasing T is due to thickening of the bilayers that is consistent with a decrease in tilt angle theta and with little change in water spacing with either T or N. Because of the opposing effects of temperature on area per chain Ac and tilt angle 0, the area expansivity alpha A is quite small. A qualitative theoretical model based on competing head and chain interactions accounts for our results. PMID:8842227

Studies of mixed-chain diacyl phosphatidylcholines with highly asymmetric acyl chains: a Fourier transform infrared spectroscopic study of interfacial hydration and hydrocarbon chain packing in the mixed interdigitated gel phase.

PubMed Central

Lewis, R N; McElhaney, R N

1993-01-01

The mixed interdigitated gel phases of unlabeled, specifically 13C = O-labeled, and specifically chain-perdeuterated samples of 1-O-eicosanoyl, 2-O-lauroyl phosphatidylcholine and 1-O-decanoyl, 2-O-docosanoyl phosphatidylcholine were studied by infrared spectroscopy. Our results suggest that at the liquid-crystalline/gel phase transition temperatures of these lipids, there is a greater redistribution in the populations of free and hydrogen-bonded ester carbonyl groups than is commonly observed with symmetric chain n-saturated diacyl phosphatidylcholines. The formation of the mixed interdigitated gel phase coincides with the appearance of a marked asymmetry in the contours of the C = O stretching band, a process which becomes more pronounced as the temperature is reduced. This asymmetry is ascribed to the emergence of a predominant lipid population consisting of free sn1- and hydrogen-bonded (hydrated) sn2-ester carbonyl groups. This suggests that the region of the mixed interdigitated bilayer polar/apolar interface near to the sn1-ester carbonyl group is less hydrated than is the case with the noninterdigitated gel-phase bilayers formed by normal symmetric chain phosphatidylcholines. In the methylene deformation region of the spectrum, the unlabeled lipids exhibit a pronounced splitting of the CH2 scissoring bands. This splitting is significantly attenuated when the short chains are perdeuterated and collapses completely upon perdeuteration of the long chains, irrespective of whether the long (or short) chains are esterified to the sn1 or sn2 positions of the glycerol backbone. These results are consistent with a global hydrocarbon chain packing motif in which the zigzag planes of the hydrocarbon chains are perpendicular to each other and the sites occupied by long chains are twice as numerous as those occupied by short chains. The experimental support for this chain-packing motif enabled more detailed considerations of the possible ways in which these lipid molecules are assembled in the mixed interdigitated gel phase. Generally, our results are compatible with a previously proposed model in which the mixed interdigitated gel phase is an assembly of repeat units which consists of two phosphatidylcholine molecules forming a triple-chain structure with the long chains traversing the bilayer and with the methyl termini of the shorter chains opposed at the bilayer center. Our data also suggest that the packing format which is most consistent with our results and previously published work is one in which the hydrocarbon chains of each repeat unit are parallel to each other with the repeat units themselves being perpendicularly packed. PMID:8298016

ESTIMATION OF FREE HYDROCARBON VOLUME FROM FLUID LEVELS IN MONITORING WELLS

EPA Science Inventory

Under the assumption of local vertical equilibrium, fluid pressure distributions specified from well fluid levels in monitoring wells may be used to predict water and hydrocarbon saturation profiles given expressions for air-water-hydrocarbon saturation-pressure relations. Verti...

A numerical study of mobility in thin films of fullerene derivatives.

PubMed

Mackenzie, Roderick C I; Frost, Jarvist M; Nelson, Jenny

2010-02-14

The effect of functional group size on the electron mobility in films of fullerene derivatives is investigated numerically. A series of four C(60) derivatives are formed by attaching saturated hydrocarbon chains to the C(60) cage via a methano bridge. For each of the derivatives investigated, molecular dynamics is used to generate a realistic material morphology. Quantum chemical methods are then used to calculate intermolecular charge transfer rates. Finally, Monte Carlo methods are used to simulate time-of-flight experiments and thus calculate the electron mobility. It is found that as the length of the aliphatic side chain increases, the configurational disorder increases and thus the mobility decreases.

Cationic lipids: molecular structure/ transfection activity relationships and interactions with biomembranes.

PubMed

Koynova, Rumiana; Tenchov, Boris

2010-01-01

Abstract Synthetic cationic lipids, which form complexes (lipoplexes) with polyanionic DNA, are presently the most widely used constituents of nonviral gene carriers. A large number of cationic amphiphiles have been synthesized and tested in transfection studies. However, due to the complexity of the transfection pathway, no general schemes have emerged for correlating the cationic lipid chemistry with their transfection efficacy and the approaches for optimizing their molecular structures are still largely empirical. Here we summarize data on the relationships between transfection activity and cationic lipid molecular structure and demonstrate that the transfection activity depends in a systematic way on the lipid hydrocarbon chain structure. A number of examples, including a large series of cationic phosphatidylcholine derivatives, show that optimum transfection is displayed by lipids with chain length of approximately 14 carbon atoms and that the transfection efficiency strongly increases with increase of chain unsaturation, specifically upon replacement of saturated with monounsaturated chains.

Conversion of oligomeric starch, cellulose, or sugars to hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silks, Louis A.; Sutton, Andrew; Kim, Jin Kyung

The present invention is directed to the one step selective conversion of starch, cellulose, or glucose to molecules containing 7 to 26 contiguous carbon atoms. The invention is also directed to the conversion of those intermediates to saturated hydrocarbons. Such saturated hydrocarbons are useful as, for example, fuels.

Role of the concentration and nature of grafted groups in the adsorption of hydrocarbon vapors on silica modified by monofunctional polyfluoroalkylsilanes

NASA Astrophysics Data System (ADS)

Roshchina, T. M.; Shoniya, N. K.; Tayakina, O. Ya.; Tkachenko, O. P.; Kustov, L. M.; Bernardoni, F.; Fadeev, A. Y.

2012-03-01

The role of the grafting density of monofunctional polyfluoroalkylsilanes of the C n F2 n - 1(CH2) m Si(CH3)2Cl general formula (where n = 3, 4, and 6; and m = 2 and 3) and their composition in intermolecular interactions of the molecules of saturated and aromatic hydrocarbons with a surface of chemically modified silica is studied by means of IR spectroscopy and adsorption-static and gas chromatography. It is shown that the higher the concentration and the shorter the length of the grafted chain, the greater (by a factor of 2 to 25) the drop in the adsorption values of hydrocarbons as a result of modifications, due to an increase in the degree of oleophobization of surface upon the formation of polyorganofluorine coatings. The high specificity of the surface with respect to benzene, which is due to the active participation of the polar fragment of a grafted chain in adsorption process, is related to the features of a relatively low-density sample with a concentration of grafted perfluorobutyl groups of 1.7 nm-2. It is shown that the thermodestruction of polyfluoroalkyl silica remains virtually unobserved upon heating to 523 K in an argon flow.

The origin of aliphatic hydrocarbons in olive oil.

PubMed

Pineda, Manuel; Rojas, María; Gálvez-Valdivieso, Gregorio; Aguilar, Miguel

2017-11-01

There are many substances that can interfere with olive oil quality. Some of them are well characterized, but many others have an unknown origin. Saturated hydrocarbons make an extraordinary complex family of numerous molecules, some of them present naturally in vegetable oils. When major natural saturated hydrocarbons are analyzed by standard chromatographic methods, this complex mixture of saturated hydrocarbons appears as a hump in the chromatogram and is commonly named as unresolved complex mixture (UCM), whose origin remains unknown. In this work we studied the occurrence and the origin of aliphatic saturated hydrocarbons in olive oil. Hydrocarbons were analyzed in olive oil and along the industrial process of oil extraction. We also analyzed n-alkanes and the UCM fraction of hydrocarbons in leaf, fruit and oil from different varieties and different locations, and we also analyzed the soils at these locations. We conclude that the hydrocarbons present in olive oil do not necessarily have their origin in a contamination during olive oil elaboration; they seem to have a natural origin, as a result of olive tree metabolism and/or as the result of an intake and accumulation by the olive tree directly from the environment during its entire life cycle. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Linear alkane polymerization on a gold surface.

PubMed

Zhong, Dingyong; Franke, Jörn-Holger; Podiyanachari, Santhosh Kumar; Blömker, Tobias; Zhang, Haiming; Kehr, Gerald; Erker, Gerhard; Fuchs, Harald; Chi, Lifeng

2011-10-14

In contrast to the many methods of selectively coupling olefins, few protocols catenate saturated hydrocarbons in a predictable manner. We report here the highly selective carbon-hydrogen (C-H) activation and subsequent dehydrogenative C-C coupling reaction of long-chain (>C(20)) linear alkanes on an anisotropic gold(110) surface, which undergoes an appropriate reconstruction by adsorption of the molecules and subsequent mild annealing, resulting in nanometer-sized channels (1.22 nanometers in width). Owing to the orientational constraint of the reactant molecules in these one-dimensional channels, the reaction takes place exclusively at specific sites (terminal CH(3) or penultimate CH(2) groups) in the chains at intermediate temperatures (420 to 470 kelvin) and selects for aliphatic over aromatic C-H activation.

Measurement of chain tilt angle in fully hydrated bilayers of gel phase lecithins.

PubMed Central

Tristram-Nagle, S; Zhang, R; Suter, R M; Worthington, C R; Sun, W J; Nagle, J F

1993-01-01

The tilt angle theta tilt of the hydrocarbon chains has been determined for fully hydrated gel phase of a series of saturated lecithins. Oriented samples were prepared on glass substrates and hydrated with supersaturated water vapor. Evidence for full hydration was the same intensity pattern of the low angle lamellar peaks and the same lamellar repeat D as unoriented multilamellar vesicles. Tilting the sample permitted observation of all the wide angle arcs necessary to verify the theoretical diffraction pattern corresponding to tilting of the chains towards nearest neighbors. The length of the scattering unit corresponds to two hydrocarbon chains, requiring each bilayer to scatter coherently rather than each monolayer. For DPPC, theta tilt was determined to be 32.0 +/- 0.5 degrees at 19 degrees C, slightly larger than previous direct determinations and considerably smaller than the value required by recent gravimetric measurements. This new value allows more accurate determinations of a variety of structural parameters, such as area per lipid molecule, A = 47.2 +/- 0.5 A2, and number of water molecules of hydration, nw = 11.8 +/- 0.7. As the chain length n of the lipids was increased from 16 to 20 carbons, the parameters A and nw remained constant, suggesting that the headgroup packing is at its excluded volume limit for this range. However, theta tilt increased by 3 degrees and the chain area Ac decreased by 0.5 A2. This behavior is explained in terms of a competition between a bulk free energy term and a finite or end effect term. Images FIGURE 6 FIGURE 7 PMID:8494973

Effect of hydrocarbon to nuclear magnetic resonance (NMR) logging in tight sandstone reservoirs and method for hydrocarbon correction

NASA Astrophysics Data System (ADS)

Xiao, Liang; Mao, Zhi-qiang; Xie, Xiu-hong

2017-04-01

It is crucial to understand the behavior of the T2 distribution in the presence of hydrocarbon to properly interpret pore size distribution from NMR logging. The NMR T2 spectrum is associated with pore throat radius distribution under fully brine saturated. However, when the pore space occupied by hydrocarbon, the shape of NMR spectrum is changed due to the bulk relaxation of hydrocarbon. In this study, to understand the effect of hydrocarbon to NMR logging, the kerosene and transformer oil are used to simulate borehole crude oils with different viscosity. 20 core samples, which were separately drilled from conventional, medium porosity and permeability and tight sands are saturated with four conditions of irreducible water saturation, fully saturated with brine, hydrocarbon-bearing condition and residual oil saturation, and the corresponding NMR experiments are applied to acquire NMR measurements. The residual oil saturation is used to simulate field NMR logging due to the shallow investigation depth of NMR logging. The NMR spectra with these conditions are compared, the results illustrate that for core samples drilled from tight sandstone reservoirs, the shape of NMR spectra have much change once they pore space occupied by hydrocarbon. The T2 distributions are wide, and they are bimodal due to the effect of bulk relaxation of hydrocarbon, even though the NMR spectra are unimodal under fully brine saturated. The location of the first peaks are similar with those of the irreducible water, and the second peaks are close to the bulk relaxation of viscosity oils. While for core samples drilled from conventional formations, the shape of T2 spectra have little changes. The T2 distributions overlap with each other under these three conditions of fully brine saturated, hydrocarbon-bearing and residual oil. Hence, in tight sandstone reservoirs, the shape of NMR logging should be corrected. In this study, based on the lab experiments, seven T2 times of 1ms, 3ms, 10ms, 33ms, 100ms, 300ms and 1000ms are first used to separate the T2 distributions of the residual oil saturation as 8 parts, and 8 pore components percentage compositions are calculated, second, an optimal T2 cutoff is determined to cut the T2 spectra of fully brine saturated conditions into two parts, the left parts (with short T2 time) represent to the irreducible water, and they do not need to be corrected, only the shape for the right parts of the T2 spectra needed to be corrected. Third the relationships among the amplitudes corresponding to the T2 times large than the optimal T2 cut off and 8 pore components percentage compositions are established, and they are used to predict corrected T2 amplitudes from NMR logging under residual oil saturation. Finally, the amplitudes corresponding to the left parts and the estimated amplitudes are spliced as the corrected NMR amplitudes, and a corrected T2 spectrum can be obtained. The reliability of this method is verified by comparing the corrected results and the experimental measurements. This method is extended to field application, fully water saturated T2 distributions are extracted from field NMR logging, and they are used to precisely evaluate hydrocarbon-bearing formations pore structure.

Conversion of oligomeric starch, cellulose, hydrolysates or sugars to hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silks, Louis A; Sutton, Andrew; Kim, Jin Kyung

Embodiments of the present invention are directed to the conversion of a source material (e.g., a depolymerized oligosaccharide mixture, a monomeric sugar, a hydrolysate, or a mixture of monomeric sugars) to intermediate molecules containing 7 to 26 contiguous carbon atoms. These intermediates may also be converted to saturated hydrocarbons. Such saturated hydrocarbons are useful as, for example, fuels.

Corresponding state-based correlations for the temperature-dependent surface tension of saturated hydrocarbons

NASA Astrophysics Data System (ADS)

Tian, Jianxiang; Zhang, Cuihua; Zhang, Laibin; Zheng, Mengmeng; Liu, Shuzhen

2017-10-01

Based on the recent progresses on the corresponding state-based correlations for the temperature-dependent surface tension of saturated fluids [I. Cachadiña, A. Mulero and J. X. Tian, Fluid Phase Equilibr. 442 (2017) 68; J. X. Tian, M. M. Zheng, H. L. Yi, L. B. Zhang and S. Z. Liu, Mod. Phys. Lett. B 31 (2017) 1750110], we proposed a new correlation for saturated hydrocarbons. This correlation includes three fluid-independent parameters and inquires the critical temperature, the triple-point temperature and the surface tension at the triple-point temperature as inputs for each hydrocarbon. Results show that this correlation can reproduce NIST data with absolute average deviation (AAD) less than 1% for 10 out of 19 hydrocarbons and AAD less than 5% for 17 out of 19 hydrocarbons, clearly better than other correlations.

Stabilization of composition fluctuations in mixed membranes by hybrid lipids

NASA Astrophysics Data System (ADS)

Safran, Samuel; Palmieri, Benoit

2013-03-01

A ternary mixture model is proposed to describe composition fluctuations in mixed membranes composed of saturated, unsaturated and hybrid lipids. The asymmetric hybrid lipid has one saturated and one unsaturated hydrocarbon chain and it can reduce the packing incompatibility between saturated and unsaturated lipids. A methodology to recast the free-energy of the lattice in terms of a continuous isotropic field theory is proposed and used to analyze composition fluctuations above the critical temperature. The effect of hybrid lipids on fluctuations domains rich in saturated/unsaturated lipids is predicted. The correlation length of such fluctuations decreases significantly with increasing amounts of hybrids even if the temperature is maintained close to the critical temperature. This provides an upper bound for the domain sizes expected in rafts stabilized by hybrids, above the critical temperature. When the hybrid composition of the membrane is increased further, a crossover value is found above which ``stripe-like'' fluctuations are observed. The wavelength of these fluctuations decreases with increasing hybrid fraction and tends toward a molecular size in a membrane that contains only hybrids.

Nanoscale Packing Differences in Sphingomyelin and Phosphatidylcholine Revealed by BODIPY Fluorescence in Monolayers: Physiological Implications

PubMed Central

2015-01-01

Phosphatidycholines (PC) with two saturated acyl chains (e.g., dipalmitoyl) mimic natural sphingomyelin (SM) by promoting raft formation in model membranes. However, sphingoid-based lipids, such as SM, rather than saturated-chain PCs have been implicated as key components of lipid rafts in biomembranes. These observations raise questions about the physical packing properties of the phase states that can be formed by these two major plasma membrane lipids with identical phosphocholine headgroups. To investigate, we developed a monolayer platform capable of monitoring changes in surface fluorescence by acquiring multiple spectra during measurement of a lipid force–area isotherm. We relied on the concentration-dependent emission changes of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-labeled PC to detect nanoscale alterations in lipid packing and phase state induced by monolayer lateral compression. The BODIPY-PC probe contained an indacene ring with four symmetrically located methyl (Me) substituents to enhance localization to the lipid hydrocarbon region. Surface fluorescence spectra indicated changes in miscibility even when force–area isotherms showed no deviation from ideal mixing behavior in the surface pressure versus cross-sectional molecular area response. We detected slightly better mixing of Me4-BODIPY-8-PC with the fluid-like, liquid expanded phase of 1-palmitoyl-2-oleoyl-PC compared to N-oleoyl-SM. Remarkably, in the gel-like, liquid condensed phase, Me4-BODIPY-8-PC mixed better with N-palmitoyl-SM than dipalmitoyl-PC, suggesting naturally abundant SMs with saturated acyl chains form gel-like lipid phase(s) with enhanced ability to accommodate deeply embedded components compared to dipalmitoyl-PC gel phase. The findings reveal a fundamental difference in the lateral packing properties of SM and PC that occurs even when their acyl chains match. PMID:24564829

Organic/inorganic hybrid filters based on dendritic and cyclodextrin "nanosponges" for the removal of organic pollutants from water.

PubMed

Arkas, Michael; Allabashi, Roza; Tsiourvas, Dimitris; Mattausch, Eva-Maria; Perfler, Reinhard

2006-04-15

Long-alkyl chain functionalized poly(propylene imine) dendrimer, poly(ethylene imine) hyperbranched polymer, and beta-cyclodextrin derivatives, which are completely insoluble in water, have the property of encapsulating organic pollutants from water. Ceramic porous filters can be impregnated with these compounds resulting in hybrid organic/ inorganic filter modules. These hybrid filter modules were tested for the effective purification of water, by continuous filtration experiments, employing a variety of water pollutants. It has been established that polycyclic aromatic hydrocarbons (PAHs) can be removed very efficiently (more than 95%), and final concentrations of several ppb (microg/ L) are easily obtained. Representatives of the pollutant group of trihalogen methanes (THMs), monoaromatic hydrocarbons (BTX), and pesticides (simazine) can also be removed (>80%), although the filters are saturated considerably faster in these cases.

Oil residue contamination of continental shelf sediments of the Gulf of Mexico.

PubMed

Harding, V; Camp, J; Morgan, L J; Gryko, J

2016-12-15

We have investigated the distribution of a heavy oil residue in the coastal sediments of the Gulf of Mexico. The amount of the contamination was determined by high-temperature pyrolysis coupled with the Gas Chromatography-Mass Spectrometry (GCMS) of air-dried sediments. The pyrolysis products contain straight-chain saturated and unsaturated hydrocarbons, such as dodecane and 1-dodecene, resulting in a very characteristic pattern of double peaks in the GCMS. Hydrocarbons containing 8 to 23 carbon atoms were detected in the pyrolysis products. Using thermal pyrolysis we have found that the sediment samples collected along Texas, Louisiana, and Mississippi shores contain no detectable traces of oil residue, but most of the samples collected along Alabama and Florida shores contain ~200ppm of heavy oil residue. Copyright © 2016 Elsevier Ltd. All rights reserved.

Interlake production established using quantitative hydrocarbon well-log analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lancaster, J.; Atkinson, A.

1988-07-01

Production was established in a new pay zone of the basal Interlake Formation adjacent to production in Midway field in Williams County, North Dakota. Hydrocarbon saturation, which was computed using hydrocarbon well-log (mud-log) data, and computed permeability encouraged the operator to run casing and test this zone. By use of drilling rig parameters, drilling mud properties, hydrocarbon-show data from the mud log, drilled rock and porosity descriptions, and wireline log porosity, this new technique computes oil saturation (percent of porosity) and permeability to the invading filtrate, using the Darcy equation. The Leonardo Fee well was drilled to test the Devonianmore » Duperow, the Silurian upper Interlake, and the Ordovician Red River. The upper two objectives were penetrated downdip from Midway production and there were no hydrocarbon shows. It was determined that the Red River was tight, based on sample examination by well site personnel. The basal Interlake, however, liberated hydrocarbon shows that were analyzed by this new technology. The results of this evaluation accurately predicted this well would be a commercial success when placed in production. Where geophysical log analysis might be questionable, this new evaluation technique may provide answers to anticipated oil saturation and producibility. The encouraging results of hydrocarbon saturation and permeability, produced by this technique, may be largely responsible for the well being in production today.« less

PHYSICAL STUDIES OF PHOSPHOLIPIDS

PubMed Central

Chapman, D.; Fluck, D. J.

1966-01-01

On heating pure, fully saturated 2,3-diacyl-DL-phosphatidyl-ethanolamines and 2,3-diacylphosphatidyl-cholines (lecithins) in water to the transition temperature at which large endothermic heat changes occur, they are observed, by light microscopy, to form myelin figures. This result is discussed in terms of the large difference in the transition temperature for "melting" of the hydrocarbon chains of unsaturated and saturated phospholipids and is illustrated by means of differential thermal analysis (D.T.A.) curves. These structures have been examined by electron microscopy after negative staining and after reaction with osmium tetroxide. Typical phospholipid lamella structures are seen in the phosphatidylcholines after negative staining, and in the phosphatidyl-ethanolamines after both negative staining and osmium fixation. The distances across these lamellae have been measured. Some preliminary investigations of the nature of the osmium tetroxide reaction with the phosphatidyl-ethanolamines have been made. PMID:4165077

Use of 2,5-dimethyl-2,5-hexane diamine as a curing agent for epoxy resins

DOEpatents

Rinde, J.A.; Newey, H.A.

1981-02-24

Primary diamines are disclosed of the formula shown in a diagram wherein R is a straight chain saturated hydrocarbon of 2 to 4 carbons, a disubstituted benzene ring, or disubstituted dibenzomethane for use as a curing agent for epoxy resins. These curing agents can be used to form epoxy resin mixtures useful in filament winding and pre-impregnated fiber molding and in formulating film adhesives, powder coatings and molding powders. The epoxy mixtures form for such uses as room temperature non-reacting, intermediate stable state which has a latent cross-linking capability.

Use of 2,5-dimethyl-2,5-hexane diamine as a curing agent for epoxy resins

DOEpatents

Rinde, James A. [Livermore, CA; Newey, Herbert A. [Lafayette, CA

1981-02-24

Primary diamines of the formula ##STR1## wherein R is a straight chain saturated hydrocarbon of 2 to 4 carbons, a disubstituted benzene ring, or disubstituted dibenzo methane for use as a curing agent for epoxy resins. These curing agents can be used to form epoxy resin mixtures useful in filament winding and pre-impregnated fiber molding and in formulating film adhesives, powder coatings and molding powders. The epoxy mixtures form for such uses as room temperature non-reacting, intermediate stable state which has a latent cross-linking capability.

Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide

NASA Astrophysics Data System (ADS)

Juliá-Hernández, Francisco; Moragas, Toni; Cornella, Josep; Martin, Ruben

2017-05-01

Catalytic carbon-carbon bond formation has enabled the streamlining of synthetic routes when assembling complex molecules. It is particularly important when incorporating saturated hydrocarbons, which are common motifs in petrochemicals and biologically relevant molecules. However, cross-coupling methods that involve alkyl electrophiles result in catalytic bond formation only at specific and previously functionalized sites. Here we describe a catalytic method that is capable of promoting carboxylation reactions at remote and unfunctionalized aliphatic sites with carbon dioxide at atmospheric pressure. The reaction occurs via selective migration of the catalyst along the hydrocarbon side-chain with excellent regio- and chemoselectivity, representing a remarkable reactivity relay when compared with classical cross-coupling reactions. Our results demonstrate that site-selectivity can be switched and controlled, enabling the functionalization of less-reactive positions in the presence of a priori more reactive ones. Furthermore, we show that raw materials obtained in bulk from petroleum processing, such as alkanes and unrefined mixtures of olefins, can be used as substrates. This offers an opportunity to integrate a catalytic platform en route to valuable fatty acids by transforming petroleum-derived feedstocks directly.

Hydrocarbon saturation determination using acoustic velocities obtained through casing

DOEpatents

Moos, Daniel

2010-03-09

Compressional and shear velocities of earth formations are measured through casing. The determined compressional and shear velocities are used in a two component mixing model to provides improved quantitative values for the solid, the dry frame, and the pore compressibility. These are used in determination of hydrocarbon saturation.

Olefin separation membrane and process

DOEpatents

Pinnau, Ingo; Toy, Lora G.; Casillas, Carlos

1997-01-01

A membrane and process for separating unsaturated hydrocarbons from fluid mixtures. The membrane and process differ from previously known membranes and processes, in that the feed and permeate streams can both be dry, the membrane need not be water or solvent swollen, and the membrane is characterized by a selectivity for an unsaturated hydrocarbon over a saturated hydrocarbon having the same number of carbon atoms of at least about 20, and a pressure-normalized flux of said unsaturated hydrocarbon of at least about 5.times.10.sup.-6 cm.sup.3 (STP)/cm.sup.2 .multidot.s.multidot.cmHg, said flux and selectivity being measured with a gas mixture containing said unsaturated and saturated hydrocarbons, and in a substantially dry environment.

Anomalous dispersion due to hydrocarbons: The secret of reservoir geophysics?

USGS Publications Warehouse

Brown, R.L.

2009-01-01

When P- and S-waves travel through porous sandstone saturated with hydrocarbons, a bit of magic happens to make the velocities of these waves more frequency-dependent (dispersive) than when the formation is saturated with brine. This article explores the utility of the anomalous dispersion in finding more oil and gas, as well as giving a possible explanation about the effect of hydrocarbons upon the capillary forces in the formation. ?? 2009 Society of Exploration Geophysicists.

Olefin separation membrane and process

DOEpatents

Pinnau, I.; Toy, L.G.; Casillas, C.

1997-09-23

A membrane and process are disclosed for separating unsaturated hydrocarbons from fluid mixtures. The membrane and process differ from previously known membranes and processes, in that the feed and permeate streams can both be dry, the membrane need not be water or solvent swollen, and the membrane is characterized by a selectivity for an unsaturated hydrocarbon over a saturated hydrocarbon having the same number of carbon atoms of at least about 20, and a pressure-normalized flux of said unsaturated hydrocarbon of at least about 5{times}10{sup {minus}6}cm{sup 3}(STP)/cm{sup 2}{center_dot}s{center_dot}cmHg, said flux and selectivity being measured with a gas mixture containing said unsaturated and saturated hydrocarbons, and in a substantially dry environment. 4 figs.

Resolving biodegradation patterns of persistent saturated hydrocarbons in weathered oil samples from the Deepwater Horizon disaster.

PubMed

Gros, Jonas; Reddy, Christopher M; Aeppli, Christoph; Nelson, Robert K; Carmichael, Catherine A; Arey, J Samuel

2014-01-01

Biodegradation plays a major role in the natural attenuation of oil spills. However, limited information is available about biodegradation of different saturated hydrocarbon classes in surface environments, despite that oils are composed mostly of saturates, due to the limited ability of conventional gas chromatography (GC) to resolve this compound group. We studied eight weathered oil samples collected from four Gulf of Mexico beaches 12-19 months after the Deepwater Horizon disaster. Using comprehensive two-dimensional gas chromatography (GC × GC), we successfully separated, identified, and quantified several distinct saturates classes in these samples. We find that saturated hydrocarbons eluting after n-C22 dominate the GC-amenable fraction of these weathered samples. This compound group represented 8-10%, or 38-68 thousand metric tons, of the oil originally released from Macondo well. Saturates in the n-C22 to n-C29 elution range were found to be partly biodegraded, but to different relative extents, with ease of biodegradation decreasing in the following order: n-alkanes > methylalkanes and alkylcyclopentanes+alkylcyclohexanes > cyclic and acyclic isoprenoids. We developed a new quantitative index designed to characterize biodegradation of >n-C22 saturates. These results shed new light onto the environmental fate of these persistent, hydrophobic, and mostly overlooked compounds in the unresolved complex mixtures (UCM) of weathered oils.

Laser desorption/ionization mass spectrometry of lipids using etched silver substrates.

PubMed

Schnapp, Andreas; Niehoff, Ann-Christin; Koch, Annika; Dreisewerd, Klaus

2016-07-15

Silver-assisted laser desorption/ionization mass spectrometry can be used for the analysis of small molecules. For example, adduct formation with silver cations enables the molecular analysis of long-chain hydrocarbons, which are difficult to ionize via conventional matrix-assisted laser desorption ionization (MALDI). Here we used highly porous silver foils, produced by etching with nitric acid, as sample substrates for LDI mass spectrometry. As model system for the analysis of complex lipid mixtures, cuticular extracts of fruit flies (Drosophila melanogaster) and worker bees (Apis mellifera) were investigated. The mass spectra obtained by spotting extract onto the etched silver substrates demonstrate the sensitive detection of numerous lipid classes such as long-chain saturated and unsaturated hydrocarbons, fatty acyl alcohols, wax esters, and triacylglycerols. MS imaging of cuticular surfaces with a lateral resolution of a few tens of micrometers became possible after blotting, i.e., after transferring lipids by physical contact with the substrate. The examples of pheromone-producing male hindwings of the squinting bush brown butterfly (Bicyclus anynana) and a fingermark are shown. Because the substrates are also easy to produce, they provide a viable alternative to colloidal silver nanoparticles and other so far described silver substrates. Copyright © 2016 Elsevier Inc. All rights reserved.

Phase-Shifted Based Numerical Method for Modeling Frequency-Dependent Effects on Seismic Reflections

NASA Astrophysics Data System (ADS)

Chen, Xuehua; Qi, Yingkai; He, Xilei; He, Zhenhua; Chen, Hui

2016-08-01

The significant velocity dispersion and attenuation has often been observed when seismic waves propagate in fluid-saturated porous rocks. Both the magnitude and variation features of the velocity dispersion and attenuation are frequency-dependent and related closely to the physical properties of the fluid-saturated porous rocks. To explore the effects of frequency-dependent dispersion and attenuation on the seismic responses, in this work, we present a numerical method for seismic data modeling based on the diffusive and viscous wave equation (DVWE), which introduces the poroelastic theory and takes into account diffusive and viscous attenuation in diffusive-viscous-theory. We derive a phase-shift wave extrapolation algorithm in frequencywavenumber domain for implementing the DVWE-based simulation method that can handle the simultaneous lateral variations in velocity, diffusive coefficient and viscosity. Then, we design a distributary channels model in which a hydrocarbon-saturated sand reservoir is embedded in one of the channels. Next, we calculated the synthetic seismic data to analytically and comparatively illustrate the seismic frequency-dependent behaviors related to the hydrocarbon-saturated reservoir, by employing DVWE-based and conventional acoustic wave equation (AWE) based method, respectively. The results of the synthetic seismic data delineate the intrinsic energy loss, phase delay, lower instantaneous dominant frequency and narrower bandwidth due to the frequency-dependent dispersion and attenuation when seismic wave travels through the hydrocarbon-saturated reservoir. The numerical modeling method is expected to contribute to improve the understanding of the features and mechanism of the seismic frequency-dependent effects resulted from the hydrocarbon-saturated porous rocks.

OXYGENATION OF HYDROCARBONS USING NANOSTRUCTURED TIO2 AS A PHOTOCATALYST: A GREEN ALTERNATIVE

EPA Science Inventory

High-value organic compounds have been synthesized successfully from linear and cyclic saturated hydrocarbons by a photocatalytic oxidation process using a semiconductor material, titanium dioxide (TiO2). Various hydrocarbons were partially oxygenated in both aqueous and gaseous...

Comparison of united-atom potentials for the simulation of vapor-liquid equilibria and interfacial properties of long-chain n-alkanes up to n-C100.

PubMed

Müller, Erich A; Mejía, Andrés

2011-11-10

Canonical ensemble molecular dynamics (MD) simulations are reported which compute both the vapor-liquid equilibrium properties (vapor pressure and liquid and vapor densities) and the interfacial properties (density profiles, interfacial tensions, entropy and enthalpy of surface formation) of four long-chained n-alkanes: n-decane (n-C(10)), n-eicosane (n-C(20)), n-hexacontane (n-C(60)), and n-decacontane (n-C(100)). Three of the most commonly employed united-atom (UA) force fields for alkanes (SKS: Smit, B.; Karaborni, S.; Siepmann, J. I. J. Chem. Phys. 1995,102, 2126-2140; J. Chem. Phys. 1998,109, 352; NERD: Nath, S. K.; Escobedo, F. A.; de Pablo, J. J. J. Chem. Phys. 1998, 108, 9905-9911; and TraPPE: Martin M. G.; Siepmann, J. I. J. Phys. Chem. B1998, 102, 2569-2577.) are critically appraised. The computed results have been compared to the available experimental data and those fitted using the square gradient theory (SGT). In the latter approach, the Lennard-Jones chain equation of state (EoS), appropriately parametrized for long hydrocarbons, is used to model the homogeneous bulk phase Helmholtz energy. The MD results for phase equilibria of n-decane and n-eicosane exhibit sensible agreement both to the experimental data and EoS correlation for all potentials tested, with the TraPPE potential showing the lowest deviations. However, as the molecular chain increases to n-hexacontane and n-decacontane, the reliability of the UA potentials decreases, showing notorious subpredictions of both saturated liquid density and vapor pressure. Based on the recommended data and EoS results for the heaviest hydrocarbons, it is possible to attest, that in this extreme, the TraPPE potential shows the lowest liquid density deviations. The low absolute values of the vapor pressure preclude the discrimination among the three UA potentials studied. On the other hand, interfacial properties are very sensitive to the type of UA potential thus allowing a differentiation of the potentials. Comparing the interfacial tension MD results to the available experimental data and SGT results, the TraPPE model exhibits the lowest deviations for all hydrocarbons.

Synthesis and Solution Properties of Adamantane Containing Quaternary Ammonium Salt-type Cationic Surfactants: Hydrocarbon-based, Fluorocarbonbased and Bola-type.

PubMed

Yoshimura, Tomokazu; Okada, Mari; Matsuoka, Keisuke

2016-10-01

Quaternary ammonium salt-type cationic surfactants with an adamantyl group (hydrocarbon-type; C n AdAB, fluorocarbon-type; C m F C 3 AdAB, bola-type; Ad-s-Ad, where n, m and s represent hydrocarbon chain lengths of 8-16, fluorocarbon chain lengths of 4-8, and spacer chain length of 10-12) were synthesized via quaternization of N, N-dimethylaminoadamantane and n-alkyl bromide or 1, n-dibromoalkane. Conductivity and surface tension were measured to characterize the solution properties of the synthesized adamantyl group-containing cationic surfactants. In addition, the effects of hydrocarbon and fluorocarbon chain lengths and spacer chain length between headgroups on the measured properties were evaluated by comparison with those of conventional cationic surfactants. The critical micelle concentration (CMC) of C n AdAB and Ad-s-Ad was 2/5 of that for the corresponding conventional surfactants C n TAB and bola-type surfactants with similar number of carbons in the alkyl or alkylene chain; this was because of the increased hydrophobicity due to the adamantyl group. A linear relationship between the logarithm of CMC and the hydrocarbon chain length for C n AdAB was observed, as well as for C n TAB. The slope of the linear correlation for both surfactants was almost the same, indicating that the adamantyl group does not affect the CMC with variations in the hydrocarbon chain length. Similar to conventional surfactants C n TAB, the hydrocarbon-type C n AdAB is highly efficient in reducing the surface tension of water, despite the large occupied area per molecule resulting from the relatively bulky structure of the adamantane skeleton. On the other hand, the bola-type Ad-s-Ad resulted in increased surface tension compared to C n AdAB, indicating that the curved chain between adamantyl groups leads to poor adsorption and orientation at the air-water interface.

An interpretation of core and wireline logs for the Petrophysical evaluation of Upper Shallow Marine sandstone reservoirs of the Bredasdorp Basin, offshore South Africa

NASA Astrophysics Data System (ADS)

Magoba, Moses; Opuwari, Mimonitu

2017-04-01

This paper embodies a study carried out to assess the Petrophysical evaluation of upper shallow marine sandstone reservoir of 10 selected wells in the Bredasdorp basin, offshore, South Africa. The studied wells were selected randomly across the upper shallow marine formation with the purpose of conducting a regional study to assess the difference in reservoir properties across the formation. The data sets used in this study were geophysical wireline logs, Conventional core analysis and geological well completion report. The physical rock properties, for example, lithology, fluid type, and hydrocarbon bearing zone were qualitatively characterized while different parameters such as volume of clay, porosity, permeability, water saturation ,hydrocarbon saturation, storage and flow capacity were quantitatively estimated. The quantitative results were calibrated with the core data. The upper shallow marine reservoirs were penetrated at different depth ranging from shallow depth of about 2442m to 3715m. The average volume of clay, average effective porosity, average water saturation, hydrocarbon saturation and permeability range from 8.6%- 43%, 9%- 16%, 12%- 68% , 32%- 87.8% and 0.093mD -151.8mD respectively. The estimated rock properties indicate a good reservoir quality. Storage and flow capacity results presented a fair to good distribution of hydrocarbon flow.

Hydrogenation of liquid natural rubber via diimide reduction in hydrazine hydrate/hydrogen peroxide system

NASA Astrophysics Data System (ADS)

Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim; Yusoff, Siti Fairus M.

2015-09-01

Liquid natural rubber (LNR) with molecular weight of lower than 105 and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristics of HLNR were analyzed with Termogravimetric Analysis (TGA).

Single well tracer method to evaluate enhanced recovery

DOEpatents

Sheely, Jr., Clyde Q.; Baldwin, Jr., David E.

1978-01-01

Data useful to evaluate the effectiveness of or to design an enhanced recovery process (the recovery process involving mobilizing and moving hydrocarbons through a hydrocarbon-bearing subterranean formation from an injection well to a production well by injecting a mobilizing fluid into the injection well) are obtained by a process which comprises sequentially: determining hydrocarbon saturation in the formation in a volume in the formation near a well bore penetrating the formation, injecting sufficient of the mobilizing fluid to mobilize and move hydrocarbons from a volume in the formation near the well bore penetrating the formation, and determining by the single well tracer method a hydrocarbon saturation profile in a volume from which hydrocarbons are moved. The single well tracer method employed is disclosed by U.S. Pat. No. 3,623,842. The process is useful to evaluate surfactant floods, water floods, polymer floods, CO.sub.2 floods, caustic floods, micellar floods, and the like in the reservoir in much less time at greatly reduced costs, compared to conventional multi-well pilot test.

Polyethylene composites containing a phase change material having a C14 straight chain hydrocarbon

DOEpatents

Salyer, Ival O.

1987-01-01

A composite useful in thermal energy storage, said composite being formed of a polyethylene matrix having a straight chain alkyl hydrocarbon incorporated therein, said polyethylene being crosslinked to such a degree that said polyethylene matrix is form stable and said polyethylene matrix is capable of absorbing at least 10% by weight of said straight chain alkyl hydrocarbon; the composite is useful in forming pellets or sheets having thermal energy storage characteristics.

Chemical and biological availability of hydrocarbons in urban harbor sediments

USGS Publications Warehouse

LeBlanc, L.A.; Brownawell, Bruce J.

2002-01-01

The degradation of saturated and aromatic hydrocarbons was studied in batch slurry experiments conducted with field-aged sediments, highly impacted by hydrocarbon pollution. Experiments focused on examining the effects of desorption limitations to hydrocarbon mineralization and degradation. Degradation of PAH (e.g., naphthalene, fluorene, acenaphthene) and saturated hydrocarbons was examined in field-aged sediments collected from four sites in greater NY Harbor and western Long Island Sound. The sites were Rikers Island in far western Long Island Sound, Williamsburg Bridge in the East River, Shooters Island in the Arthur Kill, and the Kill Van Kull off Bayonne, New Jersey. Patterns of hydrocarbon desorption and degradation in weathered sediments were complicated by the mixed combustion and oil-derived hydrocarbon sources, and differed markedly from patterns seen in sediments following an oil spill. Rates of degradation in experiments with spiked sediments, especially over short timescales, did not appear to be limited by rates of desorption. This is an abstract of a paper presented at the 224th ACS National Meeting (Boston, MA 8/18-22/2002).

Current Status and Bioinspired Perspective of Electrochemical Conversion of CO2 to a Long-Chain Hydrocarbon.

PubMed

Yang, Ki Dong; Lee, Chan Woo; Jin, Kyoungsuk; Im, Sang Won; Nam, Ki Tae

2017-01-19

Electrocatalytic conversion of CO 2 into a long-chain hydrocarbon represents an important research direction in adding value to CO 2 -based chemicals and realizing its practical application. Long-chain hydrocarbons may change the current fossil fuel-based industry in that those chemicals have a similar energy density as gasoline, high compatibility with the current infrastructure, and low hydroscopicity for pipeline distribution. However, most of the electrocatalysts produce C 1 , C 2 , and C 3 chemicals, and methods for producing long-chain hydrocarbons are not available thus far. Interestingly, nature utilizes many enzymes to generate long-chain hydrocarbons using C 2 building blocks and suggests key mechanisms, inspiring new perspective in the design of electrocatalysts. In this Perspective, we present case studies to demonstrate how CO 2 and its reductive derivatives interact with the electrode surface during C-C bond formation and introduce how these issues are addressed in biological systems. We end this Perspective by outlining possible strategies to translate the natural mechanism into a heterogeneous electrode.

Differential scanning calorimetric and Fourier transform infrared spectroscopic studies of the effects of cholesterol on the thermotropic phase behavior and organization of a homologous series of linear saturated phosphatidylserine bilayer membranes.

PubMed Central

McMullen, T P; Lewis, R N; McElhaney, R N

2000-01-01

We have examined the effects of cholesterol on the thermotropic phase behavior and organization of aqueous dispersions of a homologous series of linear disaturated phosphatidylserines by high-sensitivity differential scanning calorimetry and Fourier transform infrared spectroscopy. We find that the incorporation of increasing quantities of cholesterol progressively reduces the temperature, enthalpy, and cooperativity of the gel-to-liquid-crystalline phase transition of the host phosphatidylserine bilayer, such that a cooperative chain-melting phase transition is completely or almost completely abolished at 50 mol % cholesterol, in contrast to the results of previous studies. We are also unable to detect the presence of a separate anhydrous cholesterol or cholesterol monohydrate phase in our binary mixtures, again in contrast to previous reports. We further show that the magnitude of the reduction in the phase transition temperature induced by cholesterol addition is independent of the hydrocarbon chain length of the phosphatidylserine studied. This result contrasts with our previous results with phosphatidylcholine bilayers, where we found that cholesterol increases or decreases the phase transition temperature in a chain length-dependent manner (1993. Biochemistry, 32:516-522), but is in agreement with our previous results for phosphatidylethanolamine bilayers, where no hydrocarbon chain length-dependent effects were observed (1999. Biochim. Biophys. Acta, 1416:119-234). However, the reduction in the phase transition temperature by cholesterol is of greater magnitude in phosphatidylethanolamine as compared to phosphatidylserine bilayers. We also show that the addition of cholesterol facilitates the formation of the lamellar crystalline phase in phosphatidylserine bilayers, as it does in phosphatidylethanolamine bilayers, whereas the formation of such phases in phosphatidylcholine bilayers is inhibited by the presence of cholesterol. We ascribe the limited miscibility of cholesterol in phosphatidylserine bilayers reported previously to a fractional crystallization of the cholesterol and phospholipid phases during the removal of organic solvent from the binary mixture before the hydration of the sample. In general, the results of our studies to date indicate that the magnitude of the effect of cholesterol on the thermotropic phase behavior of the host phospholipid bilayer, and its miscibility in phospholipid dispersions generally, depend on the strength of the attractive interactions between the polar headgroups and the hydrocarbon chains of the phospholipid molecule, and not on the charge of the polar headgroups per se. PMID:11023909

Cloud point phenomena for POE-type nonionic surfactants in a model room temperature ionic liquid.

PubMed

Inoue, Tohru; Misono, Takeshi

2008-10-15

The cloud point phenomenon has been investigated for the solutions of polyoxyethylene (POE)-type nonionic surfactants (C(12)E(5), C(12)E(6), C(12)E(7), C(10)E(6), and C(14)E(6)) in 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), a typical room temperature ionic liquid (RTIL). The cloud point, T(c), increases with the elongation of the POE chain, while decreases with the increase in the hydrocarbon chain length. This demonstrates that the solvophilicity/solvophobicity of the surfactants in RTIL comes from POE chain/hydrocarbon chain. When compared with an aqueous system, the chain length dependence of T(c) is larger for the RTIL system regarding both POE and hydrocarbon chains; in particular, hydrocarbon chain length affects T(c) much more strongly in the RTIL system than in equivalent aqueous systems. In a similar fashion to the much-studied aqueous systems, the micellar growth is also observed in this RTIL solvent as the temperature approaches T(c). The cloud point curves have been analyzed using a Flory-Huggins-type model based on phase separation in polymer solutions.

Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

DOEpatents

Lilga, Michael A.; Hallen, Richard T.; Albrecht, Karl O.; Cooper, Alan R.; Frye, John G.; Ramasamy, Karthikeyan Kallupalayam

2018-04-03

Systems, processes, and catalysts are disclosed for obtaining fuel and fuel blends containing selected ratios of open-chain and closed-chain fuel-range hydrocarbons suitable for production of alternate fuels including gasolines, jet fuels, and diesel fuels. Fuel-range hydrocarbons may be derived from ethylene-containing feedstocks and ethanol-containing feedstocks.

Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

DOEpatents

Lilga, Michael A.; Hallen, Richard T.; Albrecht, Karl O.; Cooper, Alan R.; Frye, John G.; Ramasamy, Karthikeyan Kallupalayam

2017-05-30

Systems, processes, and catalysts are disclosed for obtaining fuel and fuel blends containing selected ratios of open-chain and closed-chain fuel-range hydrocarbons suitable for production of alternate fuels including gasolines, jet fuels, and diesel fuels. Fuel-range hydrocarbons may be derived from ethylene-containing feedstocks and ethanol-containing feedstocks.

Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

DOEpatents

Lilga, Michael A.; Hallen, Richard T.; Albrecht, Karl O.; Cooper, Alan R.; Frye, John G.; Ramasamy, Karthikeyan Kallupalayam

2017-09-26

Systems, processes, and catalysts are disclosed for obtaining fuels and fuel blends containing selected ratios of open-chain and closed-chain fuel-range hydrocarbons suitable for production of alternate fuels including gasolines, jet fuels, and diesel fuels. Fuel-range hydrocarbons may be derived from ethylene-containing feedstocks and ethanol-containing feedstocks.

Mineral oil and synthetic hydrocarbons in cosmetic lip products.

PubMed

Niederer, M; Stebler, T; Grob, K

2016-04-01

Lipsticks and lip care products may contain saturated hydrocarbons which either stem from mineral oil saturated hydrocarbons (MOSH) or are synthetic, that is polyolefin oligomeric saturated hydrocarbons (POSH). Some of these hydrocarbons are strongly accumulated and form granulomas in human tissues, which prompted Cosmetics Europe (former Colipa) to issue a recommendation for their use in lip care and oral products. From 2012 to 2014, MOSH+POSH were determined in 175 cosmetic lip products taken from the Swiss market in order to estimate their contribution to human exposure. Mineral oil saturated hydrocarbons and POSH were extracted and analysed by GC with FID. Areas were integrated as a total as well as by mass ranges with cuts at n-C25 and n-C34 to characterize the molecular mass distribution. About 68% of the products contained at least 5% MOSH+POSH (total concentration). For regular users, these products would be major contributors to their MOSH+POSH exposure. About 31% of the products contained more than 32% MOSH+POSH. Their regular usage would amount in an estimated MOSH+POSH exposure exceeding the highest estimated dietary exposure. The majority of the products contained hydrocarbons with a molecular mass range which was not in line with the recommendations of Cosmetics Europe. Taking into account that material applied to the lips largely ends up being ingested, MOSH and POSH levels should be reduced in the majority of cosmetic lip products. As the extensive evaluation of the data available on MOSH (EFSA J., 10, 2012, 2704) did not enable the specification of limits considered as safe, the present level of dietary exposure and its evaluation as 'of potential concern' provide the relevant bench mark, which means that lip products should contain clearly less than 5% MOSH+POSH. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Bathymetry and composition of Titan's Ontario Lacus derived from Monte Carlo-based waveform inversion of Cassini RADAR altimetry data

NASA Astrophysics Data System (ADS)

Mastrogiuseppe, M.; Hayes, A. G.; Poggiali, V.; Lunine, J. I.; Lorenz, R. D.; Seu, R.; Le Gall, A.; Notarnicola, C.; Mitchell, K. L.; Malaska, M.; Birch, S. P. D.

2018-01-01

Recently, the Cassini RADAR was used to sound hydrocarbon lakes and seas on Saturn's moon Titan. Since the initial discovery of echoes from the seabed of Ligeia Mare, the second largest liquid body on Titan, a dedicated radar processing chain has been developed to retrieve liquid depth and microwave absorptivity information from RADAR altimetry of Titan's lakes and seas. Herein, we apply this processing chain to altimetry data acquired over southern Ontario Lacus during Titan fly-by T49 in December 2008. The new signal processing chain adopts super resolution techniques and dedicated taper functions to reveal the presence of reflection from Ontario's lakebed. Unfortunately, the extracted waveforms from T49 are often distorted due to signal saturation, owing to the extraordinarily strong specular reflections from the smooth lake surface. This distortion is a function of the saturation level and can introduce artifacts, such as signal precursors, which complicate data interpretation. We use a radar altimetry simulator to retrieve information from the saturated bursts and determine the liquid depth and loss tangent of Ontario Lacus. Received waveforms are represented using a two-layer model, where Cassini raw radar data are simulated in order to reproduce the effects of receiver saturation. A Monte Carlo based approach along with a simulated waveform look-up table is used to retrieve parameters that are given as inputs to a parametric model which constrains radio absorption of Ontario Lacus and retrieves information about the dielectric properties of the liquid. We retrieve a maximum depth of 50 m along the radar transect and a best-fit specific attenuation of the liquid equal to 0.2 ± 0.09 dB m-1 that, when converted into loss tangent, gives tanδ = 7 ± 3 × 10-5. When combined with laboratory measured cryogenic liquid alkane dielectric properties and the variable solubility of nitrogen in ethane-methane mixtures, the best-fit loss tangent is consistent with a ternary mixture of 51% methane, 38% ethane and 11% nitrogen by volume.

Catalysts for synthesizing various short chain hydrocarbons

DOEpatents

Colmenares, Carlos

1991-01-01

Method and apparatus (10), including novel photocatalysts, are disclosed for the synthesis of various short chain hydrocarbons. Light-transparent SiO.sub.2 aerogels doped with photochemically active uranyl ions (18) are fluidized in a fluidized-bed reactor (12) having a transparent window (16), by hydrogen and CO, C.sub.2 H.sub.4 or C.sub.2 H.sub.6 gas mixtures (20), and exposed to radiation (34) from a light source (32) external to the reactor (12), to produce the short chain hydrocarbons (36).

Going Beyond, Going Further: Chemical Properties of Commonly Available Hydrocarbons.

ERIC Educational Resources Information Center

Perina, Ivo

1985-01-01

Background information, procedures used, and safety considerations are provided for experiments using natural gas. They include: (1) exploding a mixture of natural gas and oxygen; (2) testing for unsaturated hydrocarbons in natural gas; (3) substituting higher saturated hydrocarbons contained in kerosene with bromine; and (4) the pyrolysis of…

Study of the mineralization effect on the distribution of lipids in sediments from the Cretan Sea: Evidence for hydrocarbon degradation and starvation stress

NASA Astrophysics Data System (ADS)

Polymenakou, Paraskevi N.; Tselepides, Anastasios; Stephanou, Euripides G.

2005-11-01

Sedimentary diagenetic processes alter the composition and distribution of different lipid compounds. In the present study alterations mediated by microbial communities were investigated along a bathymetric gradient (100 m at 35°23'N-25°09'E, 617 m at 35°33'N-25°08'E, 1494 m at 35°44'N-25°08'E) over the continental margin of northern Crete (Greece, Eastern Mediterranean Sea). Bacterial abundances and distribution were studied using phospholipid linked fatty acids (PLFA), in the range of C 8-C 22, released from intact phospholipids. Lipid components (aliphatic hydrocarbons, free fatty acids, glycerides and glycolipids) were studied over a 2-month incubation period. Carbon mineralization rates at all stations indicated an uneven distribution of active aerobic bacteria with values decreasing towards the deeper stations. PLFA homologue profiles denoted that aerobic gram negative and sulfur oxidizing bacteria dominated microbial communities while the anaerobic, gram positive and sulfate reducing bacteria occurred only in traces. The n-alkane (NA) composition revealed a strong predominance of homologues with odd carbon numbers suggesting an important terrestrial contribution to the sediments. The estimated descriptive ratios of NA, the sum of short chain NA (C 15-C 20) and long chain NA (C 21-C 36) to 17 α( H),21 β( H)-C 30-hopane, before and after a two-month incubation period, indicated the occurrence of hydrocarbon degradation processes. Increased ratios of saturated to unsaturated fatty acids were also recorded after the incubation indicating the starvation of bacterial communities by the end of the experiments.

Petrophysical evaluation of the hydrocarbon potential of the Lower Cretaceous Kharita clastics, North Qarun oil field, Western Desert, Egypt

NASA Astrophysics Data System (ADS)

Teama, Mostafa A.; Nabawy, Bassem S.

2016-09-01

Based on the available well log data of six wells chosen in the North Qarun oil field in the Western Desert of Egypt, the petrophysical evaluation for the Lower Cretaceous Kharita Formation was accomplished. The lithology of Kharita Formation was analyzed using the neutron porosity-density and the neutron porosity-gamma ray crossplots as well as the litho-saturation plot. The petrophysical parameters, include shale volume, effective porosity, water saturation and hydrocarbon pore volume, were determined and traced laterally in the studied field through the iso-parametric maps. The lithology crossplots of the studied wells show that the sandstone is the main lithology of the Kharita Formation intercalated with some calcareous shale. The cutoff values of shale volume, porosity and water saturation for the productive hydrocarbon pay zones are defined to be 40%, 10% and 50%, respectively, which were determined, based on the applied crossplots approach and their limits. The iso-parametric contour maps for the average reservoir parameters; such as net-pay thickness, average porosity, shale volume, water saturation and the hydrocarbon pore volume were illustrated. From the present study, it is found that the Kharita Formation in the North Qarun oil field has promising reservoir characteristics, particularly in the northwestern part of the study area, which is considered as a prospective area for oil accumulation.

Diverse physiological effects of long-chain saturated fatty acids: implications for cardiovascular disease.

PubMed

Flock, Michael R; Kris-Etherton, Penny M

2013-03-01

The purpose of this review is to discuss the metabolism of long-chain saturated fatty acids and the ensuing effects on an array of metabolic events. Individual long-chain saturated fatty acids exhibit unique biological properties. Dietary saturated fat absorption varies depending on chain-length and the associated food matrix. The in-vivo metabolism of saturated fatty acids varies depending on the individual fatty acid and the nutritional state of the individual. A variety of fatty acid metabolites are formed, each with their own unique structure and properties that warrant further research. Replacing saturated fatty acids with unsaturated fatty acids improves the blood lipid profile and reduces cardiovascular disease risk, although the benefits depend on the specific saturated fatty acid(s) being replaced. Acknowledging the complexity of saturated fatty acid metabolism and associated metabolic events is important when assessing their effects on cardiovascular disease risk. Investigating the biological effects of saturated fatty acids will advance our understanding of how they affect cardiovascular disease risk.

The diverse nature of saturated fats and the case of medium-chain triglycerides: how one recommendation may not fit all.

PubMed

Bhavsar, Nilam; St-Onge, Marie-Pierre

2016-03-01

The adverse cardiovascular health effects of saturated fats have been debated recently since the publication of studies reporting no increase in cardiovascular risk with saturated fat intakes. We purport that this may be because of the varied nature of saturated fats, which range in length from 2 to over 20 carbon atoms, and review evidence surrounding the cardiovascular health effects of medium-chain triglycerides (MCT). MCTs are saturated fats of shorter chain length than other, more readily consumed saturated fats. Studies have reported that consumption of MCT may lead to improvements in body composition without adversely affecting cardio-metabolic risk factors. There may also be synergistic actions between MCT and n-3 polyunsaturated fats that may lead to improvements in cardiovascular health. It is clinically relevant to distinguish between sources of saturated fats for cardiovascular health. Medium, and possibly shorter chain, saturated fats behave differently than long-chain saturated fats and should not be judged similarly when it comes to their cardio-metabolic health effects. Given their neutral, and potentially beneficial cardiovascular health effects, they should not be categorized together.

A Novel Philosophy for a First Course in Organic Chemistry.

ERIC Educational Resources Information Center

Newman, Melvin S.

1982-01-01

Focusing on research is suggested as an approach for teaching organic chemistry for nonmajors. Topics of saturated hydrocarbons and unsaturated hydrocarbons are used as examples to illustrate the approach. (SK)

Partial oxidation of methane by pulsed corona discharges

NASA Astrophysics Data System (ADS)

Hoeben, W. F. L. M.; Boekhoven, W.; Beckers, F. J. C. M.; van Heesch, E. J. M.; Pemen, A. J. M.

2014-09-01

Pulsed corona-induced partial oxidation of methane in humid oxygen or carbon dioxide atmospheres has been investigated for future fuel synthesis applications. The obtained product spectrum is wide, i.e. saturated, unsaturated and oxygen-functional hydrocarbons. The generally observed methane conversion levels are 6-20% at a conversion efficiency of about 100-250 nmol J-1. The main products are ethane, ethylene and acetylene. Higher saturated hydrocarbons up to C6 have been detected. The observed oxygen-functional hydrocarbons are methanol, ethanol and lower concentrations of aldehydes, ketones, dimethylether and methylformate. Methanol seems to be exclusively produced with CH4/O2 mixtures at a maximum production efficiency of 0.35 nmol J-1. CH4/CO2 mixtures appear to yield higher hydrocarbons. Carboxylic acids appear to be mainly present in the aqueous reactor phase, possibly together with higher molecular weight species.

Hydrogenation of liquid natural rubber via diimide reduction in hydrazine hydrate/hydrogen peroxide system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim

Liquid natural rubber (LNR) with molecular weight of lower than 10{sup 5} and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristicsmore » of HLNR were analyzed with Termogravimetric Analysis (TGA)« less

Influence of Parameters of a Reactive Interatomic Potential on the Properties of Saturated Hydrocarbons

DTIC Science & Technology

2017-01-01

Methodology 3 2.1 Modified Embedded-Atom Method Theory 3 2.1.1 Embedding Energy Function 3 2.1.2 Screening Factor 8 2.1.3 Modified Embedded-Atom...Simulation Methodology 2.1 Modified Embedded-Atom Method Theory In the EAM and MEAM formalisms1,2,5 the total energy of a system of atoms (Etot) is...An interatomic potential for saturated hydrocarbons using the modified embedded-atom method (MEAM), a semiempirical many-body potential based on

Geophysical Responses of Hydrocarbon-impacted Zones at the Various Contamination Conditions

NASA Astrophysics Data System (ADS)

Kim, C.; Ko, K.; Son, J.; Kim, J.

2008-12-01

One controlled experiment and two field surveys were conducted to investigate the geoelectrical responses of hydrocarbon-contaminated zones, so called smeared zone, on the geophysical data at the hydrocarbon- contaminated sites with various conditions. One controlled physical model experiment with GPR using fresh gasoline and two different 3-D electrical resistivity investigations at the aged sites. One field site (former military facilities for arms maintenance) was mainly contaminated with lubricating oils and the other (former gas station) was contaminated with gasoline and diesel, respectively. The results from the physical model experiment show that GPR signals were enhanced when LNAPL was present as a residual saturation in the water-saturated system due to less attenuation of the electromagnetic energy through the soil medium of the hydrocarbon-impacted zone (no biodegradation), compared to when the medium was saturated with only water (no hydrocarbon impaction). In the former gas station site, 3-D resistivity results demonstrate that the highly contaminated zones were imaged with low resistivity anomalies since the biodegradation of petroleum hydrocarbons has been undergone for many years, causing the drastic increase in the TDS at the hydrocarbon-impacted zones. Finally, 3-D resistivity data obtained from the former military maintenance site show that the hydrocarbon-contaminated zones show high resistivity anomalies since the hydrocarbons such as lubricating oils at the contaminated soils were not greatly influenced by microbial degradation and has relatively well kept their original physical properties of high electrical resistivity. The results of the study illustrated that the hydrocarbon-impacted zones under various contamination conditions yielded various geophysical responses which include (1) enhanced GPR amplitudes at the fresh LNAPL (Gasoline to middle distillates) spill sites, (2) low electrical resistivity anomalies due to biodegradation at the aged LNAPL- impacted sites, and (3) high electrical resistivity anomalies at the fresh or aged sites contaminated with residual products of crude oils (lubricating oils). The study results also show that the geophysical methods, as a non-invasive sounding technique, can be effectively applied to mapping hydrocarbon-contaminated zones.

Small hydrocarbons on metal surfaces: adsorption-induced changes in electronic and geometric structure as seen by X-ray absorption spectroscopy.

PubMed

Wöll, C

2001-03-01

Monolayers of several unsaturated and saturated hydrocarbons (ethylene, acetylene, benzene, n-hexane, cyclohexane, n-octane, n-hexatriacontane) adsorbed on a number of different metal surfaces [Cu(111), Au(111), Ru(0001) and Pt(111)] have been investigated by carbon K-edge X-ray absorption spectroscopy (XAS). Whereas the corresponding multilayer data qualitatively resemble the core-excitation spectra observed for the free molecules, generally significant modifications are observed in the monolayer data. For the saturated hydrocarbons, a strong quenching of the Rydberg R resonance at 287.7 eV and the appearance of a new broad feature at around 285.1 eV (M resonance) is observed for molecules in direct contact with the metal surfaces. In the case of the unsaturated hydrocarbons, for a number of metals, distinct new features are seen in the XAS data, revealing significant intramolecular distortions.

Diversity and Functional Analysis of Bacterial Communities Associated with Natural Hydrocarbon Seeps in Acidic Soils at Rainbow Springs, Yellowstone National Park

PubMed Central

Hamamura, Natsuko; Olson, Sarah H.; Ward, David M.; Inskeep, William P.

2005-01-01

In this paper we describe the bacterial communities associated with natural hydrocarbon seeps in nonthermal soils at Rainbow Springs, Yellowstone National Park. Soil chemical analysis revealed high sulfate concentrations and low pH values (pH 2.8 to 3.8), which are characteristic of acid-sulfate geothermal activity. The hydrocarbon composition of the seep soils consisted almost entirely of saturated, acyclic alkanes (e.g., n-alkanes with chain lengths of C15 to C30, as well as branched alkanes, predominately pristane and phytane). Bacterial populations present in the seep soils were phylogenetically characterized by 16S rRNA gene clone library analysis. The majority of the sequences recovered (>75%) were related to sequences of heterotrophic acidophilic bacteria, including Acidisphaera spp. and Acidiphilium spp. of the α-Proteobacteria. Clones related to the iron- and sulfur-oxidizing chemolithotroph Acidithiobacillus spp. were also recovered from one of the seep soils. Hydrocarbon-amended soil-sand mixtures were established to examine [14C]hexadecane mineralization and corresponding changes in the bacterial populations using denaturing gradient gel electrophoresis (DGGE) of 16S rRNA gene fragments. Approximately 50% of the [14C]hexadecane added was recovered as 14CO2 during an 80-day incubation, and this was accompanied by detection of heterotrophic acidophile-related sequences as dominant DGGE bands. An alkane-degrading isolate was cultivated, whose 16S rRNA gene sequence was identical to the sequence of a dominant DGGE band in the soil-sand mixture, as well as the clone sequence recovered most frequently from the original soil. This and the presence of an alkB gene homolog in this isolate confirmed the alkane degradation capability of one population indigenous to acidic hydrocarbon seep soils. PMID:16204508

Volume-translated cubic EoS and PC-SAFT density models and a free volume-based viscosity model for hydrocarbons at extreme temperature and pressure conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burgess, Ward A.; Tapriyal, Deepak; Morreale, Bryan D.

2013-12-01

This research focuses on providing the petroleum reservoir engineering community with robust models of hydrocarbon density and viscosity at the extreme temperature and pressure conditions (up to 533 K and 276 MPa, respectively) characteristic of ultra-deep reservoirs, such as those associated with the deepwater wells in the Gulf of Mexico. Our strategy is to base the volume-translated (VT) Peng–Robinson (PR) and Soave–Redlich–Kwong (SRK) cubic equations of state (EoSs) and perturbed-chain, statistical associating fluid theory (PC-SAFT) on an extensive data base of high temperature (278–533 K), high pressure (6.9–276 MPa) density rather than fitting the models to low pressure saturated liquidmore » density data. This high-temperature, high-pressure (HTHP) data base consists of literature data for hydrocarbons ranging from methane to C{sub 40}. The three new models developed in this work, HTHP VT-PR EoS, HTHP VT-SRK EoS, and hybrid PC-SAFT, yield mean absolute percent deviation values (MAPD) for HTHP hydrocarbon density of ~2.0%, ~1.5%, and <1.0%, respectively. An effort was also made to provide accurate hydrocarbon viscosity models based on literature data. Viscosity values are estimated with the frictional theory (f-theory) and free volume (FV) theory of viscosity. The best results were obtained when the PC-SAFT equation was used to obtain both the attractive and repulsive pressure inputs to f-theory, and the density input to FV theory. Both viscosity models provide accurate results at pressures to 100 MPa but experimental and model results can deviate by more than 25% at pressures above 200 MPa.« less

Diversity and functional analysis of bacterial communities associated with natural hydrocarbon seeps in acidic soils at Rainbow Springs, Yellowstone National Park.

PubMed

Hamamura, Natsuko; Olson, Sarah H; Ward, David M; Inskeep, William P

2005-10-01

In this paper we describe the bacterial communities associated with natural hydrocarbon seeps in nonthermal soils at Rainbow Springs, Yellowstone National Park. Soil chemical analysis revealed high sulfate concentrations and low pH values (pH 2.8 to 3.8), which are characteristic of acid-sulfate geothermal activity. The hydrocarbon composition of the seep soils consisted almost entirely of saturated, acyclic alkanes (e.g., n-alkanes with chain lengths of C15 to C30, as well as branched alkanes, predominately pristane and phytane). Bacterial populations present in the seep soils were phylogenetically characterized by 16S rRNA gene clone library analysis. The majority of the sequences recovered (>75%) were related to sequences of heterotrophic acidophilic bacteria, including Acidisphaera spp. and Acidiphilium spp. of the alpha-Proteobacteria. Clones related to the iron- and sulfur-oxidizing chemolithotroph Acidithiobacillus spp. were also recovered from one of the seep soils. Hydrocarbon-amended soil-sand mixtures were established to examine [14C]hexadecane mineralization and corresponding changes in the bacterial populations using denaturing gradient gel electrophoresis (DGGE) of 16S rRNA gene fragments. Approximately 50% of the [14C]hexadecane added was recovered as 14CO2 during an 80-day incubation, and this was accompanied by detection of heterotrophic acidophile-related sequences as dominant DGGE bands. An alkane-degrading isolate was cultivated, whose 16S rRNA gene sequence was identical to the sequence of a dominant DGGE band in the soil-sand mixture, as well as the clone sequence recovered most frequently from the original soil. This and the presence of an alkB gene homolog in this isolate confirmed the alkane degradation capability of one population indigenous to acidic hydrocarbon seep soils.

LIPIDS OF SARCINA LUTEA II.

PubMed Central

Albro, Phillip W.; Huston, Charles K.

1964-01-01

Albro, Phillip W. (Ft. Detrick, Frederick, Md.), and Charles K. Huston. Lipids of Sarcina lutea. II. Hydrocarbon content of the lipid extracts. J. Bacteriol. 88:981–986. 1964.—The hydrocarbon fraction from Sarcina lutea lipid extracts was characterized by a combination of thin-layer and gas-liquid chromatography and infrared spectroscopy. A total of 37 components were observed by gas-liquid chromatography of this material. A breakdown of the components into classes indicated a composition consisting of 88.9% n-saturates, 1.2% monoenes, 2.1% dienes, 5.0% trienes, and 0.6% branched-saturates. Less than 0.1% of the hydrocarbon material was aromatic. No attempt was made in this study to relate the composition to either origin or function in the cell. PMID:14222808

Unctuous ZrO2 nanoparticles with improved functional attributes as lubricant additives

NASA Astrophysics Data System (ADS)

Espina Casado, Jorge; Fernández González, Alfonso; José del Reguero Huerga, Ángel; Rodríguez-Solla, Humberto; Díaz-García, Marta Elena; Badía-Laíño, Rosana

2017-12-01

One of the main drawbacks in the application of metal-oxide nanoparticles as lubricant additives is their poor stability in organic media, despite the good anti-wear, friction-reducing and high-load capacity properties described for these materials. In this work, we present a novel procedure to chemically cap the surface of ZrO2 nanoparticles (ZrO2NPs) with long hydrocarbon chains in order to obtain stable dispersions of ZrO2NPs in non-aqueous media without disrupting their attributes as lubricant additives. C-8, C-10 and C-16 saturated flexible chains were attached to the ZrO2NP surface and their physical and chemical characterization was performed by transmission electron microscopy, thermogravimetric analysis, attenuated total reflectance Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy and solid-state nuclear magnetic resonance. The dispersion stability of the modified ZrO2NPs in non-aqueous media was studied using static multiple light scattering. Tribological tests demonstrated that dispersions of the long-chain capped ZrO2NPs in base lubricating oils exhibited low friction coefficients and improved the anti-wear properties of the base oil when compared with the raw lubricating oil.

Phase change compositions

DOEpatents

Salyer, Ival O.; Griffen, Charles W.

1986-01-01

Compositions containing crystalline, long chain, alkyl hydrocarbons as phase change materials including cementitious compositions containing the alkyl hydrocarbons neat or in pellets or granules formed by incorporating the alkyl hydrocarbons in polymers or rubbers; and polymeric or elastomeric compositions containing alkyl hydrocarbons.

Phase change compositions

DOEpatents

Salyer, Ival O.

1989-01-01

Compositions containing crystalline, straight chain, alkyl hydrocarbons as phase change materials including cementitious compositions containing the alkyl hydrocarbons neat or in pellets or granules formed by incorporating the alkyl hydrocarbons in polymers or rubbers; and polymeric or elastomeric compositions containing alkyl hydrocarbons.

The thermal degradation of 5 alpha (H)-cholestane during closed-system pyrolysis

NASA Astrophysics Data System (ADS)

Abbott, Geoffrey D.; Bennett, Barry; Stuart Fetch, G.

1995-06-01

Involatile hydrocarbons were identified following the heating of 5α(H)-cholestane in water with reaction vessel walls composed of 316 grade stainless steel and borosilicate glass. These analyses were compared with the hydrocarbon product compositions from closed-system pyrolysis experiments with no added water. Unsaturated hydrocarbons dominate their saturated counterparts following hydrous pyrolysis in both stainless steel-316 and borosilicate glass. In the absence of added water the converse is true in that saturated components dominate the hydrocarbon mixture. Backbone rearrangement in the steroid nucleus leading to spirosterene formation was only observed under aqueous conditions in both borosilicate glass and stainless steel-316 vessels. These comparisons demonstrate that water, as opposed to reaction vessel surface catalytic effects, plays a central role in mediating hydrocarbon degradation during closed-system hydrous pyrolysis. 5α(H)-cholestane degradation under aqueous conditions is a complex composite of dissociative and rearrangement processes. These include (I) carbon-carbon bond cleavage in the sidechains as well as the ring system, (2) dehydrogenation, and (3) backbone rearrangement. These laboratory experiments provide a product description of the involatile hydrocarbons which will be the basis for a mechanistic study of 5α(H)-cholestane degradation in hot water.

Organic metamorphism in the Lower Mississippian-Upper Devonian Bakken shales-II: Soxhlet extraction.

USGS Publications Warehouse

Price, L.C.; Ging, T.; Love, A.; Anders, D.

1986-01-01

We report on Soxhlet extraction (and subsequent related analyses) of 39 Lower Mississippian-Upper Devonian Bakken shales from the North Dakota portion of the Williston Basin, and analyses of 28 oils from the Basin. Because of the influence of primary petroleum migration, no increase in the relative or absolute concentrations of hydrocarbons or bitumen was observed at the threshold of intense hydrocarbon generation (TIHG), or during mainstage hydrocarbon generation in the Bakken shales. Thus, the maturation indices that have been so useful in delineating the TIHG and mainstage hydrocarbon generation in other studies were of no use in this study, where these events could clearly be identified only by Rock-Eval pyrolysis data. The data of this study demonstrate that primary petroleum migration is a very efficient process. Four distinctive classes of saturated hydrocarbon gas chromatograms from the Bakken shales arose from facies, maturation, and primary migration controls. As a consequence of maturation, the % of saturated hydrocarbons increased in the shale extract at the expense of decreases in the resins and asphaltenes. Measurements involving resins and asphaltenes appear to be excellent maturation indices in the Bakken shales. Two different and distinct organic facies were present in immature Bakken shales. -from Authors

The Perturbational MO Method for Saturated Systems.

ERIC Educational Resources Information Center

Herndon, William C.

1979-01-01

Summarizes a theoretical approach using nonbonding MO's and perturbation theory to correlate properties of saturated hydrocarbons. Discussion is limited to correctly predicted using this method. Suggests calculations can be carried out quickly in organic chemistry. (Author/SA)

Data on pigments and long-chain fatty compounds identified in Dietzia sp. A14101 grown on simple and complex hydrocarbons

PubMed Central

Hvidsten, Ina; Mjøs, Svein Are; Bødtker, Gunhild; Barth, Tanja

2015-01-01

This data article provides: 1. An overview of tentatively identified long chain compounds in Dietzia sp. A14101 grown on simple and complex hydrocarbons; 2. Preliminary Identification of pigments in bacterial material obtained from incubation with a hydrocarbon (dodecane, n-C12) as the only carbon and energy source; 3. Some pictures to illustrate the cell surface charge test. PMID:26442286

Biofiltration of gasoline and diesel aliphatic hydrocarbons.

PubMed

Halecky, Martin; Rousova, Jana; Paca, Jan; Kozliak, Evguenii; Seames, Wayne; Jones, Kim

2015-02-01

The ability of a biofilm to switch between the mixtures of mostly aromatic and aliphatic hydrocarbons was investigated to assess biofiltration efficiency and potential substrate interactions. A switch from gasoline, which consisted of both aliphatic and aromatic hydrocarbons, to a mixture of volatile diesel n-alkanes resulted in a significant increase in biofiltration efficiency, despite the lack of readily biodegradable aromatic hydrocarbons in the diesel mixture. This improved biofilter performance was shown to be the result of the presence of larger size (C₉-C(12)) linear alkanes in diesel, which turned out to be more degradable than their shorter-chain (C₆-C₈) homologues in gasoline. The evidence obtained from both biofiltration-based and independent microbiological tests indicated that the rate was limited by biochemical reactions, with the inhibition of shorter chain alkane biodegradation by their larger size homologues as corroborated by a significant substrate specialization along the biofilter bed. These observations were explained by the lack of specific enzymes designed for the oxidation of short-chain alkanes as opposed to their longer carbon chain homologues.

Process for functionalizing alkanes

DOEpatents

Bergman, Robert G.; Janowicz, Andrew H.; Periana, Roy A.

1988-01-01

Process for functionalizing saturated hydrocarbons comprising: (a) reacting said saturated hydrocarbons of the formula: R.sub.1 H wherein H represents a hydrogen atom; and R.sub.1 represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRh[P(R.sub.2).sub.3 ]H.sub.2 wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical; Rh represents a rhodium atom; P represents a phosphorus atom; R.sub.2 represents a hydrocarbon radical; H represents a hydrogen atom, in the presence of ultraviolet radiation to form a hydridoalkyl complex of the formula: CpRh[P(R.sub.2).sub.3 ](R.sub.1)H (b) reacting said hydridoalkyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X''X'''X'''' or CHX'X''X''' wherein X', X'', X'", X"" represent halogens selected from bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula: CpRhPMe.sub.3 RX; and, (c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e., ambient) to form a functional haloalkyl compound.

Pyrolysis of polyethylene terephthalate containing real waste plastics using Ni loaded zeolite catalysts

NASA Astrophysics Data System (ADS)

Al-asadi, M.; Miskolczi, N.

2018-05-01

In this work the pyrolysis of polyethylene terephthalate (PET) containing real waste plastic was investigated using different Ni loaded catalysts: Ni/ZSM-5, Ni/y-zeolite, Ni/β-zeolite and Ni/natural zeolite (clinoptilolite). Raw materials were pyrolyzed in a horizontal tubular reactor between 600 and 900°C using 10% of catalysts. It was found, that both temperature increasing and catalysts presence can increase the gas yields, however owing to gasification reactions, the pyrolysis oil yield decreased with increasing temperature. Ni/y-zeolite catalyst had the most benefit in gas yield increasing at low temperature; however Ni/ZSM-5 showed advanced property in gas yield increasing at high temperature. Gases contained hydrogen, carbon oxides and hydrocarbons, which composition was significantly affected by catalysts. Ni loaded zeolites favoured to the formation of hydrogen and branched hydrocarbons; furthermore the concentrations of both CO and CO2 were also increased as function of elevated temperature. That phenomenon was attributed to the further decomposition of PET, especially to the side chain scission reactions. Owing to the Boudouard reaction, the ratio of CO2/CO can increased with temperature. Pyrolysis oils were the mixtures of n-saturated, n-unsaturated, branched, oxygen free aromatics and oxygenated hydrocarbons. Temperature increasing has a significant effect to the aromatization and isomerization reactions, while the catalysts can efficiently decreased the concentration of oxygen containing compounds.

Improved zeolite regeneration processes for preparing saturated branched-chain fatty acids

USDA-ARS?s Scientific Manuscript database

Ferrierite zeolite solid is an excellent catalyst for the skeletal isomerization of unsaturated linear-chain fatty acids (i.e., oleic acid) to unsaturated branched-chain fatty acids (i.e., iso-oleic acid) follow by hydrogenation to give saturated branched-chain fatty acids (i.e., isostearic acid). ...

Evidence for asymmetric edge-on Langmuir monolayer: Application to surface potential measurements

NASA Astrophysics Data System (ADS)

El Abed, A.; Ionov, R.; Goldmann, M.; Fontaine, P.; Billard, J.; Peretti, P.

2001-10-01

We show, using surface pressure vs. molecular area isotherm measurements and synchrotron grazing X-ray diffraction, that 4BCD12 molecules, which consist of a central flexible bowl-like core to which eight long lateral hydrocarbon chains are bound, form a stable edge-on monolayer. Experimental data indicate that six lateral hydrocarbon chains orient upwards to form a quasi-rectangular lattice of 43° tilted hydrocarbon chains. The obtained axially asymmetric phase, which we label edge26-on, allows using surface potential measurements, for the validation of literature electric models of a single monolayer spread at the air-water interface.

One-step production of long-chain hydrocarbons from waste-biomass-derived chemicals using bi-functional heterogeneous catalysts.

PubMed

Wen, Cun; Barrow, Elizabeth; Hattrick-Simpers, Jason; Lauterbach, Jochen

2014-02-21

In this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels.

Simple model of inhibition of chain-branching combustion processes

NASA Astrophysics Data System (ADS)

Babushok, Valeri I.; Gubernov, Vladimir V.; Minaev, Sergei S.; Miroshnichenko, Taisia P.

2017-11-01

A simple kinetic model has been suggested to describe the inhibition and extinction of flame propagation in reaction systems with chain-branching reactions typical for hydrocarbon systems. The model is based on the generalised model of the combustion process with chain-branching reaction combined with the one-stage reaction describing the thermal mode of flame propagation with the addition of inhibition reaction steps. Inhibitor addition suppresses the radical overshoot in flame and leads to the change of reaction mode from the chain-branching reaction to a thermal mode of flame propagation. With the increase of inhibitor the transition of chain-branching mode of reaction to the reaction with straight-chains (non-branching chain reaction) is observed. The inhibition part of the model includes a block of three reactions to describe the influence of the inhibitor. The heat losses are incorporated into the model via Newton cooling. The flame extinction is the result of the decreased heat release of inhibited reaction processes and the suppression of radical overshoot with the further decrease of the reaction rate due to the temperature decrease and mixture dilution. A comparison of the results of modelling laminar premixed methane/air flames inhibited by potassium bicarbonate (gas phase model, detailed kinetic model) with the results obtained using the suggested simple model is presented. The calculations with the detailed kinetic model demonstrate the following modes of combustion process: (1) flame propagation with chain-branching reaction (with radical overshoot, inhibitor addition decreases the radical overshoot down to the equilibrium level); (2) saturation of chemical influence of inhibitor, and (3) transition to thermal mode of flame propagation (non-branching chain mode of reaction). The suggested simple kinetic model qualitatively reproduces the modes of flame propagation with the addition of the inhibitor observed using detailed kinetic models.

Short-term phenotypic plasticity in long-chain cuticular hydrocarbons

PubMed Central

Thomas, Melissa L.; Simmons, Leigh W.

2011-01-01

Cuticular hydrocarbons provide arthropods with the chemical equivalent of the visually extravagant plumage of birds. Their long chain length, together with the number and variety of positions in which methyl branches and double bonds occur, provide cuticular hydrocarbons with an extraordinary level of information content. Here, we demonstrate phenotypic plasticity in an individual's cuticular hydrocarbon profile. Using solid-phase microextraction, a chemical technique that enables multiple sampling of the same individual, we monitor short-term changes in cuticular hydrocarbon profiles of individual crickets, Teleogryllus oceanicus, in response to a social challenge. We experimentally manipulate the dominance status of males and find that dominant males, on losing fights with other dominant males, change their hydrocarbon profile to more closely resemble that of a subordinate. This result demonstrates that cuticular hydrocarbons can be far more responsive to changes in social dominance than previously realized. PMID:21367785

Method for fabricating hafnia films

DOEpatents

Hu, Michael Z [Knoxville, TN

2007-08-21

The present invention comprises a method for fabricating hafnia film comprising the steps of providing a substrate having a surface that allows formation of a self-assembled monolayer thereon via covalent bonding; providing an aqueous solution that provides homogeneous hafnium ionic complexes and hafnium nanoclusters wherein the aqueous solution is capable of undergoing homogeneous precipitation under controlled conditions for a desired period of time at a controlled temperature and controlled solution acidity for desired nanocluster nucleation and growth kinetics, desired nanocluster size, desired growth rate of film thickness and desired film surface characteristics. The method further comprising forming the self-assembled monolayer on the surface of the substrate wherein the self-assembled monolayer comprises a plurality of hydrocarbon chains cross-linked together along the surface of the substrate, the hydrocarbon chains being uniformly spaced from one another and wherein each of the hydrocarbon chains having a functional anchoring group at a first end of the chain covalently bonded with the surface of the substrate and each of the hydrocarbon chains having a functional terminating group projected away from the surface wherein the functional terminating group provides a bonding site for the hafnium film to grow; and exposing the substrate to the aqueous solution for a desired period of time at a controlled temperature wherein the hafnium ionic complexes and the hafnium nanoclusters are deposited on the bonding site of the functional terminating group thereby forming the hafnia film wherein the hafnium bonded to the hydrocarbons and to one another provide a uniform ordered arrangement defined by the uniform arrangement of the hydrocarbons.

Concentration and saturation effects of tethered polymer chains on adsorbing surfaces

NASA Astrophysics Data System (ADS)

Descas, Radu; Sommer, Jens-Uwe; Blumen, Alexander

2006-12-01

We consider end-grafted chains at an adsorbing surface under good solvent conditions using Monte Carlo simulations and scaling arguments. Grafting of chains allows us to fix the surface concentration and to study a wide range of surface concentrations from the undersaturated state of the surface up to the brushlike regime. The average extension of single chains in the direction parallel and perpendicular to the surface is analyzed using scaling arguments for the two-dimensional semidilute surface state according to Bouchaud and Daoud [J. Phys. (Paris) 48, 1991 (1987)]. We find good agreement with the scaling predictions for the scaling in the direction parallel to the surface and for surface concentrations much below the saturation concentration (dense packing of adsorption blobs). Increasing the grafting density we study the saturation effects and the oversaturation of the adsorption layer. In order to account for the effect of excluded volume on the adsorption free energy we introduce a new scaling variable related with the saturation concentration of the adsorption layer (saturation scaling). We show that the decrease of the single chain order parameter (the fraction of adsorbed monomers on the surface) with increasing concentration, being constant in the ideal semidilute surface state, is properly described by saturation scaling only. Furthermore, the simulation results for the chains' extension from higher surface concentrations up to the oversaturated state support the new scaling approach. The oversaturated state can be understood using a geometrical model which assumes a brushlike layer on top of a saturated adsorption layer. We provide evidence that adsorbed polymer layers are very sensitive to saturation effects, which start to influence the semidilute surface scaling even much below the saturation threshold.

Odd-even chain packing, molecular and thermal models for some long chain sodium(I) n-alkanoates

NASA Astrophysics Data System (ADS)

Nelson, Peter N.; Ellis, Henry A.

2014-10-01

A homologous series of sodium(I) n-alkanoates, NaCnH2n-1O2, with chain lengths n = 8-18, inclusive, have been synthesized and their structural and thermal properties investigated via Fourier Transform Infrared and Solid State 13C NMR spectroscopies, X-ray powder diffraction, Thermogravimetry, Differential Scanning Calorimetry, Polarizing light microscopy and variable temperature Infrared spectroscopy. The measurements show that metal-carboxylate coordination is via asymmetric chelating bidentate bonding with extensive carboxyl group inter-molecular interactions in which four oxygen atoms are bonded tetrahedrally to a sodium atom. Furthermore, the compounds crystallize in a monoclinic crystal system with the hydrocarbon chains in the fully extended all-trans conformation, advancing along the c-axis. Moreover, the chains are packed as tilted (θ ∼ 63°), non-overlapping, tail-to-tail lamellar bilayers that are not in the same plane, within a lamellar. Though these compounds are nearly isostructural, there are subtle differences in the packing of the hydrocarbon chains in the crystal lattice, resulting in odd-even alternation in the terminal methyl group asymmetric stretching vibration and chemical shift. These differences arise from the relative vertical distances between hydrocarbon planes within the lamellar; such that, for odd-chain compounds, larger inter-planar distances result in less efficient packing in the crystal lattice and hence, lower inter-planar van der Waals interactions between hydrocarbon chains. Thermal traces, for all compounds, show several partially reversible solid-solid pre-melting transitions associated with different degrees of gauche conformers in the alkyl chains. The reversible gauche-trans isomerism, of the methylene groups, is kinetically controlled; hence, super-cooling of the melt and other transitions, are observed for all compounds. The kinetics of chain reversion follow the exponential law of nucleation, though complicated by competing processes. Thermogravimetric data show that all compounds decompose at temperatures in excess of 690 K; therefore, free radical thermal cracking of the hydrocarbon chains, in conjunction with decarboxylation is proposed for their non-oxidative degradation mechanism.

A Study of the Nephrotoxicity and Metabolism of Tetralin and Indan in Fischer 344 Rats

DTIC Science & Technology

1989-05-01

5, a jet fuel composed of aliphatic and aromatic hydrocarbons with the majority of the straight-chain hydrocarbons being between C10 and C15...hydrocarbon of intermediate boiling point and volatility and is similar to the civilian jet fuel , A-1. DFM is a mixture of long chain aliphatic...to compliment earlier research on jet fuel , JP-10, cis- and trans- decalin, and tetralin, it was anticipated some enlightenment could be obtained on

Experimental determination of methane dissolution from simulated subsurface oil leakages

NASA Astrophysics Data System (ADS)

Sauthoff, W.; Peltzer, E. T.; Walz, P. M.; Brewer, P. G.

2013-12-01

Subsurface oil leakages and increased offshore drilling efforts have raised concern over the fate of hydrocarbon mixtures of oil and gas in ocean environments. Recent wellhead and pipeline failures in the Gulf of Mexico are extreme examples of this problem. Understanding the mechanism and rate of vertical transport of hydrocarbon chemical species is necessary to predict the environmental impact of subsurface leakages. In a series of controlled experiments, we carried out a deep-sea field experiment in Monterey Canyon to investigate the behavior of a gas-saturated liquid hydrocarbon mass rising from the seafloor. Aboard the R/V Rachel Carson, we used the ROV Ventana to transport a laboratory prepared volume of decane (C10H22) saturated with methane gas (CH4) to mimic a subsurface seafloor discharge. We released the oil and gas mixture into a vertically oriented open bottom glass tube followed by methane loss rate measurements both at discrete depths, and during rapid, continuous vehicle ascent from 800 to 100 m water depth to monitor changes in dissolution and bubble nucleation. Using laser Raman techniques and HD video we quantified the chemical state of the hydrocarbon fluid, including rate of methane gas dissolution. The primary methane Raman peak was readily observable within the decane C-H stretching complex. Variation in the amount of gas dissolved in the oil greatly influences oil plume density and in turn oil plume vertical rise rate. Our results show that the rise rate of the hydrocarbon mass significantly exceeds the rate at which the excess methane was lost by dissolution. This result implies that vertical transport of methane in the saturated hydrocarbon liquid phase can greatly exceed a gas bubble plume ascending the water column from a seafloor source. These results and observations may be applicable to improved understanding of the composition, distribution, and environmental fate of leaked hydrocarbon mixtures and inform remediation efforts.

Sonolysis of hydrocarbons in aqueous solution

NASA Astrophysics Data System (ADS)

Hart, Edwin J.; Fischer, Christian-Herbert; Henglein, Arnim

Water was irradiated with 300 kHz ultrasound under an argon atmosphere containing various amounts of methane and ethane. Limited studies were also made on ethylene, acetylene, propane and butane. The methane and ethane irradiations were carried out over the hydrocarbon-argon range of 2-100%. Maximum decomposition occurs at 15% for methane and 10% for ethane. While hydrogen is a dominant product in both cases, acetylene, ethylene and ethane are prominent products, too. Propane, propene and propin form in lesser quantities. 2-methyl-propane, n-butane, l-butene, 2-methyl-butene, butadiene and n-butin have also been identified. These hydrocarbons are similar to those found in pyrolysis and in fuel rich combustion experiments. Carbon monoxide is an important product at hydrocarbon concentrations less than 40% establishing water was an oxygen delivering reactant under these conditions. In the case of methane, the ratio of ethylene plus acetylene to ethane is used to estimate the effective temperature in the cavitation bubble. A temperature of about 2800 K is obtained for bubbles containing argon (plus water vapor and 20% CH 4) and T = 2000 K for pure methane. The rate of decomposition for unsaturated hydrocarbons is substantially greater than for the saturated ones. Low molecular weight products are mainly formed from saturated hydrocarbons whereas polymerization products are mainly formed from the unsaturated hydrocarbons. The decomposition of acetylene in argon bubbles is one of the fastest sonolytic processes.

Improvement of mineral oil saturated and aromatic hydrocarbons determination in edible oil by liquid-liquid-gas chromatography with dual detection.

PubMed

Zoccali, Mariosimone; Barp, Laura; Beccaria, Marco; Sciarrone, Danilo; Purcaro, Giorgia; Mondello, Luigi

2016-02-01

Mineral oils, which are mainly composed of saturated hydrocarbons and aromatic hydrocarbons, are widespread food contaminants. Liquid chromatography coupled to gas chromatography with flame ionization detection represents the method of choice to determine these two families. However, despite the high selectivity of this technique, the presence of olefins (particularly squalene and its isomers) in some samples as in olive oils, does not allow the correct quantification of the mineral oil aromatic hydrocarbons fraction, requiring additional off-line tools to eliminate them. In the present research, a novel on-line liquid chromatography coupled to gas chromatography method is described for the determination of hydrocarbon contamination in edible oils. Two different liquid chromatography columns, namely a silica one (to retain the bulk of the matrix) and a silver-ion one (which better retains the olefins), were coupled in series to obtain the mineral oil aromatic hydrocarbons hump free of interfering peaks. Furthermore, the use of a simultaneous dual detection, flame ionization detector and triple quadrupole mass spectrometer allowed us not only to quantify the mineral oil contamination, but also to evaluate the presence of specific markers (i.e. hopanes) to confirm the petrogenic origin of the contamination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

RADIOLYSIS OF ORGANIC COMPOUNDS IN THE ADSORBED STATE

DOEpatents

Sutherland, J.W.; Allen, A.O.

1961-10-01

>A method of forming branch chained hydrocarbons by means of energetic penetrating radiation is described. A solid zeolite substrate is admixed with a cobalt ion and is irradiated with a hydrocarbon adsorbed therein. Upon irradiation with gamma rays, there is an increased yield of branched and lower molecular straight chain compounds. (AEC)

Catalytic cracking of model compounds of bio-oil over HZSM-5 and the catalyst deactivation.

PubMed

Chen, Guanyi; Zhang, Ruixue; Ma, Wenchao; Liu, Bin; Li, Xiangping; Yan, Beibei; Cheng, Zhanjun; Wang, Tiejun

2018-08-01

The catalytic cracking upgrading reactions over HZSM-5 of different model compounds of bio-oil have been studied with a self-designed fluid catalytic cracking (FCC) equipment. Typical bio-oil model compounds, such as acetic acid, guaiacol, n-heptane, acetol and ethyl acetate, were chosen to study the products distribution, reaction pathway and deactivation of catalysts. The results showed: C 6 -C 8 aromatic hydrocarbons, C 2 -C 4 olefins, C 1 -C 5 alkanes, CO and CO 2 were the main products, and the selectivity of olefins was: ethylene>propylene>butylene. Catalyst characterization methods, such as FI-IR, TG-TPO and Raman, were used to study the deactivation mechanism of catalysts. According to the catalyst characterization results, a catalyst deactivation mechanism was proposed as follows: Firstly, the precursor which consisted of a large number of long chain saturated aliphatic hydrocarbons and a small amount CC of aromatics formed on the catalyst surface. Then the active sites of catalysts had been covered, the coke type changed from thermal coke to catalytic coke and gradually blocked the channels of the molecular sieve, which accelerated the deactivation of catalyst. Copyright © 2018 Elsevier B.V. All rights reserved.

Metabolic Engineering of Oleaginous Yeasts for Fatty Alcohol Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Wei; Wei, Hui; Knoshaug, Eric

To develop pathways for advanced biological upgrading of sugars to hydrocarbons, we are seeking biological approaches to produce high carbon efficiency intermediates amenable to separations and catalytic upgrading to hydrocarbon fuels. In this study, we successfully demonstrated fatty alcohol production by oleaginous yeasts Yarrowia lipolytica and Lipomyces starkeyi by expressing a bacteria-derived fatty acyl-CoA reductase (FAR). Moreover, we find higher extracellular distribution of fatty alcohols produced by FAR-expressing L. starkeyi strain as compared to Y. lipolytica strain, which would benefit the downstream product recovery process. In both oleaginous yeasts, long chain length saturated fatty alcohols were predominant, accounting for moremore » than 85% of the total fatty alcohols produced. To the best of our knowledge, this is the first report of fatty alcohol production in L. starkeyi. Taken together, our work demonstrates that in addition to Y. lipolytica, L. starkeyi can also serve as a platform organism for production of fatty acid-derived biofuels and bioproducts via metabolic engineering. We believe strain and process development both will significantly contribute to our goal of producing scalable and cost-effective fatty alcohols from renewable biomass.« less

Induction log responses to layered, dipping, and anisotropic formations: Induction log shoulder-bed corrections to anisotropic formations and the effect of shale anisotropy in thinly laminated sand/shale sequences

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hagiwara, Teruhiko

1996-12-31

Induction log responses to layered, dipping, and anisotropic formations are examined analytically. The analytical model is especially helpful in understanding induction log responses to thinly laminated binary formations, such as sand/shale sequences, that exhibit macroscopically anisotropic: resistivity. Two applications of the analytical model are discussed. In one application we examine special induction log shoulder-bed corrections for use when thin anisotropic beds are encountered. It is known that thinly laminated sand/shale sequences act as macroscopically anisotropic: formations. Hydrocarbon-bearing formations also act as macroscopically anisotropic formations when they consist of alternating layers of different grain-size distributions. When such formations are thick, inductionmore » logs accurately read the macroscopic conductivity, from which the hydrocarbon saturation in the formations can be computed. When the laminated formations are not thick, proper shoulder-bed corrections (or thin-bed corrections) should be applied to obtain the true macroscopic formation conductivity and to estimate the hydrocarbon saturation more accurately. The analytical model is used to calculate the thin-bed effect and to evaluate the shoulder-bed corrections. We will show that the formation resistivity and hence the hydrocarbon saturation are greatly overestimated when the anisotropy effect is not accounted for and conventional shoulder-bed corrections are applied to the log responses from such laminated formations.« less

Thermodynamic functions of hydration of hydrocarbons at 298.15 K and 0.1 MPa

NASA Astrophysics Data System (ADS)

Plyasunov, Andrey V.; Shock, Everett L.

2000-02-01

An extensive compilation of experimental data yielding the infinite dilution partial molar Gibbs energy of hydration Δ hGO, enthalpy of hydration Δ hHO, heat capacity of hydration Δ hCpO, and volume V2O, at the reference temperature and pressure, 298.15 K and 0.1 MPa, is presented for hydrocarbons (excluding polyaromatic compounds) and monohydric alcohols. These results are used in a least-squares procedure to determine the numerical values of the corresponding properties of the selected functional groups. The simple first order group contribution method, which in general ignores nearest-neighbors and steric hindrance effects, was chosen to represent the compiled data. Following the precedent established by Cabani et al. (1981), the following groups are considered: CH 3, CH 2, CH, C for saturated hydrocarbons; c-CH 2, c-CH, c-C for cyclic saturated hydrocarbons; CH ar, C ar for aromatic hydrocarbons (containing the benzene ring); C=C, C≡C for double and triple bonds in linear hydrocarbons, respectively; c-C=C for the double bond in cyclic hydrocarbons; H for a hydrogen atom attached to the double bond (both in linear and cyclic hydrocarbons) or triple bond; and OH for the hydroxyl functional group. In addition it was found necessary to include the "pseudo"-group I(C-C) to account for the specific interactions of the neighboring hydrocarbon groups attached to the benzene or cyclic ring (in the latter case only for cis-isomers). Results of this study, the numerical values of the group contributions, will allow in most cases reasonably accurate estimations of Δ hGO, Δ hHO, Δ hCpO, and V2O at 298.15 K, 0.1 MPa for many hydrocarbons involved in geochemical and environmental processes.

Amino acids and hydrocarbons approximately 3,800-Myr old in the Isua rocks, southwestern Greenland

NASA Technical Reports Server (NTRS)

Nagy, B.; Engel, M. H.; Zumberge, J. E.; Ogino, H.; Chang, S. Y.

1981-01-01

Results of an analysis of amino acids and hydrocarbons found in the Isua banded iron formation, which contains the oldest known rocks on earth, are discussed. Similarities are pointed out between the relative amino acid abundances of the Isua rocks and those of lichens found on their surfaces, and a lack of substantial racemization indicated by the low D/L ratios in the 3800-million year old rock samples is noted. Experimental results showing the possibility of amino acid diffusion from lichens into the rocks are presented. Comparisons of the Isua rock amino acid D/L ratios with those reported for samples from other regions indicates that none of the Isua amino acids are older than a few tens of thousands to a few hundred thousand years. Analyses of the saturated hydrocarbons of the Isua samples reveals no odd carbon number preference, which may indicate antiquity, however laboratory experiments have shown that amino acids and aromatic and saturated aliphatic hydrocarbons could not have survived the metamorphic history of the Isua rocks. The evidence presented thus suggests that the amino acids and hydrocarbons found are not of the age of the sediments.

Oxidative stress in entomopathogenic fungi grown on insect-like hydrocarbons.

PubMed

Huarte-Bonnet, Carla; Juárez, M Patricia; Pedrini, Nicolás

2015-08-01

Entomopathogenic fungi mostly attack their insect hosts by penetration through the cuticle. The outermost insect surface is covered by a lipid-rich layer, usually composed of very long chain hydrocarbons. These fungi are apt to grow on straight chain hydrocarbons (alkanes) as the sole carbon source. Insect-like hydrocarbons are first hydroxylated by a microsomal P450 monooxygenase system, and then fully catabolized by peroxisomal β-oxidation reactions in Beauveria bassiana. In this review, we will discuss lipid metabolism adaptations in alkane-grown fungi, and how an oxidative stress scenario is established under these conditions. Fungi have to pay a high cost for hydrocarbon utilization; high levels of reactive oxygen species are produced and a concomitant antioxidant response is triggered in fungal cells to cope with this drawback.

VERTICAL INTEGRATION OF THREE-PHASE FLOW EQUATIONS FOR ANALYSIS OF LIGHT HYDROCARBON PLUME MOVEMENT

EPA Science Inventory

A mathematical model is derived for areal flow of water and light hydrocarbon in the presence of gas at atmospheric pressure. Closed-form expressions for the vertically integrated constitutive relations are derived based on a three-phase extension of the Brooks-Corey saturation-...

40 CFR 261.31 - Hazardous wastes from non-specific sources.

Code of Federal Regulations, 2011 CFR

2011-07-01

... free radical catalyzed processes. These chlorinated aliphatic hydrocarbons are those having carbon... spent desiccant wastes from the production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic hydrocarbons are those having carbon chain...

40 CFR 261.31 - Hazardous wastes from non-specific sources.

Code of Federal Regulations, 2010 CFR

2010-07-01

... free radical catalyzed processes. These chlorinated aliphatic hydrocarbons are those having carbon... spent desiccant wastes from the production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic hydrocarbons are those having carbon chain...

Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.

2018-04-17

A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol % ethylene and at least 35 vol % of hydrocarbon compounds containing at least eight carbon atoms.

Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.

2015-11-13

A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100°C and up to 550°C, wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol % ethylene and at least 35 vol % of hydrocarbon compounds containing at least eight carbon atoms.

Process for functionalizing alkanes

DOEpatents

Bergman, R.G.; Janowicz, A.H.; Periana-Pillai, R.A.

1984-06-12

Process for functionalizing saturated hydrocarbons selectively in the terminal position comprises: (a) reacting said saturated hydrocarbons with a metal complex CpRhPMe/sub 3/H/sub 2/ in the presence of ultraviolet radiation at -60/sup 0/ to -17/sup 0/C to form a hydridoalkyl complex CpRhPMe/sub 3/RH; (b) reacting said hydridoalkyl complex with a haloform CHX/sub 3/ at -60/sup 0/ to -17/sup 0/C to form the corresponding haloalkyl complex of step (a) CpRhPMe/sub 3/RX; and (c) reacting said haloalkyl complex with halogen -60 to 25/sup 0/C to form a functional haloalkyl compound.

Process for functionalizing alkanes

DOEpatents

Bergman, Robert G.; Janowicz, Andrew H.; Periana-Pillai, Roy A.

1985-01-01

Process for functionalizing saturated hydrocarbons selectively in the terminal position comprising: (a) reacting said saturated hydrocarbons of the formula: RH where: H represents a hydrogen atom, and R represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRhPMe.sub.3 H.sub.2 where: Cp represents a pentamethylated cyclopentadienyl radical, Rh represents a rhodium atom, P represents a phosphorous atom, Me represents a methyl group, H represents a hydrogen atom, in the presence of ultraviolet radiation at a temperature maintained at about -60.degree. to -17.degree. C. to form a hydridoalkyl complex of the formula: CpRhPMe.sub.3 RH (b) reacting said hydridoalkyl complex with a haloform of the formula: CHX.sub.3 where: X represents a bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula: CpRhPMe.sub.3 RX; and, (c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e. ambient) to form a functional haloalkyl compound.

Mineral oil barrier sequential polymer treatment for recycled paper products in food packaging

NASA Astrophysics Data System (ADS)

Paul, Uttam C.; Fragouli, Despina; Bayer, Ilker S.; Mele, Elisa; Conchione, Chiara; Cingolani, Roberto; Moret, Sabrina; Athanassiou, Athanassia

2017-01-01

Recycled cellulosic paperboards may include mineral oils after the recycle process, which together with their poor water resistance limit their use as food packaging materials. In this work, we demonstrate that a proper functionalization of the recycled paper with two successive polymer treatments, imposes a mineral oil migration barrier and simultaneously renders it waterproof and grease resistant, making it an ideal material for food contact. The first poly (methyl methacrylate) treatment penetrates the paper network and creates a protective layer around every fiber, permitting thus the transformation of the paperboard to a hydrophobic material throughout its thickness, reducing at the same time the mineral oil migration. Subsequently, the second layer with a cyclic olefin copolymer fills the open pores of the surface, and reduces the mineral oil hydrocarbons migration at levels below those proposed by the BMEL. Online liquid chromatography-gas chromatography coupled with flame ionization detection quantitatively demonstrate that this dual functional treatment prevents the migration of both saturated (mineral oil saturated hydrocarbons) and aromatic hydrocarbon (mineral oil aromatic hydrocarbons) mineral oils from the recycled paperboard to a dry food simulant.

Learning and discrimination of cuticular hydrocarbons in a social insect

PubMed Central

van Wilgenburg, Ellen; Felden, Antoine; Choe, Dong-Hwan; Sulc, Robert; Luo, Jun; Shea, Kenneth J.; Elgar, Mark A.; Tsutsui, Neil D.

2012-01-01

Social insect cuticular hydrocarbon (CHC) mixtures are among the most complex chemical cues known and are important in nest-mate, caste and species recognition. Despite our growing knowledge of the nature of these cues, we have very little insight into how social insects actually perceive and discriminate among these chemicals. In this study, we use the newly developed technique of differential olfactory conditioning to pure, custom-designed synthetic colony odours to analyse signal discrimination in Argentine ants, Linepithema humile. Our results show that tri-methyl alkanes are more easily learned than single-methyl or straight-chain alkanes. In addition, we reveal that Argentine ants can discriminate between hydrocarbons with different branching patterns and the same chain length, but not always between hydrocarbons with the same branching patterns but different chain length. Our data thus show that biochemical characteristics influence those compounds that ants can discriminate between, and which thus potentially play a role in chemical signalling and nest-mate recognition. PMID:21831880

Calorimetric and spectroscopic studies of the thermotropic phase behavior of lipid bilayer model membranes composed of a homologous series of linear saturated phosphatidylserines.

PubMed Central

Lewis, R N; McElhaney, R N

2000-01-01

The thermotropic phase behavior of lipid bilayer model membranes composed of the even-numbered, N-saturated 1,2-diacyl phosphatidylserines was studied by differential scanning calorimetry and by Fourier-transform infrared and (31)P-nuclear magnetic resonance spectroscopy. At pH 7.0, 0.1 M NaCl and in the absence of divalent cations, aqueous dispersions of these lipids, which have not been incubated at low temperature, exhibit a single calorimetrically detectable phase transition that is fully reversible, highly cooperative, and relatively energetic, and the transition temperatures and enthalpies increase progressively with increases in hydrocarbon chain length. Our spectroscopic observations confirm that this thermal event is a lamellar gel (L(beta))-to-lamellar liquid crystalline (L(alpha)) phase transition. However, after low temperature incubation, the L(beta)/L(alpha) phase transition of dilauroyl phosphatidylserine is replaced by a higher temperature, more enthalpic, and less cooperative phase transition, and an additional lower temperature, less enthalpic, and less cooperative phase transition appears in the longer chain phosphatidylserines. Our spectroscopic results indicate that this change in thermotropic phase behavior when incubated at low temperatures results from the conversion of the L(beta) phase to a highly ordered lamellar crystalline (L(c)) phase. Upon heating, the L(c) phase of dilauroyl phosphatidylserine converts directly to the L(alpha) phase at a temperature slightly higher than that of its original L(beta)/L(alpha) phase transition. Calorimetrically, this process is manifested by a less cooperative but considerably more energetic, higher-temperature phase transition, which replaces the weaker L(beta)/L(alpha) phase transition alluded to above. However, with the longer chain compounds, the L(c) phase first converts to the L(beta) phase at temperatures some 10-25 degrees C below that at which the L(beta) phase converts to the L(alpha) phase. Our results also suggest that shorter chain homologues form L(c) phases that are structurally related to, but more ordered than, those formed by the longer chain homologues, but that these L(c) phases are less ordered than those formed by other phospholipids. These studies also suggest that polar/apolar interfaces of the phosphatidylserine bilayers are more hydrated than those of other glycerolipid bilayers, possibly because of interactions between the polar headgroup and carbonyl groups of the fatty acyl chains. PMID:11023908

Influence of biopolymers on the solubility of branched-chain amino acids and stability of their solutions.

PubMed

Hong, Chi Rac; Lee, Gyu Whan; Paik, Hyun-Dong; Chang, Pahn-Shick; Choi, Seung Jun

2018-01-15

This study confirmed the possibility of biopolymer-type stabilizers to increase the saturation concentration of branched-chain amino acids by preventing their crystallization/precipitation. Although microfluidization increased the initial solubility, it failed to increase the saturation concentration of the branched-chain amino acids. The saturation concentration of the branched-chain amino acids increased from 3.81% to 4.42% and 4.85% after the incorporation of food hydrocolloids and proteins, respectively. However, the branched-chain amino acids:stabilizer ratio did not affect the solubility. In the case of food hydrocolloid-based solutions, crystal formation and growth of branched-chain amino acids occurred during storage, resulting in the precipitation of branched-chain amino acid crystals. However, food proteins effectively increased the stability of the solubilized branched-chain amino acids. The improved solubility and stability of the solubilized branched-chain amino acids could be attributed to interactions between the functional groups (carboxyl, amine, sulfate, aliphatic, aromatic, etc.) of the stabilizer and the branched-chain amino acid molecules. Copyright © 2017 Elsevier Ltd. All rights reserved.

Molecular Tracers of Saturated and Polycyclic Aromatic Hydrocarbon Inputs into Central Park Lake, New York City

PubMed Central

YAN, BEIZHAN; ABRAJANO, TEOFILO A.; BOPP, RICHARD F.; CHAKY, DAMON A.; BENEDICT, LUCILLE A.; CHILLRUD, STEVEN N.

2011-01-01

Saturated hydrocarbons (SH) and polycyclic aromatic hydrocarbons (PAHs) have been quantified in a sediment core obtained from Central Park Lake, New York City. Radionuclides 210Pb and 137Cs were used to assign approximate dates to each individual section in the core. The dating profile based on 210Pb matches very well with the time constraints provided by 137Cs. Radionuclide-derived depositional dates are consistent with temporal information from the petroleum-indicator ratio U/R [the ratio of unresolved complex mixture (UCM) to saturated hydrocarbons in the aliphatic fraction] and the history of fuel use in the NYC area. Ratios of 1,7-dimethylphenanthrane (DMP) to 1,7-DMP plus 2,6-DMP [1,7/(1,7 + 2,6)-DMP], retene to retene plus chrysene [Ret/(Ret + Chy)], and fluoranthene to fluoranthene plus pyrene [Fl/(Fl + Py)] provide additional source discrimination throughout the core. Results show that the ratio U/R is sensitive to petroleum inputs and Ret/(Ret + Chy) is responsive to contributions from softwood combustion, whereas both Fl/(Fl + Py) and 1,7/(1,7 + 2,6)-DMP can be used to discriminate among wood, coal, and petroleum combustion sources. Combined use of these ratios suggests that in New York City, wood combustion dominated 100 years ago, with a shift to coal combustion occurring from the 1900s to the 1950s. Petroleum use began around the 1920s and has dominated since the 1940s. PMID:16201624

Molecular tracers of saturated and polycyclic aromatic hydrocarbon inputs into Central Park Lake, New York City.

PubMed

Yan, Beizhan; Abrajano, Teofilo A; Bopp, Richard F; Chaky, Damon A; Benedict, Lucille A; Chillrud, Steven N

2005-09-15

Saturated hydrocarbons (SH) and polycyclic aromatic hydrocarbons (PAHs) have been quantified in a sediment core obtained from Central Park Lake, New York City. Radionuclides 210Pb and 137Cs were used to assign approximate dates to each individual section in the core. The dating profile based on 210Pb matches very well with the time constraints provided by 137Cs. Radionuclide-derived depositional dates are consistent with temporal information from the petroleum-indicator ratio U/R [the ratio of unresolved complex mixture (UCM)to saturated hydrocarbons in the aliphatic fraction] and the history of fuel use in the NYC area. Ratios of 1,7-dimethylphenanthrane (DMP) to 1,7-DMP plus 2,6-DMP [1,7/(1,7 + 2,6)-DMP], retene to retene plus chrysene [Ret/(Ret + Chy)], and fluoranthene to fluoranthene plus pyrene [FI/(FI + Py)] provide additional source discrimination throughoutthe core. Results show that the ratio U/R is sensitive to petroleum inputs and Ret/(Ret + Chy) is responsive to contributions from softwood combustion, whereas both FI/(FI + Py) and 1,7/ (1,7 + 2,6)-DMP can be used to discriminate among wood, coal, and petroleum combustion sources. Combined use of these ratios suggests that in New York City, wood combustion dominated 100 years ago, with a shift to coal combustion occurring from the 1900s to the 1950s. Petroleum use began around the 1920s and has dominated since the 1940s.

Columnar to Nematic Mesophase Transition: Binary Mixtures of Copper Soaps with Hydrocarbons

NASA Astrophysics Data System (ADS)

Seghrouchni, R.; Skoulios, A.

1995-09-01

Copper (II) soaps are known to produce columnar mesophases at high temperatures. The polar groups of the soap molecules are stacked over one another within columns surrounded by the paraffin chains in a disordered conformation and laterally arranged according to a two-dimensional hexagonal lattice. Upon addition of a hydrocarbon, the mesophases swell homogeneously. The hydrocarbon molecules locate themselves among the disordered chains of the soap molecules, the columnar cores remain perfectly unchanged, keeping a constant intra-columnar stacking period, and the hexagonal lattice expands in proportion to the amount of hydrocarbon added to the system. Beyond a certain degree of swelling, the columnar mesophases suddenly turn into a nematic mesophase through a first-order phase transition. The structural elements that align parallel to the nematic director are the very same molecular columns that are involved in the columnar mesophases. The columnar to nematic mesophase transition was studied systematically as a function of the molecular size of the soaps and hydrocarbons used as diluents and discussed on a molecular level, emphasizing such aspects as the persistence length of the paraffin chains and the location of the solvent molecules among the columns.

Source profiles for nonmethane organic compounds in the atmosphere of Cairo, Egypt.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doskey, P. V.; Fukui, Y.; Sultan, M.

1999-07-01

Profiles of the sources of nonmethane organic compounds (NMOCs) were developed for emissions from vehicles, petroleum fuels (gasoline, liquefied petroleum gas (LPG), and natural gas), a petroleum refinery, a smelter, and a cast iron factory in Cairo, Egypt. More than 100 hydrocarbons and oxygenated hydrocarbons were tentatively identified and quantified. Gasoline-vapor and whole-gasoline profiles could be distinguished from the other profiles by high concentrations of the C{sub 5} and C{sub 6} saturated hydrocarbons. The vehicle emission profile was similar to the whole-gasoline profile, with the exception of the unsaturated and aromatic hydrocarbons, which were present at higher concentrations in themore » vehicle emission profile. High levels of the C{sub 2}-C{sub 4} saturated hydrocarbons, particularly n-butane, were characteristic features of the petroleum refinery emissions. The smelter and cast iron factory emissions were similar to the refinery emissions; however, the levels of benzene and toluene were greater in the former two sources. The LPG and natural gas emissions contained high concentrations of n-butane and ethane, respectively. The NMOC source profiles for Cairo were distinctly different from profiles for U.S. sources, indicating that NMOC source profiles are sensitive to the particular composition of petroleum fuels that are used in a location.« less

Hydrocarbon Potential in Sandstone Reservoir Isolated inside Low Permeability Shale Rock (Case Study: Beruk Field, Central Sumatra Basin)

NASA Astrophysics Data System (ADS)

Diria, Shidqi A.; Musu, Junita T.; Hasan, Meutia F.; Permono, Widyo; Anwari, Jakson; Purba, Humbang; Rahmi, Shafa; Sadjati, Ory; Sopandi, Iyep; Ruzi, Fadli

2018-03-01

Upper Red Bed, Menggala Formation, Bangko Formation, Bekasap Formation and Duri Formationare considered as the major reservoirs in Central Sumatra Basin (CSB). However, Telisa Formation which is well-known as seal within CSB also has potential as reservoir rock. Field study discovered that lenses and layers which has low to high permeability sandstone enclosed inside low permeability shale of Telisa Formation. This matter is very distinctive and giving a new perspective and information related to the invention of hydrocarbon potential in reservoir sandstone that isolated inside low permeability shale. This study has been conducted by integrating seismic data, well logs, and petrophysical data throughly. Facies and static model are constructed to estimate hydrocarbon potential resource. Facies model shows that Telisa Formation was deposited in deltaic system while the potential reservoir was deposited in distributary mouth bar sandstone but would be discontinued bedding among shale mud-flat. Besides, well log data shows crossover between RHOB and NPHI, indicated that distributary mouth bar sandstone is potentially saturated by hydrocarbon. Target area has permeability ranging from 0.01-1000 mD, whereas porosity varies from 1-30% and water saturation varies from 30-70%. The hydrocarbon resource calculation approximates 36.723 MSTB.

Hydrocarbon geochemistry of cold seeps in the Monterey Bay National Marine Sanctuary

USGS Publications Warehouse

Lorenson, T.D.; Kvenvolden, K.A.; Hostettler, F.D.; Rosenbauer, R.J.; Orange, D.L.; Martin, J.B.

2002-01-01

Samples from four geographically and tectonically discrete cold seeps named Clam Flat, Clamfield, Horseshoe Scarp South, and Tubeworm City, within the Monterey Bay National Marine Sanctuary were analyzed for their hydrocarbon content. The sediment contains gaseous hydrocarbons and CO2, as well as high molecular weight aliphatic and aromatic hydrocarbons with various combinations of thermogenic and biogenic contributions from petroleum, marine, and terrigenous sources. Of particular interest is the cold seep site at Clamfield which is characterized by the presence of thermogenic hydrocarbons including oil that can likely be correlated with oil-saturated strata at Majors Creek near Davenport, CA, USA. At Clam Flat, the evidence for thermogenic hydrocarbons is equivocal. At Horseshoe Scarp South and Tubeworm City, hydrocarbon gases, mainly methane, are likely microbial in origin. These varied sources of hydrocarbon gases highlight the diverse chemical systems that appear at cold seep communities. ?? 2002 Elsevier Science B.V. All rights reserved.

A new approach for bio-jet fuel generation from palm oil and limonene in the absence of hydrogen.

PubMed

Zhang, Jingjing; Zhao, Chen

2015-12-18

The traditional methodology includes a carbon-chain shortening strategy to produce bio-jet fuel from lipids via a two-stage process with hydrogen. Here, we propose a new solution using a carbon-chain filling strategy to convert C10 terpene and lipids to jet fuel ranged hydrocarbons with aromatic hydrocarbon ingredients in the absence of hydrogen.

Structural analysis by reductive cleavage with LiAlH4 of an allyl ether choline-phospholipid, archaetidylcholine, from the hyperthermophilic methanoarchaeon Methanopyrus kandleri

PubMed Central

Nishihara, Masateru; Morii, Hiroyuki; Matsuno, Koji; Ohga, Mami; Stetter, Karl O.; Koga, Yosuke

2002-01-01

A choline-containing phospholipid (PL-4) in Methanopyrus kandleri cells was identified as archaetidylcholine, which has been described by Sprott et al. (1997). The PL-4 consisted of a variety of molecular species differing in hydrocarbon composition. Most of the PL-4 was acid-labile because of its allyl ether bond. The identity of PL-4 was confirmed by thin-layer chromatography (TLC) followed by positive staining with Dragendorff-reagent and fast-atom bombardment–mass spectrometry. A new method of LiAlH4 hydrogenolysis was developed to cleave allyl ether bonds and recover the corresponding hydrocarbons. We confirmed the validity of the LiAlH4 method in a study of the model compound synthetic unsaturated archaetidic acid (2,3-di-O-geranylgeranyl-sn-glycerol-1-phosphate). Saturated ether bonds were not cleaved by the LiAlH4 method. The hydrocarbons formed following LiAlH4 hydrogenolysis of PL-4 were identified by gas–liquid chromatography and mass spectrometry. Four kinds of hydrocarbons with one to four double bonds were detected: 47% of the hydrocarbons had four double bonds; 11% had three double bonds; 14% had two double bonds; 7% had one double bond; and 6% were saturated species. The molecular species composition of PL-4 was also estimated based on acid lability: 77% of the molecular species had two acid-labile hydrocarbons; 11% had one acid-labile and one acid-stable hydrocarbon; and 11% had two acid-stable hydrocarbons. To our knowledge, this is the first report of a specific chemical degradation method for the structural analysis of allyl ether phospholipid in archaea. PMID:15803650

Isolation and Characterization of Hydrocarbon-Degrading Yeast Strains from Petroleum Contaminated Industrial Wastewater

PubMed Central

Gargouri, Boutheina; Mhiri, Najla; Karray, Fatma; Aloui, Fathi; Sayadi, Sami

2015-01-01

Two yeast strains are enriched and isolated from industrial refinery wastewater. These strains were observed for their ability to utilize several classes of petroleum hydrocarbons substrates, such as n-alkanes and aromatic hydrocarbons as a sole carbon source. Phylogenetic analysis based on the D1/D2 variable domain and the ITS-region sequences indicated that strains HC1 and HC4 were members of the genera Candida and Trichosporon, respectively. The mechanism of hydrocarbon uptaking by yeast, Candida, and Trichosporon has been studied by means of the kinetic analysis of hydrocarbons-degrading yeasts growth and substrate assimilation. Biodegradation capacity and biomass quantity were daily measured during twelve days by gravimetric analysis and gas chromatography coupled with mass spectrometry techniques. Removal of n-alkanes indicated a strong ability of hydrocarbon biodegradation by the isolated yeast strains. These two strains grew on long-chain n-alkane, diesel oil, and crude oil but failed to grow on short-chain n-alkane and aromatic hydrocarbons. Growth measurement attributes of the isolates, using n-hexadecane, diesel oil, and crude oil as substrates, showed that strain HC1 had better degradation for hydrocarbon substrates than strain HC4. In conclusion, these yeast strains can be useful for the bioremediation process and decreasing petroleum pollution in wastewater contaminated with petroleum hydrocarbons. PMID:26339653

Isolation and Characterization of Hydrocarbon-Degrading Yeast Strains from Petroleum Contaminated Industrial Wastewater.

PubMed

Gargouri, Boutheina; Mhiri, Najla; Karray, Fatma; Aloui, Fathi; Sayadi, Sami

2015-01-01

Two yeast strains are enriched and isolated from industrial refinery wastewater. These strains were observed for their ability to utilize several classes of petroleum hydrocarbons substrates, such as n-alkanes and aromatic hydrocarbons as a sole carbon source. Phylogenetic analysis based on the D1/D2 variable domain and the ITS-region sequences indicated that strains HC1 and HC4 were members of the genera Candida and Trichosporon, respectively. The mechanism of hydrocarbon uptaking by yeast, Candida, and Trichosporon has been studied by means of the kinetic analysis of hydrocarbons-degrading yeasts growth and substrate assimilation. Biodegradation capacity and biomass quantity were daily measured during twelve days by gravimetric analysis and gas chromatography coupled with mass spectrometry techniques. Removal of n-alkanes indicated a strong ability of hydrocarbon biodegradation by the isolated yeast strains. These two strains grew on long-chain n-alkane, diesel oil, and crude oil but failed to grow on short-chain n-alkane and aromatic hydrocarbons. Growth measurement attributes of the isolates, using n-hexadecane, diesel oil, and crude oil as substrates, showed that strain HC1 had better degradation for hydrocarbon substrates than strain HC4. In conclusion, these yeast strains can be useful for the bioremediation process and decreasing petroleum pollution in wastewater contaminated with petroleum hydrocarbons.

Metastable ripple phase of fully hydrated dipalmitoylphosphatidylcholine as studied by small angle x-ray scattering

PubMed Central

Yao, Haruhiko; Matuoka, Sinzi; Tenchov, Boris; Hatta, Ichiro

1991-01-01

Fully hydrated dipalmitoylphosphatidylcholine (DPPC) undergoes liquid crystalline to metastable Pβ, phase transition in cooling. A small angle x-ray scattering study has been performed for obtaining further evidence about the structure of this phase. From a high-resolution observation of x-ray diffraction profiles, a distinct multipeak pattern has become obvious. Among them the (01) reflection in the secondary ripple structure is identified clearly. There are peaks assigned straightforwardly to (10) and (20) reflections in the primary ripple structure and peaks assigned to (10) and (20) reflections in the secondary ripple structure. Therefore the multipeak pattern is due to superposition of the reflections cause by the primary and secondary ripple structures. The lattice parameters are estimated as follows: for the primary ripple structure a = 7.09 nm, b = 13.64 nm, and γ = 95°, and for the secondary ripple structure a = 8.2 nm, b = 26.6 nm, and γ = 90°. The lattice parameters thus obtained for the secondary ripple structure are not conclusive, however. The hydrocarbon chains in the primary ripple structure have been reported as being tilted against the bilayer plane and, on the other hand, the hydrocarbon chains in the secondary ripple structure are likely to be perpendicular to the bilayer plane. This fact seems to be related to a sequential mechanism of phase transitions. On heating from the Lβ, phase where the hydrocarbon chains are tilted the primary ripple structure having tilted hydrocarbon chains takes place and on cooling from the Lα phase where the hydrocarbon chains are not tilted the secondary ripple structure with untilted chains tends to be stabilized. It appears that the truly metastable ripple phase is expressed by the second ripple structure although in the course of the actual cooling transition both the secondary and primary ripple structures form and coexist. PMID:19431787

Natural and synthetic oviposition stimulants forCatolaccus grandis (Burks) females.

PubMed

Guerra, A A; Martinez, S; Sonia Del Rio, H

1994-07-01

Oviposition behavior was elicited fromCatolaccus grandis (Burks) (Hymenoptera: Pteromalidae) females, an ectoparasitoid of the boll weevil,Anthonomus grandis Boheman (Coleoptera: Curculionidae), by smears of freshly cut cotton bolls or smears of extracts prepared with boll weevil damaged or undamaged cotton boll tissues. Oviposition behavior was also elicited fromC. grandis females by smears made withn-pentane,n-hexane,n-heptane, and isooctane. This is the first report of oviposition behavior elicited for any parasitoid by these short-chain saturated hydrocarbons (alkanes), introducing a new concept on the chemical mediation of parasitoid behavior during host selection. Oviposition behavior was also elicited fromC. grandis females by volatiles emanating from an artificial diet devoid of insect components that was specifically developed for the in vitro rearing of ectoparasitoids. The possible use of a synergistic combination ofn-hexane and diet to optimize the mechanized production of noncontaminated eggs is also discussed.

Effects of soil water saturation on sampling equilibrium and kinetics of selected polycyclic aromatic hydrocarbons.

PubMed

Kim, Pil-Gon; Roh, Ji-Yeon; Hong, Yongseok; Kwon, Jung-Hwan

2017-10-01

Passive sampling can be applied for measuring the freely dissolved concentration of hydrophobic organic chemicals (HOCs) in soil pore water. When using passive samplers under field conditions, however, there are factors that might affect passive sampling equilibrium and kinetics, such as soil water saturation. To determine the effects of soil water saturation on passive sampling, the equilibrium and kinetics of passive sampling were evaluated by observing changes in the distribution coefficient between sampler and soil (K sampler/soil ) and the uptake rate constant (k u ) at various soil water saturations. Polydimethylsiloxane (PDMS) passive samplers were deployed into artificial soils spiked with seven selected polycyclic aromatic hydrocarbons (PAHs). In dry soil (0% water saturation), both K sampler/soil and k u values were much lower than those in wet soils likely due to the contribution of adsorption of PAHs onto soil mineral surfaces and the conformational changes in soil organic matter. For high molecular weight PAHs (chrysene, benzo[a]pyrene, and dibenzo[a,h]anthracene), both K sampler/soil and k u values increased with increasing soil water saturation, whereas they decreased with increasing soil water saturation for low molecular weight PAHs (phenanthrene, anthracene, fluoranthene, and pyrene). Changes in the sorption capacity of soil organic matter with soil water content would be the main cause of the changes in passive sampling equilibrium. Henry's law constant could explain the different behaviors in uptake kinetics of the selected PAHs. The results of this study would be helpful when passive samplers are deployed under various soil water saturations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dual pore-connectivity and flow-paths affect shale hydrocarbon production

NASA Astrophysics Data System (ADS)

Hayman, N. W.; Daigle, H.; Kelly, E. D.; Milliken, K. L.; Jiang, H.

2016-12-01

Aided with integrated characterization approaches of droplet contact angle measurement, mercury intrusion capillary pressure, low-pressure gas physisorption, scanning electron microscopy, and small angle neutron scattering, we have systematically studied how pore connectivity and wettability are associated with mineral and organic matter phases of shales (Barnett, Bakken, Eagle Ford), as well as their influence on macroscopic fluid flow and hydrocarbon movement, from the following complementary tests: vacuum saturation with vacuum-pulling on dry shale followed with tracer introduction and high-pressure intrusion, tracer diffusion into fluid-saturated shale, fluid and tracer imbibition into partially-saturated shale, and Wood's metal intrusion followed with imaging and elemental mapping. The first three tests use tracer-bearing fluids (hydrophilic API brine and hydrophobic n-decane) fluids with a suite of wettability tracers of different sizes and reactivities developed in our laboratory. These innovative and integrated approaches indicate a Dalmatian wettability behavior at a scale of microns, limited connectivity (<500 microns from shale sample edge) shale pores, and disparity of well-connected hydrophobic pore network ( 10 nm) and sparsely connected hydrophilic pore systems (>50-100 nm), which is linked to the steep initial decline and low overall recovery because of the limited connection of hydrocarbon molecules in the shale matrix to the stimulated fracture network.

Dual pore-connectivity and flow-paths affect shale hydrocarbon production

NASA Astrophysics Data System (ADS)

Hu, Q.; Barber, T.; Zhang, Y.; Md Golam, K.

2017-12-01

Aided with integrated characterization approaches of droplet contact angle measurement, mercury intrusion capillary pressure, low-pressure gas physisorption, scanning electron microscopy, and small angle neutron scattering, we have systematically studied how pore connectivity and wettability are associated with mineral and organic matter phases of shales (Barnett, Bakken, Eagle Ford), as well as their influence on macroscopic fluid flow and hydrocarbon movement, from the following complementary tests: vacuum saturation with vacuum-pulling on dry shale followed with tracer introduction and high-pressure intrusion, tracer diffusion into fluid-saturated shale, fluid and tracer imbibition into partially-saturated shale, and Wood's metal intrusion followed with imaging and elemental mapping. The first three tests use tracer-bearing fluids (hydrophilic API brine and hydrophobic n-decane) fluids with a suite of wettability tracers of different sizes and reactivities developed in our laboratory. These innovative and integrated approaches indicate a Dalmatian wettability behavior at a scale of microns, limited connectivity (<500 microns from shale sample edge) shale pores, and disparity of well-connected hydrophobic pore network ( 10 nm) and sparsely connected hydrophilic pore systems (>50-100 nm), which is linked to the steep initial decline and low overall recovery because of the limited connection of hydrocarbon molecules in the shale matrix to the stimulated fracture network.

Temperature-induced changes in lecithin model membranes detected by novel covalent spin-labelled phospholipids.

PubMed

Stuhne-Sekalec, L; Stanacev, N Z

1977-02-01

Several spin-labelled phospholipids carrying covalently bound 5-doxylstearic acid (2-(3-carboxydecyl)-2-hexyl-4,4-dimethyl-3-oxazolidinoxyl) were intercalated in liposomes of saturated and unsaturated lecithins. Temperature-induced changes of these liposomes, detected by the spin-labelled phospholipids, were found to be in agreement with the previously described transitions of hydrocarbon chains of host lecithins detected by different probes and different techniques, establishing that spin-labelled phosopholipids are sensitive probes for the detection of temperature-induced changes in lecithin model membranes. In addition to the detection of already-known transitions in lecithin liposomes, the coexistence of two distinctly different enviroments was observed above the characteristic transition temperature. This phenomenon was tentatively attributed to the influence of the lecithin polar group on the fluidity of fatty acyl chains near the polar group. Combined with other results from the literature, the coexistence of two environments could be associated with the coexistence of two conformational isomers of lecithin, differing in the orientation of the polar head group with respect to the plane of bilayer. These findings have been discussed in view of the present state of knowledge regarding temperature-induced changes in model membranes.

Comparison of the nutrient content of children's menu items at US restaurant chains, 2010-2014.

PubMed

Deierlein, Andrea L; Peat, Kay; Claudio, Luz

2015-08-15

To determine changes in the nutritional content of children's menu items at U.S. restaurant chains between 2010 and 2014. The sample consisted of 13 sit down and 16 fast-food restaurant chains ranked within the top 50 US chains in 2009. Nutritional information was accessed in June-July 2010 and 2014. Descriptive statistics were calculated for nutrient content of main dishes and side dishes, as well as for those items that were added, removed, or unchanged during the study period. Nutrient content of main dishes did not change significantly between 2010 and 2014. Approximately one-third of main dishes at fast-food restaurant chains and half of main dishes at sit down restaurant chains exceeded the 2010 Dietary Guidelines for Americans recommended levels for sodium, fat, and saturated fat in 2014. Improvements in nutrient content were observed for side dishes. At sit down restaurant chains, added side dishes contained over 50% less calories, fat, saturated fat, and sodium, and were more likely to contain fruits/vegetables compared to removed sides (p < 0.05 for all comparisons). Added side dishes at fast-food restaurant chains contained less saturated fat (p < 0.05). The majority of menu items, especially main dishes, available to children still contain high amounts of calories, fat, saturated fat, and sodium. Efforts must be made by the restaurant industry and policy makers to improve the nutritional content of children's menu items at restaurant chains to align with the Dietary Guidelines for Americans. Additional efforts are necessary to help parents and children make informed choices when ordering at restaurant chains.

Effects of molecular size and structure on self-diffusion coefficient and viscosity for saturated hydrocarbons having six carbon atoms.

PubMed

Iwahashi, Makio; Kasahara, Yasutoshi

2007-01-01

Self-diffusion coefficients and viscosities for the saturated hydrocarbons having six carbon atoms such as hexane, 2-methylpentane (2MP), 3-methylpentane (3MP), 2,2-dimethylbutane (22DMB), 2,3-dimethylbutane (23DMB), methylcyclopentane (McP) and cyclohexane (cH) were measured at various constant temperatures; obtained results were discussed in connection with their molar volumes, molecular structures and thermodynamic properties. The values of self-diffusion coefficients as the microscopic property were inversely proportional to those of viscosities as the macroscopic property. The order of their viscosities was almost same to those of their melting temperatures and enthalpies of fusion, which reflect the attractive interactions among their molecules. On the other hand, the order of the self-diffusion coefficients inversely related to the order of the melting temperatures and the enthalpies of the fusion. Namely, the compound having the larger attractive interaction mostly shows the less mobility in its liquid state, e.g., cyclohexane (cH), having the largest attractive interaction and the smallest molar volume exhibits an extremely large viscosity and small self-diffusion coefficient comparing with other hydrocarbons. However, a significant exception was 22DMB, being most close to a sphere: In spite of the smallest attractive interaction and the largest molar volume of 22DMB in the all samples, it has the thirdly larger viscosity and the thirdly smaller self-diffusion coefficient. Consequently, the dynamical properties such as self-diffusion and viscosity for the saturated hydrocarbons are determined not only by their attractive interactions but also by their molecular structures.

Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures: constraints from mineral buffered laboratory experiments

NASA Astrophysics Data System (ADS)

Seewald, Jeffrey S.

2001-05-01

Organic matter, water, and minerals coexist at elevated temperatures and pressures in sedimentary basins and participate in a wide range of geochemical processes that includes the generation of oil and natural gas. A series of laboratory experiments were conducted at 300 to 350°C and 350 bars to examine chemical interactions involving low molecular weight aqueous hydrocarbons with water and Fe-bearing minerals under hydrothermal conditions. Mineral buffers composed of hematite-magnetite-pyrite, hematite-magnetite, and pyrite-pyrrhotite-magnetite were added to each experiment to fix the redox state of the fluid and the activity of reduced sulfur species. During each experiment the chemical system was externally modified by addition of ethene, ethane, propene, 1-butene, or n-heptane, and variations in the abundance of aqueous organic species were monitored as a function of time and temperature. Results of the experiments indicate that decomposition of aqueous n-alkanes proceeds through a series of oxidation and hydration reactions that sequentially produce alkenes, alcohols, ketones, and organic acids as reaction intermediaries. Organic acids subsequently undergo decarboxylation and/or oxidation reactions to form carbon dioxide and shorter chain saturated hydrocarbons. This alteration assemblage is compositionally distinct from that produced by thermal cracking under anhydrous conditions, indicating that the presence of water and minerals provide alternative reaction pathways for the decomposition of hydrocarbons. The rate of hydrocarbon oxidation decreases substantially under reducing conditions and in the absence of catalytically active aqueous sulfur species. These results represent compelling evidence that the stability of aqueous hydrocarbons at elevated temperatures in natural environments is not a simple function of time and temperature alone. Under the appropriate geochemical conditions, stepwise oxidation represents a mechanism for the decomposition of low molecular weight hydrocarbons and the production of methane-rich ("dry") natural gas. Evaluation of aqueous reaction products generated during the experiments within a thermodynamic framework indicates that alkane-alkene, alkene-ketone, and alkene-alcohol reactions attained metastable thermodynamic equilibrium states. This equilibrium included water and iron-bearing minerals, demonstrating the direct involvement of inorganic species as reactants during organic transformations. The high reactivity of water and iron-bearing minerals suggests that they represent abundant sources of hydrogen and oxygen available for the formation of hydrocarbons and oxygenated alteration products. Thus, variations in elemental kerogen composition may not accurately reflect the timing and extent of hydrocarbon, carbon dioxide, and organic acid generation in sedimentary basins. This study demonstrates that the stabilities of aqueous hydrocarbons are strongly influenced by inorganic sediment composition at elevated temperatures. Incorporation of such interactions into geochemical models will greatly improve prediction of the occurrence of hydrocarbons in natural environments over geologic time.

Single well surfactant test to evaluate surfactant floods using multi tracer method

DOEpatents

Sheely, Clyde Q.

1979-01-01

Data useful for evaluating the effectiveness of or designing an enhanced recovery process said process involving mobilizing and moving hydrocarbons through a hydrocarbon bearing subterranean formation from an injection well to a production well by injecting a mobilizing fluid into the injection well, comprising (a) determining hydrocarbon saturation in a volume in the formation near a well bore penetrating formation, (b) injecting sufficient mobilizing fluid to mobilize and move hydrocarbons from a volume in the formation near the well bore, and (c) determining the hydrocarbon saturation in a volume including at least a part of the volume of (b) by an improved single well surfactant method comprising injecting 2 or more slugs of water containing the primary tracer separated by water slugs containing no primary tracer. Alternatively, the plurality of ester tracers can be injected in a single slug said tracers penetrating varying distances into the formation wherein the esters have different partition coefficients and essentially equal reaction times. The single well tracer method employed is disclosed in U.S. Pat. No. 3,623,842. This method designated the single well surfactant test (SWST) is useful for evaluating the effect of surfactant floods, polymer floods, carbon dioxide floods, micellar floods, caustic floods and the like in subterranean formations in much less time and at much reduced cost compared to conventional multiwell pilot tests.

Critical temperatures and a critical chain length in saturated diacylphosphatidylcholines: calorimetric, ultrasonic and Monte Carlo simulation study of chain-melting/ordering in aqueous lipid dispersions.

PubMed

Kharakoz, Dmitry P; Panchelyuga, Maria S; Tiktopulo, Elizaveta I; Shlyapnikova, Elena A

2007-12-01

Chain-ordering/melting transition in a series of saturated diacylphosphatidylcholines (PCs) in aqueous dispersions have been studied experimentally (calorimetric and ultrasonic techniques) and theoretically (an Ising-like lattice model). The shape of the calorimetric curves was compared with the theoretical data and interpreted in terms of the lateral interactions and critical temperatures determined for each lipid studied. A critical chain length has been found (between 16 and 17 C-atoms per chain) which subdivides PCs into two classes with different phase behavior. In shorter lipids, the transition takes place above their critical temperatures meaning that this is an intrinsically continuous transition. In longer lipids, the transition occurs below the critical temperatures of the lipids, meaning that the transition is intrinsically discontinuous (first-order). This conclusion was supported independently by the ultrasonic relaxation sensitive to density fluctuations. Interestingly, it is this length that is the most abundant among the saturated chains in biological membranes.

Improved synthesis and characterization of saturated branched-chain fatty acid isomers

USDA-ARS?s Scientific Manuscript database

The development of viable technologies for producing green products from renewable fats and oils is highly desirable since such materials can serve as replacements for non-renewable and poorly biodegradable petroleum-based products. Mixtures of saturated branched-chain fatty acid isomers (sbc-FAs),...

Systems and methods for preparation and separation of products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gilliam, Ryan J.; Boggs, Bryan; Self, Kyle

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with hydrogen gas, an unsaturated hydrocarbon, and/or a saturated hydrocarbon to form products.

Used Oil and Its Regulation in the United States

DTIC Science & Technology

1988-09-30

product containing significant quantities of alkyl, naphthenic , and aromatic hydrocarbons. The oil may also contain additives to improve its...delivered to the re-refiners each year is disposed of primarily in the process residues including spent clay, acid sludge, and wastewater.13 8 13 7 Frank...hydrocarbon structure into three main groups: parafinic, naphthenic , and aromatic. Paraffinic (alkanic) crude oils contain mostly saturated straight and

Systems and methods for preparation and separation of products

DOEpatents

Gilliam, Ryan J.; Boggs, Bryan; Self, Kyle; Leclerc, Margarete K.; Gorer, Alexander; Weiss, Michael J.; Miller, John H.; Mohanta, Samaresh

2015-12-01

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with hydrogen gas, an unsaturated hydrocarbon, and/or a saturated hydrocarbon to form products.

Cuticular hydrocarbons as a tool for the identification of insect species: Puparial cases from Sarcophagidae

PubMed Central

Braga, Marina Vianna; Pinto, Zeneida Teixeira; de Carvalho Queiroz, Margareth Maria; Matsumoto, Nana; Blomquist, Gary James

2013-01-01

The external surface of all insects is covered by a species-specific complex mixture of highly stable, very long chain cuticular hydrocarbons (CHCs). Gas chromatography coupled to mass spectrometry was used to identify CHCs from four species of Sarcophagidae, Peckia (Peckia) chrysostoma, Peckia (Pattonella) intermutans, Sarcophaga (Liopygia) ruficornis and Sarcodexia lambens. The identified CHCs were mostly a mixture of n-alkanes, monomethylalkanes and dimethylalkanes with linear chain lengths varying from 23 to 33 carbons. Only two alkenes were found in all four species. S. lambens had a composition of CHCs with linear chain lengths varying from C23 to C33, while the other three species linear chain lengths from 24 to 31 carbons. n-Heptacosane, n-nonacosane and 3-methylnonacosane, n-triacontane and n-hentriacontane occurred in all four species. The results show that these hydrocarbon profiles may be used for the taxonomic differentiation of insect species and are a useful additional tool for taxonomic classification, especially when only parts of the insect specimen are available. PMID:23932943

Production of High Density Aviation Fuels via Novel Zeolite Catalyst Routes

DTIC Science & Technology

1989-10-23

range fraction of a naphthenic crude; saturation of an aromatic FCC cycle stock I the appropriate boiling range: saturation of an appropriate boiling...aromatic hydrocarbons and selected aromatic feedstocks to the corresponding mono- and dicyclic naphthenes in the aviation turbine fuel boiling range; and...Paraffins from Naphthenic Refinery Feed Streams .......... 8 Solvent Extraction ........................................... 8 Shape Selective Catalytic

Conversion of 2,3-butanediol to 2-butanol, olefins and fuels

DOEpatents

Lilga, Michael A.; Lee, Guo-Shuh; Lee, Suh-Jane

2016-12-13

Embodiments of an integrated method for step-wise conversion of 2,3-butanediol to 2-butanol, and optionally to hydrocarbons, are disclosed. The method includes providing an acidic catalyst, exposing a composition comprising aqueous 2,3-butanediol to the acidic catalyst to produce an intermediate composition comprising methyl ethyl ketone, providing a hydrogenation catalyst that is spatially separated from the acidic catalyst, and subsequently exposing the intermediate composition to the hydrogenation catalyst to produce a composition comprising 2-butanol. The method may further include subsequently exposing the composition comprising 2-butanol to a deoxygenation catalyst, and deoxygenating the 2-butanol to form hydrocarbons. In some embodiments, the hydrocarbons comprise olefins, such as butenes, and the method may further include subsequently exposing the hydrocarbons to a hydrogenation catalyst to form saturated hydrocarbons.

Structural Determinants of the Transient Receptor Potential 1 (TRPV1) Channel Activation by Phospholipid Analogs*

PubMed Central

Morales-Lázaro, Sara L.; Serrano-Flores, Barbara; Llorente, Itzel; Hernández-García, Enrique; González-Ramírez, Ricardo; Banerjee, Souvik; Miller, Duane; Gududuru, Veeresh; Fells, James; Norman, Derek; Tigyi, Gabor; Escalante-Alcalde, Diana; Rosenbaum, Tamara

2014-01-01

The transient receptor potential vanilloid 1 (TRPV1) ion channel is a polymodal protein that responds to various stimuli, including capsaicin (the pungent compound found in chili peppers), extracellular acid, and basic intracellular pH, temperatures close to 42 °C, and several lipids. Lysophosphatidic acid (LPA), an endogenous lipid widely associated with neuropathic pain, is an agonist of the TRPV1 channel found in primary afferent nociceptors and is activated by other noxious stimuli. Agonists or antagonists of lipid and other chemical natures are known to possess specific structural requirements for producing functional effects on their targets. To better understand how LPA and other lipid analogs might interact and affect the function of TRPV1, we set out to determine the structural features of these lipids that result in the activation of TRPV1. By changing the acyl chain length, saturation, and headgroup of these LPA analogs, we established strict requirements for activation of TRPV1. Among the natural LPA analogs, we found that only LPA 18:1, alkylglycerophosphate 18:1, and cyclic phosphatidic acid 18:1, all with a monounsaturated C18 hydrocarbon chain activate TRPV1, whereas polyunsaturated and saturated analogs do not. Thus, TRPV1 shows a more restricted ligand specificity compared with LPA G-protein-coupled receptors. We synthesized fatty alcohol phosphates and thiophosphates and found that many of them with a single double bond in position Δ9, 10, or 11 and Δ9 cyclopropyl group can activate TRPV1 with efficacy similar to capsaicin. Finally, we developed a pharmacophore and proposed a mechanistic model for how these lipids could induce a conformational change that activates TRPV1. PMID:25035428

Structural determinants of the transient receptor potential 1 (TRPV1) channel activation by phospholipid analogs.

PubMed

Morales-Lázaro, Sara L; Serrano-Flores, Barbara; Llorente, Itzel; Hernández-García, Enrique; González-Ramírez, Ricardo; Banerjee, Souvik; Miller, Duane; Gududuru, Veeresh; Fells, James; Norman, Derek; Tigyi, Gabor; Escalante-Alcalde, Diana; Rosenbaum, Tamara

2014-08-29

The transient receptor potential vanilloid 1 (TRPV1) ion channel is a polymodal protein that responds to various stimuli, including capsaicin (the pungent compound found in chili peppers), extracellular acid, and basic intracellular pH, temperatures close to 42 °C, and several lipids. Lysophosphatidic acid (LPA), an endogenous lipid widely associated with neuropathic pain, is an agonist of the TRPV1 channel found in primary afferent nociceptors and is activated by other noxious stimuli. Agonists or antagonists of lipid and other chemical natures are known to possess specific structural requirements for producing functional effects on their targets. To better understand how LPA and other lipid analogs might interact and affect the function of TRPV1, we set out to determine the structural features of these lipids that result in the activation of TRPV1. By changing the acyl chain length, saturation, and headgroup of these LPA analogs, we established strict requirements for activation of TRPV1. Among the natural LPA analogs, we found that only LPA 18:1, alkylglycerophosphate 18:1, and cyclic phosphatidic acid 18:1, all with a monounsaturated C18 hydrocarbon chain activate TRPV1, whereas polyunsaturated and saturated analogs do not. Thus, TRPV1 shows a more restricted ligand specificity compared with LPA G-protein-coupled receptors. We synthesized fatty alcohol phosphates and thiophosphates and found that many of them with a single double bond in position Δ9, 10, or 11 and Δ9 cyclopropyl group can activate TRPV1 with efficacy similar to capsaicin. Finally, we developed a pharmacophore and proposed a mechanistic model for how these lipids could induce a conformational change that activates TRPV1. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-04-07

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: and for olefinic hydrocarbons: where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Formation evaluation of gas hydrate-bearing marine sediments on the Blake Ridge with downhole geochemical log measurements

USGS Publications Warehouse

Collett, T.S.; Wendlandt, R.F.

2000-01-01

The analyses of downhole log data from Ocean Drilling Program (ODP) boreholes on the Blake Ridge at Sites 994, 995, and 997 indicate that the Schlumberger geochemical logging tool (GLT) may yield useful gas hydrate reservoir data. In neutron spectroscopy downhole logging, each element has a characteristic gamma ray that is emitted from a given neutron-element interaction. Specific elements can be identified by their characteristic gamma-ray signature, with the intensity of emission related to the atomic elemental concentration. By combining elemental yields from neutron spectroscopy logs, reservoir parameters including porosities, lithologies, formation fluid salinities, and hydrocarbon saturations (including gas hydrate) can be calculated. Carbon and oxygen elemental data from the GLT was used to determine gas hydrate saturations at all three sites (Sites 994, 995, and 997) drilled on the Blake Ridge during Leg 164. Detailed analyses of the carbon and oxygen content of various sediments and formation fluids were used to construct specialized carbon/oxygen ratio (COR) fan charts for a series of hypothetical gas hydrate accumulations. For more complex geologic systems, a modified version of the standard three-component COR hydrocarbon saturation equation was developed and used to calculate gas hydrate saturations on the Blake Ridge. The COR-calculated gas hydrate saturations (ranging from about 2% to 14% bulk volume gas hydrate) from the Blake Ridge compare favorably to the gas hydrate saturations derived from electrical resistivity log measurements.

Molecular marker and stable carbon isotope analyses of carbonaceous Ambassador uranium ores of Mulga Rock in Western Australia

NASA Astrophysics Data System (ADS)

Jaraula, C.; Schwark, L.; Moreau, X.; Grice, K.; Bagas, L.

2013-12-01

Mulga Rock is a multi-element deposit containing uranium hosted by Eocene peats and lignites deposited in inset valleys incised into Permian rocks of the Gunbarrel Basin and Precambrian rocks of the Yilgarn Craton and Albany-Fraser Orogen. Uranium readily adsorbs onto minerals or phytoclasts to form organo-uranyl complexes. This is important in pre-concentrating uranium in this relatively young ore deposit with rare uraninite [UO2] and coffinite [U(SiO4)1-x(OH)4x], more commonly amorphous and sub-micron uranium-bearing particulates. Organic geochemical and compound-specific stable carbon isotope analyses were conducted to identify possible associations of molecular markers with uranium accumulation and to recognize effect(s) of ionizing radiation on molecular markers. Samples were collected from the Ambassador deposit containing low (<200 ppm) to high (>2000 ppm) uranium concentrations. The bulk rock C/N ratios of 82 to 153, Rock-Eval pyrolysis yields of 316 to 577 mg hydrocarbon/g TOC (Hydrogen Index, HI) and 70 to 102 mg CO2/g TOC (Oxygen Index, OI) are consistent with a terrigenous and predominantly vascular plant OM source deposited in a complex shallow water system, ranging from lacustrine to deltaic, swampy wetland and even shallow lake settings as proposed by previous workers. Organic solvent extracts were separated into saturated hydrocarbon, aromatic hydrocarbon, ketone, and a combined free fatty acid and alcohol fraction. The molecular profiles appear to vary with uranium concentration. In samples with relatively low uranium concentrations, long-chain n-alkanes, alcohols and fatty acids derived from epicuticular plant waxes dominate. The n-alkane distributions (C27 to C31) reveal an odd/even preference (Carbon Preference Index, CPI=1.5) indicative of extant lipids. Average δ13C of -27 to -29 ‰ for long-chain n-alkanes is consistent with a predominant C3 plant source. Samples with relatively higher uranium concentrations contain mostly intermediate-length n-alkanes, ketones, alcohols, and fatty acids (C20 to C24) with no preferential distribution (CPI~1). Intermediate length n-alkanes have modest carbon isotope enrichment compared to long-chain n-alkanes. These shorter-chain hydrocarbons are interpreted to represent alteration products. The diversity and relative abundance of ketones in highly mineralised Mulga Rock peats and lignites are not consistent with aerobic and diagenetic degradation of terrigenous OM in oxic environments. Moreover, molecular changes cannot be associated with thermal breakdown due to the low maturity of the deposits. It is possible that the association of high uranium concentrations and potential radiolysis resulted in the oxidation of alcohol functional groups into aldehydes and ketones and breakdown of highly aliphatic macromolecules (i.e. spores, pollen, cuticles, and algal cysts). These phytoclasts are usually considered to be recalcitrant as they evolved to withstand chemical and physical degradation. Previous petrographic analyses show that spores, pollen and wood fragments are preferentially enriched in uranium. Their molecular compositions are feasible sources of short- to intermediate-length n-alkanes that dominate the mineralised peats and lignites.

Surface science studies of ethene containing model interstellar ices

NASA Astrophysics Data System (ADS)

Puletti, F.; Whelan, M.; Brown, W. A.

2011-05-01

The formation of saturated hydrocarbons in the interstellar medium (ISM) is difficult to explain only by taking into account gas phase reactions. This is mostly due to the fact that carbonium ions only react with H_2 to make unsaturated hydrocarbons, and hence no viable route to saturated hydrocarbons has been postulated to date. It is therefore likely that saturation processes occur via surface reactions that take place on interstellar dust grains. One of the species of interest in this family of reactions is C_2H_4 (ethene) which is an intermediate in several molecular formation routes (e.g. C_2H_2 → C_2H_6). To help to understand some of the surface processes involving ethene, a study of ethene deposited on a dust grain analogue surface (highly oriented pyrolytic graphite) held under ultra-high vacuum at 20 K has been performed. The adsorption and desorption of ethene has been studied both in water-free and water-dominated model interstellar ices. A combination of temperature programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) have been used to identify the adsorbed and trapped species and to determine the kinetics of the desorption processes. In all cases, ethene is found to physisorb on the carbonaceous surface. As expected water has a very strong influence on the desorption of ethene, as previously observed for other model interstellar ice systems.

Stigmastane and hopanes as conserved biomarkers for estimating oil biodegradation in a former refinery plant-contaminated soil.

PubMed

Gagni, Simona; Cam, Darinn

2007-05-01

In the last decade, a refinery plant located in Lido Adriano, East Ravenna (Italy) has been subject to mineral oil contamination. The mineral crude oil, extracted from the offshore in Adriatic sea, consisted of 78% aliphatics, cyclic alkanes and saturated polycyclic hydrocarbons, 9% aromatics, polycyclic aromatic hydrocarbons (PAHs) and alkylated derivatives, and 13% of tars/asphaltenes. Analysis of soil after 10 years of natural attenuation revealed a complete depletion of linear (n-C(9)-C(24)), light aromatics (C1-C3/benzenes) and PAHs (C2/naphthalene, C1/phenanthrene); besides a substantial degradation of isoprenoids prystane and phytane, branched and cyclic alkanes. The remaining contaminants which withstood to natural degradation was saturated polycyclic hydrocarbons (perhydro-PAH derivatives), unsaturated polycyclic hydrocarbons (tetrahydro, dihydro-PAH derivatives), terpanes, steranes and unidentified compounds. Such residues resulted in 80% reduction of its concentration after two months of laboratory treatment. Samples were extracted by organic solvents, separated by silica/alumina gel column chromatography and analyzed by gas chromatography-mass selective detector (GC-MSD). Identification and quantification of aliphatic, cyclic alkanes, typical PAHs, terpanes and steranes were carried out to chromatograms of M/Z=85, 83, individual M/Zs, M/Z=191 and 217, respectively. The present work shows that, among numerous biomarkers present in the source oil, stigmastane and two isomers of hopane showed invariable concentrations after laboratory experiments that mimic natural biodegradation in the field, so they can be used as conserved internal biomarkers. These are very useful tools to assess alterations in less stable classes of saturated compounds contained in petroleum. Marked degradation of perhydro, tetrahydro, dihydro-PAH derivatives in the laboratory treatment has been evidenced.

Alpha-helix to beta-sheet transition in long-chain poly-l-lysine: Formation of alpha-helical fibrils by poly-l-lysine.

PubMed

Cieślik-Boczula, Katarzyna

2017-06-01

The temperature-induced α-helix to β-sheet transition in long-chain poly-l-lysine (PLL), accompanied by the gauche-to-trans isomerization of CH 2 groups in the hydrocarbon side chains of Lys amino acid residues, and formation of β-sheet as well as α-helix fibrillar aggregates of PLL have been studied using Fourier-transform infrared (FT-IR) and vibrational circular dichroism (VCD) spectroscopy, and transmission electron microscopy (TEM). In a low-temperature alkaline water solution or in a methanol-rich water mixture, the secondary structure of PLL is represented by α-helical conformations with unordered and gauche-rich hydrocarbon side chains. Under these conditions, PLL molecules aggregate into α-helical fibrils. PLLs dominated by extended antiparallel β-sheet structures with highly ordered trans-rich hydrocarbon side chains are formed in a high-temperature range at alkaline pD and aggregate into fibrillar, protofibrillar, and spherical forms. Presented data support the idea that fibrillar aggregation is a varied phenomenon possible in repetitive structural elements with not only a β-sheet-rich conformation, but also an α-helical-rich conformation. Copyright © 2017 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

Curable liquid hydrocarbon prepolymers containing hydroxyl groups and process for producing same

NASA Technical Reports Server (NTRS)

Rhein, R. A.; Ingham, J. D. (Inventor)

1978-01-01

Production of hydroxyl containing curable liquid hydrocarbon prepolymers by ozonizing a high molecular weight saturated hydrocarbon polymer such as polyisobutylene or ethylene propylene rubber is discussed. The ozonized material is reduced using reducing agents, preferably diisobutyl aluminum hydride, to form the hydroxyl containing liquid prepolymers having a substantially lower molecular weight than the parent polymer. The resulting curable liquid hydroxyl containing prepolymers can be poured into a mold and readily cured, with reactants such as toluene diisocyanate, to produce highly stable elastomers having a variety of uses such as binders for solid propellants.

[Component and content changes of volatiles from Chinese cabbage damaged by Plutella xylostella].

PubMed

Yang, Guang; You, Minsheng; Wei, Hui

2004-11-01

The study showed that Chinese cabbage, Brassica campestris could release a variety of volatiles, especially when infested by Plutella xylostella larvae. Among these volatiles, saturated hydrocarbon was dominant, aromatic hydrocarbon was the second, and unsaturated hydrocarbon, aldehyde, alcohol, ketone, acid and heteroaromatic compounds were existed with a small amount. Chinese cabbage damaged by Plutella xylostella larvae produced 3 times of volatiles in amount with more species than the control. The volatiles from control plants were mostly of small molecular weight, and those from Chinese cabbage damaged by Plutella xylostella were mostly of high molecular weight.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rostron, B.; Toth, J.

Lenticular reservoirs are accompanied by diagnostic pore-pressure anomalies when situated in a field of formation-fluid flow. Computer simulations have shown that these anomalies depend on the size and shape of the lens, the direction and intensity of flow, and the hydraulic conductivity contrast between the lens and the surrounding rock. Furthermore, the anomalies reflect the position of the petroleum-saturated portion of a lens since hydraulic conductivity is related to hydrocarbon content. Studies to date have shown that for an oil-free lens a pair of oppositely directed, symmetrical pressure anomalies exists. Pore-pressure distributions from drill-stem tests in mature, well-explored regions canmore » be compared to computer-simulated pore-pressure anomaly patterns. Results can be interpreted in terms of the lens geometry and degree of hydrocarbon saturation.« less

Activation of lecithin: cholesterol acyltransferase by human apolipoprotein A-IV.

PubMed

Steinmetz, A; Utermann, G

1985-02-25

Human plasma apoproteins (apo) A-I and A-IV both activate the enzyme lecithin:cholesterol acyltransferase (EC 2.3.1.43). Lecithin:cholesterol acyltransferase activity was measured by the conversion of [4-14C] cholesterol to [4-14C]cholesteryl ester using artificial phospholipid/cholesterol/[4-14C]cholesterol/apoprotein substrates. The substrate was prepared by the addition of apoprotein to a sonicated aqueous dispersion of phospholipid/cholesterol/[4-14C]cholesterol. The activation of lecithin:cholesterol acyltransferase by apo-A-I and -A-IV differed, depending upon the nature of the hydrocarbon chains of the sn-L-alpha-phosphatidylcholine acyl donor. Apo-A-I was a more potent activator than apo-A-IV with egg yolk lecithin, L-alpha-dioleoylphosphatidylcholine, and L-alpha-phosphatidylcholine substituted with one saturated and one unsaturated fatty acid regardless of the substitution position. When L-alpha-phosphatidylcholine esterified with two saturated fatty acids was used as acyl donor, apo-A-IV was more active than apo-A-I in stimulating the lecithin:cholesterol acyltransferase reaction. Complexes of phosphatidylcholines substituted with two saturated fatty acids served as substrate for lecithin:cholesterol acyltransferase even in the absence of any activator protein. Essentially the same results were obtained when substrate complexes (phospholipid-cholesterol-[4-14C]cholesterol-apoprotein) were prepared by a detergent dialysis procedure. Apo-A-IV-L-alpha-dimyristoylphosphatidylcholine complexes thus prepared were shown to be homogeneous particles by column chromatography and density gradient ultracentrifugation. It is concluded that apo-A-IV is able to facilitate the lecithin:cholesterol acyltransferase reaction in vitro.

Update of on-line coupled liquid chromatography - gas chromatography for the analysis of mineral oil hydrocarbons in foods and cosmetics.

PubMed

Biedermann, Maurus; Munoz, Celine; Grob, Koni

2017-10-27

On-line coupled high performance liquid chromatography-gas chromatography-flame ionization detection (HPLC-GC-FID) is the most widely used method for the analysis of mineral oil hydrocarbons in food, food contact materials, tissues and cosmetics. With comprehensive two-dimensional gas chromatography (GCxGC), a tool became available for better establishing the elution sequence of the various types of hydrocarbons from the HPLC column used for isolating the mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). The performance of a heavily used HPLC column with reduced retention for MOAH was investigated to improve the robustness of the method. Updates are recommended that render the MOSH/MOAH separation less dependent of the state of the HPLC column and more correct in cases of highly refined mineral oil products of high molecular mass. Cyclohexyl cyclohexane (Cycy), used as internal standard, turned out to be eluted slightly after cholestane (Cho); apparently the size exclusion effect predominates the extra retention by ring number on the 60Å pore size silica gel. Hence, Cycy can be used to determine the end of the MOSH fraction. Long chain alkyl benzenes were eluted earlier than tri-tert. butyl benzene (Tbb). It is proposed to start the MOAH transfer immediately after the MOSH fraction and use a gradient causing breakthrough of dichloromethane (visible in the UV chromatogram) at a time suitable to elute perylene (Per) at the end of the fraction. In this way, a decrease in retention power of the HPLC column can be tolerated without adjustment of the MOAH fraction until some MOAH start being eluted into the MOSH fraction. This critical point can be checked either with di(2-ethylhexyl) benzene (DEHB) as a marker or the HPLC-UV chromatogram. Finally, based on new findings in rats and human tissues, it is recommended to integrate the MOSH and MOAH up to the retention time of the n-alkane C40. Copyright © 2017 Elsevier B.V. All rights reserved.

The influence of hydrocarbons in changing the mechanical and acoustic properties of a carbonate reservoir: implications of laboratory results on larger scale processes

NASA Astrophysics Data System (ADS)

Trippetta, Fabio; Ruggieri, Roberta; Geremia, Davide; Brandano, Marco

2017-04-01

Understanding hydraulic and mechanical processes that acted in reservoir rocks and their effect on the rock properties is of a great interest for both scientific and industry fields. In this work we investigate the role of hydrocarbons in changing the petrophysical properties of rock by merging laboratory, outcrops, and subsurface data focusing on the carbonate-bearing Majella reservoir (Bolognano formation). This reservoir represents an interesting analogue for subsurface carbonate reservoirs and is made of high porosity (8 to 28%) ramp calcarenites saturated by hydrocarbon in the state of bitumen at the surface. Within this lithology clean and bitumen bearing samples were investigated. For both groups, density, porosity, P and S wave velocity, at increasing confining pressure and deformation tests were conducted on cylindrical specimens with BRAVA apparatus at the HP-HT Laboratory of the Istituto Nazionale di Geofisica e Vulcanologia (INGV) in Rome, Italy. The performed petrophysical characterization, shows a very good correlation between Vp, Vs and porosity and a pressure independent Vp/Vs ratio while the presence of bitumen within samples increases both Vp and Vs. P-wave velocity hysteresis measured at ambient pressure after 100 MPa of applied confining pressure, suggests an almost pure elastic behaviour for bitumen-bearing samples and a more inelastic behaviour for cleaner samples. Calculated dynamic Young's modulus is larger for bitumen-bearing samples and these data are confirmed by cyclic deformation tests where the same samples generally record larger strength, larger Young's modulus and smaller permanent strain respect to clean samples. Starting from laboratory data, we also derived a synthetic acoustic model highlighting an increase in acoustic impedance for bitumen-bearing samples. Models have been also performed simulating a saturation with decreasing API° hydrocarbons, showing opposite effects on the seismic properties of the reservoir respect to bitumen. In order to compare our laboratory results at larger scale we selected 11 outcrops of the same lithofacies of laboratory samples both clean and bitumen-saturated. Fractures orientations, from the scan-line method, are similar for the two types of outcrops and they follow the same trends of literature data collected on older rocks. On the other hand, spacing data show very lower fracture density for bitumen-saturated outcrops confirming laboratory observations. In conclusion, laboratory experiments highlight a more elastic behaviour for bitumen-bearing samples and saturated outcrops are less prone to fracture respect to clean outcrops. Presence of bitumen has, thus, a positive influence on mechanical properties of the reservoir while acoustic model suggests that lighter oils should have an opposite effect. Geologically, this suggests that hydrocarbons migration in the study area predates the last stage of deformation giving also clues about a relatively high density of the oil when deformation began.

The origin of high hydrocarbon groundwater in shallow Triassic aquifer in Northwest Guizhou, China.

PubMed

Liu, Shan; Qi, Shihua; Luo, Zhaohui; Liu, Fangzhi; Ding, Yang; Huang, Huanfang; Chen, Zhihua; Cheng, Shenggao

2018-02-01

Original high hydrocarbon groundwater represents a kind of groundwater in which hydrocarbon concentration exceeds 0.05 mg/L. The original high hydrocarbon will significantly reduce the environment capacity of hydrocarbon and lead environmental problems. For the past 5 years, we have carried out for a long-term monitoring of groundwater in shallow Triassic aquifer in Northwest Guizhou, China. We found the concentration of petroleum hydrocarbon was always above 0.05 mg/L. The low-level anthropogenic contamination cannot produce high hydrocarbon groundwater in the area. By using hydrocarbon potential, geochemistry and biomarker characteristic in rocks and shallow groundwater, we carried out a comprehensive study in Dalongjing (DLJ) groundwater system to determine the hydrocarbon source. We found a simplex hydrogeology setting, high-level water-rock-hydrocarbon interaction and obviously original hydrocarbon groundwater in DLJ system. The concentration of petroleum hydrocarbon in shallow aquifer was found to increase with the strong water-rock interaction. Higher hydrocarbon potential was found in the upper of Guanling formation (T 2 g 3 ) and upper of Yongningzhen formation (T 1 yn 4 ). Heavily saturated carbon was observed from shallow groundwater, which presented similar distribution to those from rocks, especially from the deeper groundwater. These results indicated that the high concentrations of original hydrocarbon in groundwater could be due to the hydrocarbon release from corrosion and extraction out of strata over time.

Microbial communities involved in methane production from hydrocarbons in oil sands tailings.

PubMed

Siddique, Tariq; Penner, Tara; Klassen, Jonathan; Nesbø, Camilla; Foght, Julia M

2012-09-04

Microbial metabolism of residual hydrocarbons, primarily short-chain n-alkanes and certain monoaromatic hydrocarbons, in oil sands tailings ponds produces large volumes of CH(4) in situ. We characterized the microbial communities involved in methanogenic biodegradation of whole naphtha (a bitumen extraction solvent) and its short-chain n-alkane (C(6)-C(10)) and BTEX (benzene, toluene, ethylbenzene, and xylenes) components using primary enrichment cultures derived from oil sands tailings. Clone libraries of bacterial 16S rRNA genes amplified from these enrichments showed increased proportions of two orders of Bacteria: Clostridiales and Syntrophobacterales, with Desulfotomaculum and Syntrophus/Smithella as the closest named relatives, respectively. In parallel archaeal clone libraries, sequences affiliated with cultivated acetoclastic methanogens (Methanosaetaceae) were enriched in cultures amended with n-alkanes, whereas hydrogenotrophic methanogens (Methanomicrobiales) were enriched with BTEX. Naphtha-amended cultures harbored a blend of these two archaeal communities. The results imply syntrophic oxidation of hydrocarbons in oil sands tailings, with the activities of different carbon flow pathways to CH(4) being influenced by the primary hydrocarbon substrate. These results have implications for predicting greenhouse gas emissions from oil sands tailings repositories.

Scent gland constituents of the Middle American burrowing python, Loxocemus bicolor (Serpentes: Loxocemidae).

PubMed

Schulze, Thies; Weldon, Paul J; Schulz, Stefan

2017-07-14

Analysis by gas chromatography/mass spectrometry of the scent gland secretions of male and female Middle American burrowing pythons (Loxocemus bicolor) revealed the presence of over 300 components including cholesterol, fatty acids, glyceryl monoalkyl ethers, and alcohols. The fatty acids, over 100 of which were identified, constitute most of the compounds in the secretions and show the greatest structural diversity. They include saturated and unsaturated, unbranched and mono-, di-, and trimethyl-branched compounds ranging in carbon-chain length from 13 to 24. The glyceryl monoethers possess saturated or unsaturated, straight or methyl-branched alkyl chains ranging in carbon-chain length from 13 to 24. Alcohols, which have not previously been reported from the scent glands, possess straight, chiefly saturated carbon chains ranging in length from 13 to 24. Sex or individual differences in secretion composition were not observed. Compounds in the scent gland secretions of L. bicolor may deter offending arthropods, such as ants.

Bayesian inversion of seismic and electromagnetic data for marine gas reservoir characterization using multi-chain Markov chain Monte Carlo sampling

NASA Astrophysics Data System (ADS)

Ren, Huiying; Ray, Jaideep; Hou, Zhangshuan; Huang, Maoyi; Bao, Jie; Swiler, Laura

2017-12-01

In this study we developed an efficient Bayesian inversion framework for interpreting marine seismic Amplitude Versus Angle and Controlled-Source Electromagnetic data for marine reservoir characterization. The framework uses a multi-chain Markov-chain Monte Carlo sampler, which is a hybrid of DiffeRential Evolution Adaptive Metropolis and Adaptive Metropolis samplers. The inversion framework is tested by estimating reservoir-fluid saturations and porosity based on marine seismic and Controlled-Source Electromagnetic data. The multi-chain Markov-chain Monte Carlo is scalable in terms of the number of chains, and is useful for computationally demanding Bayesian model calibration in scientific and engineering problems. As a demonstration, the approach is used to efficiently and accurately estimate the porosity and saturations in a representative layered synthetic reservoir. The results indicate that the seismic Amplitude Versus Angle and Controlled-Source Electromagnetic joint inversion provides better estimation of reservoir saturations than the seismic Amplitude Versus Angle only inversion, especially for the parameters in deep layers. The performance of the inversion approach for various levels of noise in observational data was evaluated - reasonable estimates can be obtained with noise levels up to 25%. Sampling efficiency due to the use of multiple chains was also checked and was found to have almost linear scalability.

Electronic transport in disordered chains with saturable nonlinearity

NASA Astrophysics Data System (ADS)

dos Santos, J. L. L.; Nguyen, Ba Phi; de Moura, F. A. B. F.

2015-10-01

In this work we study numerically the dynamics of an initially localized wave packet in one-dimensional disordered chains with saturable nonlinearity. By using the generalized discrete nonlinear Schrödinger equation, we calculate two different physical quantities as a function of time, which are the participation number and the mean square displacement from the excitation site. From detailed numerical analysis, we find that the saturable nonlinearity can promote a sub-diffusive spreading of the wave packet even in the presence of diagonal disorder for a long time. In addition, we also investigate the effect of the saturated nonlinearity for initial times of the electronic evolution thus showing the possibility of mobile breather-like modes.

Interaction of cholesterol with sphingomyelins and acyl-chain-matched phosphatidylcholines: a comparative study of the effect of the chain length.

PubMed Central

Ramstedt, B; Slotte, J P

1999-01-01

In this study we have synthesized sphingomyelins (SM) and phosphatidylcholines (PC) with amide-linked or sn-2 linked acyl chains with lengths from 14 to 24 carbons. The purpose was to examine how the chain length and degree of unsaturation affected the interaction of cholesterol with these phospholipids in model membrane systems. Monolayers of saturated SMs and PCs with acyl chain lengths above 14 carbons were condensed and displayed a high collapse pressure ( approximately 70 mN/m). Monolayers of N-14:0-SM and 1(16:0)-2(14:0)-PC had a much lower collapse pressure (58-60 mN/m) and monounsaturated SMs collapsed at approximately 50 mN/m. The relative interaction of cholesterol with these phospholipids was determined at 22 degreesC by measuring the rate of cholesterol desorption from mixed monolayers (50 mol % cholesterol; 20 mN/m) to beta-cyclodextrin in the subphase (1.7 mM). The rate of cholesterol desorption was lower from saturated SM monolayers than from chain-matched PC monolayers. In SM monolayers, the rate of cholesterol desorption was very slow for all N-linked chains, whereas for PC monolayers we could observe higher desorption rates from monolayers of longer PCs. These results show that cholesterol interacts favorably with SMs (low rate of desorption), whereas its interaction (or miscibility) with long chain PCs is weaker. Introduction of a single cis-unsaturation in the N-linked acyl chain of SMs led to faster rates of cholesterol desorption as compared with saturated SMs. The exception was monolayers of N-22:1-SM and N-24:1-SM from which cholesterol desorbed almost as slowly as from the corresponding saturated SM monolayers. The results of this study suggest that cholesterol is most likely capable of interacting with all physiologically relevant (including long-chain) SMs present in the plasma membrane of cells. PMID:9929492

New ordered metastable phases between the gel and subgel phases in hydrated phospholipids.

PubMed Central

Tenchov, B; Koynova, R; Rapp, G

2001-01-01

Formation of low-temperature ordered gel phases in several fully hydrated phosphatidylethanolamines (PEs) and phosphatidylcholines (PCs) with saturated chains as well as in dipalmitoylphosphatidylglycerol (DPPG) was observed by synchrotron x-ray diffraction, microcalorimetry, and densitometry. The diffraction patterns recorded during slow cooling show that the gel-phase chain reflection cooperatively splits into two reflections, signaling a transformation of the usual gel phase into a more ordered phase, with an orthorhombic chain packing (the Y-transition). This transition is associated with a small decrease (2-4 microl/g) or inflection of the partial specific volume. It is fully reversible with the temperature and displays in heating direction as a small (0.1-0.7 kcal/mol) endothermic event. We recorded a Y-transition in distearoyl PE, dipalmitoyl PE (DPPE), mono and dimethylated DPPE, distearoyl PC, dipalmitoyl PC, diC(15)PC, and DPPG. No such transition exists in dimyristoyl PE and dilauroyl PE where the gel L(beta) phase transforms directly into subgel L(c) phase, as well as in the unsaturated dielaidoyl PE. The PE and PC low-temperature phases denoted L(R1) and SGII, respectively, have different hydrocarbon chain packing. The SGII phase is with tilted chains, arranged in an orthorhombic lattice of two-nearest-neighbor type. Except for the PCs, it was also registered in ionized DPPG. In the L(R1) phase, the chains are perpendicular to the bilayer plane and arranged in an orthorhombic lattice of four-nearest-neighbor type. It was observed in PEs and in protonated DPPG. The L(R1) and SGII phases are metastable phases, which may only be formed by cooling the respective gel L(beta) and L(beta') phases, and not by heating the subgel L(c) phase. Whenever present, they appear to represent an indispensable intermediate step in the formation of the latter phase. PMID:11259300

L-cysteine-derived ambidextrous gelators of aromatic solvents and ethanol/water mixtures.

PubMed

Pal, Amrita; Dey, Joykrishna

2013-02-19

A series of L-cysteine-derived double hydrocarbon chain amphiphilic gelators L-(3-alkyl-carbamoylsulfanyl)-2-(3-alkylurido)propionic acid with different hydrocarbon chain lengths (C6-C16) was designed and synthesized. These gelators efficiently gelate only aromatic solvents. The gelation ability increased with the increase of chain length up to C14, but then it dropped with further increase of chain length. The C12 and C14 derivatives also gelled ethanol/water mixtures. The gels were characterized by a number of methods, including FT-IR, NMR, and XRD spectroscopy, electron microscopy, and rheology. The amphiphiles were observed to form either flat lamellar or ribbonlike aggregates in aromatic solvents as well as in ethanol/water mixtures. The gelation in all the solvents employed was observed to be thermoreversible. The gel-to-sol transition temperature as well as mechanical strength of the organogels were observed to increase with the hydrocarbon chain length. Both types of gels of C8-C16 amphiphiles have gel-to-sol transition temperatures above the physiological temperature (310 K). FT-IR and variable temperature (1)H NMR measurements suggested that van der Waals interactions have major contribution in the gelation process. The gel-to-sol transition temperature and mechanical strength of the organogels in ethanol/water mixtures was observed to be higher than those of benzene organogel.

Elemental sulfur identified in urine of cheetah, Acinonyx jubatus.

PubMed

Burger, Ben V; Visser, Runine; Moses, Alvira; Le Roux, Maritha

2006-06-01

The urine of the cheetah, Acinonyx jubatus, is almost odorless, and probably for this reason, it has not attracted much attention from scientists. Using gas chromatography-mass spectrometry, we identified 27 and 37 constituents in the headspace vapor of the urine of male and female cheetah, respectively. These constituents, composed of hydrocarbons, short-chain ethers, aldehydes, saturated and unsaturated cyclic and acyclic ketones, 2-acetylfuran, dimethyl disulfide, dimethyl sulfone, phenol, myristic acid (tetradecanoic acid), urea, and elemental sulfur, are all present in the headspace vapor in very small quantities; dimethyl disulfide is present in such a low concentration that it cannot be detected by the human nose. This is only the second example of elemental sulfur being secreted or excreted by an animal. It is hypothesized that the conversion of sulfur-containing compounds in the cheetah's diet to elemental sulfur and to practically odorless dimethyl sulfone enables this carnivore to operate as if "invisible" to the olfactory world of its predators as well as its prey, which would increase its chances of survival.

Bayesian inversion of seismic and electromagnetic data for marine gas reservoir characterization using multi-chain Markov chain Monte Carlo sampling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ren, Huiying; Ray, Jaideep; Hou, Zhangshuan

In this study we developed an efficient Bayesian inversion framework for interpreting marine seismic amplitude versus angle (AVA) and controlled source electromagnetic (CSEM) data for marine reservoir characterization. The framework uses a multi-chain Markov-chain Monte Carlo (MCMC) sampler, which is a hybrid of DiffeRential Evolution Adaptive Metropolis (DREAM) and Adaptive Metropolis (AM) samplers. The inversion framework is tested by estimating reservoir-fluid saturations and porosity based on marine seismic and CSEM data. The multi-chain MCMC is scalable in terms of the number of chains, and is useful for computationally demanding Bayesian model calibration in scientific and engineering problems. As a demonstration,more » the approach is used to efficiently and accurately estimate the porosity and saturations in a representative layered synthetic reservoir. The results indicate that the seismic AVA and CSEM joint inversion provides better estimation of reservoir saturations than the seismic AVA-only inversion, especially for the parameters in deep layers. The performance of the inversion approach for various levels of noise in observational data was evaluated – reasonable estimates can be obtained with noise levels up to 25%. Sampling efficiency due to the use of multiple chains was also checked and was found to have almost linear scalability.« less

Use of dissolved and vapor‐phase gases to investigate methanogenic degradation of petroleum hydrocarbon contamination in the subsurface

USGS Publications Warehouse

Amos, Richard T.; Mayer, K. Ulrich; Bekins, Barbara A.; Delin, Geoffrey N.; Williams, Randi L.

2005-01-01

At many sites contaminated with petroleum hydrocarbons, methanogenesis is a significant degradation pathway. Techniques to estimate CH4 production, consumption, and transport processes are needed to understand the geochemical system, provide a complete carbon mass balance, and quantify the hydrocarbon degradation rate. Dissolved and vapor‐phase gas data collected at a petroleum hydrocarbon contaminated site near Bemidji, Minnesota, demonstrate that naturally occurring nonreactive or relatively inert gases such as Ar and N2 can be effectively used to better understand and quantify physical and chemical processes related to methanogenic activity in the subsurface. In the vadose zone, regions of Ar and N2 depletion and enrichment are indicative of methanogenic and methanotrophic zones, and concentration gradients between the regions suggest that reaction‐induced advection can be an important gas transport process. In the saturated zone, dissolved Ar and N2 concentrations are used to quantify degassing driven by methanogenesis and also suggest that attenuation of methane along the flow path, into the downgradient aquifer, is largely controlled by physical processes. Slight but discernable preferential depletion of N2 over Ar, in both the saturated and unsaturated zones near the free‐phase oil, suggests reactivity of N2 and is consistent with other evidence indicating that nitrogen fixation by microbial activity is taking place at this site.

Lipids of Pseudomonas aeruginosa Cells Grown on Hydrocarbons and on Trypticase Soy Broth1

PubMed Central

Edmonds, Paul; Cooney, J. J.

1969-01-01

Lipids were extracted from cells of Pseudomonas aeruginosa grown on a pure hydrocarbon (tridecane), mixed hydrocarbons (JP-4 jet fuel), and on Trypticase Soy Broth. Total lipids produced from each substrate represented from 7.1 to 8.2% of cellular dry weight, of which 5.0 to 6.4% were obtained before cellular hydrolysis (free lipids) and 1.7 to 2.0% were extracted after cellular hydrolysis (bound lipids). Free lipids from cells grown on each medium were separated into four fractions by thin-layer chromatography. All fractions were present in cells from each type of medium, and the “neutral fraction” constituted the largest fraction. The fatty acid composition of free lipids was determined by gas-liquid chromatography. Cells grown on each medium contained saturated and unsaturated C14 to C20 fatty acids. Trace amounts of C13 fatty acids were found in tridecane-grown cells. Saturated C16 and C18 were the major acids present in all cells. Quantitative differences were found in fatty acids produced on the three media, but specific correlations between substrate carbon sources and fatty acid content of cells were not evident. Tridecane-grown cells contained only traces of C13 acid and small amounts of C15 and C17 acids, suggesting that the organism's fatty acids were derived from de novo synthesis rather than by direct incorporation of the hydrocarbon. PMID:4976464

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-01-01

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n+1).gtoreq.x.gtoreq.O and for olefinic hydrocarbons: 2n.gtoreq.x.gtoreq.O where n is the number of carbon atoms in the product and x ismore » the molar amount of water in the reaction mixture.« less

Halotolerance and effect of salt on hydrophobicity in hydrocarbon-degrading bacteria.

PubMed

Longang, Adégilns; Buck, Chris; Kirkwood, Kathlyn M

2016-01-01

Hydrocarbon-contaminated environments often also experience co-contamination with elevated levels of salt. This paper investigates the occurrence of halotolerance among several hydrocarbon-degrading bacteria, as an initial assessment of the importance of salt contamination to bioremediation strategies. Halotolerance was common, but not ubiquitous, among the 12 hydrocarbon-degrading bacteria tested, with many strains growing at up to 75 or 100 g NaCl L(-1) in rich medium. Greater sensitivity to elevated salt concentrations was observed among aromatics degraders compared to saturates degraders, and in defined medium compared to rich medium. Observed effects of high salt concentrations included increased lag times and decreased maximum growth. Many strains exhibited flocculation at elevated salt concentrations, but this did not correlate to any patterns in cell surface hydrophobicity, measured using the Bacterial Adhesion to Hydrocarbon assay. The occurrence of halotolerance in hydrocarbon-degrading bacteria suggests the potential for native microorganisms to contribute to the bioremediation of oil and salt co-contaminated sites, and indicates the need for a better understanding of the relationship between halotolerance and hydrocarbon biodegradation capabilities.

Effect of unsaturation on the absorption of ethane and ethylene in imidazolium-based ionic liquids.

PubMed

Moura, Leila; Mishra, Manas; Bernales, Varinia; Fuentealba, Patricio; Padua, Agilio A H; Santini, Catherine C; Costa Gomes, Margarida F

2013-06-20

The influence of the presence of imidazolium side chain unsaturation on the solubility of ethane and ethylene was studied in three ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide-saturated alkyl side-chain in the cation; 1-methyl-3-(buten-3-yl)imidazolium bis(trifluorosulfonyl)imide-double bond in the side-chain of the cation; and 1-methyl-3-benzylimidazolium bis(trifluorosulfonyl)imide-benzyl group in the side-chain of the cation. The solubility of both gases decreases when the side-chain of the cations is functionalized with an unsaturated group. This can be explained by a less favorable enthalpy of solvation. The difference of solubility between ethane and ethylene can be explained from a balance of enthalpic and entropic factors: for the ionic liquid with the saturated alkyl side-chain and the benzyl-substituted side-chain, it is the favorable entropy of solvation that explains the larger ethylene solubility, whereas in the case of the saturated side-chain, it is the more favorable enthalpy of solvation. Molecular simulation allowed the identification of the mechanisms of solvation and the preferential solvation sites for each gas in the different ionic liquids. Simulations have shown that the entropy of solvation is more favorable when the presence of the gas weakens the cation-anion interactions or when the gas can be solvated near different sites of the ionic liquid.

Bayesian inversion of seismic and electromagnetic data for marine gas reservoir characterization using multi-chain Markov chain Monte Carlo sampling

DOE PAGES

Ren, Huiying; Ray, Jaideep; Hou, Zhangshuan; ...

2017-10-17

In this paper we developed an efficient Bayesian inversion framework for interpreting marine seismic Amplitude Versus Angle and Controlled-Source Electromagnetic data for marine reservoir characterization. The framework uses a multi-chain Markov-chain Monte Carlo sampler, which is a hybrid of DiffeRential Evolution Adaptive Metropolis and Adaptive Metropolis samplers. The inversion framework is tested by estimating reservoir-fluid saturations and porosity based on marine seismic and Controlled-Source Electromagnetic data. The multi-chain Markov-chain Monte Carlo is scalable in terms of the number of chains, and is useful for computationally demanding Bayesian model calibration in scientific and engineering problems. As a demonstration, the approach ismore » used to efficiently and accurately estimate the porosity and saturations in a representative layered synthetic reservoir. The results indicate that the seismic Amplitude Versus Angle and Controlled-Source Electromagnetic joint inversion provides better estimation of reservoir saturations than the seismic Amplitude Versus Angle only inversion, especially for the parameters in deep layers. The performance of the inversion approach for various levels of noise in observational data was evaluated — reasonable estimates can be obtained with noise levels up to 25%. Sampling efficiency due to the use of multiple chains was also checked and was found to have almost linear scalability.« less

Bayesian inversion of seismic and electromagnetic data for marine gas reservoir characterization using multi-chain Markov chain Monte Carlo sampling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ren, Huiying; Ray, Jaideep; Hou, Zhangshuan

In this paper we developed an efficient Bayesian inversion framework for interpreting marine seismic Amplitude Versus Angle and Controlled-Source Electromagnetic data for marine reservoir characterization. The framework uses a multi-chain Markov-chain Monte Carlo sampler, which is a hybrid of DiffeRential Evolution Adaptive Metropolis and Adaptive Metropolis samplers. The inversion framework is tested by estimating reservoir-fluid saturations and porosity based on marine seismic and Controlled-Source Electromagnetic data. The multi-chain Markov-chain Monte Carlo is scalable in terms of the number of chains, and is useful for computationally demanding Bayesian model calibration in scientific and engineering problems. As a demonstration, the approach ismore » used to efficiently and accurately estimate the porosity and saturations in a representative layered synthetic reservoir. The results indicate that the seismic Amplitude Versus Angle and Controlled-Source Electromagnetic joint inversion provides better estimation of reservoir saturations than the seismic Amplitude Versus Angle only inversion, especially for the parameters in deep layers. The performance of the inversion approach for various levels of noise in observational data was evaluated — reasonable estimates can be obtained with noise levels up to 25%. Sampling efficiency due to the use of multiple chains was also checked and was found to have almost linear scalability.« less

FORMULA 206-1x BIO-WASH™

EPA Pesticide Factsheets

Technical product bulletin: this surface washing agent is most effective on hydrocarbon and bio-organic soiling on hard surfaces including beaches, shorelines, and rocks; specifically to aid in the removal of oil and oil saturated soiling.

Organic Experiments for Introductory Chemistry.

ERIC Educational Resources Information Center

Rayner-Canham, Geoff

1985-01-01

Describes test-tube organic chemistry procedures (using comparatively safe reagents) for the beginning student. These procedures are used to: examine differences between saturated and unsaturated hydrocarbons; compare structural isomers; and compare organic and inorganic acids and bases. (DH)

CYP63A2, a catalytically versatile fungal P450 monooxygenase capable of oxidizing higher-molecular-weight polycyclic aromatic hydrocarbons, alkylphenols, and alkanes.

PubMed

Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E; Yadav, Jagjit S

2013-04-01

Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills).

CYP63A2, a Catalytically Versatile Fungal P450 Monooxygenase Capable of Oxidizing Higher-Molecular-Weight Polycyclic Aromatic Hydrocarbons, Alkylphenols, and Alkanes

PubMed Central

Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E.

2013-01-01

Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills). PMID:23416995

Accumulation of petroleum hydrocarbons in intracellular lipid bodies of the freshwater diatom Synedra acus subsp. radians.

PubMed

Shishlyannikov, Sergey M; Nikonova, Alyona A; Klimenkov, Igor V; Gorshkov, Alexander G

2017-01-01

The accumulation of hydrophobic compounds by phytoplankton plays a crucial role in the biogeochemical cycle of persistent organic pollutants (POPs) in aquatic environments. We studied the accumulation of polycyclic aromatic hydrocarbons (PAHs) in the freshwater diatom Synedra acus subsp. radians during its cultivation with crude oil hydrocarbons, using epifluorescent and laser confocal microscopy as well as gas chromatography-mass spectrometry (GC/MS) analysis. Our results revealed that in the presence of crude oil or an extract of a crude oil/n-hexane solution (light oil), S. acus subsp. radians accumulated PAHs in its lipid bodies. During cultivation in the presence of a crude oil/n-hexane solution, the cells selectively accumulated C12-C18 alkanes, with a preference for C15 and C16 homologues. The length of n-alkane hydrocarbon chains accumulated in cells was similar to the acyl chains of fatty acids of the diatom. We therefore suggest that the insertion of n-alkanes into the membrane lipid bilayer promotes the transmembrane transport of PAH in diatoms. Our results confirm the hypothesis that diatoms play a role in the elimination of hydrophobic hydrocarbons from aquatic systems.

Frustrated spin chains in strong magnetic field: Dilute two-component Bose gas regime

NASA Astrophysics Data System (ADS)

Kolezhuk, A. K.; Heidrich-Meisner, F.; Greschner, S.; Vekua, T.

2012-02-01

We study the ground state of frustrated spin-S chains in a strong magnetic field in the immediate vicinity of saturation. In strongly frustrated chains, the magnon dispersion has two degenerate minima at inequivalent momenta ±Q, and just below the saturation field the system can be effectively represented as a dilute one-dimensional lattice gas of two species of bosons that correspond to magnons with momenta around ±Q. We present a theory of effective interactions in such a dilute magnon gas that allows us to make quantitative predictions for arbitrary values of the spin. With the help of this method, we are able to establish the magnetic phase diagram of frustrated chains close to saturation and study phase transitions between several nontrivial states, including a two-component Luttinger liquid, a vector chiral phase, and phases with bound magnons. We study those phase transitions numerically and find a good agreement with our analytical predictions.

Large-Scale Multiphase Flow Modeling of Hydrocarbon Migration and Fluid Sequestration in Faulted Cenozoic Sedimentary Basins, Southern California

NASA Astrophysics Data System (ADS)

Jung, B.; Garven, G.; Boles, J. R.

2011-12-01

Major fault systems play a first-order role in controlling fluid migration in the Earth's crust, and also in the genesis/preservation of hydrocarbon reservoirs in young sedimentary basins undergoing deformation, and therefore understanding the geohydrology of faults is essential for the successful exploration of energy resources. For actively deforming systems like the Santa Barbara Basin and Los Angeles Basin, we have found it useful to develop computational geohydrologic models to study the various coupled and nonlinear processes affecting multiphase fluid migration, including relative permeability, anisotropy, heterogeneity, capillarity, pore pressure, and phase saturation that affect hydrocarbon mobility within fault systems and to search the possible hydrogeologic conditions that enable the natural sequestration of prolific hydrocarbon reservoirs in these young basins. Subsurface geology, reservoir data (fluid pressure-temperature-chemistry), structural reconstructions, and seismic profiles provide important constraints for model geometry and parameter testing, and provide critical insight on how large-scale faults and aquifer networks influence the distribution and the hydrodynamics of liquid and gas-phase hydrocarbon migration. For example, pore pressure changes at a methane seepage site on the seafloor have been carefully analyzed to estimate large-scale fault permeability, which helps to constrain basin-scale natural gas migration models for the Santa Barbara Basin. We have developed our own 2-D multiphase finite element/finite IMPES numerical model, and successfully modeled hydrocarbon gas/liquid movement for intensely faulted and heterogeneous basin profiles of the Los Angeles Basin. Our simulations suggest that hydrocarbon reservoirs that are today aligned with the Newport-Inglewood Fault Zone were formed by massive hydrocarbon flows from deeply buried source beds in the central synclinal region during post-Miocene time. Fault permeability, capillarity forces between the fault and juxtaposition of aquifers/aquitards, source oil saturation, and rate of generation control the efficiency of a petroleum trap and carbon sequestration. This research is focused on natural processes in real geologic systems, but our results will also contribute to an understanding of the subsurface behavior of injected anthropogenic greenhouse gases, especially when targeted storage sites may be influenced by regional faults, which are ubiquitous in the Earth's crust.

New method for determining heats of combustion of gaseous hydrocarbons

NASA Technical Reports Server (NTRS)

Singh, J. J.; Sprinkle, D. R.; Puster, R. L.

1985-01-01

As a spin off of a system developed for monitoring and controlling the oxygen concentration in the Langley 8-foot High Temperature Tunnel, a highly accurate on-line technique was developed for determining heats of combustion of natural gas samples. It is based on measuring the ratio m/n, where m is the (volumetric) flowrate of oxygen required to enrich the carrier air in which the test gas flowing at the rate n is burned, such that the mole fraction of oxygen in the combustion product gases equals that in the carrier air. The m/n ratio is directly related to the heats of combustion of the saturated hydrocarbons present in the natural gas. A measurement of the m/n ratio for the test gas can provide a direct means of determination of its heat of combustion by using the calibration graph relating the m/n values for pure saturated hydrocarbons with their heats of combustion. The accuracy of the technique is determine solely by the accuracy with which the flowrates m and n can be measured and is of the order of 2 percent in the present study. The theoretical principles and experimental results are discussed.

Bioremediation and phytoremediation of total petroleum hydrocarbons (TPH) under various conditions.

PubMed

McIntosh, Patrick; Schulthess, Cristian P; Kuzovkina, Yulia A; Guillard, Karl

2017-08-03

Remediation of contaminated soils is often studied using fine-textured soils rather than low-fertility sandy soils, and few studies focus on recontamination events. This study compared aerobic and anaerobic treatments for remediation of freshly introduced used motor oil on a sandy soil previously phytoremediated and bioacclimated (microorganisms already adapted in the soil environment) with some residual total petroleum hydrocarbon (TPH) contamination. Vegetated and unvegetated conditions to remediate anthropogenic fill containing residual TPH that was spiked with nonaqueous phase liquids (NAPLs) were evaluated in a 90-day greenhouse pot study. Vegetated treatments used switchgrass (Panicum virgatum). The concentration of aerobic bacteria were orders of magnitude higher in vegetated treatments compared to unvegetated. Nevertheless, final TPH concentrations were low in all saturated soil treatments, and high in the presence of switchgrass. Concentrations were also low in unvegetated pots with fertilizer. Acclimated indigenous microbial communities were shown to be more effective in breaking down hydrocarbons than introducing microbes from the addition of plant treatments in sandy soils. Remediation of fresh introduced NAPLs on pre-phytoremediated and bioacclimated soil was most efficient in saturated, anaerobic environments, probably due to the already pre-established microbial associations, easily bioavailable contaminants, and optimized soil conditions for microbial establishment and survival.

Polymerizable disilanols having in-chain perfluoroalkyl groups

NASA Technical Reports Server (NTRS)

Patterson, W. J.; Morris, D. E. (Inventor)

1973-01-01

Disilanols containing in-chain perfluoroalkyl and aromatic groups and the process by which they were prepared are discussed. The disilanols, when reacted with a diaminosilane and cured, produce polymeric material resistant to hydrocarbon fuels and stable at elevated temperatures.

The Proceedings of the Conference on Assessment of Ecological Impacts of Oil Spills Held 14-17 Jun 1978, Keystone, Colorado.

DTIC Science & Technology

1978-01-01

the physical and chemical principles involved in the combustion of hydrocarbons is beyond the scope of this study . But, two factors , temperature and...In this study fifty-five saturated and aromatic hydrocarbons were Individually quantitated. Percent recoveries and relative response factors for the...FROM THE SUPERTANKER ‘M~~ULA’, Roy W . Hann 354 BIOLOGICAL STUDIES OF THE METULA OIL SPILL , Dale Straughan 364 SINKING OF OIL IN LOS ANGELES HARBOR

Guerbet compounds

USDA-ARS?s Scientific Manuscript database

Guerbet alcohols are of significant commercial interest for various applications, including in lubricants and surfactant systems, due to their great fluidity range, high oxidative stability, and good lubricity imparted by the saturated hydrocarbon backbone, branching, and the presence of an OH group...

Geochemical character and origin of oils in Ordovician reservoir rock, Illinois and Indiana, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guthrie, J.M.; Pratt, L.M.

1995-11-01

Twenty-three oils produced from reservoirs within the Ordovician Galena Group (Trenton equivalent) and one oil from the Mississippian Ste. Genevieve Limestone in the Illinois and Indiana portions of the Illinois basin are characterized. Two end-member oil groups (1) and (2) and one intermediate group (1A) are identified using conventional carbon isotopic analysis of whole and fractionated oils, gas chromatography (GC) of saturated hydrocarbon fractions, isotope-ratio-monitoring gas chromatography/mass spectrometry (irm-GC/MS) of n-alkanes ranging from C{sub 15} to C{sub 25}, and gas chromatography/mass spectrometry (GC/MS) of the aromatic hydrocarbon fractions. Group 1 is characterized by high odd-carbon predominance in mid-chain n-alkanes (C{submore » 15}-C{sub 19}), low abundance Of C{sub 20+}, n-alkanes, and an absence of pristane and phytane. Group IA is characterized by slightly lower odd-carbon predominance of mid-chain n-alkanes, greater abundance of C{sub 20+} n-alkanes compared to group 1, and no pristane and phytane. Conventional correlations of oil to source rock based on carbon isotopic-type curves and hopane (m/z 191) and sterane (m/z 217) distributions are of limited use in distinguishing Ordovician-reservoired oil groups and determining their origin. Oil to source rock correlations using the distribution and carbon isotopic composition of n-alkanes and the m/z 133 chromatograms of n-alkylarenes show that groups 1 and 1A originated from strata of the Upper Ordovician Galena Group. Group 2 either originated solely from the Upper Ordovician Maquoketa Group or from a mixture of oils generated from the Maquoketa Group and the Galena Group. The Mississippian-reservoired oil most likely originated from the Devonian New Albany Group. The use of GC, irm-GC/MS, and GC/MS illustrates the value of integrated molecular and isotopic approaches for correlating oil groups with source rocks.« less

Infrared spectroscopy for the determination of hydrocarbon types in jet fuels

NASA Technical Reports Server (NTRS)

Buchar, C. S.

1981-01-01

The concentration of hydrocarbon types in conventional jet fuels and synfuels can be measured using a computerized infrared spectrophotometer. The computerized spectrophotometer is calibrated using a fuel of known aromatic and olefinic content. Once calibration is completed, other fuels can be rapidly analyzed using an analytical program built into the computer. The concentration of saturates can be calculated as 100 percent minus the sum of the aromatic and olefinic concentrations. The analysis of a number of jet fuels produced an average standard deviation of 1.76 percent for aromatic types and one of 3.99 percent for olefinic types. Other substances such as oils and organic mixtures can be analyzed for their hydrocarbon content.

Application of capillary gas chromatography mass spectrometry/computer techniques to synoptic survey of organic material in bed sediment

USGS Publications Warehouse

Steinheimer, T.R.; Pereira, W.E.; Johnson, S.M.

1981-01-01

A bed sediment sample taken from an area impacted by heavy industrial activity was analyzed for organic compounds of environmental significance. Extraction was effected on a Soxhlet apparatus using a freeze-dried sample. The Soxhlet extract was fractionated by silica gel micro-column adsorption chromatography. Separation and identification of the organic compounds was accomplished by capillary gas chromatography/mass spectrometry techniques. More than 50 compounds were identified; these include saturated hydrocarbons, olefins, aromatic hydrocarbons, alkylated polycyclic aromatic hydrocarbons, and oxygenated compounds such as aldehydes and ketones. The role of bed sediments as a source or sink for organic pollutants is discussed. ?? 1981.

Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

NASA Technical Reports Server (NTRS)

Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

1986-01-01

The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

1985-11-06

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Aromatic ring generation as a dust precursor in acetylene discharges

NASA Astrophysics Data System (ADS)

De Bleecker, Kathleen; Bogaerts, Annemie; Goedheer, Wim

2006-04-01

Production of aromatic hydrocarbon compounds as an intermediate step for particle formation in low-pressure acetylene discharges is investigated via a kinetic approach. The detailed chemical reaction mechanism contains 140 reactions among 55 species. The cyclic hydrocarbon chemistry is mainly based on studies of polycyclic aromatic hydrocarbon formation in cosmic environments. The model explicitly includes organic chain, cyclic molecules, radicals, and ions up to a size of 12 carbon atoms. The calculated density profiles show that the aromatic formation yields are quite significant, suggesting that aromatic compounds play a role in the underlying mechanisms of particle formation in hydrocarbon plasmas.

Dispersants as Used in Response to the MC252-Spill Lead to Higher Mobility of Polycyclic Aromatic Hydrocarbons in Oil-Contaminated Gulf of Mexico Sand

PubMed Central

Zuijdgeest, Alissa; Huettel, Markus

2012-01-01

After the explosion of the Deepwater Horizon oil rig, large volumes of crude oil were washed onto and embedded in the sandy beaches and sublittoral sands of the Northern Gulf of Mexico. Some of this oil was mechanically or chemically dispersed before reaching the shore. With a set of laboratory-column experiments we show that the addition of chemical dispersants (Corexit 9500A) increases the mobility of polycyclic aromatic hydrocarbons (PAHs) in saturated permeable sediments by up to two orders of magnitude. Distribution and concentrations of PAHs, measured in the solid phase and effluent water of the columns using GC/MS, revealed that the mobility of the PAHs depended on their hydrophobicity and was species specific also in the presence of dispersant. Deepest penetration was observed for acenaphthylene and phenanthrene. Flushing of the columns with seawater after percolation of the oiled water resulted in enhanced movement by remobilization of retained PAHs. An in-situ benthic chamber experiment demonstrated that aromatic hydrocarbons are transported into permeable sublittoral sediment, emphasizing the relevance of our laboratory column experiments in natural settings. We conclude that the addition of dispersants permits crude oil components to penetrate faster and deeper into permeable saturated sands, where anaerobic conditions may slow degradation of these compounds, thus extending the persistence of potentially harmful PAHs in the marine environment. Application of dispersants in nearshore oil spills should take into account enhanced penetration depths into saturated sands as this may entail potential threats to the groundwater. PMID:23209777

Production of saturated and unsaturated silahydrocarbon mixtures using rhodium catalyst, and to products produced thereby

DOE Office of Scientific and Technical Information (OSTI.GOV)

Onopchenki, A.; Sabourin, E.T.

1986-02-25

This patent describes a process for the production of a mixture of saturated and unstaurated silahydrocarbons. This process contacts an admixture consisting of (A) at least one alpha-olefin containing from 2 to about 20 carbon atoms per molecule, and (B) at least one alkylsilane selected from the group consisting of (i) a dialkylsilane (ii) a trialkylsilane (iii) mixtures thereof, with a catalyst consisting of a homogeneous monomeric rhodium-containing catalyst having a basicity substantially equal to or less than that provided by a rhodium-containing catalyst having a triphenyl phosphine ligand or a heterogeneous rhodium-containing catalyst in a halogen-free inert solvent. Themore » process conducted at a temperature of from about 30/sup 0/ to about 200/sup 0/C., a weight ratio of olefin to alkylsilane of from about 0.5 to about 20 to one and a catalyst concentration of from about 1 x 10-/sup 5/ to about 1 x 10-/sup 2/ millimoles of catalyst per millimole alkylsilane, to produce a mixture containing saturated silane hydrocarbons and an unsaturated silahydrocarbon. Inclusive with the proviso that the molecular weight of the unsaturated silane hydrocarbon is above 300.« less

Partially Acetylated Sugarcane Bagasse For Wicking Oil From Contaminated Wetlands

EPA Science Inventory

Sugarcane bagasse was partially acetylated to enhance its oil-wicking ability in saturated environments while holding moisture for hydrocarbon biodegradation. The water sorption capacity of raw bagasse was reduced fourfold after treatment, which indicated considerably increased ...

Molecular dynamics simulation of interactions between a sodium dodecyl sulfate micelle and a poly(ethylene oxide) polymer.

PubMed

Shang, Barry Z; Wang, Zuowei; Larson, Ronald G

2008-03-13

We have performed atomistic molecular dynamics simulations of an anionic sodium dodecyl sulfate (SDS) micelle and a nonionic poly(ethylene oxide) (PEO) polymer in aqueous solution. The micelle consisted of 60 surfactant molecules, and the polymer chain lengths varied from 20 to 40 monomers. The force field parameters for PEO were adjusted by using 1,2-dimethoxymethane (DME) as a model compound and matching its hydration enthalpy and conformational behavior to experiment. Excellent agreement with previous experimental and simulation work was obtained through these modifications. The simulated scaling behavior of the PEO radius of gyration was also in close agreement with experimental results. The SDS-PEO simulations show that the polymer resides on the micelle surface and at the hydrocarbon-water interface, leading to a selective reduction in the hydrophobic contribution to the solvent-accessible surface area of the micelle. The association is mainly driven by hydrophobic interactions between the polymer and surfactant tails, while the interaction between the polymer and sulfate headgroups on the micelle surface is weak. The 40-monomer chain is mostly wrapped around the micelle, and nearly 90% of the monomers are adsorbed at low PEO concentration. Simulations were also performed with multiple 20-monomer chains, and gradual addition of polymer indicates that about 120 monomers are required to saturate the micelle surface. The stoichiometry of the resulting complex is in close agreement with experimental results, and the commonly accepted "beaded necklace" structure of the SDS-PEO complex is recovered by our simulations.

Antennal olfactory responses of adult meadow spittlebug, Philaenus spumarius, to volatile organic compounds (VOCs)

PubMed Central

Ganassi, Sonia; Pistillo, Marco O.; Di Domenico, Carmela; De Cristofaro, Antonio; Di Palma, Antonella Marta

2017-01-01

The meadow spittlebug, Philaenus spumarius L. (Hemiptera, Aphrophoridae) is a commonly found vector of Xylella fastidiosa Wells et al. (1987) strain subspecies pauca associated with the “Olive Quick Decline Syndrome” in Italy. To contribute to the knowledge of the adult P. spumarius chemoreceptivity, electroantennographic (EAG) responses of both sexes to 50 volatile organic compounds (VOCs) including aliphatic aldehydes, alcohols, esters, and ketones, terpenoids, and aromatics were recorded. Measurable EAG responses were elicited by all compounds tested. In both sexes, octanal, 2-octanol, 2-decanone, (E)-2-hexenyl acetate, and vanillin elicited the strongest antennal amplitude within the chemical groups of aliphatic saturated aldehydes, aliphatic alcohols, aliphatic acetates and aromatics, respectively. Male and female EAG responses to sulcatol, (±)linalool, and sulcatone were higher than those to other terpenoinds. In both sexes, the weakest antennal stimulants were phenethyl alcohol and 2-pentanone. Sexual differences in the EAG amplitude were found only for four of test compounds suggesting a general similarity between males and females in antennal sensitivity. The olfactory system of both sexes proved to be sensitive to changes in stimulus concentration, carbon chain length, and compound structure. Compounds with short carbon chain length (C5—C6) elicited lower EAG amplitudes than compounds with higher carbon chain length (C9—C10) in all classes of aliphatic hydrocarbons with different functional groups. The elucidation of the sensitivity profile of P. spumarius to a variety of VOCs provides a basis for future identification of behaviorally-active compounds useful for developing semiochemical-based control strategies of this pest. PMID:29287108

Toxicological and ecotoxicological properties of gas-to-liquid (GTL) products. 1. Mammalian toxicology.

PubMed

Boogaard, Peter J; Carrillo, Juan-Carlos; Roberts, Linda G; Whale, Graham F

2017-02-01

Gas-to-liquid (GTL) products are synthetic hydrocarbons produced from natural gas using a Fischer-Tropsch process. This process yields a synthetic crude oil that consists of saturated hydrocarbons, primarily linear alkanes, with increasing amounts of branched (methyl-groups) alkanes as the chains get longer. In addition, small amounts of cycloalkanes (branched cyclopentanes and cyclohexanes) may be formed as the polymerization reaction prolongs. This synthetic crude can subsequently be refined to a range of products very similar to petroleum refining. However, in contrast to their petroleum-derived analogs, GTL products are essentially free of unsaturated or aromatic constituents and also no sulfur-, oxygen-, or nitrogen-containing constituents are present. From a regulatory perspective, GTL products are new substances which require extensive testing to assess their hazardous properties. As a consequence, a wide range of GTL products, covering the entire portfolio of GTL products, have been tested over the past few years in a wide variety of toxicological studies, including reproductive and prenatal development toxicity studies. This review provides an overview of the hazardous properties of the various GTL products. In general, the data collected on GTL products provide strong proof that they exert minimal health effects. In addition, these data provide supporting evidence for what is known on the mechanisms of mammalian toxicology of their petroleum-derived analogs. In the few cases where adverse effects were found for the GTL substances, these were usually less severe than the adverse effects observed with their petroleum-derived analogs.

A case study of the intrinsic bioremediation of petroleum hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barker, G.W.; Raterman, K.T.; Fisher, J.B.

1995-12-31

Condensate liquids have been found to contaminate soil and groundwater at two gas production sites in the Denver Basin operated by Amoco Production Co. These sites have been closely monitored since July 1993 to determine whether intrinsic aerobic or anaerobic bioremediation of hydrocarbons occurs at a sufficient rate and to an adequate endpoint to support a no-intervention decision. Groundwater monitoring and analysis of soil cores suggest that intrinsic bioremediation is occurring at these sites by multiple pathways including aerobic oxidation, Fe{sup 3+} reduction, and sulfate reduction. In laboratory experiments the addition of gas condensate hydrocarbons to saturated soil from themore » gas production site stimulated sulfate reduction under anaerobic and oxygen-limiting conditions, and nitrate and Fe{sup 3+} reduction under oxygen-limiting conditions, compared to biotic controls that lacked hydrocarbon and sterile controls. The sulfate reduction corresponded to a reduction in the amount of toluene relative to other hydrocarbons. These results confirmed that subsurface soils at the gas production site have the potential for intrinsic bioremediation of hydrocarbons.« less

Finite time thermodynamics and the quasi-stability of closed-systems of natural hydrocarbon mixtures

NASA Astrophysics Data System (ADS)

Planche, H.

1996-11-01

The isothermal pyrolysis at 372°C, between 400 and 500 bars, of a paraffinic liquid hydrocarbon (natural physical conditions: 195°C, 1000 bars) has been performed over 3 months in order to observe composition changes and to calculate the total Gibbs energy of the fluid hydrocarbon mixture G(t). The approach of a G minimum corresponding to a reversible equilibrium of the composition has been detected. This is consistent with the observation of a significant C 11+ paraffin neo-formation flux after 2 months pyrolysis, and the overall stabilization trend for the fluid composition. The calculated stable composition of the saturates family is consistent with the one asymptotically reached after 1000 h of pyrolysis. This stable composition contains significant amounts of C 6+ paraffins. Assuming the functionality of G in the time-composition space to be conserved when changing temperature from pyrolysis back to the initial fluid natural condition, the stable composition extrapolated at 195°C is that of a liquid hydrocarbon, very close to the natural oil used in the pyrolysis experiments. The observed concentration of most of molecular components of mature oils would thus be controlled by the effective equilibrium of a reversible chemical network. The reversibility of the oil saturates to gas + aromatics conversion is most probably the reason why C 11+ paraffins may survive for as long as 100 Ma in the range 300 to 350°C as literature shows for hyper-mature rock extracts.

Energy, saturated fat, and sodium were lower in entrées at chain restaurants at 18 months compared with 6 months following the implementation of mandatory menu labeling regulation in King County, Washington.

PubMed

Bruemmer, Barbara; Krieger, Jim; Saelens, Brian E; Chan, Nadine

2012-08-01

Policies on menu labeling have been proposed as a method to improve the food environment. However, there is little information on the nutrient content of chain restaurant menu items and changes over time. To evaluate the energy, saturated fat, and sodium content of entrées 6 and 18 months post-implementation of restaurant menu labeling in King County of Washington State for items that were on the menu at both time periods, and across all items at 6 and 18 months and to compare energy content to recommendations provided by the 2005 Dietary Guidelines for Americans. Eligible restaurants included sit-down and quick-service chains (eg, burgers, pizza, sandwiches/subs, and Tex-Mex) subject to King County regulations with four or more establishments. One establishment per chain was audited at each time period. Hypothesis one examined entrées that were on the menu at both time periods using a paired t test and hypothesis two compared quartiles at 6 months to the distribution at 18 months using a Mantel-Haentzel odds ratios and 95% CIs, and a Cochrane-Armitage test for trend. The content of entrées at 18 months was compared with one-third (assuming three meals per day) of the nutrient intake recommendations for adults provided by the 2005 Dietary Guidelines for Americans. The audit included 37 eligible chains of 92 regulated chains. Energy contents were lower (all chains -41, sit down -73, and quick service -19; paired t tests P<0.0001) for entrées that were on the menu at both time periods. There was a significant trend across quartiles for a decrease in energy, saturated fat, and sodium for all entrées at sit-down chains only. At 18 months entrées not designated for children exceeded 56%, 77%, and 89% of the energy, saturated fat, and sodium guidelines, respectively. Modest improvements in the nutrient content of sit-down and quick-service restaurant entrées occurred but overall levels for energy, saturated fat, and sodium are excessive. Copyright © 2012 Academy of Nutrition and Dietetics. Published by Elsevier Inc. All rights reserved.

Programmable Self-assembly of Hydrocarbon-capped Nanoparticles: Role of Chain Conformations

NASA Astrophysics Data System (ADS)

Waltmann, Curt; Horst, Nathan; Travesset, Alex

Nanoparticle superlattices (NPS), i.e. crystalline arrangements of nanoparticles, are materials with fascinating structures, which in many cases are not possible to attain from simple atoms or molecules. They also span a wide range of possible applications such as metamaterials, new energy sources, catalysis, and many others. In this talk, we present a theoretical and computational description of the self-assembly of nanoparticles with hydrocarbons as capping ligands. Usually, these systems have been described with hard sphere packing models. In this talk, we show that the conformations of the hydrocarbon chains play a fundamental role in determining the equilibrium phases, including and especially in binary systems. The work of CW was supported by a DOE-SULI internship from May-December 2016, and by NSF, DMR-CMMT 1606336 CDS&E: Design Principles for Ordering Nanoparticles into Super-crystals after January 1st.

A Study of the Nephrotoxicity and Metabolism of Tetralin and Indan in Fischer 344 Rats.

DTIC Science & Technology

1988-02-08

evaluated petroleum and shale-derived JP-5, a jet fuel composed of aliphatic and aromatic hydrocarbons with the majority of the straight-chain hydrocarbons...much like gasoline. JP-8 is a mixture of hydrocarbon of intermediate boiling point and volatility and is similar to the civilian jet fuel , A-1. DFM is a...conventional versus shale-derived JP-5 jet fuel : Light microscopy, hematologic, and serum chemistry studies. Toxicol Appl Pharmacol, 57, 302-317 (1981

New generalized corresponding states correlation for surface tension of normal saturated liquids

NASA Astrophysics Data System (ADS)

Yi, Huili; Tian, Jianxiang

2015-08-01

A new simple correlation based on the principle of corresponding state is proposed to estimate the temperature-dependent surface tension of normal saturated liquids. The new correlation contains three coefficients obtained by fitting 17,051 surface tension data of 38 saturated normal liquids. These 38 liquids contain refrigerants, hydrocarbons and some other inorganic liquids. The new correlation requires only the triple point temperature, triple point surface tension and critical point temperature as input and is able to well represent the experimental surface tension data for each of the 38 saturated normal liquids from the triple temperature up to the point near the critical point. The new correlation gives absolute average deviations (AAD) values below 3% for all of these 38 liquids with the only exception being octane with AAD=4.30%. Thus, the new correlation gives better overall results in comparison with other correlations for these 38 normal saturated liquids.

AVO in North of Paria, Venezuela: Gas methane versus condensate reservoirs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Regueiro, J.; Pena, A.

1996-07-01

The gas fields of North of Paria, offshore eastern Venezuela, present a unique opportunity for amplitude variations with offset (AVO) characterization of reservoirs containing different fluids: gas-condensate, gas (methane) and water (brine). AVO studies for two of the wells in the area, one with gas-condensate and the other with gas (methane) saturated reservoirs, show interesting results. Water sands and a fluid contact (condensate-water) are present in one of these wells, thus providing a control point on brine-saturated properties. The reservoirs in the second well consist of sands highly saturated with methane. Clear differences in AVO response exist between hydrocarbon-saturated reservoirsmore » and those containing brine. However, it is also interesting that subtle but noticeable differences can be interpreted between condensate-and methane-saturated sands. These differences are attributed to differences in both in-situ fluid density and compressibility, and rock frame properties.« less

Assessment of molecular marker compounds as an index of the biodegradation of diesel fuel hydrocarbons in soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Voos, G.; Mills, G.; O`Neill, J.

1996-10-01

The weathering of petroleum hydrocarbons in the soil environment is the sum of biological, physical and chemical processes. It is often difficult to clearly discern microbial from abiotic contributions to the overall process. This is especially important in assessing the effectiveness of various in-situ bioremediation technologies. We examined molecular marker compounds, including pristane, phytane, diterpenoid hydrocarbons, farnesane and norpristane, and the ratios n-C17/pristane and n-C18/phytane to evaluate their use as an index of biodegradation of diesel fuel in contaminated soil. The study was conducted using microcosms containing 200 g of contaminated soil. Microcosms were destructively sampled on days 0, 1,more » 2, 4, 8, 14, 33 and 64 of the experiment. The soil was analyzed for straight-chained, branched-chained, and alicyclic petroleum hydrocarbons using high-resolution gas chromatography. Results indicate that by day 33 of the experiment, pristane and phytane were present at significantly greater concentrations than their corresponding n-alkanes and the other marker compounds analyzed. There is a strong correlation between the amount of pristane and phytane present in the soil and the amount of total extractable petroleum hydrocarbons (TEPH) measured during the course of the experiment.« less

Analysis of mycolic acids from a group of corynebacteria by capillary gas chromatography and mass spectrometry.

PubMed

Gailly, C; Sandra, P; Verzele, M; Cocito, C

1982-06-15

The cell wall of leprosy-derived corynebacteria (a group of 'diphtheroids' isolated from human leprosy lesions and patients' blood) was previously shown to contain, in addition to peptidoglycan and arabinogalactan, mycolic acids. These alpha-branched beta-hydroxy fatty acids were attributed to the corynomycolic group, according to their RF in monodimensional thin-layer chromatography. In the present work, mycolic acids from leprosy-derived and reference corynebacteria have been fractionated by monodimensional and bidimensional thin-layer chromatography and by gas chromatography. Pyrolyzed mycolic acids have been analyzed on conventional packed columns, whereas intact methyl esters of mycolic acids with free and silylated beta-hydroxyl group have been analyzed on capillary columns, and their structure has been established by mass spectrometry. In all leprosy-derived corynebacteria, some 20 components containing 24-36 carbon atoms and 0-4 double bonds were obtained. The three major groups had 32, 34 and 36 carbons, and the frequency of unsaturated versus saturated chains increased proportionally to the molecular weight. For comparison, the main components of a reference corynebacterium. Corynebacterium diphtheriae PW8, had 30 and 32 carbons, and their hydrocarbon chains were essentially saturated. This work confirms the relative chemical homogeneity of different leprosy-derived corynebacteria and describes some peculiar traits in the chemical structure of this group of organisms. In addition, it shows the complexity of the mycolic acid fraction of corynebacterial cell wall and suggests that the mycolic acid pattern is a sort of fingerprint of each bacterial strain grown under standard conditions. Finally, the fractionation of intact corynomycolic acid methyl esters with free or silylated beta-hydroxyl group by capillary gas chromatography proved to be the best analytical procedure at present available for resolving this complex mixture of corynomycolate isomers. Structural determination of silylated samples by mass spectrometry is preferred because they have more diagnostic fragments.

Identification and distribution of sulfate reducing bacteria and sulphur-oxidising bacteria in northern South China Sea

NASA Astrophysics Data System (ADS)

Mao, S.; Zhu, X.; Guan, H.; Wu, D.; Wu, N.

2015-12-01

Fatty acids are one of the major components in modern marine sediments. It is well known that the saturated short-chain FAs were typically to be from vascular plants, algae, bacteria, and other sources, while the saturated long-chain FAs are the major components found in leaf waxes, suberin, and cutin in terrestrial higher plants. So the lipid biomarkers of fatty acids in Site 4B from Shenhu Area, northern South China Sea were investigated in Recent research supported from the 973 Program (2009CB219506), and the resources of branched fatty acids and monounsaturated fatty acids were mainly discussed. The results reveal that i/a15:0, i/a17:0, 16:1ω5, 18:1ω9 and 10me16:0 are derived from sulfate reducing bacteria (SRB), while 16:1ω7t/c and 18:1ω7 are originated from sulphur-oxidising bacteria (SOB). The biomakers of methanotrophs such as 16:1ω6/8 and 18:1ω6/8 were not detected in the sediments which coincide with more positive carbon isotope values of the fatty acids in the sediments. The stable relationship between SRB and SOB below 97cm in the sediments reflects the relative stable oxidative and reductive depositional environment which may be connected with the sulphur cycle in the sediments, that is carried out as sulfate is reduced to sulfide, and then sulfide is oxidized to sulfate and elemental sulfur, at last elemental sulfur is disproportionated to sulfide and sulfate. The frequently changed relationship of SRB and SOB above 97cm in the sediments indicates intensely changing oxidative and reductive sedimental environment, that may related with diapir structure around Site 4B, which also brings about hydrocarbon seepage leading to increasing biomass at 97cm.

40 CFR 79.33 - Motor vehicle diesel fuel.

Code of Federal Regulations, 2010 CFR

2010-07-01

... data may be for such shorter period. (1) Hydrocarbon composition (aromatic content, olefin content, saturate content), with the methods of analysis identified; (2) Polynuclear organic material content, sulfur content, and trace element content, with the methods of analysis identified; (3) Distillation...

Self-Assemblies of novel molecules, VECAR

NASA Astrophysics Data System (ADS)

Shrestha, Bijay; Kim, Hye-Young; Lee, Soojin; Novak, Brian; Moldovan, Dorel

2015-03-01

VECAR is a newly synthesized molecule, which is an amphiphilic antioxidant molecule that consists of two molecular groups, vitamin-E and Carnosine, linked by a hydrocarbon chain. The hydrocarbon chain is hydrophobic and both vitamin-E and Carnosine ends are hydrophilic. In the synthesis process, the length of the hydrophobic chain of VECAR molecules can vary from the shortest (n =0) to the longest (n =18), where n indicates the number of carbon atoms in the chain. We conducted MD simulation studies of self-assembly of VECAR molecules in water using GROMACS on LONI HPC resources. Our study shows that there is a strong correlation between the shape and atomistic structure of the self-assembled nano-structures (SANs) and the chain-length (n) of VECAR molecules. We will report the results of data analyses including the atomistic structure of each SANs and the dynamic and energetic mechanisms of their formation as function of time. In summary, both VECAR molecules of chain-length n =18 and 9 form worm-like micelles, which may be used as a drug delivery system. This research is supported by the Louisiana Board of Regents-RCS Grant (LEQSF(2012-15)-RD-A-19).

Effect of lipid structure on the dipole potential of phosphatidylcholine bilayers.

PubMed

Clarke, R J

1997-07-25

A fluorescent ratio method utilizing styrylpyridinium dyes has recently been suggested for the measurement of the membrane dipole potential. Up to now only qualititative measurements have been possible. Here the fluorescence excitation ratio of the dye di-8-ANEPPS has been measured in lipid vesicles composed of a range of saturated and unsaturated phosphatidylcholines. It has been found that the fluorescence ratio is inversely proportional to the surface area occupied by the lipid in its fully hydrated state. This finding allows, by extra- and interpolation, the packing density to be estimated of phosphatidylcholines for which X-ray crystallographic data are not yet available. Comparison of the fluorescence data with literature data of the dipole potential from electrical measurements on monolayers and bilayers allows a calibration curve to be constructed, so that a quantitative determination of the dipole potential using di-8-ANEPPS is possible. It has been found that the value of the dipole potential decreases with increasing unsaturation and, in the case of unsaturated lipids, with increasing length of the hydrocarbon chains. This effect can be explained by the effects of chain packing on the spacing between the headgroups. In addition to the effects of lipid structure on membrane fluidity, these measurements demonstrate the possibility of a direct electrical mechanism for lipid regulation of protein function, in particular of ion transport proteins.

Laboratory spectroscopic analyses of electron irradiated alkanes and alkenes in solar system ices

NASA Astrophysics Data System (ADS)

Hand, K. P.; Carlson, R. W.

2012-03-01

We report results from laboratory experiments of 10 keV electron irradiation of thin ice films of water and short-chain hydrocarbons at ˜10-8 Torr and temperatures ranging from 70-100 K. Hydrocarbon mixtures include water with C3H8, C3H6, C4H10 (butane and isobutane), and C4H8, (1-butene and cis/trans-2-butene). The double bonds of the alkenes in our initial mixtures were rapidly destroyed or converted to single carbon bonds, covalent bonds with hydrogen, bonds with -OH (hydroxyl), bonds with oxygen (C-O), or double bonds with oxygen (carbonyl). Spectra resulting from irradiation of alkane and alkene ices are largely indistinguishable; the initial differences in film composition are destroyed and the resulting mixture includes long-chain, branched aliphatics, aldehydes, ketones, esters, and alcohols. Methane was observed as a product during radiolysis but CO was largely absent. We find that while some of the carbon is oxidized and lost to CO2 formation, some carbon is sequestered into highly refractory, long-chain aliphatic compounds that remain as a thin residue even after the ice film has been raised to standard temperature and pressure. We conclude that the high availability of hydrogen in our experiments leads to the formation of the formyl radical which then serves as the precursor for formaldehyde and polymerization of longer hydrocarbon chains.

Cuticular Waxes of Arabidopsis thaliana Shoots: Cell-Type-Specific Composition and Biosynthesis

PubMed Central

Hegebarth, Daniela; Jetter, Reinhard

2017-01-01

It is generally assumed that all plant epidermis cells are covered with cuticles, and the distinct surface geometries of pavement cells, guard cells, and trichomes imply functional differences and possibly different wax compositions. However, experiments probing cell-type-specific wax compositions and biosynthesis have been lacking until recently. This review summarizes new evidence showing that Arabidopsis trichomes have fewer wax compound classes than pavement cells, and higher amounts of especially long-chain hydrocarbons. The biosynthesis machinery generating this characteristic surface coating is discussed. Interestingly, wax compounds with similar, long hydrocarbon chains had been identified previously in some unrelated species, not all of them bearing trichomes. PMID:28686187

Novel long-chain anteiso-alkanes and anteiso-alkanoic acids in Antarctic rocks colonized by living and fossil cryptoendolithic microorganisms

NASA Technical Reports Server (NTRS)

Matsumoto, G. I.; Friedmann, E. I.; Watanuki, K.; Ocampo-Friedmann, R.

1992-01-01

Saponified extracts of rock samples colonized by cryptoendolithic microbial communities from the McMurdo Dry Valleys of Southern Victoria Land, Antarctica, were separated into hydrocarbon and fatty acid fractions by silica gel column chromatography. Hydrocarbons and methyl esters of fatty acids were analyzed by capillary gas chromatography-mass spectrometry. Unusually, a suite of long-chain anteiso-alkanes (a-C20 to a-C30) and anteiso-alkanoic acids (a-C20 to a-C30) were detected in many samples, together with straight-chain, branched and/or cyclic and acyclic isoprenoid compounds. These novel compounds are probably derived from unidentified heterotrophic bacteria or symbiotic processes in a unique microbial community in the Antarctic cold desert and suggest the occurrence of a special biosynthetic pathway. Long-chain anteiso-alkanes are probably formed through microbial decarboxylation of corresponding anteiso-alkanoic acids. They may serve as new biomarkers in environmental and geochemical studies.

Empirical correlation between hydrophobic free energy and aqueous cavity surface area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reynolds, J.A.; Gilbert, D.B.; Tanford, C.

1974-08-01

The unitary free energy of transfer of a hydrocarbon molecule from a hydrocarbon solvent to an aqueous medium is a measure of the hydrophobic interaction in the aqueous medium. We have reexamined available data on this phenomenon and have confirmed that the free energy for saturated hydrocarbons is proportional to the surface area of the cavity created by the solute in the aqueous solution, with the same proportionality constant for linear, branched, and cyclic hydrocarbon molecules. The numerical value of the proportionality constant is uncertain because absolute and self-consistent area measurements are not available. We estimate that it falls betweenmore » 20 and 25 cal/mole per Angstrom/sup 2/ at 25/sup 0/ (for areas measured at the distance of closest approach of water molecules), which is significantly less than the figure of 33 cal/mole per Angstrom/sup 2/ that has been assigned to the same parameter by Hermann.« less

Effects of Hydrocarbon Extraction on Landscapes of the Appalachian Basin

USGS Publications Warehouse

Slonecker, Terry E.; Milheim, Lesley E.; Roig-Silva, Coral M.; Kalaly, Siddiq S.

2015-09-30

The need for energy resources has created numerous economic opportunities for hydrocarbon extraction in the Appalachian basin. The development of alternative energy natural gas resources from deep-shale drilling techniques, along with conventional natural gas extraction methods, has created a flurry of wells, roads, pipelines, and related infrastructure across many parts of the region. An unintended and sometimes overlooked consequence of these activities is their effect on the structure and function of the landscape and ecosystems. The collective effect of over 100,000 hydrocarbon extraction permits for oil, coal bed methane, Marcellus and Utica Shale natural gas wells, and other types of hydrocarbon gases and their associated infrastructure has saturated much of the landscape and disturbed the natural environment in the Appalachian basin. The disturbance created by the sheer magnitude of the development of these collective wells and infrastructure directly affects how the landscape and ecosystems function and how they provide ecological goods and services. 

Direct Detection of Hardly Detectable Hidden Chirality of Hydrocarbons and Deuterated Isotopomers by a Helical Polyacetylene through Chiral Amplification and Memory.

PubMed

Maeda, Katsuhiro; Hirose, Daisuke; Okoshi, Natsuki; Shimomura, Kouhei; Wada, Yuya; Ikai, Tomoyuki; Kanoh, Shigeyoshi; Yashima, Eiji

2018-03-07

We report the first direct chirality sensing of a series of chiral hydrocarbons and isotopically chiral compounds (deuterated isotopomers), which are almost impossible to detect by conventional optical spectroscopic methods, by a stereoregular polyacetylene bearing 2,2'-biphenol-derived pendants. The polyacetylene showed a circular dichroism due to a preferred-handed helix formation in response to the hardly detectable hidden chirality of saturated tertiary or chiroptical quaternary hydrocarbons, and deuterated isotopomers. In sharp contrast to the previously reported sensory systems, the chirality detection by the polyacetylene relies on an excess one-handed helix formation induced by the chiral hydrocarbons and deuterated isotopomers via significant amplification of the chirality followed by its static memory, through which chiral information on the minute and hidden chirality can be stored as an excess of a single-handed helix memory for a long time.

n-hydrocarbons conversions over metal-modified solid acid catalysts

NASA Astrophysics Data System (ADS)

Zarubica, A.; Ranđelović, M.; Momčilović, M.; Radulović, N.; Putanov, P.

2013-12-01

The quality of a straight-run fuel oil can be improved if saturated n-hydrocarbons of low octane number are converted to their branched counterparts. Poor reactivity of traditional catalysts in isomerization reactions imposed the need for the development of new catalysts among which noble metal promoted acid catalysts, liquid and/or solid acid catalysts take a prominent place. Sulfated zirconia and metal promoted sulfated zirconia exhibit high activity for the isomerization of light alkanes at low temperatures. The present paper highlights the original results which indicate that the modification of sulfated zirconia by incorporation of metals (platinum and rhenium) significantly affects catalytic performances in n-hydrocarbon conversion reactions. Favourable activity/selectivity of the promoted sulfated zirconia depends on the crystal phase composition, critical crystallites sizes, platinum dispersion, total acidity and type of acidity. Attention is also paid to the recently developed solid acid catalysts used in other conversion reactions of hydrocarbons.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bence, A.E.; Burns, W.A.

A procedure has been developed that discriminates Exxon Valdez crude from other sources of hydrocarbons found in Prince Williams Sound and the Gulf of Alaska. The procedure uses polycyclic aromatic hydrocarbon (PAH) distributions, measured by gas chromatography/mass spectrometry (GC/MS), to fingerprint sample extracts. The relative abundances of alkylated phenanthrenes, dibenzothiophenes, and chrysenes are used to differentiate Exxon Valdez crude and its weathering products from other hydrocarbons. Saturate fraction distributions are used to confirm the PAH identification whenever possible. The procedure has been applied to the more than 1,500 PAH analyses of tissues reported by the Oil Spill Health Task Force,more » formed after the spill to assess subsistence food safety, and nearly 4,700 PAH analyses of biological samples in PWSOIL, the government`s damage-assessment chemistry database. These two datasets constitute the largest collection of hydrocarbon analyses of biological samples form the spill-impact zone. 70 refs., 14 figs., 8 tabs.« less

Phenomenological model and phase behavior of saturated and unsaturated lipids and cholesterol.

PubMed

Putzel, G Garbès; Schick, M

2008-11-15

We present a phenomenological theory for the phase behavior of ternary mixtures of cholesterol and saturated and unsaturated lipids, one that describes both liquid and gel phases. It leads to the following description of the mechanism of the phase behavior: In a binary system of the lipids, phase separation occurs when the saturated chains are well ordered, as in the gel phase, simply due to packing effects. In the liquid phase, the saturated ones are not sufficiently well ordered for separation to occur. The addition of cholesterol, however, increases the saturated lipid order to the point that phase separation is once again favorable. Our theory addresses this last mechanism-the means by which cholesterol-mediated ordering of membrane lipids leads to liquid-liquid immiscibility. It produces, for the system above the main chain transition of the saturated lipid, phase diagrams in which there can be liquid-liquid phase separation in the ternary system but not in any of the binary ones, while below that temperature it yields the more common phase diagram in which a gel phase, rich in saturated lipid, appears in addition to the two liquid phases.

Systems and methods for separation and purification of products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weiss, Michael Joseph; Gilliam, Ryan J.; Self, Kyle

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with an unsaturated hydrocarbon and/or a saturated hydrocarbon to form products. Separation and/or purification of the products as well as of the metal ions in the lower oxidation state and the higher oxidation state, is provided herein.

Evaporation and Hydrocarbon Chain Conformation of Surface Lipid Films

PubMed Central

Sledge, Samiyyah M.; Khimji, Hussain; Borchman, Douglas; Oliver, Alexandria; Michael, Heidi; Dennis, Emily K.; Gerlach, Dylan; Bhola, Rahul; Stephen, Elsa

2016-01-01

Purpose The inhibition of the rate of evaporation (Revap) by surface lipids is relevant to reservoirs and dry eye. Our aim was to test the idea that lipid surface films inhibit Revap. Methods Revap were determined gravimetrically. Hydrocarbon chain conformation and structure were measured using a Raman microscope. Six 1-hydroxyl hydrocarbons (11–24 carbons in length) and human meibum were studied. Reflex tears were obtained from a 62-year-old male. Results The Raman scattering intensity of the lipid film deviated by about 7 % for hydroxyl lipids and varied by 21 % for meibum films across the entire film at a resolution of 5 µm2. All of the surface lipids were ordered. Revap of the shorter chain hydroxyl lipids were slightly (7%) but significantly lower compared with the longer chain hydroxyl lipids. Revap of both groups was essentially similar to that of buffer. A hydroxyl lipid film did not influence Revap over an estimated average thickness range of 0.69 to >6.9 µm. Revap of human tears and buffer with and without human meibum (34.4 µm thick) was not significantly different. Revap of human tears was not significantly different from buffer. Conclusions Human meibum and hydroxyl lipids, regardless of their fluidity, chain length, or thickness did not inhibit Revap of buffer or tears even though they completely covered the surface. It is unlikely that hydroxyl lipids can be used to inhibit Revap of reservoirs. Our data do not support the widely accepted (yet unconfirmed) idea that the tear film lipid layer inhibits Revap of tears. PMID:27395776

Structural analyses of polymorphic transitions of sn-1, 3-distearoyl-2-oleoylglycerol (SOS) and sn-1, 3-dioleoyl-2-stearoylglycerol (OSO): assessment on steric hindrance of unsaturated and saturated acyl chain interactions.

PubMed

Yano, J; Sato, K; Kaneko, F; Small, D M; Kodali, D R

1999-01-01

Polymorphic transformations in two saturated-unsaturated mixed acid triacylglycerols, SOS (sn -1,3-distearoyl-2-oleoylglycerol) and OSO (sn -1,3-dioleoyl-2-stearoylglycerol), have been studied by FT-IR spectroscopy using deuterated specimens in which stearoyl chains are fully deuterated. A reversible phase transition between sub alpha and alpha and a series of irreversible transitions (alpha-->gamma-->beta'-->beta (beta2, beta1) for SOS and alpha-->beta'-->beta for OSO) were studied with an emphasis on the conformational ordering process of stearoyl and oleoyl chains. The alpha-->sub alpha reversible transition was due to the orientational change of stearoyl chains in the lateral directions from the hexagonal subcell to a perpendicularly packed one. As the first stage of the series of irreversible transitions from alpha to beta, the conformational ordering of saturated chains took place in the alpha-->gamma transition of SOS and in the alpha-->beta' transition of OSO; one stearoyl chain in SOS and OSO takes the all-trans conformation and the second stearoyl chain in SOS takes the bent conformation like those observed in the most stable beta-type. As the final stage, the ordering of unsaturated chains occurred in the beta'-->beta transition both for SOS and OSO. A conversion in the layered structure from bilayer to trilayer was also accompanied by the conformational ordering in the alpha-->gamma transition of SOS and in the beta'-->beta transition of OSO.

Acyl chain unsaturation modulates distribution of lecithin molecular species between mixed micelles and vesicles in model bile. Implications for particle structure and metastable cholesterol solubilities.

PubMed

Cohen, D E; Carey, M C

1991-08-01

We determined the distribution of lecithin molecular species between vesicles and mixed micelles in cholesterol super-saturated model biles (molar taurocholate-lecithin-cholesterol ratio 67:23:10, 3 g/dl, 0.15 M NaCl, pH approximately 6-7) that contained equimolar synthetic lecithin mixtures or egg yolk or soybean lecithins. After apparent equilibration (48 h), biles were fractionated by Superose 6 gel filtration chromatography at 20 degrees C, and lecithin molecular species in the vesicle and mixed micellar fractions were quantified as benzoyl diacylglycerides by high performance liquid chromatography. With binary lecithin mixtures, vesicles were enriched with lecithins containing the most saturated sn-1 or sn-2 chains by as much as 2.4-fold whereas mixed micelles were enriched in the more unsaturated lecithins. Vesicles isolated from model biles composed of egg yolk (primarily sn-1 16:0 and 18:0 acyl chains) or soy bean (mixed saturated and unsaturated sn-1 acyl chains) lecithins were selectively enriched (6.5-76%) in lecithins with saturated sn-1 acyl chains whereas mixed micelles were enriched with lecithins composed of either sn-1 18:1, 18:2, and 18:3 unsaturated or sn-2 20:4, 22:4, and 22:6 polyunsaturated chains. Gel filtration, lipid analysis, and quasielastic light scattering revealed that apparent micellar cholesterol solubilities and metastable vesicle cholesterol/lecithin molar ratios were as much as 60% and 100% higher, respectively, in biles composed of unsaturated lecithins. Acyl chain packing constraints imposed by distinctly different particle geometries most likely explain the asymmetric distribution of lecithin molecular species between vesicles and mixed micelles in model bile as well as the variations in apparent micellar cholesterol solubilities and vesicle cholesterol/lecithin molar ratios.(ABSTRACT TRUNCATED AT 250 WORDS)

HOMOGENEOUS CATALYSTS FOR THE PARTIAL-OXYGENATION OF SATURATED HYDROCARBONS WITH HYDROGEN PERIOXIDE

EPA Science Inventory

A Methodology for the Evaluation of Process Sustainability
Michael Gonzalez*, Raymond Smith and Thomas Becker

United States Environmental Protection Agency; Office of Research and Development; Sustainable Technologies Division; 26 West Martin Luther King Drive; Cincinna...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rostron, B.; Toth, J.

Lenticular reservoirs are accompanied by diagnostic pore-pressure anomalies when situated in a field of formation-fluid flow. Computer simulations have shown that these anomalies depend on the size and shape of the lens, the direction and intensity of flow, and the hydraulic conductivity contrast between the lens and the surrounding rock. Furthermore, the anomalies reflect the position of the petroleum-saturated portion of a lens since hydraulic conductivity is related to hydrocarbon content. Studies to date have shown that for an oil-free lens a pair of oppositely directed, symmetrical pressure anomalies exists. Each pair consists of a positive and a negative anomaly,more » respectively, at the downstream and upstream ends of the lens. A 2000-m long lens could generate a 200-kPa anomaly in a commonly occurring gravity-flow field. A lens that is filled with hydrocarbons will create a lower conductivity reservoir thus causing negative anomalies at the downstream and positive anomalies at the upstream ends of the lens. The paired anomaly for a partially full lens falls in between these two end members. Pore-pressure distributions from drill-stem tests in mature, well-explored regions can be compared to computer-simulated pore-pressure anomaly patterns. Results can be interpreted in terms of the lens geometry and degree of hydrocarbon saturation.« less

Line active hybrid lipids determine domain size in phase separation of saturated and unsaturated lipids.

PubMed

Brewster, Robert; Safran, Samuel A

2010-03-17

A simple model of the line activity of a hybrid lipid (e.g., POPC) with one fully saturated chain and one partially unsaturated chain demonstrates that these lipids preferentially pack at curved interfaces between phase-separated saturated and unsaturated domains. We predict that the domain sizes typically range from tens to hundreds of nm, depending on molecular interactions and parameters such as molecular volume and area per headgroup in the bulk fluid phase. The role of cholesterol is taken into account by an effective change in the headgroup areas and the domain sizes are predicted to increase with cholesterol concentration. Copyright 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Acoustic and mechanical response of reservoir rocks under variable saturation and effective pressure.

PubMed

Ravazzoli, C L; Santos, J E; Carcione, J M

2003-04-01

We investigate the acoustic and mechanical properties of a reservoir sandstone saturated by two immiscible hydrocarbon fluids, under different saturations and pressure conditions. The modeling of static and dynamic deformation processes in porous rocks saturated by immiscible fluids depends on many parameters such as, for instance, porosity, permeability, pore fluid, fluid saturation, fluid pressures, capillary pressure, and effective stress. We use a formulation based on an extension of Biot's theory, which allows us to compute the coefficients of the stress-strain relations and the equations of motion in terms of the properties of the single phases at the in situ conditions. The dry-rock moduli are obtained from laboratory measurements for variable confining pressures. We obtain the bulk compressibilities, the effective pressure, and the ultrasonic phase velocities and quality factors for different saturations and pore-fluid pressures ranging from normal to abnormally high values. The objective is to relate the seismic and ultrasonic velocity and attenuation to the microstructural properties and pressure conditions of the reservoir. The problem has an application in the field of seismic exploration for predicting pore-fluid pressures and saturation regimes.

Effects of imidazolium-based ionic surfactants on the size and dynamics of phosphatidylcholine bilayers with saturated and unsaturated chains.

PubMed

Lee, Hwankyu

2015-07-01

Imidazolium-based ionic surfactants of different sizes were simulated with 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayers. Regardless of the phospholipid type, larger surfactants at higher concentrations more significantly insert into the bilayer and increase the bilayer-surface size, in agreement with experiments and previous simulations. Insertion of surfactants only slightly decreases the bilayer thickness, as also observed in experiments. Although the surfactant insertion and its effect on the bilayer size and thickness are similar in different types of bilayers, the volume fractions of surfactants in the bilayer are higher for DMPC bilayers than for POPC and DOPC bilayers. In particular, ionic surfactants with four hydrocarbons yield their volume fractions of 4.6% and 8.7%, respectively, in POPC and DMPC bilayers, in quantitative agreement with experimental values of ∼5% and ∼10%. Also, the inserted surfactants increase the lateral diffusivity of the bilayer, which depends on the bilayer type. These findings indicate that although the surfactant insertion does not depend on the bilayer type, the effects of surfactants on the volume fraction and bilayer dynamics occur more significantly in the DMPC bilayer because of the smaller area per lipid and shorter saturated tails, which helps explain the experimental observations regarding different volume fractions of surfactants in POPC and DMPC bilayers. Copyright © 2015 Elsevier Inc. All rights reserved.

A potential bioactive hard-stock fat replacer comprised of a molecular gel.

PubMed

Rogers, Michael A; Spagnuolo, Paul A; Wang, Tzu-Min; Angka, Leonard

2017-05-01

Short-chain ceramides, such as N -acetoyl-d-erythro-sphingosine (C2), have a remarkable ability to structure edible oils, such as canola oil, into self-standing organogels without any added saturated or trans fats. These short-chain ceramides are ubiquitously found in foods ranging from eggs to soybeans. As the ceramide fatty acid chain length increases, there is an increase in the melting temperature of the organogel and a decrease in the elastic modulus. Gelation ability is lost at 2 wt% when the fatty acid chain length increases to six carbons; however, organogels form at 5 wt% up to 18 carbons. Short-chain ceramides, C2, decrease cell viability of colon, prostate, ovarian, and leukemia cell lines, while ceramides with long-chain fatty acids, C18, do not affect the viability of these cancer cell lines. This suggests that a bioactive spreadable fat, with no trans or added saturated fat, with the potential to alter the viability of cancer cell growth, is possible.

Tocopherol activity correlates with its location in a membrane: A new perspective on the anti-oxidant Vitamin E

NASA Astrophysics Data System (ADS)

Marquardt, Drew; Williams, Justin; Kucerka, Norbert; Atkinson, Jeffrey; Katsaras, John; Wassall, Stephen; Harroun, Thad

2013-03-01

There are no proven health benefits to supplementing with Vitamin E, so why do we require it for healthy living? The whole notion that vitamin E is an in-vivo antioxidant is now being seriously questioned. Using neutron diffraction and supporting techniques, we have correlated vitamin E's location in model membranes with its antioxidant activity. experiments were conducted using phosphatidylcholine (PC) bilayers whose fatty acid chains varied in their degree of unsaturation. We observe vitamin E up-right in all lipids examined, with its overall height in the bilayer lipid dependant. Interestingly we observe vitamin E's hydroxyl in the headgroup region of the bilayer for both the fully saturated and poly unsaturated lipids. Vitamin E was most effective at intercepting water borne oxidants than radical initiated within the bilayer core. However for lipids where vitamin E resides slightly lower (glycerol backbone) we observe comparable antioxidant activity against both water borne and hydrocarbon borne oxidants. Thus showing lipid species can modulate the location of vitamin E's activity.

Sodium, saturated fat, and trans fat content per 1,000 kilocalories: temporal trends in fast-food restaurants, United States, 2000-2013.

PubMed

Urban, Lorien E; Roberts, Susan B; Fierstein, Jamie L; Gary, Christine E; Lichtenstein, Alice H

2014-12-31

Intakes of sodium, saturated fat, and trans fat remain high despite recommendations to limit these nutrients for cardiometabolic risk reduction. A major contributor to intake of these nutrients is foods prepared outside the home, particularly from fast-food restaurants. We analyzed the nutrient content of frequently ordered items from 3 US national fast-food chains: fried potatoes (large French fries), cheeseburgers (2-oz and 4-oz), and a grilled chicken sandwich. We used an archival website to obtain data on sodium, saturated fat, and trans fat content for these items from 2000 through 2013. The amount of each nutrient per 1,000 kcal was calculated to determine whether there were trends in product reformulation. Sodium content per 1,000 kcal differed widely among the 3 chains by food item, precluding generalizations across chains. During the 14-year period, sodium content per 1,000 kcal for large French fries remained high for all 3 chains, although the range narrowed from 316-2,000 mg per 1,000 kcal in 2000 to 700-1,420 mg per 1,000 kcal in 2013. Among the items assessed, cheeseburgers were the main contributor of saturated fat, and there was little change in content per 1,000 kcal for this item during the 14-year period. In contrast, there was a sharp decline in saturated and trans fat content of large French fries per 1,000 kcal. Post-2009, the major contributor of trans fat per 1,000 kcal was cheeseburgers; trans fat content of this item remained stable during the 14-year period. With the exception of French fries, little evidence was found during the 14-year period of product reformulation by restaurants to become more consistent with dietary guidance to reduce intakes of sodium and saturated fat.

RECOVERY OF METAL VALUES FROM AQUEOUS SOLUTIONS BY SOLVENT EXTRACTION

DOEpatents

Moore, R.L.

1959-09-01

An organic solvent mixure is described for extracting actinides from aqueous solutions; the solvent mixture consists of from 10 to 25% by volume of tributyl phosphate and the remainder a chlorine-fluorine-substituted saturated hydrocarbon having two carbon atoms in the molecule.

Migration of selected hydrocarbon contaminants into dry semolina and egg pasta packed in direct contact with virgin paperboard and polypropylene film.

PubMed

Barp, Laura; Suman, Michele; Lambertini, Francesca; Moret, Sabrina

2015-01-01

Migration of mineral oil saturated hydrocarbons (MOSH), polyolefin oligomeric saturated hydrocarbons (POSH), and polyalphaolefins (PAO from hot melts) into dry semolina and egg pasta packed in direct contact with virgin paperboard or polypropylene (PP) flexible film was studied. Migration was monitored during shelf life (up to 24 months), through storage in a real supermarket (packs kept on shelves), conditions preventing exchange with the surrounding environment (packs wrapped in aluminium foil), and storage in a warehouse (packs inside of the transport box of corrugated board). Semolina pasta packed in virgin paperboard (without hot melts) had a MOSH content lower than 1.0 mg kg(-1). An increasing contamination with PAO belonging to the adhesives used to close the boxes was detected in egg pasta, wrapped in aluminium (1.5 and 5 mg kg(-1) after 3 and 24 months, respectively). An environmental contribution to total hydrocarbon contamination was observed in egg pasta kept on shelves that, after 3 and 24 months, showed levels of PAO/MOSH < C25 around 3 and 10 mg kg(-1), respectively. The migration of POSH from PP film into egg pasta wrapped in aluminium was around 0.6 mg kg(-1) after 3 months of contact and reached 1.7 mg kg(-1) after 24 months of contact. After 9 months of contact, semolina pasta packed in PP film and stored in the transport box showed that some MOSH migrated into the pasta from the board of the transport box (through the plastic film).

Introduction to fatty acids and lipids.

PubMed

Burdge, Graham C; Calder, Philip C

2015-01-01

The purpose of this article is to describe the structure, function and metabolism of fatty acids and lipids that are of particular importance in the context of parenteral nutrition. Lipids are a heterogeneous group of molecules that share the common property of hydrophobicity. Lipids range in structure from simple short hydrocarbon chains to more complex molecules, including triacylglycerols, phospholipids and sterols and their esters. Lipids within each class may differ structurally. Fatty acids are common components of complex lipids, and these differ according to chain length and the presence, number and position of double bonds in the hydrocarbon chain. Structural variation among complex lipids and among fatty acids gives rise to functional differences that result in different impacts upon metabolism and upon cell and tissue responses. Fatty acids and complex lipids exhibit a variety of structural variations that influence their metabolism and their functional effects. © 2015 S. Karger AG, Basel.

Low temperature hydrothermal maturation of organic matter in sediments from the Atlantis II Deep, Red Sea.

PubMed

Simoneit, B R; Grimalt, J O; Hayes, J M; Hartman, H

1987-01-01

Hydrocarbons and bulk organic matter of two sediment cores (No. 84 and 126, CHAIN 61 cruise) located within the Atlantis II Deep have been analyzed. Although the brines overlying the coring areas were reported to be sterile, microbial inputs and minor terrestrial sources the major sedimentary organic material. This input is derived from the upper water column above the brines. Both steroid and triterpenoid hydrocarbons show that extensive acid-catalyzed reactions are occurring in the sediments. In comparison with other hydrothermal (Guaymas Basin) or intrusive systems (Cape Verde Rise), the Atlantis II Deep exhibits a lower degree of thermal maturation. This is easily deduced from the elemental composition of the kerogens and the absence of polynuclear aromatic hydrocarbons of a pyrolytic origin in the bitumen. The lack of carbon number preference among the n-alkanes suggests, especially in the case of the long chain homologs, that the organic matter of Atlantis II Deep sediments has undergone some degree of catagenesis. However, the yields of hydrocarbons are much lower than those observed in other hydrothermal areas. The effect of lower temperature and poor source-rock characteristics appear to be responsible for the differences.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krotov, V.V.; Staroverov, S.M.; Nesterenko, P.N.

A series of heterogeneous catalysts for asymmetric Michael additions was synthesized based on ephedrine chemically bound to the surface of silica. The length of the hydrocarbon chain binding the active center to the support surface affects the sign of rotation of the reaction product from the asymmetric addition of thiophenol to benzylideneacetophenone. Grafting ephedrine to the silica surface via a short hydrocarbon chain results in a change in the configuration of the reaction product. Silanol groups on the silica surface are involved in the transition state, as evidenced by data obtained using silica which has been exhaustively treated with trimethylchlorosilane.more » The absolute specific rotation of 1,3-diphenyl-3-thiophenylpropan-1-one has been established.« less

Inhibition of telomerase by linear-chain fatty acids: a structural analysis.

PubMed Central

Oda, Masako; Ueno, Takamasa; Kasai, Nobuyuki; Takahashi, Hirotada; Yoshida, Hiromi; Sugawara, Fumio; Sakaguchi, Kengo; Hayashi, Hideya; Mizushina, Yoshiyuki

2002-01-01

In the present study, we have found that mono-unsaturated linear-chain fatty acids in the cis configuration with C(18) hydrocarbon chains (i.e. oleic acid) strongly inhibited the activity of human telomerase in a cell-free enzymic assay, with an IC(50) value of 8.6 microM. Interestingly, fatty acids with hydrocarbon chain lengths below 16 or above 20 carbons substantially decreased the potency of inhibition of telomerase. Moreover, the cis-mono-unsaturated C(18) linear-chain fatty acid oleic acid was the strongest inhibitor of all the fatty acids tested. A kinetic study revealed that oleic acid competitively inhibited the activity of telomerase ( K (i)=3.06 microM) with respect to the telomerase substrate primer. The energy-minimized three-dimensional structure of the linear-chain fatty acid was calculated and modelled. A molecule width of 11.53-14.26 A (where 1 A=0.1 nm) in the C(16) to C(20) fatty acid structure was suggested to be important for telomerase inhibition. The three-dimensional structure of the telomerase active site (i.e. the substrate primer-binding site) appears to have a pocket that could bind oleic acid, with the pocket being 8.50 A long and 12.80 A wide. PMID:12121150

Structural and phase transition changes of sodium dodecyl sulfate micellar solution in alcohols probed by small-angle neutron scattering (SANS)

NASA Astrophysics Data System (ADS)

Putra, Edy Giri Rachman; Patriati, Arum

2015-04-01

Small-angle neutron scattering (SANS) measurements on 0.3M sodium dodecyl sulfate (SDS) micellar solutions have been performed in the presence of n-alcohols, from ethanol to decanol at different alcohol concentrations, 2-10 wt%. The ellipsoid micellar structure which occurred in the 0.3M SDS in aqueous solution with the size range of 30-50 Å has different behavior at various hydrocarbon chain length and concentration of alcohols. At low concentration and short chain-length of alcohols, such as ethanol, propanol, and butanol, the size of micelles reduced and had a spherical-like structure. The opposite effect occurred as medium to long chain alcohols, such as hexanol, octanol and decanol was added into the 0.3M SDS micellar solutions. The micelles structure changed to be more elongated in major axis and then crossed the critical phase transition from micellar solution into liquid crystal phase as lamellar structure emerged by further addition of alcohols. The inter-lamellar distances were also depending on the hydrocarbon chain length and concentration of alcohols. In the meantime, the persistent micellar structures occurred in addition of medium chain of n-alcohol, pentanol at all concentrations.

Tensile Fracture of Welded Polymer Interfaces: Miscibility, Entanglements, and Crazing

DOE PAGES

Ge, Ting; Grest, Gary S.; Robbins, Mark O.

2014-09-26

Large-scale molecular simulations are performed to investigate tensile failure of polymer interfaces as a function of welding time t. Changes in the tensile stress, mode of failure and interfacial fracture energy G I are correlated to changes in the interfacial entanglements as determined from Primitive Path Analysis. Bulk polymers fail through craze formation, followed by craze breakdown through chain scission. At small t welded interfaces are not strong enough to support craze formation and fail at small strains through chain pullout at the interface. Once chains have formed an average of about one entanglement across the interface, a stable crazemore » is formed throughout the sample. The failure stress of the craze rises with welding time and the mode of craze breakdown changes from chain pullout to chain scission as the interface approaches bulk strength. The interfacial fracture energy G I is calculated by coupling the simulation results to a continuum fracture mechanics model. As in experiment, G I increases as t 1/2 before saturating at the average bulk fracture energy G b. As in previous studies of shear strength, saturation coincides with the recovery of the bulk entanglement density. Before saturation, G I is proportional to the areal density of interfacial entanglements. Immiscibiltiy limits interdiffusion and thus suppresses entanglements at the interface. Even small degrees of immisciblity reduce interfacial entanglements enough that failure occurs by chain pullout and G I << G b.« less

Nile Red Detection of Bacterial Hydrocarbons and Ketones in a High-Throughput Format

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pinzon, NM; Aukema, KG; Gralnick, JA

A method for use in high-throughput screening of bacteria for the production of long-chain hydrocarbons and ketones by monitoring fluorescent light emission in the presence of Nile red is described. Nile red has previously been used to screen for polyhydroxybutyrate (PHB) and fatty acid esters, but this is the first report of screening for recombinant bacteria making hydrocarbons or ketones. The microtiter plate assay was evaluated using wild-type and recombinant strains of Shewanella oneidensis and Escherichia coli expressing the enzyme OleA, previously shown to initiate hydrocarbon biosynthesis. The strains expressing exogenous Stenotrophomonas maltophilia oleA, with increased levels of ketone productionmore » as determined by gas chromatography-mass spectrometry, were distinguished with Nile red fluorescence. Confocal microscopy images of S. oneidensis oleA-expressing strains stained with Nile red were consistent with a membrane localization of the ketones. This differed from Nile red staining of bacterial PHB or algal lipid droplets that showed intracellular inclusion bodies. These results demonstrated the applicability of Nile red in a high-throughput technique for the detection of bacterial hydrocarbons and ketones. IMPORTANCE In recent years, there has been renewed interest in advanced biofuel sources such as bacterial hydrocarbon production. Previous studies used solvent extraction of bacterial cultures followed by gas chromatography-mass spectrometry (GC-MS) to detect and quantify ketones and hydrocarbons (Beller HR, Goh EB, Keasling JD, Appl. Environ. Microbiol. 76: 1212-1223, 2010; Sukovich DJ, Seffernick JL, Richman JE, Gralnick JA, Wackett LP, Appl. Environ. Microbiol. 76: 3850-3862, 2010). While these analyses are powerful and accurate, their labor-intensive nature makes them intractable to high-throughput screening; therefore, methods for rapid identification of bacterial strains that are overproducing hydrocarbons are needed. The use of high-throughput evaluation of bacterial and algal hydrophobic molecule production via Nile red fluorescence from lipids and esters was extended in this study to include hydrocarbons and ketones. This work demonstrated accurate, high-throughput detection of high-level bacterial long-chain ketone and hydrocarbon production by screening for increased fluorescence of the hydrophobic dye Nile red.« less

LABORATORY AND FIELD RESULTS LINKING HIGH BULK CONDUCTIVITIES TO THE MICROBIAL DEGRADATION OF PETROLEUM HYDROCARBONS

EPA Science Inventory

Diesel contaminated layer (i.e. 32-45 cm) was the most geoelectrically conductive and showed the peak microbial activity. Below the saturated zone microbial enhanced mineral weathering increases the ionic concentration of pore fluids, leading to increased bulk electrical conducit...

The Influence of Process Conditions on the Chemical Composition of Pine Wood Catalytic Pyrolysis Oils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pereira, J.; Agblevor, F. A.; Beis, S. H.

Pine wood samples were used as model feedstock to study the properties of catalytic fast pyrolysis oils. The influence of two commercial zeolite catalysts (BASF and SudChem) and pretreatment of the pine wood with sodium hydroxide on pyrolysis products were investigated. The pyrolysis oils were first fractionated using column chromatography and characterized using GC-MS. Long chain aliphatic hydrocarbons, levoglucosan, aldehydes and ketones, guaiacols/syringols, and benzenediols were the major compounds identified in the pyrolysis oils. The catalytic pyrolysis increased the polycyclic hydrocarbons fraction. Significant decreases in phthalate derivatives using SudChem and long chain aliphatics using BASF catalyst were observed. Significant amountsmore » of aromatic heterocyclic hydrocarbons and benzene derivatives were formed, respectively, using BASF and SudChem catalysts. Guaiacyl/syringyl and benzenediols derivatives were partly suppressed by the zeolite catalysts, while the sodium hydroxide treatment enriched phenolic derivatives. Zeolite catalyst and sodium hydroxide were employed together; they showed different results for each catalyst.« less

Evaluation of on-line pyrolysis coupled to isotope ratio mass spectrometry for the determination of position-specific (13)C isotope composition of short chain n-alkanes (C6-C12).

PubMed

Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro

2016-06-01

We measured (13)C intramolecular isotopic composition of commercially available short-chain hydrocarbons (n-C6-n-C12) using (13)C-NMR. Results show that the main variation is between the terminal and the sub-terminal C-atom positions. Site-preference (difference in δ(13)C values between terminal and sub-terminal C-atom positions) among all the samples varies between -12.2‰ and +8.4‰. Comparison of these results with those obtained using on-line pyrolysis coupled with GC-C-IRMS show that the thermal cracking of hydrocarbons occurs with a good isotopic fidelity between terminal and sub-terminal C-atom positions of the starting material and the related pyrolysis products (methane and ethylene). On-line pyrolysis coupled with GC-C-IRMS can thus be used for tracing hydrocarbons biogeochemical processes. Copyright © 2016 Elsevier B.V. All rights reserved.

Irradiation Products On Dwarf Planet Makemake

NASA Astrophysics Data System (ADS)

Brown, M. E.; Schaller, E. L.; Blake, G. A.

2015-03-01

The dark, reddish tinged surfaces of icy bodies in the outer solar system are usually attributed to the long term irradiation of simple hydrocarbons leading to the breaking of C-H bonds, loss of hydrogen, and the production of long carbon chains. While the simple hydrocarbon methane is stable and detected on the most massive bodies in the Kuiper Belt, evidence of active irradiation chemistry is scant except for the presence of ethane on methane-rich Makemake and the possible detections of ethane on more methane-poor Pluto and Quaoar. We have obtained deep high signal-to-noise spectra of Makemake from 1.4 to 2.5 μm in an attempt to trace the radiation chemistry in the outer solar system beyond the initial ethane formation. We present the first astrophysical detection of solid ethylene and evidence for acetylene and high-mass alkanes—all expected products of the continued irradiation of methane, and use these species to map the chemical pathway from methane to long-chain hydrocarbons.

The Influence of Process Conditions on the Chemical Composition of Pine Wood Catalytic Pyrolysis Oils

DOE PAGES

Pereira, J.; Agblevor, F. A.; Beis, S. H.

2012-01-01

Pine wood samples were used as model feedstock to study the properties of catalytic fast pyrolysis oils. The influence of two commercial zeolite catalysts (BASF and SudChem) and pretreatment of the pine wood with sodium hydroxide on pyrolysis products were investigated. The pyrolysis oils were first fractionated using column chromatography and characterized using GC-MS. Long chain aliphatic hydrocarbons, levoglucosan, aldehydes and ketones, guaiacols/syringols, and benzenediols were the major compounds identified in the pyrolysis oils. The catalytic pyrolysis increased the polycyclic hydrocarbons fraction. Significant decreases in phthalate derivatives using SudChem and long chain aliphatics using BASF catalyst were observed. Significant amountsmore » of aromatic heterocyclic hydrocarbons and benzene derivatives were formed, respectively, using BASF and SudChem catalysts. Guaiacyl/syringyl and benzenediols derivatives were partly suppressed by the zeolite catalysts, while the sodium hydroxide treatment enriched phenolic derivatives. Zeolite catalyst and sodium hydroxide were employed together; they showed different results for each catalyst.« less

The growth of carbon chains in IRC +10216 mapped with ALMA⋆

PubMed Central

Agúndez, M.; Cernicharo, J.; Quintana-Lacaci, G.; Castro-Carrizo, A.; Velilla Prieto, L.; Marcelino, N.; Guélin, M.; Joblin, C.; Martín-Gago, J. A.; Gottlieb, C. A.; Patel, N. A.; McCarthy, M. C.

2017-01-01

Linear carbon chains are common in various types of astronomical molecular sources. Possible formation mechanisms involve both bottom-up and top-down routes. We have carried out a combined observational and modeling study of the formation of carbon chains in the C-star envelope IRC +10216, where the polymerization of acetylene and hydrogen cyanide induced by ultraviolet photons can drive the formation of linear carbon chains of increasing length. We have used ALMA to map the emission of λ 3 mm rotational lines of the hydrocarbon radicals C2H, C4H, and C6H, and the CN-containing species CN, C3N, HC3N, and HC5N with an angular resolution of ~1″. The spatial distribution of all these species is a hollow, 5-10″ wide, spherical shell located at a radius of 10-20″ from the star, with no appreciable emission close to the star. Our observations resolve the broad shell of carbon chains into thinner sub-shells which are 1-2″ wide and not fully concentric, indicating that the mass loss process has been discontinuous and not fully isotropic. The radial distributions of the species mapped reveal subtle differences: while the hydrocarbon radicals have very similar radial distributions, the CN-containing species show more diverse distributions, with HC3N appearing earlier in the expansion and the radical CN extending later than the rest of the species. The observed morphology can be rationalized by a chemical model in which the growth of polyynes is mainly produced by rapid gas-phase chemical reactions of C2H and C4H radicals with unsaturated hydrocarbons, while cyanopolyynes are mainly formed from polyynes in gas-phase reactions with CN and C3N radicals. PMID:28469283

Evaporation and Hydrocarbon Chain Conformation of Surface Lipid Films.

PubMed

Sledge, Samiyyah M; Khimji, Hussain; Borchman, Douglas; Oliver, Alexandria L; Michael, Heidi; Dennis, Emily K; Gerlach, Dylan; Bhola, Rahul; Stephen, Elsa

2016-10-01

The inhibition of the rate of evaporation (R evap ) by surface lipids is relevant to reservoirs and dry eye. Our aim was to test the idea that lipid surface films inhibit R evap . R evap were determined gravimetrically. Hydrocarbon chain conformation and structure were measured using a Raman microscope. Six 1-hydroxyl hydrocarbons (11-24 carbons in length) and human meibum were studied. Reflex tears were obtained from a 62-year-old male. The Raman scattering intensity of the lipid film deviated by about 7 % for hydroxyl lipids and varied by 21 % for meibum films across the entire film at a resolution of 5 μm 2 . All of the surface lipids were ordered. R evap of the shorter chain hydroxyl lipids were slightly (7%) but significantly lower compared with the longer chain hydroxyl lipids. R evap of both groups was essentially similar to that of buffer. A hydroxyl lipid film did not influence R evap over an estimated average thickness range of 0.69 to >6.9 μm. R evap of human tears and buffer with and without human meibum (34.4 μm thick) was not significantly different. R evap of human tears was not significantly different from buffer. Human meibum and hydroxyl lipids, regardless of their fluidity, chain length, or thickness did not inhibit R evap of buffer or tears even though they completely covered the surface. It is unlikely that hydroxyl lipids can be used to inhibit R evap of reservoirs. Our data do not support the widely accepted (yet unconfirmed) idea that the tear film lipid layer inhibits R evap of tears. Copyright © 2016 Elsevier Inc. All rights reserved.

Microbial Community Response to Simulated Petroleum Seepage in Caspian Sea Sediments

PubMed Central

Stagars, Marion H.; Mishra, Sonakshi; Treude, Tina; Amann, Rudolf; Knittel, Katrin

2017-01-01

Anaerobic microbial hydrocarbon degradation is a major biogeochemical process at marine seeps. Here we studied the response of the microbial community to petroleum seepage simulated for 190 days in a sediment core from the Caspian Sea using a sediment-oil-flow-through (SOFT) system. Untreated (without simulated petroleum seepage) and SOFT sediment microbial communities shared 43% bacterial genus-level 16S rRNA-based operational taxonomic units (OTU0.945) but shared only 23% archaeal OTU0.945. The community differed significantly between sediment layers. The detection of fourfold higher deltaproteobacterial cell numbers in SOFT than in untreated sediment at depths characterized by highest sulfate reduction rates and strongest decrease of gaseous and mid-chain alkane concentrations indicated a specific response of hydrocarbon-degrading Deltaproteobacteria. Based on an increase in specific CARD-FISH cell numbers, we suggest the following groups of sulfate-reducing bacteria to be likely responsible for the observed decrease in aliphatic and aromatic hydrocarbon concentration in SOFT sediments: clade SCA1 for propane and butane degradation, clade LCA2 for mid- to long-chain alkane degradation, clade Cyhx for cycloalkanes, pentane and hexane degradation, and relatives of Desulfobacula for toluene degradation. Highest numbers of archaea of the genus Methanosarcina were found in the methanogenic zone of the SOFT core where we detected preferential degradation of long-chain hydrocarbons. Sequencing of masD, a marker gene for alkane degradation encoding (1-methylalkyl)succinate synthase, revealed a low diversity in SOFT sediment with two abundant species-level MasD OTU0.96. PMID:28503173

Upgrade of Long-chain Hydrocarbons by Low Pressure Oxygen Plasmas

NASA Astrophysics Data System (ADS)

Patiño, Pedro; Méndez, Bernardo; Gambús, Gloria

1998-10-01

Huge known heavy oil deposits in many countries remain largely untapped. The API gravity of crude oils has been decreasing by about 0.17% per year, this meaning that there will be an urgent need for economically viable new technologies to upgrade the heavy oil for the refineries. The same applies to the residues of several refineries processes. This work will present the results of the application of a plasma process to upgrade long-chain hydrocarbons, namely, tridecane, tetradecane, and squalane (shark oil). They are high boiling point alkanes, the latter being a C_30H_62 with six methyl groups attached to various carbon positions on the chain. An oxygen plasma, created by a high voltage glow discharge, reached the low vapor pressure surface of each liquid hydrocarbon. This (2 mL) was cooled down to temperatures close to its freezing point in a glass reactor. Applied power was 24 W for times of reaction between 30 and 60 minutes and oxygen pressures from 0.1 to 0.4 mbar. Products were analyzed by IR and NMR spectroscopies. The ^1H and ^13C NMR spectra showed that the most important products were secondary alcohols and the corresponding ketones, for tridecane and tetradecane. For squalane, tertiary alcohols were first. Total conversions are tipically 90 to 100%

Method for machining steel with diamond tools

DOEpatents

Casstevens, J.M.

1984-01-01

The present invention is directed to a method for machine optical quality finishes and contour accuracies of workpieces of carbon-containing metals such as steel with diamond tooling. The wear rate of the diamond tooling is significantly reduced by saturating the atmosphere at the interface of the workpiece and the diamond tool with a gaseous hydrocarbon during the machining operation. The presence of the gaseous hydrocarbon effectively eliminates the deterioration of the diamond tool by inhibiting or preventing the conversion of the diamond carbon to graphite carbon at the point of contact between the cutting tool and the workpiece.

Method for machining steel with diamond tools

DOEpatents

Casstevens, John M.

1986-01-01

The present invention is directed to a method for machining optical quality inishes and contour accuracies of workpieces of carbon-containing metals such as steel with diamond tooling. The wear rate of the diamond tooling is significantly reduced by saturating the atmosphere at the interface of the workpiece and the diamond tool with a gaseous hydrocarbon during the machining operation. The presence of the gaseous hydrocarbon effectively eliminates the deterioration of the diamond tool by inhibiting or preventing the conversion of the diamond carbon to graphite carbon at the point of contact between the cutting tool and the workpiece.

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength

DOE PAGES

Ge, Ting; Robbins, Mark O.; Perahia, Dvora; ...

2014-07-25

Self-healing of polymer films often takes place as the molecules diffuse across a damaged region, above their melting temperature. Using molecular dynamics simulations we probe the healing of polymer films and compare the results with those obtained for thermal welding of homopolymer slabs. These two processes differ from each other in their interfacial structure since damage leads to increased polydispersity and more short chains. A polymer sample was cut into two separate films that were then held together in the melt state. The recovery of the damaged film was followed as time elapsed and polymer molecules diffused across the interface.more » The mass uptake and formation of entanglements, as obtained from primitive path analysis, are extracted and correlated with the interfacial strength obtained from shear simulations. We find that the diffusion across the interface is signifcantly faster in the damaged film compared to welding because of the presence of short chains. Though interfacial entanglements increase more rapidly for the damaged films, a large fraction of these entanglements are near chain ends. As a result, the interfacial strength of the healing film increases more slowly than for welding. For both healing and welding, the interfacial strength saturates as the bulk entanglement density is recovered across the interface. However, the saturation strength of the damaged film is below the bulk strength for the polymer sample. At saturation, cut chains remain near the healing interface. They are less entangled and as a result they mechanically weaken the interface. When the strength of the interface saturates, the number of interfacial entanglements scales with the corresponding bulk entanglement density. Chain stiffness increases the density of entanglements, which increases the strength of the interface. Our results show that a few entanglements across the interface are sufficient to resist interfacial chain pullout and enhance the mechanical strength.« less

Role of internal motions and molecular geometry on the NMR relaxation of hydrocarbons

NASA Astrophysics Data System (ADS)

Singer, P. M.; Asthagiri, D.; Chen, Z.; Valiya Parambathu, A.; Hirasaki, G. J.; Chapman, W. G.

2018-04-01

The role of internal motions and molecular geometry on 1H NMR relaxation rates in liquid-state hydrocarbons is investigated using MD (molecular dynamics) simulations of the autocorrelation functions for intramolecular and intermolecular 1H-1H dipole-dipole interactions. The effects of molecular geometry and internal motions on the functional form of the autocorrelation functions are studied by comparing symmetric molecules such as neopentane and benzene to corresponding straight-chain alkanes n-pentane and n-hexane, respectively. Comparison of rigid versus flexible molecules shows that internal motions cause the intramolecular and intermolecular correlation-times to get significantly shorter, and the corresponding relaxation rates to get significantly smaller, especially for longer-chain n-alkanes. Site-by-site simulations of 1H's across the chains indicate significant variations in correlation times and relaxation rates across the molecule, and comparison with measurements reveals insights into cross-relaxation effects. Furthermore, the simulations reveal new insights into the relative strength of intramolecular versus intermolecular relaxation as a function of internal motions, as a function of molecular geometry, and on a site-by-site basis across the chain.

Consistency between health risks and microbial response mechanism of various petroleum components in a typical wastewater-irrigated farmland.

PubMed

Zhang, Juan; Fan, Shu-kai

2016-06-01

Various petroleum components possess distinctive migration and toxicity characteristics. Evaluation of contamination levels on the basis of total concentrations of petroleum hydrocarbons in soil and groundwater is limited. Hunpu, a typical wastewater-irrigated area, is located at the southwest of Shenyang City, Liaoning Province, China. In this study, various fractions, exposure pathways, and soil microbial communities were taken into account to make petroleum contamination evaluation more effective and precise in the region. The concentrations and hazard quotients of aliphatic fractions, as the bulk of an oil, verified that the groundwater must not be drunk directly. The total concentrations of aliphatic hydrocarbons (TAHs) for C10-34 were 68.90-199.87 μg g(-1) in soil in Hunpu, which required cleanup according to Oklahoma criteria. However, both health and ecological risks indicated that petroleum contamination in surface soil was not serious. Microbes may use aliphatic fractions as carbon and energy source for their growth, which was indicated by positive correlation between them. TAHsC12-16 posed highest human health risks and had the most significant effect on the soil microbial composition, although its concentration was low in both the groundwater and the soil. Straight-, branched-chain saturated, and cyclopropyl phospholipid fatty acids had more closely positive correlation with TAHsC12-16, which indicated that regulation of bacterial membrane fluidity to toxic petroleum pollutants. This study can also provide the guidelines for assessment and management of petroleum contamination. Copyright © 2016 Elsevier Ltd. All rights reserved.

How Many Calories? Look at the Menu!

MedlinePlus

... food choices. This regulation will apply in chain restaurants and retail food establishments with more than 20 ... salad bar, or ordering pasta at a chain restaurant. In addition, nutrition information – like sodium or saturated ...

Water saturation effects on elastic wave attenuation in porous rocks with aligned fractures

NASA Astrophysics Data System (ADS)

Amalokwu, Kelvin; Best, Angus I.; Sothcott, Jeremy; Chapman, Mark; Minshull, Tim; Li, Xiang-Yang

2014-05-01

Elastic wave attenuation anisotropy in porous rocks with aligned fractures is of interest to seismic remote sensing of the Earth's structure and to hydrocarbon reservoir characterization in particular. We investigated the effect of partial water saturation on attenuation in fractured rocks in the laboratory by conducting ultrasonic pulse-echo measurements on synthetic, silica-cemented, sandstones with aligned penny-shaped voids (fracture density of 0.0298 ± 0.0077), chosen to simulate the effect of natural fractures in the Earth according to theoretical models. Our results show, for the first time, contrasting variations in the attenuation (Q-1) of P and S waves with water saturation in samples with and without fractures. The observed Qs/Qp ratios are indicative of saturation state and the presence or absence of fractures, offering an important new possibility for remote fluid detection and characterization.

Impact of dia- and catagenesis on sulphur and oxygen sequestration of biomarkers as revealed by artificial maturation of an immature sedimentary rock

USGS Publications Warehouse

Koopmans, M.P.; De Leeuw, J. W.; Lewan, M.D.; Sinninghe, Damste J.S.

1996-01-01

Hydrous pyrolysis of an immature (R(a)??? 0.25%) sulphur-rich marl from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin was carried out at 160C ??? T ???330 C for 72 h, to study the effect of progressive diagenesis and early catagenesis on the abundance and distribution of sulphur-containing and sulphur- and oxygen-linked carbon skeletons in low-molecular-weight and highmolecular-weight fractions (e.g. kerogen). To this end, compounds in the saturated hydrocarbon fraction, monoaromatic hydrocarbon fraction, polyaromatic hydrocarbon fraction, alkylsulphide fraction and ketone fraction were quantified, as well as compounds released after desulphurisation of the polar fraction and HI/LiAIH4 treatment of the desulphurised polar fraction. Sulphur-bound phytane and (20R)-5??,14??,17??(H) and (20R)-5??,14??,17??(H) C27 C29 steranes in the polar fraction become less abundant with increasing maturation temperature, whereas the amount of their corresponding hydrocarbons increases in the saturated hydrocarbon fraction. Carbon skeletons that are bound in the kerogen by multiple bonds (e.g. C38 n-alkane and isorenieratane) are first released into the polar fraction, and then as free hydrocarbons. These changes occur at relatively low levels of thermal maturity (R(a) <0.6%), as evidenced by the 'immature' values of biomarker maturity parameters such as the ????/(????+ ???? + ????) C35 hopane ratio and the 22S/(22S + 22R)-17??,21??(H) C35 hopane ratio. Sulphur- and oxygen-bound moieties, present in the polar fraction, are not stable with increasing thermal maturation. However, alkylthiophenes, ketones. 1,2-di-n-alkylbenzenes and free n-alkanes seem to be stable thermal degradation products of these sulphur- and oxygen-bound moieties. Thus, apart from free n-alkanes, which are abundantly present in more mature sedimentary rocks and crude oils, alkylthiophenes, 1,2-di-n-alkylbenzenes and ketones can also be expected to occur. The positions of the thiophene moiety and the carbonyl group coincide with the original positions of the functional groups of their precursors. Thus, important information about palaeobiochemicals is retained throughout the sequestration/degradation process.

Optoelectronics sensors of hydrocarbons based on NDIR technique

NASA Astrophysics Data System (ADS)

Prokopiuk, Artur

2017-08-01

Saturated hydrocarbons are mainly nontoxic, but as extremely flammable gases forming explosive mixtures with air. The Lower Explosive Level (LEL) for methane is 4.4%, which is very dangerous in the mining industry. Methane is also an asphyxiant gas causing coma or death. Therefore, continuous monitoring of the hydrocarbons concentration is very important. Optoelectronic methods are very attractive for this application, especially nondispersive infrared (NDIR) technique. It enables a direct, fast, and selective measurement of different gas concentrations. NDIR sensors have many advantages, which make them very promising for use as hydrocarbon detectors. Despite a lot of benefits, common used NDIR sensors have some disadvantages. They need periodic calibration and have limited detection range, from 100ppm. These parameters can be improved thanks to modernization detection scheme and use of newest IR sources and detectors. During Analyses selected IR sources and detectors were taken into account. Absorption spectra of analyzed hyrdrocarbons were studied to minimize impact interfering gases like carbon dioxide and water.

Impact of Reservoir Fluid Saturation on Seismic Parameters: Endrod Gas Field, Hungary

NASA Astrophysics Data System (ADS)

El Sayed, Abdel Moktader A.; El Sayed, Nahla A.

2017-12-01

Outlining the reservoir fluid types and saturation is the main object of the present research work. 37 core samples were collected from three different gas bearing zones in the Endrod gas field in Hungary. These samples are belonging to the Miocene and the Upper - Lower Pliocene. These samples were prepared and laboratory measurements were conducted. Compression and shear wave velocity were measured using the Sonic Viewer-170-OYO. The sonic velocities were measured at the frequencies of 63 and 33 kHz for compressional and shear wave respectively. All samples were subjected to complete petrophysical investigations. Sonic velocities and mechanical parameters such as young’s modulus, rigidity, and bulk modulus were measured when samples were saturated by 100%-75%-0% brine water. Several plots have been performed to show the relationship between seismic parameters and saturation percentages. Robust relationships were obtained, showing the impact of fluid saturation on seismic parameters. Seismic velocity, Poisson’s ratio, bulk modulus and rigidity prove to be applicable during hydrocarbon exploration or production stages. Relationships among the measured seismic parameters in gas/water fully and partially saturated samples are useful to outline the fluid type and saturation percentage especially in gas/water transitional zones.

Calculating in situ degradation rates of hydrocarbon compounds in deep waters of the Gulf of Mexico.

PubMed

Thessen, Anne E; North, Elizabeth W

2017-09-15

Biodegradation is an important process for hydrocarbon weathering that influences its fate and transport, yet little is known about in situ biodegradation rates of specific hydrocarbon compounds in the deep ocean. Using data collected in the Gulf of Mexico below 700m during and after the Deepwater Horizon oil spill, we calculated first-order degradation rate constants for 49 hydrocarbons and inferred degradation rate constants for an additional 5 data-deficient hydrocarbons. Resulting calculated (not inferred) half-lives of the hydrocarbons ranged from 0.4 to 36.5days. The fastest degrading hydrocarbons were toluene (k=-1.716), methylcyclohexane (k=-1.538), benzene (k=-1.333), and C1-naphthalene (k=-1.305). The slowest degrading hydrocarbons were the large straight-chain alkanes, C-26 through C-33 (k=-0.0494 through k=-0.007). Ratios of C-18 to phytane supported the hypothesis that the primary means of degradation in the subsurface was microbial biodegradation. These degradation rate constants can be used to improve models describing the fate and transport of hydrocarbons in the event of an accidental deep ocean oil spill. Copyright © 2017 Elsevier Ltd. All rights reserved.

Alkanes in fungal spores.

PubMed

Oró, J; Laseter, J L; Weber, D

1966-10-21

The chlamydospores of Ustilago maydis, U. nuda, and Sphacelotheca reiliana were analyzed by gas chromatography and mass spectrometry for their hydrocarbon contents. For the first time we observed that they contain paraffinic hydrocarbons; the average contents were 42, 58, and 146 parts per million, respectively. n-Alkanes having odd numbers of carbon atoms predom-inate, with carbon-chain lengths ranging from C(14) to C(37). The major alkanes are n-C(27) in U. maydis, n-C(27) and n-C(35) in U. nuda, and n-C(29) in S. reiliana. Each type of spore carried a distinctly characteristic population of hydrocarbons.

Temporary protection of metals against atmospheric corrosion by saturated straight chain aliphatic monocarboxylates. Mechanisms of inhibition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kapin, C.; Steinmetz, P.; Steinmetz, J.

1998-12-31

This work was devoted to the investigations of the ability of saturated straight chain aliphatic monocarboxylates to inhibit corrosion of mild steel and zinc in aerated aqueous solutions. Performances of inhibitors were shown to be dependent on their chain length, their concentration and the immersion duration. Both crystallographic parameters and solubilities of iron and zinc carboxylates were determined. Then potential-pH diagrams of iron and zinc in water were built taking the presence of metallic soaps into account. According to these diagrams, the passivation of metals was attributed to the growth of films containing metallic soaps. This model confirms that previouslymore » proposed for inhibition of copper and magnesium by the same carboxylates.« less

Application of high-performance liquid chromatography with ultraviolet diode array detection and refractive index detection to the determination of class composition and to the analysis of gasoline.

PubMed

Kamiński, Marian; Kartanowicz, Rafał; Przyjazny, Andrzej

2004-03-12

A method of effective application of normal-phase high-performance liquid chromatography (NP-HPLC) with ultraviolet diode array detection (DAD) and refractive index detection (RID) for the determination of class composition of gasoline and its components, i.e. for the determination of content of alkenes, aromatic and saturated hydrocarbons in gasoline meeting modern quality standards, has been developed. An aminopropyl-bonded silica stationary phase was used along with n-hexane or n-heptane as the mobile phase. A DAD signal integrated over the 207-240 nm range was used to determine alkenes. This eliminates the necessity of separating alkenes from saturates, because the latter do not absorb UV radiation above 200 nm. The content of aromatic hydrocarbons is determined by means of a refractive index detector. Calibration was based on hydrocarbon type composition determined by the fluorescent indicator adsorption method, ASTM D1319. The results obtained by the developed method were found to be consistent with those obtained by fluorescent indicator adsorption or by a multidimensional GC method (PIONA) (ASTM D5443). The method can be applied to gasoline meeting recent quality standards, irrespective of refining technology used in the production of gasoline components, including gasoline with various contents of oxygenates. The developed method cannot be used to determine the hydrocarbon type composition of gasoline that contains as a component the so-called pyrocondensate, i.e. the fraction with a boiling point up to 220 degrees C, obtained through thermal pyrolysis of distillation residues of crude oil or coal and, consequently, does not meet the quality standards. The paper includes the procedure for identification of this type of gasoline.

The Metabolism of Tetralin in Fischer 344 Rats

DTIC Science & Technology

1986-04-01

evaluated petroleum and shale-derived JP-5, a jet fuel composed of aliphatic and aromatic hydrocarbons with the majority of the straight-chain...much like gasoline. JP-8 is a mixture of hydrocarbons of intermediate boiling point and volatility and is similar to the civilian jet fuel , A-1. DFM...toxicity of conventional versus shale-derived JP-5 jet fuel : Light microscopy, hematologic, and serum chemistry studies. Toxicol Appl Pharmacol, 57

The influence of slavemaking lifestyle, caste and sex on chemical profiles in Temnothorax ants: insights into the evolution of cuticular hydrocarbons

PubMed Central

Kleeberg, Isabelle

2017-01-01

Chemical communication is central for the formation and maintenance of insect societies. Generally, social insects only allow nest-mates into their colony, which are recognized by their cuticular hydrocarbons (CHCs). Social parasites, which exploit insect societies, are selected to circumvent host recognition. Here, we studied whether chemical strategies to reduce recognition evolved convergently in slavemaking ants, and whether they extend to workers, queens and males alike. We studied CHCs of three social parasites and their related hosts to investigate whether the parasitic lifestyle selects for specific chemical traits that reduce host recognition. Slavemaker profiles were characterized by shorter-chained hydrocarbons and a shift from methyl-branched alkanes to n-alkanes, presumably to reduce recognition cue quantity. These shifts were consistent across independent origins of slavery and were found in isolated ants and those emerging in their mother colony. Lifestyle influenced profiles of workers most profoundly, with little effect on virgin queen profiles. We detected an across-species caste signal, with workers, for which nest-mate recognition is particularly important, carrying more and longer-chained hydrocarbons and males exhibiting a larger fraction of n-alkanes. This comprehensive study of CHCs across castes and species reveals how lifestyle-specific selection can result in convergent evolution of chemical phenotypes. PMID:28298345

Plausible surface models for Titan

NASA Technical Reports Server (NTRS)

Lunine, Jonathan I.

1992-01-01

Current understanding of the nature of Titan's surface and some new ideas for explaining the curious radar returns from Saturn's largest satellite are reviewed. Pre-Voyager models of the surface, based largely on cosmochemistry and the discovery of atmospheric methane, allowed for a range of possibilities, including pure methane oceans. The Voyager 1 flyby ruled out this last possibility, replacing it with compelling observational arguments in favor of a mixed light hydrocarbon and nitrogen ocean. Ground based radar observations indicated a surprisingly reflective surface which is inconsistent with a hydrocarbon ocean and more reminiscent of the Galilean Satellites. Nonetheless, passive radiometric measurements of the surface do not support the notion that Titan's surface is like that of the Galilean satellites. One of the arguments against hydrocarbon oceans reflecting radar energy is that most solid, complex hydrocarbon and nitriles will be denser than the liquid and sink. Nonetheless, many of the aerosol species will coagulate in highly nonspherical patterns, and some species probably polymerize in long chains. Such chains will have very low sedimendation velocities in the ocean and may remain near the surface through ocean mixing process. The prospect of an oceanic 'soup' of polar polymers acting as volume reflectors at radio wevelengths suggests that the interpretation of radar observations needs evaluation.

Desorption of hydrocarbon chains by association with ionic and nonionic surfactants under flow as a mechanism for enhanced oil recovery.

PubMed

Terrón-Mejía, Ketzasmin A; López-Rendón, Roberto; Goicochea, Armando Gama

2017-08-29

The need to extract oil from wells where it is embedded on the surfaces of rocks has led to the development of new and improved enhanced oil recovery techniques. One of those is the injection of surfactants with water vapor, which promotes desorption of oil that can then be extracted using pumps, as the surfactants encapsulate the oil in foams. However, the mechanisms that lead to the optimal desorption of oil and the best type of surfactants to carry out desorption are not well known yet, which warrants the need to carry out basic research on this topic. In this work, we report non equilibrium dissipative particle dynamics simulations of model surfactants and oil molecules adsorbed on surfaces, with the purpose of studying the efficiency of the surfactants to desorb hydrocarbon chains, that are found adsorbed over flat surfaces. The model surfactants studied correspond to nonionic and cationic surfactants, and the hydrocarbon desorption is studied as a function of surfactant concentration under increasing Poiseuille flow. We obtain various hydrocarbon desorption isotherms for every model of surfactant proposed, under flow. Nonionic surfactants are found to be the most effective to desorb oil and the mechanisms that lead to this phenomenon are presented and discussed.

Identifying Methane Sources in Groundwater; Quantifying Changes in Compositional and Stable Isotope Values during Multiphase Transport

NASA Astrophysics Data System (ADS)

Larson, T.; Sathaye, K.

2014-12-01

A dramatic expansion of hydraulic fracturing and horizontal drilling for natural gas in unconventional reserves is underway. This expansion is fueling considerable public concern, however, that extracted natural gas, reservoir brines and associated fracking fluids may infiltrate to and contaminate shallower (< 500m depth) groundwater reservoirs, thereby posing a health threat. Attributing methane found in shallow groundwater to either deep thermogenic 'fracking' operations or locally-derived shallow microbial sources utilizes geochemical methods including alkane wetness and stable carbon and hydrogen isotope ratios of short chain (C1-C5) hydrocarbons. Compared to shallow microbial gas, thermogenic gas is wetter and falls within a different range of δ13C and δD values. What is not clear, however, is how the transport of natural gas through water saturated geological media may affect its compositional and stable isotope values. What is needed is a means to differentiate potential flow paths of natural gas including 'fast paths' along preexisting fractures and drill casings vs. 'slow paths' through low permeability rocks. In this study we attempt quantify transport-related effects using experimental 1-dimensional two-phase column experiments and analytical solutions to multi-phase gas injection equations. Two-phase experimental results for an injection of natural gas into a water saturated column packed with crushed illite show that the natural gas becomes enriched in methane compared to ethane and propane during transport. Carbon isotope measurements are ongoing. Results from the multi-phase gas injection equations that include methane isotopologue solubility and diffusion effects predict the development of a 'bank' of methane depleted in 13C relative to 12C at the front of a plume of fugitive natural gas. These results, therefore, suggest that transport of natural gas through water saturated geological media may complicate attribution methods needed to distinguish thermogenic and microbial methane.

Dietary fat sources differentially modulate intestinal barrier and hepatic inflammation in alcohol-induced liver injury in rats

PubMed Central

Zhong, Wei; Li, Qiong; Xie, Guoxiang; Sun, Xiuhua; Tan, Xiaobing; Sun, Xinguo; Jia, Wei

2013-01-01

Endotoxemia is a causal factor in the development of alcoholic liver injury. The present study aimed at determining the interactions of ethanol with different fat sources at the gut-liver axis. Male Sprague-Dawley rats were pair fed control or ethanol liquid diet for 8 wk. The liquid diets were based on a modified Lieber-DeCarli formula, with 30% total calories derived from corn oil (rich in polyunsaturated fatty acids). To test the effects of saturated fats, corn oil in the ethanol diet was replaced by either cocoa butter (CB, rich in long-chain saturated fatty acids) or medium-chain triglycerides (MCT, exclusively medium-chain saturated fatty acids). Ethanol feeding increased hepatic lipid accumulation and inflammatory cell infiltration and perturbed hepatic and serum metabolite profiles. Ethanol feeding with CB or MCT alleviated ethanol-induced liver injury and attenuated ethanol-induced metabolic perturbation. Both CB and MCT also normalized ethanol-induced hepatic macrophage activation, cytokine expression, and neutrophil infiltration. Ethanol feeding elevated serum endotoxin level, which was normalized by MCT but not CB. In accordance, ethanol-induced downregulations of intestinal occludin and zonula occludens-1 were normalized by MCT but not CB. However, CB normalized ethanol-increased hepatic endotoxin level in association with upregulation of an endotoxin detoxifying enzyme, argininosuccinate synthase 1 (ASS1). Knockdown ASS1 in H4IIEC3 cells resulted in impaired endotoxin clearance and upregulated cytokine expression. These data demonstrate that the protection of saturated fats against alcohol-induced liver injury occur via different actions at the gut-liver axis and are chain length dependent. PMID:24113767

Sediment-associated aliphatic and aromatic hydrocarbons in coastal British Columbia, Canada: concentrations, composition, and associated risks to protected sea otters.

PubMed

Harris, Kate A; Yunker, Mark B; Dangerfield, Neil; Ross, Peter S

2011-10-01

Sediment-associated hydrocarbons can pose a risk to wildlife that rely on benthic marine food webs. We measured hydrocarbons in sediments from the habitat of protected sea otters in coastal British Columbia, Canada. Alkane concentrations were dominated by higher odd-chain n-alkanes at all sites, indicating terrestrial plant inputs. While remote sites were dominated by petrogenic polycyclic aromatic hydrocarbons (PAHs), small harbour sites within sea otter habitat and sites from an urban reference area reflected weathered petroleum and biomass and fossil fuel combustion. The partitioning of hydrocarbons between sediments and adjacent food webs provides an important exposure route for sea otters, as they consume ∼25% of their body weight per day in benthic invertebrates. Thus, exceedences of PAH sediment quality guidelines designed to protect aquatic biota at 20% of the sites in sea otter habitat suggest that sea otters are vulnerable to hydrocarbon contamination even in the absence of catastrophic oil spills. Copyright © 2011 Elsevier Ltd. All rights reserved.

From labdanes to drimanes. Degradation of the side chain of dihydrozamoranic acid.

PubMed

Rodilla, Jesús M L; Díez, D; Urones, J G; Rocha, Pedro M

2004-04-30

A new route for the degradation of the saturated side chain of dihydrozamoranic acid has been devised, giving an advanced intermediate, compound 14, useful for the synthesis of insect antifeedants such as warburganal and polygodial.

Identifying future directions for subsurface hydrocarbon migration research

NASA Astrophysics Data System (ADS)

Leifer, I.; Clark, J. F.; Luyendyk, B.; Valentine, D.

Subsurface hydrocarbon migration is important for understanding the input and impacts of natural hydrocarbon seepage on the environment. Great uncertainties remain in most aspects of hydrocarbon migration, including some basic mechanisms of this four-phase flow of tar, oil, water, and gas through the complex fracture-network geometry particularly since the phases span a wide range of properties. Academic, government, and industry representatives recently attended a workshop to identify the areas of greatest need for future research in shallow hydrocarbon migration.Novel approaches such as studying temporal and spatial seepage variations and analogous geofluid systems (e.g., geysers and trickle beds) allow deductions of subsurface processes and structures that remain largely unclear. Unique complexities exist in hydrocarbon migration due to its multiphase flow and complex geometry, including in-situ biological weathering. Furthermore, many aspects of the role of hydrocarbons (positive and negative) in the environment are poorly understood, including how they enter the food chain (respiration, consumption, etc.) and “percolate” to higher trophic levels. But understanding these ecological impacts requires knowledge of the emissions' temporal and spatial variability and trajectories.

Structural and phase transition changes of sodium dodecyl sulfate micellar solution in alcohols probed by small-angle neutron scattering (SANS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Putra, Edy Giri Rachman; Patriati, Arum; Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Gadjah Mada, Bulaksumur, Yogyakarta 55281, Indonesia giri@batan.go.id

2015-04-16

Small-angle neutron scattering (SANS) measurements on 0.3M sodium dodecyl sulfate (SDS) micellar solutions have been performed in the presence of n-alcohols, from ethanol to decanol at different alcohol concentrations, 2–10 wt%. The ellipsoid micellar structure which occurred in the 0.3M SDS in aqueous solution with the size range of 30–50 Å has different behavior at various hydrocarbon chain length and concentration of alcohols. At low concentration and short chain-length of alcohols, such as ethanol, propanol, and butanol, the size of micelles reduced and had a spherical-like structure. The opposite effect occurred as medium to long chain alcohols, such as hexanol,more » octanol and decanol was added into the 0.3M SDS micellar solutions. The micelles structure changed to be more elongated in major axis and then crossed the critical phase transition from micellar solution into liquid crystal phase as lamellar structure emerged by further addition of alcohols. The inter-lamellar distances were also depending on the hydrocarbon chain length and concentration of alcohols. In the meantime, the persistent micellar structures occurred in addition of medium chain of n-alcohol, pentanol at all concentrations.« less

Putative inflammatory effects of saturated fatty acids: Experimental confounders and context-specificity

USDA-ARS?s Scientific Manuscript database

Based primarily on cell culture experiments, long-chain saturated fatty acids (SFAs) are thought to promote inflammation and contribute to metabolic dysfunction through toll-like receptor activation. This, in turn, has been implicated in contributing to chronic low-grade inflammation associated with...

Production, characterization and fuel properties of alternative diesel fuel from pyrolysis of waste plastic grocery bags

USDA-ARS?s Scientific Manuscript database

Pyrolysis of HDPE waste grocery bags followed by distillation resulted in a liquid hydrocarbon mixture that consisted of saturated aliphatic paraffins (96.8%), aliphatic olefins (2.6%), and aromatics (0.6%) that corresponded to the boiling range of conventional petroleum diesel fuel (#1 diesel 182–2...

Offline Solid-phase Extraction Large-volume Injection-Gas chromatography for the Analysis of Mineral Oil-saturated Hydrocarbons in Commercial Vegetable Oils.

PubMed

Liu, Lingling; Huang, Hua; Wu, Yanwen; Li, Bingning; Ouyang, Jie

2017-09-01

An offline solid-phase extraction (SPE) approach combined with a large-volume injection (LVI)-gas chromatography-flame ionization detector (LVI-GC-FID) is improved for routine analysis of mineral oil saturated hydrocarbons (MOSH) in vegetable oils. The key procedure of the method consists in using offline SPE columns for MOSH purification. The SPE column packed with 1% Ag-activated silica gel was used to separate MOSH from triglycerides and olefins in variety of vegetable oils. The eluent of MOSH fraction was only 3 mL and the concentration step was quick with little evaporation loss. The limit of quantification (LOQ) of the method was 2.5 mg/kg and the linearity ranged from 2 to 300 mg/kg. The accuracy was assessed by measuring the recoveries from spiked oil samples and was higher than 90%. Twenty-seven commercial vegetable oils were analyzed, and different levels of MOSH contamination were detected with the highest being 259.4 mg/kg. The results suggested that it is necessary to routinely detect mineral oil contamination in vegetable oils for food safety.

Interaction of electric dipoles with phospholipid head groups. A sup 2 H and sup 31 P NMR study of phloretin and phloretin analogues in phosphatidylcholine membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bechinger, B.; Seelig, J.

1991-04-23

Phloretin, 4-hydroxyvalerophenone, and 2-hydroxy-{omega}-phenylpropiophenone are lipophilic dipolar substances that modify ionic conductances of bilayer membranes. The structural changes at the level of the head groups and the hydrocarbon chains as induced by the incorporation of phloretin and its analogues were investigated with deuterium and phosphorus nuclear magnetic resonance. Membranes composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) were selectively deuterated at the choline head group and at the hydrocarbon chains, and {sup 2}H and {sup 31}P NMR spectra were recorded with varying concentrations of dipolar agents. Incorporation of phloretin leaves the bilayer structure intact, induces only a small disordering of the hydrocarbon chains andmore » has no significant effect on the head-group dynamics. On the other hand, quite distinct structural changes are observed for the phosphocholine head group. In addition to this structural change, phloretin also modifies the hydration layer at the lipid-water interface. Much less {sup 2}H{sub 2} is adsorbed to the membrane surface when the bilayer contains phloretin, 4-hydroxyvalerophenone, or 2-hydroxy-{omega}-phenylpropiophenone. Moreover, a rather large change in the residual phosphorus chemical shielding anisotropy argues in favor of hydrogen-bond formation between the phosphate segment and the phloretin hydroxyl groups.« less

Synthesis of customized petroleum-replica fuel molecules by targeted modification of free fatty acid pools in Escherichia coli

PubMed Central

Howard, Thomas P.; Middelhaufe, Sabine; Moore, Karen; Edner, Christoph; Kolak, Dagmara M.; Taylor, George N.; Parker, David A.; Lee, Rob; Smirnoff, Nicholas; Aves, Stephen J.; Love, John

2013-01-01

Biofuels are the most immediate, practical solution for mitigating dependence on fossil hydrocarbons, but current biofuels (alcohols and biodiesels) require significant downstream processing and are not fully compatible with modern, mass-market internal combustion engines. Rather, the ideal biofuels are structurally and chemically identical to the fossil fuels they seek to replace (i.e., aliphatic n- and iso-alkanes and -alkenes of various chain lengths). Here we report on production of such petroleum-replica hydrocarbons in Escherichia coli. The activity of the fatty acid (FA) reductase complex from Photorhabdus luminescens was coupled with aldehyde decarbonylase from Nostoc punctiforme to use free FAs as substrates for alkane biosynthesis. This combination of genes enabled rational alterations to hydrocarbon chain length (Cn) and the production of branched alkanes through upstream genetic and exogenous manipulations of the FA pool. Genetic components for targeted manipulation of the FA pool included expression of a thioesterase from Cinnamomum camphora (camphor) to alter alkane Cn and expression of the branched-chain α-keto acid dehydrogenase complex and β-keto acyl-acyl carrier protein synthase III from Bacillus subtilis to synthesize branched (iso-) alkanes. Rather than simply reconstituting existing metabolic routes to alkane production found in nature, these results demonstrate the ability to design and implement artificial molecular pathways for the production of renewable, industrially relevant fuel molecules. PMID:23610415

The dissimilar effect of diacylglycerols on Ca(2+)-induced phosphatidylserine vesicle fusion.

PubMed Central

Sánchez-Migallón, M P; Aranda, F J; Gómez-Fernández, J C

1995-01-01

We have studied the effect of physiological concentrations of different diacylglycerols on Ca(2+)-induced fusion between phosphatidylserine vesicles. We monitored vesicle fusion as mixing of membrane lipids under conditions where the limiting factor was the aggregation and also in conditions where this aggregation was not the limiting factor. We found that diacylglycerols have a different modulating effect on the Ca(2+)-induced fusion: i) depending on their interfacial conformation, so that 1,2-isomers of diacylglycerols containing unsaturated or short saturated acyl chains stimulated fusion and their 1,3-isomers did not, and ii) depending on their specific type of bilayer interior perturbation, so that diacylglycerols containing unsaturated or short chain saturated acyl chains stimulated fusion but those containing long-chain saturated acyl chains did not. These requirements resembled those required for the diacylglycerol activation of protein kinase C, suggesting that diacylglycerol acts in both the specific activation of this enzyme and the induction of membrane fusion through the same perturbation of lipid structure. We found that polylysine affected the stimulatory role of 1,2-dioleoylglycerol differently, depending on whether aggregation was the limiting factor of fusion. When we studied the effect of very low concentrations of diacylglycerols on the bulk structural properties of phosphatidylserine, we found that they neither significantly perturbed the thermotropic transitions of phosphatidylserine nor affected the interaction of Ca2+ with the phosphate group of phosphatidylserine. The underlying mechanism of fusion between phosphatidylserine vesicles is discussed. PMID:7696508

Chevron: Refinery Identifies $4.4 Million in Annual Savings by Using Process Simulation Models to Perform Energy-Efficiency Assessment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

2004-05-01

In an energy-efficiency study at its refinery near Salt Lake City, Utah, Chevron focused on light hydrocarbons processing. The company found it could recover hydrocarbons from its fuel gas system and sell them. By using process simulation models of special distillation columns and associated reboilers and condensers, Chevron could predict the performance of potential equipment configuration changes and process modifications. More than 25,000 MMBtu in natural gas could be saved annually if a debutanizer upgrade project and a new saturated gas plant project were completed. Together, these projects would save $4.4 million annually.

Formation of organic compounds from simulated Titan atmosphere: perspectives of the Cassini mission.

PubMed

Koike, Toshiyuki; Kaneko, Takeo; Kobayashi, Kensei; Miyakawa, Shin; Takano, Yoshinori

2003-10-01

Gas mixtures of methane and nitrogen were subjected to proton irradiation (PI), gamma irradiation (GI), UV irradiation (UV) or spark discharges (SD), and the products were analyzed to compare possible energy sources for synthesis of organics in Titan. SD mainly gave unsaturated hydrocarbons, while PI gave saturated hydrocarbons. N-containing organics were detected in PI, GI and SD, but not in UV. The formers yielded amino acids after acid-hydrolysis of solid phase products (tholin). Comparison of the present results with those by Cassini-Huygens [correction of Heygens] mission will make it possible to prove major energy sources for organic synthesis in Titan atmosphere.

Transport properties of nonelectrolyte liquid mixtures—VI. Viscosimetric study of binary mixtures of hexafluorobenzene with aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Dymond, J. H.; Robertson, J.

1985-01-01

Viscosity coefficients for binary mixtures of hexafluorobenzene with benzene, toluene, para-xylene, and mesitylene have been measured along the saturation line at temperatures from 15 to 120°C using specially designed capillary viscometers. Densities were measured using a pyknometer and volume-change apparatus. Deviations of the viscosities from a rectilinear dependence on mole fraction are consistent with enhanced interactions between unlike species, which increase with increasing number of methyl groups on the aromatic hydrocarbon and decrease with increasing temperature. The application of the Grunberg and Nissan equation, the Hildebrand equation, and energy of activation theories to these results is examined.

The Fatty Acid Profile Analysis of Cyperus laxus Used for Phytoremediation of Soils from Aged Oil Spill-Impacted Sites Revealed That This Is a C18:3 Plant Species.

PubMed

Rivera Casado, Noemí Araceli; Montes Horcasitas, María del Carmen; Rodríguez Vázquez, Refugio; Esparza García, Fernando José; Pérez Vargas, Josefina; Ariza Castolo, Armando; Ferrera-Cerrato, Ronald; Gómez Guzmán, Octavio; Calva Calva, Graciano

2015-01-01

The effect of recalcitrant hydrocarbons on the fatty acid profile from leaf, basal corm, and roots of Cyperus laxus plants cultivated in greenhouse phytoremediation systems of soils from aged oil spill-impacted sites containing from 16 to 340 g/Kg total hydrocarbons (THC) was assessed to investigate if this is a C18:3 species and if the hydrocarbon removal during the phytoremediation process has a relationship with the fatty acid profile of this plant. The fatty acid profile was specific to each vegetative organ and was strongly affected by the hydrocarbons level in the impacted sites. Leaf extracts of plants from uncontaminated soil produced palmitic acid (C16), octadecanoic acid (C18:0), unsaturated oleic acids (C18:1-C18:3), and unsaturated eichosanoic (C20:2-C20:3) acids with a noticeable absence of the unsaturated hexadecatrienoic acid (C16:3); this finding demonstrates, for the first time, that C. laxus is a C18:3 plant. In plants from the phytoremediation systems, the total fatty acid contents in the leaf and the corm were negatively affected by the hydrocarbons presence; however, the effect was positive in root. Interestingly, under contaminated conditions, unusual fatty acids such as odd numbered carbons (C15, C17, C21, and C23) and uncommon unsaturated chains (C20:3n6 and C20:4) were produced together with a remarkable quantity of C22:2 and C24:0 chains in the corm and the leaf. These results demonstrate that weathered hydrocarbons may drastically affect the lipidic composition of C. laxus at the fatty acid level, suggesting that this species adjusts the cover lipid composition in its vegetative organs, mainly in roots, in response to the weathered hydrocarbon presence and uptake during the phytoremediation process.

Targeting of insect epicuticular lipids by the entomopathogenic fungus Beauveria bassiana: hydrocarbon oxidation within the context of a host-pathogen interaction

PubMed Central

Pedrini, Nicolás; Ortiz-Urquiza, Almudena; Huarte-Bonnet, Carla; Zhang, Shizhu; Keyhani, Nemat O.

2013-01-01

Broad host range entomopathogenic fungi such as Beauveria bassiana attack insect hosts via attachment to cuticular substrata and the production of enzymes for the degradation and penetration of insect cuticle. The outermost epicuticular layer consists of a complex mixture of non-polar lipids including hydrocarbons, fatty acids, and wax esters. Long chain hydrocarbons are major components of the outer waxy layer of diverse insect species, where they serve to protect against desiccation and microbial parasites, and as recognition molecules or as a platform for semiochemicals. Insect pathogenic fungi have evolved mechanisms for overcoming this barrier, likely with sets of lipid degrading enzymes with overlapping substrate specificities. Alkanes and fatty acids are substrates for a specific subset of fungal cytochrome P450 monooxygenases involved in insect hydrocarbon degradation. These enzymes activate alkanes by terminal oxidation to alcohols, which are further oxidized by alcohol and aldehyde dehydrogenases, whose products can enter β-oxidation pathways. B. bassiana contains at least 83 genes coding for cytochrome P450s (CYP), a subset of which are involved in hydrocarbon oxidation, and several of which represent new CYP subfamilies/families. Expression data indicated differential induction by alkanes and insect lipids and four CYP proteins have been partially characterized after heterologous expression in yeast. Gene knockouts revealed a phenotype for only one (cyp52X1) out of six genes examined to date. CYP52X1 oxidizes long chain fatty acids and participates in the degradation of specific epicuticular lipid components needed for breaching the insect waxy layer. Examining the hydrocarbon oxidizing CYP repertoire of pathogens involved in insect epicuticle degradation can lead to the characterization of enzymes with novel substrate specificities. Pathogen targeting may also represent an important co-evolutionary process regarding insect cuticular hydrocarbon synthesis. PMID:23422735

The Fatty Acid Profile Analysis of Cyperus laxus Used for Phytoremediation of Soils from Aged Oil Spill-Impacted Sites Revealed That This Is a C18:3 Plant Species

PubMed Central

Montes Horcasitas, María del Carmen; Rodríguez Vázquez, Refugio; Esparza García, Fernando José; Pérez Vargas, Josefina; Ariza Castolo, Armando; Ferrera-Cerrato, Ronald; Gómez Guzmán, Octavio

2015-01-01

The effect of recalcitrant hydrocarbons on the fatty acid profile from leaf, basal corm, and roots of Cyperus laxus plants cultivated in greenhouse phytoremediation systems of soils from aged oil spill-impacted sites containing from 16 to 340 g/Kg total hydrocarbons (THC) was assessed to investigate if this is a C18:3 species and if the hydrocarbon removal during the phytoremediation process has a relationship with the fatty acid profile of this plant. The fatty acid profile was specific to each vegetative organ and was strongly affected by the hydrocarbons level in the impacted sites. Leaf extracts of plants from uncontaminated soil produced palmitic acid (C16), octadecanoic acid (C18:0), unsaturated oleic acids (C18:1-C18:3), and unsaturated eichosanoic (C20:2-C20:3) acids with a noticeable absence of the unsaturated hexadecatrienoic acid (C16:3); this finding demonstrates, for the first time, that C. laxus is a C18:3 plant. In plants from the phytoremediation systems, the total fatty acid contents in the leaf and the corm were negatively affected by the hydrocarbons presence; however, the effect was positive in root. Interestingly, under contaminated conditions, unusual fatty acids such as odd numbered carbons (C15, C17, C21, and C23) and uncommon unsaturated chains (C20:3n6 and C20:4) were produced together with a remarkable quantity of C22:2 and C24:0 chains in the corm and the leaf. These results demonstrate that weathered hydrocarbons may drastically affect the lipidic composition of C. laxus at the fatty acid level, suggesting that this species adjusts the cover lipid composition in its vegetative organs, mainly in roots, in response to the weathered hydrocarbon presence and uptake during the phytoremediation process. PMID:26473488

Attenuation of seismic waves in rocks saturated with multiphase fluids: theory and experiments

NASA Astrophysics Data System (ADS)

Tisato, N.; Quintal, B.; Chapman, S.; Podladchikov, Y.; Burg, J. P.

2016-12-01

Albeit seismic tomography could provide a detailed image of subsurface fluid distribution, the interpretation of the tomographic signals is often controversial and fails in providing a conclusive map of the subsurface saturation. However, tomographic information is important because the upward migration of multiphase fluids through the crust of the Earth can cause hazardous events such as eruptions, explosions, soil-pollution and earthquakes. In addition, multiphase fluids, such as hydrocarbons, represent important resources for economy. Seismic tomography can be improved considering complex elastic moduli and the attenuation of seismic waves (1/Q) that quantifies the energy lost by propagating elastic waves. In particular, a significant portion of the energy carried by the propagating wave is dissipated in saturated media by the wave-induced-fluid-flow (WIFF) and the wave-induced-gas-exsolution-dissolution (WIGED) mechanism. The latter describes how a propagating wave modifies the thermodynamic equilibrium between different fluid phases causing exsolution and dissolution of gas bubbles in the liquid, which in turn causes a significant frequency-dependent 1/Q and moduli dispersion. The WIGED theory was initially postulated for bubbly magmas but was only recently demonstrated and extended to bubbly water. We report the theory and laboratory experiments that have been performed to confirm the WIGED theory. In particular, we present i) attenuation measurements performed by means of the Broad Band Attenuation Vessel on porous media saturated with water and different gases, and ii) numerical experiments validating the laboratory observations. Then, we extend the theory to fluids and pressure-temperature conditions which are typical of phreatomagmatic and hydrocarbon domains and we compare the propagation of seismic waves in bubble-free and bubble-bearing subsurface domains. This work etends the knowledge of attenuation in rocks saturated with multiphase fluid and emphasizes that the WIGED mechanism is very important to image subsurface gas plumes.

Comparison between Hydrogen and Methane Fuels in a 3-D Scramjet at Mach 8

DTIC Science & Technology

2016-06-24

performance of small chained hydrocarbons ( ethylene and methane) was compared with hydrogen to establish the importance of its lower specific energy...Report Comparison between hydrogen, methane and ethylene fuels in a 3-D Scramjet at Mach 8 Professor Michael K. Smart Chair of Hypersonic Propulsion...hydrocarbons ( ethylene and methane) was compared with hydrogen to establish the importance of its lower specific energy content and slower reaction

Genetic correlations of mid-infrared-predicted milk fatty acid groups with milk production traits.

PubMed

Fleming, A; Schenkel, F S; Malchiodi, F; Ali, R A; Mallard, B; Sargolzaei, M; Jamrozik, J; Johnston, J; Miglior, F

2018-05-01

The objective of this research was to estimate the genetic correlations between milk mid-infrared-predicted fatty acid groups and production traits in first-parity Canadian Holsteins. Contents of short-chain, medium-chain, long-chain, saturated, and unsaturated fatty acid groupings in milk samples can be predicted using mid-infrared spectral data for cows enrolled in milk recording programs. Predicted fatty acid group contents were obtained for 49,127 test-day milk samples from 10,029 first-parity Holstein cows in 810 herds. Milk yield, fat and protein yield, fat and protein percentage, fat-to-protein ratio, and somatic cell score were also available for these test days. Genetic parameters were estimated for the fatty acid groups and production traits using multiple-trait random regression test day models by Bayesian methods via Gibbs sampling. Three separate 8- or 9-trait analyses were performed, including the 5 fatty acid groups with different combinations of the production traits. Posterior standard deviations ranged from <0.001 to 0.01. Average daily genetic correlations were negative and similar to each other for the fatty acid groups with milk yield (-0.62 to -0.59) and with protein yield (-0.32 to -0.25). Weak and positive average daily genetic correlations were found between somatic cell score and the fatty acid groups (from 0.25 to 0.36). Stronger genetic correlations with fat yield, fat and protein percentage, and fat-to-protein ratio were found with medium-chain and saturated fatty acid groups compared with those with long-chain and unsaturated fatty acid groups. Genetic correlations were very strong between the fatty acid groups and fat percentage, ranging between 0.88 for unsaturated and 0.99 for saturated fatty acids. Daily genetic correlations from 5 to 305 d in milk with milk, protein yield and percentage, and somatic cell score traits showed similar patterns for all fatty acid groups. The daily genetic correlations with fat yield at the beginning of lactation were decreasing for long-chain and unsaturated fatty acid groups and increasing for short-chain fatty acids. Genetic correlations between fat percentage and fatty acids were increasing at the beginning of lactation for short- and medium-chain and saturated fatty acids, but slightly decreasing for long-chain and unsaturated fatty acid groups. These results can be used in defining fatty acid traits and breeding objectives. Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Room temperature structures and odd even behaviour of a homologous series of anhydrous lithium n-alkanoates

NASA Astrophysics Data System (ADS)

White, Nicole A. S.; Ellis, Henry A.

2008-10-01

The molecular structures of a homologous series of lithium n-alkanoates have been determined at room temperature using infrared spectroscopy, polarizing light microscopy and X-ray powder diffraction in conjunction with density and melting point measurements. For all the compounds investigated, asymmetric ionic metal-carboxylate coordination is proposed, with the molecules located within a triclinic crystal system with P1¯ space group. The molecules are nearly all of similar structure and are arranged within lamellar layers with four molecules per unit cell. The hydrocarbon chains, in nearly all trans conformation, are arranged tail-to-tail and tilted at an average angle of 55 ο to the planes containing lithium ions. The unit cell parameters such as sides: b and c increase linearly with increasing chain length whilst side a shows a linear decrease. Furthermore, the measured densities and melting points show odd-even behaviour, suggesting differences in molecular packing between odd and even chain length homologues. Geometric models are proposed to explain molecular orientation within a lamella and odd-even behaviour, involving the influence of terminal groups on the packing geometry of hydrocarbon chains within the lattice.

Effect of saturated and unsaturated fatty acid supplementation on bio-plastic production under submerged fermentation.

PubMed

Srivastava, S K; Tripathi, Abhishek Dutt

2013-10-01

Polyhydroxyalkanoates (PHAs) are intracellular reserve material stored by gram-negative bacteria under nutrient-limited condition. PHAs are utilized in biodegradable plastics (bio-plastics) synthesis due to their similarity with conventional synthetic plastic. In the present study, the effect of addition of saturated and unsaturated fatty acids (palmitic acid, stearic acid, oleic acid and linoleic acid) on the production of PHAs by the soil bacterium Alcaligenes sp. NCIM 5085 was studied. Fatty acid supplementation in basal media produced saturated and unsaturated PHAs of medium and short chain length. Gas chromatography analysis of palmitic acid-supplemented media showed the presence of short chain length (scl) PHAs which could potentially serve as precursors for bio-plastic production. The scl PHA was subsequently characterized as PHB by NMR and FTIR. On the other hand, oleic acid and linoleic acid addition showed both saturated and unsaturated PHAs of different chain lengths. Palmitic acid showed maximum PHB content of 70.8 % at concentration of 15 g l -1 under shake flask cultivation. When shake flask cultivation was scaled up in a 7.5-l bioreactor (working volume 3 l), 7.6 g l -1 PHA was produced with a PHB yield (Y P/X ) and productivity of 75.89 % and 0.14 g l -1  h, respectively.

A Novel Protocol to Analyze Short- and Long-Chain Fatty Acids Using Nonaqueous Microchip Capillary Electrophoresis

NASA Technical Reports Server (NTRS)

Cable, M. L.; Stockton, A. M.; Mora, Maria F; Willis, P. A.

2013-01-01

We propose a new protocol to identify and quantify both short- and long-chain saturated fatty acids in samples of astrobiological interest using non-aqueous microchip capillary electrophoresis (micronNACE) with laser induced fluorescence (LIF).

Catalytic hydrogenation rate of polycyclic aromatic hydrocarbons in supercritical carbon dioxide containing polymer-stabilized palladium nanoparticles.

PubMed

Liao, Weisheng; Liu, Hsin-Wang; Chen, Hsing-Jung; Chang, Wen-Yen; Chiu, Kong-Hwa; Wai, Chien M

2011-01-01

Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO₂ containing 1 MPa of H₂ at 40-50°C. Kinetic studies based on in situ UV/Vis spectra of the CO₂ phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces. Copyright © 2010 Elsevier Ltd. All rights reserved.

Liquid crystal organization of self-assembling cyclic peptides.

PubMed

Amorín, Manuel; Pérez, Ana; Barberá, Joaquín; Ozores, Haxel Lionel; Serrano, José Luis; Granja, Juan R; Sierra, Teresa

2014-01-21

Self-assembling cyclic peptides decorated with mesogens form porous columnar mesophases in which, depending on the number of hydrocarbon chains, double or single channels are formed along each column.

Hypothalamic fatty acid sensing in Senegalese sole (Solea senegalensis): response to long-chain saturated, monounsaturated, and polyunsaturated (n-3) fatty acids.

PubMed

Conde-Sieira, Marta; Bonacic, Kruno; Velasco, Cristina; Valente, Luisa M P; Morais, Sofia; Soengas, José L

2015-12-15

We assessed the presence of fatty acid (FA)-sensing mechanisms in hypothalamus of Senegalese sole (Solea senegalensis) and investigated their sensitivity to FA chain length and/or level of unsaturation. Stearate (SA, saturated FA), oleate (OA, monounsaturated FA of the same chain length), α-linolenate [ALA, a n-3 polyunsaturated fatty acid (PUFA) of the same chain length], and eicosapentanoate (EPA, a n-3 PUFA of a larger chain length) were injected intraperitoneally. Parameters related to FA sensing and neuropeptide expression in the hypothalamus were assessed after 3 h and changes in accumulated food intake after 4, 24, and 48 h. Three FA sensing systems characterized in rainbow trout were also found in Senegalese sole and were activated by OA in a way similar to that previously characterized in rainbow trout and mammals. These hypothalamic FA sensing systems were also activated by ALA, differing from mammals, where n-3 PUFAs do not seem to activate FA sensors. This might suggest additional roles and highlights the importance of n-3 PUFA in fish diets, especially in marine species. The activation of FA sensing seems to be partially dependent on acyl chain length and degree of saturation, as no major changes were observed after treating fish with SA or EPA. The activation of FA sensing systems by OA and ALA, but not SA or EPA, is further reflected in the expression of hypothalamic neuropeptides involved in the control of food intake. Both OA and ALA enhanced anorexigenic capacity compatible with the activation of FA sensing systems. Copyright © 2015 the American Physiological Society.

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength

NASA Astrophysics Data System (ADS)

Ge, Ting; Robbins, Mark O.; Perahia, Dvora; Grest, Gary S.

2014-07-01

Self-healing of polymer films often takes place as the molecules diffuse across a damaged region, above their melting temperature. Using molecular dynamics simulations we probe the healing of polymer films and compare the results with those obtained for thermal welding of homopolymer slabs. These two processes differ from each other in their interfacial structure since damage leads to increased polydispersity and more short chains. A polymer sample was cut into two separate films that were then held together in the melt state. The recovery of the damaged film was followed as time elapsed and polymer molecules diffused across the interface. The mass uptake and formation of entanglements, as obtained from primitive path analysis, are extracted and correlated with the interfacial strength obtained from shear simulations. We find that the diffusion across the interface is significantly faster in the damaged film compared to welding because of the presence of short chains. Though interfacial entanglements increase more rapidly for the damaged films, a large fraction of these entanglements are near chain ends. As a result, the interfacial strength of the healing film increases more slowly than for welding. For both healing and welding, the interfacial strength saturates as the bulk entanglement density is recovered across the interface. However, the saturation strength of the damaged film is below the bulk strength for the polymer sample. At saturation, cut chains remain near the healing interface. They are less entangled and as a result they mechanically weaken the interface. Chain stiffness increases the density of entanglements, which increases the strength of the interface. Our results show that a few entanglements across the interface are sufficient to resist interfacial chain pullout and enhance the mechanical strength.

Characterization of nonpolar lipids and selected steroids by using laser-induced acoustic desorption/chemical ionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Zhicheng; Daiya, Shivani; Kenttämaa, Hilkka I.

2011-03-01

Laser-induced acoustic desorption (LIAD) combined with ClMn(H2O)+ chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5α-cholestane, cholesta-3,5-diene, squalene, and β-carotene, were found to solely form the desired water replacement product (adduct-H2O) upon reaction with the ClMn(H2O)+ ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H2O ions, but less abundant adduct-2H2O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusivelymore » the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H2O)+ chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids.« less

Advanced Gas Hydrate Reservoir Modeling Using Rock Physics

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnell, Daniel

Prospecting for high saturation gas hydrate deposits can be greatly aided with improved approaches to seismic interpretation and especially if sets of seismic attributes can be shown as diagnostic or direct hydrocarbon indicators for high saturation gas hydrates in sands that would be of most interest for gas hydrate production. A large 3D seismic data set in the deep water Eastern Gulf of Mexico was screened for gas hydrates using a set of techniques and seismic signatures that were developed and proven in the Central deepwater Gulf of Mexico in the DOE Gulf of Mexico Joint Industry Project JIP Legmore » II in 2009 and recently confirmed with coring in 2017. A large gas hydrate deposit is interpreted in the data where gas has migrated from one of the few deep seated faults plumbing the Jurassic hydrocarbon source into the gas hydrate stability zone. The gas hydrate deposit lies within a flat-lying within Pliocene Mississippi Fan channel that was deposited outboard in a deep abyssal environment. The uniform architecture of the channel aided the evaluation of a set of seismic attributes that relate to attenuation and thin-bed energy that could be diagnostic of gas hydrates. Frequency attributes derived from spectral decomposition also proved to be direct hydrocarbon indicators by pseudo-thickness that could be only be reconciled by substituting gas hydrate in the pore space. The study emphasizes that gas hydrate exploration and reservoir characterization benefits from a seismic thin bed approach.« less

Effect of permafrost properties on gas hydrate petroleum system in the Qilian Mountains, Qinghai, Northwest China.

PubMed

Wang, Pingkang; Zhang, Xuhui; Zhu, Youhai; Li, Bing; Huang, Xia; Pang, Shouji; Zhang, Shuai; Lu, Cheng; Xiao, Rui

2014-12-01

The gas hydrate petroleum system in the permafrost of the Qilian Mountains, which exists as an epigenetic hydrocarbon reservoir above a deep-seated hydrocarbon reservoir, has been dynamic since the end of the Late Pleistocene because of climate change. The permafrost limits the occurrence of gas hydrate reservoirs by changing the pressure-temperature (P-T) conditions, and it affects the migration of the underlying hydrocarbon gas because of its strong sealing ability. In this study, we reconstructed the permafrost structure of the Qilian Mountains using a combination of methods and measured methane permeability in ice-bearing sediment permafrost. A relationship between the ice saturation of permafrost and methane permeability was established, which permitted the quantitative evaluation of the sealing ability of permafrost with regard to methane migration. The test results showed that when ice saturation is >80%, methane gas can be completely sealed within the permafrost. Based on the permafrost properties and genesis of shallow gas, we suggest that a shallow "gas pool" occurred in the gas hydrate petroleum system in the Qilian Mountains. Its formation was related to a metastable gas hydrate reservoir controlled by the P-T conditions, sealing ability of the permafrost, fault system, and climatic warming. From an energy perspective, the increasing volume of the gas pool means that it will likely become a shallow gas resource available for exploitation; however, for the environment, the gas pool is an underground "time bomb" that is a potential source of greenhouse gas.

Diagenesis of an 'overmature' gas reservoir: The Spiro sand of the Arkoma Basin, USA

USGS Publications Warehouse

Spotl, C.; Houseknecht, D.W.; Burns, S.J.

1996-01-01

The Spiro sand is a laterally extensive thin sandstone of earliest Atokan (Pennsylvanian) age that forms a major natural gas reservoir in the western Arkoma Basin, Oklahoma. Petrographic analysis reveals a variety of diagenetic alterations, the majority of which occurred during moderate to deep burial. Early diagenetic processes include calcite cementation and the formation of Fe-clay mineral peloids and coatings around quartz framework grains. These clays, which underwent transformation to well-crystallized chamosite [polytype Ib(?? = 90??)] on burial, are particularly abundant in medium-grained channel sandstones, whereas illitic clays are predominant in fine-grained interchannel sandstones. Subsequent to mechanical compaction, saddle ankerite precipitated in the reservoir at temperatures in excess of 70??C. Crude oil collected in favourable structural locations during and after ankeritization. Whereas hydrocarbons apparently halted inorganic diagenesis in oil-saturated zones, cementation continued in the underlying water-saturated zones. As reservoir temperatures increased further, hydrocarbons were cracked and a solid pyrobitumen residue remained in the reservoir. At temperatures exceeding ???140-150??C, non-syntaxial quartz cement, ferroan calcite and traces of dickite(?) locally reduced the reservoir quality. Local secondary porosity was created by carbonate cement dissolution. This alteration post-dated hydrocarbon emplacement and is probably related to late-stage infiltration of freshwater along 'leaky' faults. The study shows that the Spiro sandstone locally retained excellent porosities despite deep burial and thermal conditions that correspond to the zone of incipient very low grade metamorphism.

Densities, Viscosities and Derived Thermophysical Properties of Water-Saturated Imidazolium-Based Ionic Liquids.

PubMed

Martins, Mónia A R; Neves, Catarina M S S; Kurnia, Kiki A; Carvalho, Pedro J; Rocha, Marisa A A; Santos, Luís M N B F; Pinho, Simão P; Freire, Mara G

2016-01-15

In order to evaluate the impact of the alkyl side chain length and symmetry of the cation on the thermophysical properties of water-saturated ionic liquids (ILs), densities and viscosities as a function of temperature were measured at atmospheric pressure and in the (298.15 to 363.15) K temperature range, for systems containing two series of bis(trifluoromethylsulfonyl)imide-based compounds: the symmetric [C n C n im][NTf 2 ] (with n = 1-8 and 10) and asymmetric [C n C 1 im][NTf 2 ] (with n = 2-5, 7, 9 and 11) ILs. For water-saturated ILs, the density decreases with the increase of the alkyl side chain length while the viscosity increases with the size of the aliphatic tails. The saturation water solubility in each IL was further estimated with a reasonable agreement based on the densities of water-saturated ILs, further confirming that for the ILs investigated the volumetric mixing properties of ILs and water follow a near ideal behaviour. The water-saturated symmetric ILs generally present lower densities and viscosities than their asymmetric counterparts. From the experimental data, the isobaric thermal expansion coefficient and energy barrier were also estimated. A close correlation between the difference in the energy barrier values between the water-saturated and pure ILs and the water content in each IL was found, supporting that the decrease in the viscosity of ILs in presence of water is directly related with the decrease of the energy barrier.

Tetraterpene Synthase Substrate and Product Specificity in the Green Microalga Botryococcus braunii Race L.

PubMed

Thapa, Hem R; Tang, Su; Sacchettini, James C; Devarenne, Timothy P

2017-09-15

Recently, the biosynthetic pathway for lycopadiene, a C 40 tetraterpenoid hydrocarbon, was deciphered from the L race of Botryococcus braunii, an alga that produces hydrocarbon oils capable of being converted into combustible fuels. The lycopadiene pathway is initiated by the squalene synthase (SS)-like enzyme lycopaoctaene synthase (LOS), which catalyzes the head-to-head condensation of two C 20 geranylgeranyl diphosphate (GGPP) molecules to produce C 40 lycopaoctaene. LOS shows unusual substrate promiscuity for SS or SS-like enzymes by utilizing C 15 farnesyl diphosphate (FPP) and C 20 phytyl diphosphate in addition to GGPP as substrates. These three substrates can be combined by LOS individually or in combinations to produce six different hydrocarbons of C 30 , C 35 , and C 40 chain lengths. To understand LOS substrate and product specificity, rational mutagenesis experiments were conducted based on sequence alignment with several SS proteins as well as a structural comparison with the human SS (HSS) crystal structure. Characterization of the LOS mutants in vitro identified Ser276 and Ala288 in the LOS active site as key amino acids responsible for controlling substrate binding, and thus the promiscuity of this enzyme. Mutating these residues to those found in HSS largely converted LOS from lycopaoctaene production to C 30 squalene production. Furthermore, these studies were confirmed in vivo by expressing LOS in E. coli cells metabolically engineered to produce high FPP and GGPP levels. These studies also offer insights into tetraterpene hydrocarbon metabolism in B. braunii and provide a foundation for engineering LOS for robust production of specific hydrocarbons of a desired chain length.

What's on the menu? A review of the energy and nutritional content of US chain restaurant menus.

PubMed

Wu, Helen W; Sturm, Roland

2013-01-01

The present study aimed to (i) describe the availability of nutrition information in major chain restaurants, (ii) document the energy and nutrient levels of menu items, (iii) evaluate relationships with restaurant characteristics, menu labelling and trans fat laws, and nutrition information accessibility, and (iv) compare energy and nutrient levels against industry-sponsored and government-issued nutrition criteria. Descriptive statistics and multivariate regression analysis of the energy, total fat, saturated fat, trans fat, sodium, carbohydrate and protein levels of 29 531 regular and 1392 children's menu items [corrected]. Energy and nutrition information provided on restaurant websites or upon request, and secondary databases on restaurant characteristics. The top 400 US chain restaurants by sales, based on the 2009 list of the Restaurants & Institutions magazine. Complete nutrition information was reported for 245 (61 %) restaurants. Appetizers had more energy, fat and sodium than all other item types. Children's menu specialty beverages had more fat, saturated fat and carbohydrates than comparable regular menu beverages. The majority of main entrées fell below one-third of the US Department of Agriculture's estimated daily energy needs, but as few as 3 % were also within limits for sodium, fat and saturated fat. Main entrées had significantly more energy, fat and saturated fat in family-style restaurants than in fast-food restaurants. Restaurants that made nutrition information easily accessible on websites had significantly lower energy, fat and sodium contents across menu offerings than those providing information only upon request. The paper provides a comprehensive view of chain restaurant menu nutrition prior to nationwide labelling laws. It offers baseline data to evaluate how restaurants respond after laws are implemented.

A class of mild surfactants that keep integral membrane proteins water-soluble for functional studies and crystallization

PubMed Central

Hovers, Jens; Potschies, Meike; Polidori, Ange; Pucci, Bernard; Raynal, Simon; Bonneté, Françoise; Serrano-Vega, Maria J.; Tate, Christopher G.; Picot, Daniel; Pierre, Yves; Popot, Jean-Luc; Nehmé, Rony; Bidet, Michel; Mus-Veteau, Isabelle; Bußkamp, Holger; Jung, Karl-Heinz; Marx, Andreas; Timmins, Peter A.; Welte, Wolfram

2013-01-01

Mixed protein-surfactant micelles are used for in vitro studies and 3D crystallization when solutions of pure, monodisperse integral membrane proteins are required. However, many membrane proteins undergo inactivation when transferred from the biomembrane into micelles of conventional surfactants with alkyl chains as hydrophobic moieties. Here we describe the development of surfactants with rigid, saturated or aromatic hydrocarbon groups as hydrophobic parts. Their stabilizing properties are demonstrated with three different integral membrane proteins. The temperature at which 50% of the binding sites for specific ligands are lost is used as a measure of stability and dodecyl-β-D-maltoside (“C12-b-M”) as a reference for conventional surfactants. One surfactant increased the stability of two different G protein-coupled receptors by approximately 10°C compared to C12-b-M. Another surfactant yielded a stabilization of the human Patched protein receptor by 13°C. In addition, one of the surfactants was successfully used to stabilize and crystallize the cytochrome b6f complex from Chlamydomonas reinhardtii. The structure was solved to the same resolution as previously reported in C12-b-M. PMID:21314479

Oligomannuronates from Seaweeds as Renewable Sources for the Development of Green Surfactants

NASA Astrophysics Data System (ADS)

Benvegnu, Thierry; Sassi, Jean-François

The development of surfactants based on natural renewable resources is a concept that is gaining recognition in detergents, cosmetics, and green chemistry. This new class of biodegradable and biocompatible products is a response to the increasing consumer demand for products that are both "greener", milder, and more efficient. In order to achieve these objectives, it is necessary to use renewable low-cost biomass that is available in large quantities and to design molecular structures through green processes that show improved performance, favorable ecotoxicological properties and reduced environmental impact. Within this context, marine algae represent a rich source of complex polysaccharides and oligosaccharides with innovative structures and functional properties that may find applications as starting materials for the development of green surfactants or cosmetic actives. Thus, we have developed original surfactants based on mannuronate moieties derived from alginates (cell-wall polyuronic acids from brown seaweeds) and fatty hydrocarbon chains derived from vegetable resources. Controlled chemical and/or enzymatic depolymerizations of the algal polysaccharides give saturated and/or unsaturated functional oligomannuronates. Clean chemical processes allow the efficient transformation of the oligomers into neutral or anionic amphiphilic molecules. These materials represent a new class of surface-active agents with promising foaming/emulsifying properties.

Patent application for a process for production of effective catalysts for polymerization of unsaturated compounds (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ibing, G.

Organic compounds which contain one or more double carbon bonds per molecule frequently display the ability of polymerizing with each other and with other compounds. It is mainly compounds containing peroxide that serve as catalysts for such operations. Examples of recommended substances are hydrogen peroxide, ozone, perbenzoic acid, benzoin peroxide, peroxide-containing ethers, persulfates, etc. It was found that a catalyst of much greater effectiveness in the polymerization of unsaturated compounds can be obtained from one of the previously-known catalysts if the hydrocarbons are processed with lateral-chain substances (e.g., toluene, xylene, ethyl benzene, propyl benzene, diethyl benzene, etc.) in boiling heatmore » with damp air. In this process there develops a small measure of peroxide of previously unknown make-up, which possess outstanding catalytic effectiveness. For production of the catalyst, the aromatics are heated by return-flow cooler and conducted for several hours through an air stream which has been saturated with steam. Oxidation can be undertaken with other substances also; for example, oxygen, ozone, or compounds which give off oxygen. Activation with air, however, is the simplest way and yields the most effective catalyst. Examples of the process are provided.« less

Identification of Fatty Acids and Aliphatic Hydrocarbons in Sarcina lutea by Gas Chromatography and Combined Gas Chromatography-Mass Spectrometry

PubMed Central

Tornabene, T. G.; Gelpi, E.; Oró, J.

1967-01-01

The composition and nature of the fatty acids and hydrocarbons of Sarcina lutea were elucidated by gas chromatography and by combined gas chromatography-mass spectrometry. The distribution of fatty acids found in S. lutea showed two families of pairs, or dyads, of saturated monocarboxylic acids (C12–C18) with and without methyl branching. These pairs of fatty acids showed a pattern of iso and anteiso structures for C13, C15, and C17, and iso and normal structures for C12, C14, and C16. Only the C18 showed unsaturation. The distribution of hydrocarbons in the range C22–C29 showed two families of tetrads of unsaturated aliphatic hydrocarbons all showing methyl branching. Each tetrad was composed of four isomers identified as two iso olefins and two anteiso olefins. The only difference between the tetrads pertaining to different families was found in the relative gas chromatographic retention times of the last two components of each group. PMID:6039356

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric

Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalyticmore » system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.« less

Effect of the ultrasound-Fenton oxidation process with the addition of a chelating agent on the removal of petroleum-based contaminants from soil.

PubMed

Li, Ying; Li, Fangmin; Li, Fanxiu; Yuan, Fuqian; Wei, Pingfang

2015-12-01

The effects of ultrasonic irradiation, the chelating agent modified Fenton reaction, and a combination of ultrasound and the Fenton method in removing petroleum contaminants from a soil were studied. The results showed that the contaminant removal rate of the Fenton treatment combined with an oxalic acid chelating agent was 55.6% higher than that without a chelating agent. The average removal rate of the contaminants using the ultrasound-Fenton treatment was 59.0% higher than that without ultrasonic treatment. A combination of ultrasound and an Fe(2+)/Fe(3+)-oxalate complex-modified Fenton reagent resulted in significantly higher removal rates of n-alkanes (C(n)H(2n+2), n < 28), isoprenoid hydrocarbons, aromatic hydrocarbons, and saturated polycyclic terpenes compared with the ultrasound treatment alone or the Fenton method. The Fenton reaction and the ultrasound-Fenton treatment can unselectively remove multiple components of residual hydrocarbons and a number of benzene rings in polycyclic aromatic hydrocarbons. The chemistry of the heterocyclic compounds and the position and number of substituents can affect the degradation process.

Organic matter compounds as source indicators and tracers for marine pollution in a western Mediterranean coastal zone.

PubMed

Amorri, Jalila; Geffroy-Rodier, Claude; Boufahja, Fehmi; Mahmoudi, Ezzeddine; Aïssa, Patricia; Ksibi, Mohamed; Amblès, André

2011-11-01

Complex organic compounds found in oil and sediments linked with a particular source (such as algae, bacteria or vascular plants) are defined as biomarkers and are useful dating indicators in organic geochemistry. This paper presents the composition of the organic matter (OM) on marine surface sediments from a degraded Tunisian coast analysed by pyrolysis and gas chromatography-mass spectrometry (GC-MS). High total OM contents (0.3-4.2%) were detected with high levels of saturated linear hydrocarbons. The aliphatic lipids had contributed with up to 11.7% of the total OM, and their distribution had consisted of resolved compounds (n-alkanes and fatty acid (FAs)) and an unresolved complex mixture. Hydrocarbons, primarily n-alkanes, were ranged from 368 to 3,886 μg g(-1). The FAs (674-2,568 μg g(-1)) were dominated by derived primary production, and the short chain FAs (C16 and C18) were the most abundant throughout. The ubiquitous presence of petroleum contamination, mainly from offshore oil exploration, discharge of pollutants from rivers, shipping activities and atmospheric deposition was found in all samples. The Gabès littoral seems to be quite to very polluted near the industrial zone of Ghannouch. The C/H ratio (generally around 5.9), the thermal analysis and GC-MS of n-alkanes and FAs showed that the OM in the studied area was composed of anthropogenic/petrogenic, marine and continental sources. Our study represents an innovative approach to assessing environmental pollution. The evaluation of organic matter by examination of sterols, alkanes and fatty acids allows the identification of source, both anthropogenic and natural.

Considering the Specific Impact of Harsh Conditions and Oil Weathering on Diversity, Adaptation, and Activity of Hydrocarbon-Degrading Bacteria in Strategies of Bioremediation of Harsh Oily-Polluted Soils.

PubMed

Al Disi, Zulfa; Jaoua, Samir; Al-Thani, Dhabia; Al-Meer, Saeed; Zouari, Nabil

2017-01-01

Weathering processes change properties and composition of spilled oil, representing the main reason of failure of bioaugmentation strategies. Our purpose was to investigate the metabolic adaptation of hydrocarbon-degrading bacteria at harsh conditions to be considered to overcome the limitations of bioaugmentation strategies at harsh conditions. Polluted soils, exposed for prolonged periods to weathered oil in harsh soils and weather conditions, were used. Two types of enrichment cultures were employed using 5% and 10% oil or diesel as sole carbon sources with varying the mineral nitrogen sources and C/N ratios. The most effective isolates were obtained based on growth, tolerance to toxicity, and removal efficiency of diesel hydrocarbons. Activities of the newly isolated bacteria, in relation to the microenvironment from where they were isoalted and their interaction with the weathered oil, showed individual specific ability to adapt when exposed to such factors, to acquire metabolic potentialities. Among 39 isolates, ten identified ones by 16S rDNA genes similarities, including special two Pseudomonas isolates and one Citrobacter isolate, showed particularity of shifting hydrocarbon-degrading ability from short chain n -alkanes ( n -C12- n -C16) to longer chain n -alkanes ( n -C21- n -C25) and vice versa by alternating nitrogen source compositions and C/N ratios. This is shown for the first time.

Environmental Assessment: Installation of Thermally Stable Jet Fuel (JPTS) Above Ground Storage System Westover Air Reserve Base, Chicopee, Massachusetts

DTIC Science & Technology

2004-06-30

gasoline fuels is a result ofleaking USTs in the Aqua System Site (SS-19) to the north. Volatile petroleum hydrocarbon ( VPH ) contamination from the...in- situ enhanced bioremediation plan wilJ be implemented to reduce the concentrations of VPH that are present in soils in the groundwater saturated

Biochemical upgrading of oils

DOEpatents

Premuzic, Eugene T.; Lin, Mow S.

1999-01-12

A process for biochemical conversion of heavy crude oils is provided. The process includes contacting heavy crude oils with adapted biocatalysts. The resulting upgraded oil shows, a relative increase in saturated hydrocarbons, emulsions and oxygenates and a decrease in compounds containing in organic sulfur, organic nitrogen and trace metals. Adapted microorganisms which have been modified under challenged growth processes are also disclosed.

Biochemical upgrading of oils

DOEpatents

Premuzic, E.T.; Lin, M.S.

1999-01-12

A process for biochemical conversion of heavy crude oils is provided. The process includes contacting heavy crude oils with adapted biocatalysts. The resulting upgraded oil shows, a relative increase in saturated hydrocarbons, emulsions and oxygenates and a decrease in compounds containing organic sulfur, organic nitrogen and trace metals. Adapted microorganisms which have been modified under challenged growth processes are also disclosed. 121 figs.

Influence of crude oil cracking on distribution of hydrocarbons in the Earth's interior (experimental data)

NASA Astrophysics Data System (ADS)

Balitsky, V. S.; Balitskaya, L. V.; Penteley, S. V.; Novikova, M. A.

2012-02-01

The compositions and phase conditions of water-hydrocarbon fluids in synthetic quartz inclusions were studied by the methods of microthermometry, local IR spectroscopy, and gas-liquid chromatography. Synthetic quartz was grown in near-neutral fluoride, low-alkali bicarbonate, and alkali carbonate solutions with crude oil and its major fractions. The crystals with fluid inclusions were grown under thermal gradient conditions at relatively low temperatures (240-280°C) and pressures (6-45 MPa). After the study, the inclusions of grown crystals were subject to thermal processing in autoclaves at 350-380°C and 80-125 MPa. As a result, the initial water-hydrocarbon inclusions underwent significant changes. Hydrocarbon gases, largely methane and residual solid bitumens, appeared in their composition; the gasoline-kerosene fraction content increased substantially in liquid hydrocarbons (HCs). These changes are caused, first of all, by crude oil cracking, which is manifested already at 330°C and attains its maximum activity at 350-500°C (pressure of saturated vapor and higher). In natural conditions with increase in depths and, thus, the thermobaric parameters, this process is inevitable. According to the obtained experimental data, this very phenomenon and the existence of real thermal and baric gradients in the Earth's interior provide for the formation of vertical zoning in the distribution of hydrocarbon deposits of different types.

Determination of 15 polycyclic aromatic hydrocarbons in aquatic products by solid-phase extraction and GC-MS.

PubMed

Liu, Qiying; Guo, Yuanming; Sun, Xiumei; Hao, Qing; Cheng, Xin; Zhang, Lu

2018-02-22

We propose a method for the simultaneous determination of 15 kinds of polycyclic aromatic hydrocarbons in marine samples (muscle) employing gas chromatography with mass spectrometry after saponification with ultrasound-assisted extraction and solid-phase extraction. The experimental conditions were optimized by the response surface method. In addition, the effects of different lyes and extractants on polycyclic aromatic hydrocarbons extraction were discussed, and saturated sodium carbonate was first used as the primary saponification reaction and extracted with 10 mL of ethyl acetate and secondly 1 mol/L of sodium hydroxide and 10 mL of n-hexane were used to achieve better results. The average recovery was 67-112%. Satisfactory data showed that the method has good reproducibility with a relative standard deviation of <13%. The detection limits of polycyclic aromatic hydrocarbons were 0.02-0.13 ng/g. Compared with other methods, this method has the advantages of simple pretreatment, low solvent consumption, maximum polycyclic aromatic hydrocarbons extraction, the fast separation speed, and the high extraction efficiency. It is concluded that this method meets the batch processing requirements of the sample and can also be used to determine polycyclic aromatic hydrocarbons in other high-fat (fish, shrimp, crab, shellfish) biological samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Geochemical evaluation of upper cretaceous fruitland formation coals, San Juan Basin, New Mexico and Colorado

USGS Publications Warehouse

Michael, G.E.; Anders, D.E.; Law, B.E.

1993-01-01

Geochemical analyses of coal samples from the Upper Cretaceous Fruitland Formation in the San Juan Basin of New Mexico and Colorado were used to determine thermal maturity, type of kerogen, and hydrocarbon generation potential. Mean random vitrinite reflectance (%Rm) of the Fruitland coal ranges from 0.42 to 1.54%. Rock-Eval pyrolysis data and saturated to aromatic hydrocarbon ratio indicate that the onset of thermal hydrocarbon generation begins at about 0.60% Rm and peak generation occurs at about 0.85% Rm. Several samples have hydrogen index values between 200 and 400, indicating some potential for liquid hydrocarbon generation and a mixed Type III and II kerogen. Pentacyclic and tricyclic terpanes, steranes, aromatic steroids and methylphenanthrene maturity parameters were observed through the complete range of thermal maturity in the Fruitland coals. Aromatic pentacyclic terpanes, similar to those found in brown coals of Australia, were observed in low maturity samples, but not found above 0.80% Rm. N-alkane depleted coal samples, which occur at a thermal maturity of approx. 0.90% Rm, paralleling peak hydrocarbon generation, are fairly widespread throughout the basin. Depletion of n-alkanes in these samples may be due to gas solution stripping and migration fromthe coal seams coincident with the development of pressure induced fracturing due to hydrocarbon generation; however, biodegradation may also effect these samples. ?? 1993.

Fast co-pyrolysis of waste newspaper with high-density polyethylene for high yields of alcohols and hydrocarbons.

PubMed

Chen, Weimin; Shi, Shukai; Chen, Minzhi; Zhou, Xiaoyan

2017-09-01

Waste newspaper (WP) was first co-pyrolyzed with high-density polyethylene (HDPE) using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) to enhance the yields of alcohols and hydrocarbons. The effects of WP: HDPE feed ratio (100:0, 75:25, 50:50, 25:75, 0:100) and temperature (500-800°C) on products distribution were investigated and the interaction mechanism during co-pyrolysis was also proposed. Maximum yields of alcohols and hydrocarbons reached 85.88% (feed ratio 50:50wt.%, 600°C). Hydrogen supplements and deoxidation by HDPE and subsequently fragments recombination result in the conversion of aldehydes and ketones into branched hydrocarbons. Radicals from WP degradation favor the secondary crack for HDPE products resulting in the formation of linear hydrocarbons with low carbon number. Hydrocarbons with activated radical site from HDPE degradation were interacted with hydroxyl from WP degradation promoting the formation of linear long chain alcohols. Moreover, co-pyrolysis significantly enhanced condensable oil qualities, which were close to commercial diesel No. 0. Copyright © 2017 Elsevier Ltd. All rights reserved.

Equivalent chain lengths of all C4-C23 saturated monomethyl branched fatty acid methyl esters on methylsilicone OV-1 stationary phase.

PubMed

Kubinec, Róbert; Blaško, Jaroslav; Górová, Renáta; Addová, Gabriela; Ostrovský, Ivan; Amann, Anton; Soják, Ladislav

2011-04-01

Isomer mixtures of monomethyl branched saturated C7-C23 fatty acid methyl esters (FAME) were prepared by performing a methylene insertion reaction to the straight chain FAME and this study model was completed by using commercially available standards of C4-C7 FAME. The equivalent chain lengths (ECL) of all 220 C4-C23 monomethyl branched FAME on OV-1 stationary phase were measured, achieving an average repeatability of ±0.0004 ECL units. The monomethyl branched FAME was identified by GC on the basis of regularity of the fractional chain lengths (FCL) dependence on the number of carbon atoms (C(z)) of individual homologous series of methyl 2-, 3-, …, 21-FAME. The prediction of retention of the first homologues, having the new position of methyl group beginning at higher carbon atoms number, and analogously for the second, third, fourth, and other members of the homologous series, allowed the dependence FCL=f(C(z)) for the first and subsequent members of beginning homologous of monomethyl derivatives of FAME. The identification was confirmed by mass spectrometry. All of the methyl isomers of FAME, which could not be completely separated by gas chromatography due to having a methyl group in surroundings of the middle of the carbon chain, were resolved by mass spectrometry using deconvolution in a SIM-mode. Measured gas chromatographic and mass spectrometric data were applied for identification of the monomethyl branched saturated FAME in tongue coating. Copyright © 2011 Elsevier B.V. All rights reserved.

Fabrication and electrical characterization of Al/diazo compound containing polyoxy chain/p-Si device structure

NASA Astrophysics Data System (ADS)

Birel, Ozgul; Kavasoglu, Nese; Kavasoglu, A. Sertap; Dincalp, Haluk; Metin, Bengul

2013-03-01

Diazo-compounds are important class of chemical compounds in terms of optical and electronic properties which make them potentially attractive for device applications. Diazo compound containing polyoxy chain has been deposited on p-Si. Current-voltage characteristics of Al/diazo compound containing polyoxy chain/p-Si structure present rectifying behaviour. The Schottky barrier height (SBH), diode factor (n), reverse saturation current (Io), interface state density (Nss) of Al/diazo compound containing polyoxy chain/p-Si structure have been calculated from experimental forward bias current-voltage data measured in the temperature range 100-320 K and capacitance-voltage data measured at room temperature and 1 MHz. The calculated values of SBH have ranged from 0.041 and 0.151 eV for the high and low temperature regions. Diode factor values fluctuate between the values 14 and 18 with temperature. Such a high diode factors stem from disordered interface layer in a junction structure as stated by Brötzmann et al. [M. Brötzmann, U. Vetter, H. Hofsäss, J. Appl. Phys. 106 (2009) 063704]. The calculated values of saturation current have ranged from 3×10-11 A to 2.79×10-7 A and interface state density have ranged from 5×1011 eV-1 cm-2 and 4×1013 eV-1 cm-2 as temperature increases. Results show that Al/diazo compound containing polyoxy chain/p-Si structure is a valuable candidate for device applications in terms of low reverse saturation current and low interface state density.

A rare polyglycine type II-like helix motif in naturally occurring proteins.

PubMed

Warkentin, Eberhard; Weidenweber, Sina; Schühle, Karola; Demmer, Ulrike; Heider, Johann; Ermler, Ulrich

2017-11-01

Common structural elements in proteins such as α-helices or β-sheets are characterized by uniformly repeating, energetically favorable main chain conformations which additionally exhibit a completely saturated hydrogen-bonding network of the main chain NH and CO groups. Although polyproline or polyglycine type II helices (PP II or PG II ) are frequently found in proteins, they are not considered as equivalent secondary structure elements because they do not form a similar self-contained hydrogen-bonding network of the main chain atoms. In this context our finding of an unusual motif of glycine-rich PG II -like helices in the structure of the acetophenone carboxylase core complex is of relevance. These PG II -like helices form hexagonal bundles which appear to fulfill the criterion of a (largely) saturated hydrogen-bonding network of the main-chain groups and therefore may be regarded in this sense as a new secondary structure element. It consists of a central PG II -like helix surrounded by six nearly parallel PG II -like helices in a hexagonal array, plus an additional PG II -like helix extending the array outwards. Very related structural elements have previously been found in synthetic polyglycine fibers. In both cases, all main chain NH and CO groups of the central PG II -helix are saturated by either intra- or intermolecular hydrogen-bonds, resulting in a self-contained hydrogen-bonding network. Similar, but incomplete PG II -helix patterns were also previously identified in a GTP-binding protein and an antifreeze protein. © 2017 Wiley Periodicals, Inc.

Safety assessment of myristic acid as a food ingredient.

PubMed

Burdock, George A; Carabin, Ioana G

2007-04-01

Myristic acid is used in the food industry as a flavor ingredient. It is found widely distributed in fats throughout the plant and animal kingdom, including common human foodstuffs, such as nutmeg. Myristic acid (a 14-carbon, straight-chain saturated fatty acid) has been shown to have a low order of acute oral toxicity in rodents. It may be irritating in pure form to skin and eyes under exaggerated exposure conditions, but is not known or predicted to induce sensitization responses. Myristic acid did not induce a mutagenic response in either bacterial or mammalian systems in vitro. Relevant subchronic toxicity data are available on closely related fatty acid analogs. In particular, a NOEL of >6000mg/kg was reported for lauric acid (a 12-carbon, straight-chain saturated fatty acid) following dietary exposure to male rats for 18 weeks and a NOEL of >5000mg/kg was reported for palmitic acid (a 16-carbon, straight-chain saturated fatty acid) following dietary exposure to rats for 150 days. The data and information that are available indicate that at the current level of intake, food flavoring use of myristic acid does not pose a health risk to humans.

Genetic analysis of groups of mid-infrared predicted fatty acids in milk.

PubMed

Narayana, S G; Schenkel, F S; Fleming, A; Koeck, A; Malchiodi, F; Jamrozik, J; Johnston, J; Sargolzaei, M; Miglior, F

2017-06-01

The objective of this study was to investigate genetic variability of mid-infrared predicted fatty acid groups in Canadian Holstein cattle. Genetic parameters were estimated for 5 groups of fatty acids: short-chain (4 to 10 carbons), medium-chain (11 to 16 carbons), long-chain (17 to 22 carbons), saturated, and unsaturated fatty acids. The data set included 49,127 test-day records from 10,029 first-lactation Holstein cows in 810 herds. The random regression animal test-day model included days in milk, herd-test date, and age-season of calving (polynomial regression) as fixed effects, herd-year of calving, animal additive genetic effect, and permanent environment effects as random polynomial regressions, and random residual effect. Legendre polynomials of the third degree were selected for the fixed regression for age-season of calving effect and Legendre polynomials of the fourth degree were selected for the random regression for animal additive genetic, permanent environment, and herd-year effect. The average daily heritability over the lactation for the medium-chain fatty acid group (0.32) was higher than for the short-chain (0.24) and long-chain (0.23) fatty acid groups. The average daily heritability for the saturated fatty acid group (0.33) was greater than for the unsaturated fatty acid group (0.21). Estimated average daily genetic correlations were positive among all fatty acid groups and ranged from moderate to high (0.63-0.96). The genetic correlations illustrated similarities and differences in their origin and the makeup of the groupings based on chain length and saturation. These results provide evidence for the existence of genetic variation in mid-infrared predicted fatty acid groups, and the possibility of improving milk fatty acid profile through genetic selection in Canadian dairy cattle. Copyright © 2017 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Insights into Hydrocarbon Formation by Nitrogenase Cofactor Homologs

PubMed Central

Lee, Chi Chung; Hu, Yilin

2015-01-01

ABSTRACT The L-cluster is an all-iron homolog of nitrogenase cofactors. Driven by europium(II) diethylenetriaminepentaacetate [Eu(II)-DTPA], the isolated L-cluster is capable of ATP-independent reduction of CO and CN− to C1 to C4 and C1 to C6 hydrocarbons, respectively. Compared to its cofactor homologs, the L-cluster generates considerably more CH4 from the reduction of CO and CN−, which could be explained by the presence of a “free” Fe atom that is “unmasked” by homocitrate as an additional site for methanation. Moreover, the elevated CH4 formation is accompanied by a decrease in the amount of longer hydrocarbons and/or the lengths of the hydrocarbon products, illustrating a competition between CH4 formation/release and C−C coupling/chain extension. These observations suggest the possibility of designing simpler synthetic clusters for hydrocarbon formation while establishing the L-cluster as a platform for mechanistic investigations of CO and CN− reduction without complications originating from the heterometal and homocitrate components. PMID:25873377

Oxidation of Alkyl-substituted Cyclic Hydrocarbons by a Nocardia during Growth on n-Alkanes

PubMed Central

Davis, J. B.; Raymond, R. L.

1961-01-01

Nocardia 107-332, a soil isolate, oxidizes short-chain alkyl-substituted cyclic hydrocarbons to cyclic acids while growing on n-alkanes. Cyclic acids are produced also from relatively long-chain alkyl-substituted cyclics such as n-nonylbenzene or n-dodecylbenzene which alone support growth in a mineral-salts medium. ω-Oxidation of the alkyl substituents is followed by β-oxidation. It is of particular interest that cyclic acids such as cyclohexaneacetic and phenylacetic with C2 residual carboxylic acid substituents are resistant to further oxidation by the nocardia but cyclic acids with C1 or C3 substituents are readily oxidized and utilized for growth. The specificity of microbial oxidations is demonstrated by the conversion of p-isopropyltoluene (p-cymene) to p-isopropylbenzoic acid in n-alkane, growth-supported nocardia cultures. PMID:13720182

Evaluation of the influence of ionization states and spacers in the thermotropic phase behaviour of amino acid-based cationic lipids and the transfection efficiency of their assemblies.

PubMed

Sarker, Satya Ranjan; Arai, Satoshi; Murate, Motohide; Takahashi, Hiroshi; Takata, Masaki; Kobayashi, Toshihide; Takeoka, Shinji

2012-01-17

The influence of both the ionization states and the hydrocarbon chain spacer of a series of amino acid-based cationic lipids was evaluated in terms of gene delivery efficiency and cytotoxicity to the COS-7 cell line and compared with that of Lipofectamine 2000. We synthesized a series of amino acid-based cationic lipids with different ionization states (i.e., -NH(2), -NH(3)(+)Cl(-) or -NH(3)(+)TFA(-)) in the lysine head group and different hydrocarbon chain spacers (i.e., 0, 3, 5 or 7 carbon atoms) between the hydrophilic head group and hydrophobic moieties. In the 3-carbon series, the cationic assemblies formed a micellar structure in the presence of -NH(3)(+)Cl(-) and a vesicular structure both in the presence of -NH(2) and -NH(3)(+)TFA(-). Differential scanning calorimetry (DSC) data revealed a significantly lower (8.1°C) gel-to-liquid crystalline phase transition temperature for cationic assemblies bearing -NH(3)(+)TFA(-) when compared to their -NH(2) counterparts. Furthermore, the zeta potential of cationic assemblies having -NH(3)(+)TFA(-) in the hydrophilic head group was maximum followed by -NH(3)(+)Cl(-) and -NH(2) irrespective of their hydrocarbon chain spacer length. The gene delivery efficiency in relation to the ionization states of the hydrophilic head group was as follows: -NH(3)(+)TFA(-)>-NH(3)(+)Cl(-)>-NH(2). Copyright © 2011 Elsevier B.V. All rights reserved.

Adsorption of anionic and nonionic surfactant mixtures from synthetic detergents on soils.

PubMed

Rao, Pinhua; He, Ming

2006-05-01

Adsorption of anionic surfactant (sodium dodecylbenzenesulfonate, SDBS) and nonionic surfactant (an alcohol ethoxylates with 12 carbons and 9 oxyethyl groups, A12E9) mixtures, widely used as the major constituents of synthetic detergents in China and become the most common pollutants in the environment, on soils was conducted to investigate the behavior of mixed surfactants in soils. The effects of addition order and mixing ratios of two surfactants, associated with pH and ion strength in solutions, on adsorptions were considered. The results show that saturated adsorption amount of SDBS and A12E9 on soils decreased respectively when A12E9 was added into soils firstly compared with that secondly, possibly resulting from the screening of A12E9 to part adsorption sites on soils and the hydrocarbon chain-chain interactions between SDBS and A12E9. The adsorption of SDBS and A12E9 on soils was enhanced each other at pre-plateau region of isotherms. At plateau region of isotherms, the adsorption of SDBS on soils decreased with the increase of molar fraction of A12E9 in mixed surfactant solutions, while that of A12E9 increased except the molar ratio of SDBS to A12E9 0.0:1.0. With the increase of pH in mixed surfactant solutions, adsorption amount of SDBS and A12E9 on soils decreased, respectively. The reduction of ion strength in soils resulted in the decrease of adsorption amount of SDBS and A12E9 on soils, respectively.

Review of data on the dermal penetration of mineral oils and waxes used in cosmetic applications.

PubMed

Petry, T; Bury, D; Fautz, R; Hauser, M; Huber, B; Markowetz, A; Mishra, S; Rettinger, K; Schuh, W; Teichert, T

2017-10-05

Mineral oils and waxes used in cosmetic products, also referred to as "personal care products" outside the European Union, are mixtures of predominantly saturated hydrocarbons consisting of straight-chain, branched and ring structures with carbon chain lengths greater than C16. They are used in skin and lip care cosmetic products due to their excellent skin tolerance as well as their high protecting and cleansing performance and broad viscosity options. Recently, concerns have been raised regarding potential adverse health effects of mineral oils and waxes from dermal application of cosmetics. In order to be able to assess the risk for the consumer the dermal penetration potential of these ingredients has to be evaluated. The scope and objective of this review are to identify and summarize publicly available literature on the dermal penetration of mineral oils and waxes as used in cosmetic products. For this purpose, a comprehensive literature search was conducted. A total of 13 in vivo (human, animal) and in vitro studies investigating the dermal penetration of mineral oils and waxes has been identified and analysed. The majority of the substances were dermally adsorbed to the stratum corneum and only a minor fraction reached deeper skin layers. Overall, there is no evidence from the various studies that mineral oils and waxes are percutaneously absorbed and become systemically available. Thus, given the absence of dermal uptake, mineral oils and waxes as used in cosmetic products do not present a risk to the health of the consumer. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Microbial synthesis of medium-chain chemicals from renewables.

PubMed

Sarria, Stephen; Kruyer, Nicholas S; Peralta-Yahya, Pamela

2017-12-01

Linear, medium-chain (C8-C12) hydrocarbons are important components of fuels as well as commodity and specialty chemicals. As industrial microbes do not contain pathways to produce medium-chain chemicals, approaches such as overexpression of endogenous enzymes or deletion of competing pathways are not available to the metabolic engineer; instead, fatty acid synthesis and reversed β-oxidation are manipulated to synthesize medium-chain chemical precursors. Even so, chain lengths remain difficult to control, which means that purification must be used to obtain the desired products, titers of which are typically low and rarely exceed milligrams per liter. By engineering the substrate specificity and activity of the pathway enzymes that generate the fatty acyl intermediates and chain-tailoring enzymes, researchers can boost the type and yield of medium-chain chemicals. Development of technologies to both manipulate chain-tailoring enzymes and to assay for products promises to enable the generation of g/L yields of medium-chain chemicals.

Synthesis and surface properties of polyurethane end-capped with hybrid hydrocarbon/fluorocarbon double-chain phospholipid.

PubMed

Li, Jiehua; Zhang, Yi; Yang, Jian; Tan, Hong; Li, Jianshu; Fu, Qiang

2013-05-01

To improve hemocompatibility of biomedical polyurethanes (PUs), a series of new fluorinated phospholipid end-capped polyurethanes (FPCPUs) as blending PU additives were designed and synthesized using diphenyl methane diisocyanate and 1,4-butanediol as hard segment, poly(tetramethylene glycol), polypropylene glycol, polycarbonate diols, and polyethylene glycol as soft segments, respectively, aminofunctionalized hybrid hydrocarbon/fluorocarbon double-chain phospholipid as end-capper. The bulk structures and surface properties of the obtained FPCPUs were fully characterized by (1)H NMR, Fourier transform infrared, gel permeation chromatography, X-ray photoelectron spectroscopy, differential scanning calorimetry, atomic force microscopy, and water contact angle measurement. It was found that the phosphatidylcholine groups could enrich on the surfaces and subsurfaces with the help of the fluorocarbon chains and self-assemble into mimic biomembrane on these polymer surfaces. These surfaces could effectively suppress fibrinogen adsorption, as evaluated by enzyme-linked immunosorbent assay method. Our work indicates that the FPCPUs should be one of the most potential modified additives for enhancing hemocompatibility of traditional medical PUs. Copyright © 2012 Wiley Periodicals, Inc.

Modeling of Interfacial Modification Effects on Thermal Conductivity of Carbon Nanotube Composites

NASA Technical Reports Server (NTRS)

Clancy, Thomas C.; Gates, Thomas S.

2006-01-01

The effect of functionalization of carbon nanotubes on the thermal conductivity of nanocomposites has been studied using a multi-scale modeling approach. These results predict that grafting linear hydrocarbon chains to the surface of a single wall carbon nanotube with covalent chemical bonds should result in a significant increase in the thermal conductivity of these nanocomposites. This is due to the decrease in the interfacial thermal (Kapitza) resistance between the single wall carbon nanotube and the surrounding polymer matrix upon chemical functionalization. The nanocomposites studied here consist of single wall carbon nanotubes in a bulk poly(ethylene vinyl acetate) matrix. The nanotubes are functionalized by end-grafting linear hydrocarbon chains of varying length to the surface of the nanotube. The effect which this functionalization has on the interfacial thermal resistance is studied by molecular dynamics simulation. Interfacial thermal resistance values are calculated for a range of chemical grafting densities and with several chain lengths. These results are subsequently used in an analytical model to predict the resulting effect on the bulk thermal conductivity of the nanocomposite.

Hydrocarbon emissions speciation in diesel and biodiesel exhausts

NASA Astrophysics Data System (ADS)

Payri, Francisco; Bermúdez, Vicente R.; Tormos, Bernardo; Linares, Waldemar G.

Diesel engine emissions are composed of a long list of organic compounds, ranging from C 2 to C 12+, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic. The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed. Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed. The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.

Melt coaxial electrospinning: a versatile method for the encapsulation of solid materials and fabrication of phase change nanofibers.

PubMed

McCann, Jesse T; Marquez, Manuel; Xia, Younan

2006-12-01

We have developed a method based on melt coaxial electrospinning for fabricating phase change nanofibers consisting of long-chain hydrocarbon cores and composite sheaths. This method combines melt electrospinning with a coaxial spinneret and allows for nonpolar solids such as paraffins to be electrospun and encapsulated in one step. Shape-stabilized, phase change nanofibers have many potential applications as they are able to absorb, hold, and release large amounts of thermal energy over a certain temperature range by taking advantage of the large heat of fusion of long-chain hydrocarbons. We have focused on compounds with melting points near room temperature (octadecane) and body temperature (eicosane) as these temperature ranges are most valuable in practice. We have produced thermally stable, phase change materials up to 45 wt % octadecane, as measured by differential scanning calorimetry. In addition, the resultant fibers display novel segmented morphologies for the cores due to the rapid solidification of the hydrocarbons driven by evaporative cooling of the carrier solution. Aside from the fabrication of phase change nanofibers, the melt coaxial method is promising for applications related to microencapsulation and controlled release of drugs.

Molecular dynamics study of intermediate phase of long chain alkyl sulfonate/water systems.

PubMed

Poghosyan, Armen H; Arsenyan, Levon H; Shahinyan, Aram A

2013-01-08

Using atomic level simulation we aimed to investigate various intermediate phases of the long chain alkyl sulfonate/water system. Overall, about 800 ns parallel molecular dynamics simulation study was conducted for a surfactant/water system consisting of 128 sodium pentadecyl sulfonate and 2251 water molecules. The GROMACS software code with united atom force field was applied. Despite some differences, the analysis of main structural parameters is in agreement with X-ray experimental findings. The mechanism of self-assembly of SPDS molecules was also examined. At T = 323 K we obtained both tilted fully interdigitated and liquid crystalline-like disordered hydrocarbon chains; hence, the presence of either gel phase that coexists with a lamellar phase or metastable gel phase with fraction of gauche configuration can be assumed. Further increase of temperature revealed that the system underwent a transition to a lamellar phase, which was clearly identified by the presence of fully disordered hydrocarbon chains. The transition from gel-to-fluid phase was implemented by simulated annealing treatment, and the phase transition point at T = 335 K was identified. The surfactant force field in its presented set is surely enabled to fully demonstrate the mechanism of self-assembly and the behavior of phase transition making it possible to get important information around the phase transition point.

Short-chain alkanes fuel mussel and sponge Cycloclasticus symbionts from deep-sea gas and oil seeps.

PubMed

Rubin-Blum, Maxim; Antony, Chakkiath Paul; Borowski, Christian; Sayavedra, Lizbeth; Pape, Thomas; Sahling, Heiko; Bohrmann, Gerhard; Kleiner, Manuel; Redmond, Molly C; Valentine, David L; Dubilier, Nicole

2017-06-19

Cycloclasticus bacteria are ubiquitous in oil-rich regions of the ocean and are known for their ability to degrade polycyclic aromatic hydrocarbons (PAHs). In this study, we describe Cycloclasticus that have established a symbiosis with Bathymodiolus heckerae mussels and poecilosclerid sponges from asphalt-rich, deep-sea oil seeps at Campeche Knolls in the southern Gulf of Mexico. Genomic and transcriptomic analyses revealed that, in contrast to all previously known Cycloclasticus, the symbiotic Cycloclasticus appears to lack the genes needed for PAH degradation. Instead, these symbionts use propane and other short-chain alkanes such as ethane and butane as carbon and energy sources, thus expanding the limited range of substrates known to power chemosynthetic symbioses. Analyses of short-chain alkanes in the environment of the Campeche Knolls symbioses revealed that these are present at high concentrations (in the μM to mM range). Comparative genomic analyses revealed high similarities between the genes used by the symbiotic Cycloclasticus to degrade short-chain alkanes and those of free-living Cycloclasticus that bloomed during the Deepwater Horizon oil spill. Our results indicate that the metabolic versatility of bacteria within the Cycloclasticus clade is higher than previously assumed, and highlight the expanded role of these keystone species in the degradation of marine hydrocarbons.

Directed assembly of binary monolayers with a high protein affinity: infrared reflection absorption spectroscopy (IRRAS) and surface plasmon resonance (SPR).

PubMed

Du, Xuezhong; Wang, Yuchun

2007-03-08

Infrared reflection absorption spectroscopy (IRRAS) and surface plasmon resonance (SPR) techniques have been employed to investigate human serum albumin (HSA) binding to binary monolayers of zwitterionic dipalmitoylphosphatidylcholine (DPPC) and cationic dioctadecyldimethylammonium bromide (DOMA). At the air-water interface, the favorable electrostatic interaction between DPPC and DOMA leads to a dense chain packing. The tilt angle of the hydrocarbon chains decreases with increasing mole fraction of DOMA (X(DOMA)) in the monolayers at the surface pressure 30 mN/m: DPPC ( approximately 30 degrees ), X(DOMA) = 0.1 ( approximately 15 degrees ), and X(DOMA) = 0.3 ( approximately 0 degrees ). Negligible protein binding to the DPPC monolayer is observed in contrast to a significant binding to the binary monolayers. After HSA binding, the hydrocarbon chains at X(DOMA) = 0.1 undergo an increase in tilt angle from 15 degrees to 25 approximately 30 degrees , and the chains at X(DOMA) = 0.3 remain almost unchanged. The two components in the monolayers deliver through lateral reorganization, induced by the protein in the subphase, to form multiple interaction sites favorable for protein binding. The surfaces with a high protein affinity are created through the directed assembly of binary monolayers for use in biosensing.

Short-chain alkanes fuel mussel and sponge Cycloclasticus symbionts from deep-sea gas and oil seeps

PubMed Central

Rubin-Blum, Maxim; Antony, Chakkiath Paul; Borowski, Christian; Sayavedra, Lizbeth; Pape, Thomas; Sahling, Heiko; Bohrmann, Gerhard; Kleiner, Manuel; Redmond, Molly C.; Valentine, David L.; Dubilier, Nicole

2017-01-01

Cycloclasticus bacteria are ubiquitous in oil-rich regions of the ocean and are known for their ability to degrade polycyclic aromatic hydrocarbons (PAHs). In this study, we describe Cycloclasticus that have established a symbiosis with Bathymodiolus heckerae mussels and poecilosclerid sponges from asphalt-rich, deep-sea oil seeps at Campeche Knolls in the southern Gulf of Mexico. Genomic and transcriptomic analyses revealed that in contrast to all known Cycloclasticus, the symbiotic Cycloclasticus appeared to lack the genes needed for PAH degradation. Instead, these symbionts use propane and other short-chain alkanes such as ethane and butane as carbon and energy sources, thus expanding the limited range of substrates known to power chemosynthetic symbioses. Analyses of short-chain alkanes in the environment of the Campeche Knolls symbioses revealed that these are present at high concentrations (in the µM to mM range). Comparative genomic analyses revealed high similarities between the genes used by the symbiotic Cycloclasticus to degrade short-chain alkanes and those of free-living Cycloclasticus that bloomed during the Deepwater Horizon (DWH) oil spill. Our results indicate that the metabolic versatility of bacteria within the Cycloclasticus clade is higher than previously assumed, and highlight the expanded role of these keystone species in the degradation of marine hydrocarbons. PMID:28628098

Mass transfer model of nanoparticle-facilitated contaminant transport in saturated porous media.

PubMed

Johari, Wan Lutfi Wan; Diamessis, Peter J; Lion, Leonard W

2010-02-01

A one-dimensional model has been evaluated for transport of hydrophobic contaminants, such as polycyclic aromatic hydrocarbon (PAH) compounds, facilitated by synthetic amphiphilic polyurethane (APU) nanoparticles in porous media. APU particles synthesized from poly(ethylene glycol)-modified urethane acrylate (PMUA) precursor chains have been shown to enhance the desorption rate and mobility of phenanthrene (PHEN) in soil. A reversible process governed by attachment and detachment rates was considered to describe the PMUA binding in soil in addition to PMUA transport through advection and dispersion. Ultimately, an irreversible second-order PMUA attachment rate in which the fractional soil saturation capacity with PMUA was a rate control was found to be adequate to describe the retention of PMUA particles. A gamma-distributed site model (GS) was used to describe the spectrum of physical/chemical constraints for PHEN transfer from solid to aqueous phases. Instantaneous equilibrium was assumed for PMUA-PHEN interactions. The coupled model for PMUA and PHEN behavior successfully described the enhanced elution profile of PHEN by PMUA. Sensitivity analysis was performed to analyze the significance of model parameters on model predictions. The adjustable parameter alpha in the gamma-distribution shapes the contaminant desorption distribution profile as well as elution and breakthrough curves. Model simulations show the use of PMUA can be also expected to improve the release rate of PHEN in soils with higher organic carbon content. The percentage removal of PHEN mass over time is shown to be influenced by the concentration of PMUA added and this information can be used to optimize cost and time require to accomplish a desired remediation goal. Copyright 2009 Elsevier Ltd. All rights reserved.

Influence of Water Saturation on Thermal Conductivity in Sandstones

NASA Astrophysics Data System (ADS)

Fehr, A.; Jorand, R.; Koch, A.; Clauser, C.

2009-04-01

Information on thermal conductivity of rocks and soils is essential in applied geothermal and hydrocarbon maturation research. In this study, we investigate the dependence of thermal conductivity on the degree of water saturation. Measurements were made on five sandstones from different outcrops in Germany. In a first step, we characterized the samples with respect to mineralogical composition, porosity, and microstructure by nuclear magnetic resonance (NMR) and mercury injection. We measured thermal conductivity with an optical scanner at different levels of water saturation. Finally we present a simple and easy model for the correlation of thermal conductivity and water saturation. Thermal conductivity decreases in the course of the drying of the rock. This behaviour is not linear and depends on the microstructure of the studied rock. We studied different mixing models for three phases: mineral skeleton, water and air. For argillaceous sandstones a modified arithmetic model works best which considers the irreducible water volume and different pore sizes. For pure quartz sandstones without clay minerals, we use the same model for low water saturations, but for high water saturations a modified geometric model. A clayey sandstone rich in feldspath shows a different behaviour which cannot be explained by simple models. A better understanding will require measurements on additional samples which will help to improve the derived correlations and substantiate our findings.

Dependence of Thermal Conductivity on Water Saturation of Sandstones

NASA Astrophysics Data System (ADS)

Fehr, A.; Jorand, R.; Koch, A.; Clauser, C.

2008-12-01

Information on thermal conductivity of rocks and soils is essential in applied geothermal and hydrocarbon maturation research. In this study, we investigate the dependence of thermal conductivity on the degree of water saturation. Measurements were made on five sandstones from different outcrops in Germany. In a first step, we characterized the samples with respect to mineralogical composition, porosity, and microstructure by nuclear magnetic resonance (NMR) and mercury injection. We measured thermal conductivity with an optical scanner at different levels of water saturation. Finally we present a simple and easy model for the correlation of thermal conductivity and water saturation. Thermal conductivity decreases in the course of the drying of the rock. This behaviour is not linear and depends on the microstructure of the studied rock. We studied different mixing models for three phases: mineral skeleton, water and air. For argillaceous sandstones a modified arithmetic model works best which considers the irreducible water volume and different pore sizes. For pure quartz sandstones without clay minerals, we use the same model for low water saturations, but for high water saturations a modified geometric model. A clayey sandstone rich in feldspath shows a different behaviour which cannot be explained by simple models. A better understanding will require measurements on additional samples which will help to improve the derived correlations and substantiate our findings.

Hydrocarbon generation and expulsion in shale Vs. carbonate source rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leythaeuser, D.; Krooss, B.; Hillebrand, T.

1993-09-01

For a number of commercially important source rocks of shale and of carbonate lithologies, which were studied by geochemical, microscopical, and petrophysical techniques, a systematic comparison was made of the processes on how hydrocarbon generation and migration proceed with maturity progress. In this way, several fundamental differences between both types of source rocks were recognized, which are related to differences of sedimentary facies and, more importantly, of diagenetic processes responsible for lithification. Whereas siliciclastic sediments lithify mainly by mechanical compaction, carbonate muds get converted into lithified rocks predominantly by chemical diagenesis. With respect to their role as hydrocarbon source rocks,more » pressure solution processes appear to be key elements. During modest burial stages and prior to the onset of hydrocarbon generation reactions by thermal decomposition of kerogen, pressure solution seams and stylolites. These offer favorable conditions for hydrocarbon generation and expulsion-a three-dimensional kerogen network and high organic-matter concentrations that lead to effective saturation of the internal pore fluid system once hydrocarbon generation has started. As a consequence, within such zones pore fluids get overpressured, leading ultimately to fracturing. Petroleum expulsion can then occur at high efficiencies and in an explosive fashion, whereby clay minerals and residual kerogen particles are squeezed in a toothpaste-like fashion into newly created fractures. In order to elucidate several of the above outlined steps of hydrocarbon generation and migration processes, open-system hydrous pyrolysis experiments were performed. This approach permits one to monitor changes in yield and composition of hydrocarbon products generated and expelled at 10[degrees]C temperature increments over temperature range, which mimics in the laboratory the conditions prevailing in nature over the entire liquid window interval.« less

Trophic structure of amoeba communities near roots of Medicago sativa after contamination with fuel oil no. 6.

PubMed

Cortés-Pérez, Sandra; Rodríguez-Zaragoza, Salvador; Mendoza-López, Ma Remedios

2014-02-01

Root exudation increases microbial activity, selecting bacterial and fungal communities that metabolize organic matter such as hydrocarbons. However, a strong contamination pulse of hydrocarbons around plant roots may reorganize the soil's microbial trophic structure toward amoebae feeding on bacteria. We conducted a microcosm experiment to elucidate the effect of Medicago sativa on the trophic structure of naked amoebae after a strong pulse of pollution (50,000 ppm of fuel oil no. 6, which is a mixture of long chains ranging from C10 to C28). Plants were seeded 24 h after contamination and species of amoebae in the microcosms were identified at 1, 30, and 60 days after pollution. Several species from three trophic groups of naked amoeba were still alive 24 h after the hydrocarbon pulse. Non-planted microcosms harbored three trophic groups after 60 days, while planted ones nourished four groups. The bacterivore group was the most diverse in all microcosms, followed by protist-eaters and omnivores. The quantity of amoebae was significantly higher (3.4×10(3) organisms/g soil) in the planted pots than in the non-planted ones (1.3×10(3) organisms/g soil after 30 days of pollution (P ≤ 0.01). The shortest hydrocarbon chains (C10-C14) disappeared or diminished in all microcosms, and the longest ones increased in the planted ones. M. sativa thus exerted a positive effect on species richness, quantity, and the composition of amoebae trophic groups in contaminated soil. This indirect effect on bacterial predators is another key factor underlying hydrocarbon assimilation by living organisms during phytoremediation.

[Characterization of a thermophilic Geobacillus strain DM-2 degrading hydrocarbons].

PubMed

Liu, Qing-kun; Wang, Jun; Li, Guo-qiang; Ma, Ting; Liang, Feng-lai; Liu, Ru-lin

2008-12-01

A thermophilic Geobacillus strain DM-2 from a deep-subsurface oil reservoir was investigated on its capability of degrading crude oil under various conditions as well as its characters on degrading hydrocarbons in optimal conditions. The results showed that Geobacillus strain DM-2 was able to degrade crude oil under anoxic wide-range conditions with pH ranging from 4.0 to 10.0, high temperature in the range of 45-70 degrees C and saline concentration ranging from 0.2% to 3.0%. Furthermore, the optimal temperature and pH value for utilizing hydrocarbons by the strain were 60 degrees C and 7.0, respectively. Under such optimal conditions, the strain utilized liquid paraffine emulsified by itself as its carbon source for growth; further analysis by gas chromatography (GC) and infrared absorption spectroscopy demonstrated that it was able to degrade n-alkanes (C14-C30), branched-chain alkanes and aromatic hydrocarbons in crude oil and could also utilize long-chain n-alkanes from C16 to C36, among of which the degradation efficiency of C28 was the highest, up to 88.95%. One metabolite of the strain oxidizing alkanes is fatty acid.While utilizing C16 as carbon source for 5 d, only one fatty acid-acetic acid was detected by HPLC and MS as the product, with the amount of 0.312 g/L, which indicated that it degraded n-alkanes with pathway of inferior terminal oxidation,and then followed by a beta-oxidation pathway. Due to its characters of efficient emulsification, high-performance degradation of hydrocarbons and fatty-acid production under high temperature and anoxic condition, the strain DM-2 may be potentially applied to oil-waste treatment and microbial enhanced heavy oil recovery in extreme conditions.

Compound- and position-specific carbon isotopic signatures of abiogenic hydrocarbons from on-land serpentinite-hosted Hakuba Happo hot spring in Japan

NASA Astrophysics Data System (ADS)

Suda, Konomi; Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro; Ueno, Yuichiro

2017-06-01

It has been proposed that serpentinite-hosted hydrothermal/hot spring systems played a significant role in the origin and early evolution of life on early Earth because abiogenic synthesis of organic compounds may accompany serpentinization. However, production mechanisms for apparently abiogenic hydrocarbons that have been observed in the ongoing serpentinizing systems are still poorly constrained. We report a new geochemical study of hydrocarbons in an on-land serpentinite-hosted hot spring in Hakuba Happo, Japan. We have conducted both compound-specific and position-specific carbon isotopic analyses of the observed C1 to C5 hydrocarbons. A positive linear relationship between the δ13C values and the inverse carbon number is found in C1 to C5 straight-chain alkanes in the Happo sample. This isotopic trend is consistent with a simple polymerization model developed in this study. Our model assumes that, for any particular alkane, all of the subsequently added carbons have the same isotopic composition, and those are depleted in 13C with respect to the first carbon in the growing carbon chain. The fit of this model suggests that Happo alkanes can be produced via polymerization from methane with a constant kinetic isotopic fractionation of -8.9 ± 1.0‰. A similar carbon isotopic relationship among alkanes has been observed in some serpentinite-hosted seafloor hydrothermal systems, indicating that the same process is responsible for the abiological hydrocarbon in general serpentinization fields, not only in the Hakuba Happo hot spring. Moreover, our model is also applicable to other potentially abiogenic natural gases and experimentally synthesized hydrocarbon products. For the first time, the intramolecular 13C composition of propane from a natural sample derived from a serpentinite-hosted system was determined. The intramolecular 13C distribution in propane shows the important potential to identify different polymerization mechanisms that cannot be discriminated by compound-specific isotopic analysis.

Bioaccumulation of petroleum hydrocarbons in arctic amphipods in the oil development area of the Alaskan Beaufort Sea.

PubMed

Neff, Jerry M; Durell, Gregory S

2012-04-01

An objective of a multiyear monitoring program, sponsored by the US Department of the Interior, Bureau of Ocean Energy Management was to examine temporal and spatial changes in chemical and biological characteristics of the Arctic marine environment resulting from offshore oil exploration and development activities in the development area of the Alaskan Beaufort Sea. To determine if petroleum hydrocarbons from offshore oil operations are entering the Beaufort Sea food web, we measured concentrations of hydrocarbons in tissues of amphipods, Anonyx nugax, sediments, Northstar crude oil, and coastal peat, collected between 1999 and 2006 throughout the development area. Mean concentrations of polycyclic aromatic hydrocarbons (PAH), saturated hydrocarbons (SHC), and sterane and triterpane petroleum biomarkers (StTr) were not significantly different in amphipods near the Northstar oil production facility, before and after it came on line in 2001, and in amphipods from elsewhere in the study area. Forensic analysis of the profiles (relative composition and concentrations) of the 3 hydrocarbon classes revealed that hydrocarbon compositions were different in amphipods, surface sediments where the amphipods were collected, Northstar crude oil, and peat from the deltas of 4 North Slope rivers. Amphipods and sediments contained a mixture of petrogenic, pyrogenic, and biogenic PAH. The SHC in amphipods were dominated by pristane derived from zooplankton, indicating that the SHC were primarily from the amphipod diet of zooplankton detritus. The petroleum biomarker StTr profiles did not resemble those in Northstar crude oil. The forensic analysis revealed that hydrocarbons in amphipod tissues were not from oil production at Northstar. Hydrocarbons in amphipod tissues were primarily from their diet and from river runoff and coastal erosion of natural diagenic and fossil terrestrial materials, including seep oils, kerogens, and peat. Offshore oil and gas exploration and development do not appear to be causing an increase in petroleum hydrocarbon contamination of the Beaufort Sea food web. Copyright © 2011 SETAC.

Enhanced CAH dechlorination in a low permeability, variably-saturated medium

USGS Publications Warehouse

Martin, J.P.; Sorenson, K.S.; Peterson, L.N.; Brennan, R.A.; Werth, C.J.; Sanford, R.A.; Bures, G.H.; Taylor, C.J.; ,

2002-01-01

An innovative pilot-scale field test was performed to enhance the anaerobic reductive dechlorination (ARD) of chlorinated aliphatic hydrocarbons (CAHs) in a low permeability, variably-saturated formation. The selected technology combines the use of a hydraulic fracturing (fracking) technique with enhanced bioremediation through the creation of highly-permeable sand- and electron donor-filled fractures in the low permeability matrix. Chitin was selected as the electron donor because of its unique properties as a polymeric organic material and based on the results of lab studies that indicated its ability to support ARD. The distribution and impact of chitin- and sand-filled fractures to the system was evaluated using hydrologic, geophysical, and geochemical parameters. The results indicate that, where distributed, chitin favorably impacted redox conditions and supported enhanced ARD of CAHs. These results indicate that this technology may be a viable and cost-effective approach for remediation of low-permeability, variably saturated systems.

The role of clay minerals in the preservation of organic matter in sediments of Qinghai Lake, NW China

USGS Publications Warehouse

Yu, Bingsong; Dong, Hailiang; Jiang, Hongchen; Lv, Guo; Eberl, Dennis D.; Li, Shanying; Kim, Jinwook

2009-01-01

The role of saline lake sediments in preserving organic matter has long been recognized. In order to further understand the preservation mechanisms, the role of clay minerals was studied. Three sediment cores, 25, 57, and 500 cm long, were collected from Qinghai Lake, NW China, and dissected into multiple subsamples. Multiple techniques were employed, including density fractionation, X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), total organic carbon (TOC) and carbon compound analyses, and surface area determination. The sediments were oxic near the water-sediment interface, but became anoxic at depth. The clay mineral content was as much as 36.8%, consisting mostly of illite, chlorite, and halloysite. The TEM observations revealed that organic matter occurred primarily as organic matter-clay mineral aggregates. The TOC and clay mineral abundances are greatest in the mid-density fraction, with a positive correlation between the TOC and mineral surface area. The TOC of the bulk sediments ranges from 1 to 3% with the non-hydrocarbon fraction being predominant, followed by bitumen, saturated hydrocarbon, aromatic hydrocarbons, and chloroform-soluble bitumen. The bimodal distribution of carbon compounds of the saturated hydrocarbon fraction suggests that organic matter in the sediments was derived from two sources: terrestrial plants and microorganisms/algae. Depthrelated systematic changes in the distribution patterns of the carbon compounds suggest that the oxidizing conditions and microbial abundance near the water-sediment interface promote degradation of labile organic matter, probably in adsorbed form. The reducing conditions and small microbial biomass deeper in the sediments favor preservation of organic matter, because of the less labile nature of organic matter, probably occurring within clay mineral-organic matter aggregates that are inaccessible to microorganisms. These results have important implications for our understanding of mechanisms of organic matter preservation in saline lake sediments.

Coconut endocarp and mesocarp as both biosorbents of dissolved hydrocarbons in fuel spills and as a power source when exhausted.

PubMed

Luis-Zarate, Victor Hugo; Rodriguez-Hernandez, Mayra Cecilia; Alatriste-Mondragon, Felipe; Chazaro-Ruiz, Luis Felipe; Rangel-Mendez, Jose Rene

2018-04-01

Health and environmental problems associated with the presence of toxic aromatic compounds in water from oil spills have motivated research to develop effective and economically viable strategies to remove these pollutants. In this work, coconut shell (endocarp), coconut fiber (mesocarp) and coconut shell with fiber (endocarp and mesocarp) obtained from coconut (Cocos nucifera) waste were evaluated as biosorbents of benzene, toluene and naphthalene from water, considering the effect of the solution pH (6-9) and the presence of dissolved organic matter (DOM) in natural water (14 mg/L). In addition, the heat capacity of saturated biosorbents was determined to evaluate their potential as an alternative power source to conventional fossil fuels. Tests of N 2 physisorption, SEM, elemental and fiber analysis, ATR-FTIR and acid-based titrations were performed in order to understand the materials' characteristics, and to elucidate the biosorbents' hydrocarbon adsorption mechanism. Coconut fiber showed the highest adsorption capacities (222, 96 and 5.85 mg/g for benzene, toluene and naphthalene, respectively), which was attributed to its morphologic characteristics and to its high concentration of phenolic groups, associated with the lignin structure. The pH of the solution did not have a significant influence on the removal of the contaminants, and the presence of DOM improved the adsorption capacities of aromatic hydrocarbons. The adsorption studies showed biphasic isotherms, which highlighted the strong affinity between the molecules adsorbed on the biosorbents and the aromatic compounds remaining in the solution. Finally, combustion heat analysis of coconut waste saturated with soluble hydrocarbons showed that the heat capacity increased from 4407.79 cal/g to 5064.43 ± 11.6 cal/g, which is comparable with that of woody biomass (3400-4000 cal/g): this waste biomass with added value could be a promising biofuel. Copyright © 2018 Elsevier Ltd. All rights reserved.

Distribution, activity and function of short-chain alkane degrading phylotypes in hydrothermal vent sediments

NASA Astrophysics Data System (ADS)

Adams, M. M.; Joye, S. B.; Hoarfrost, A.; Girguis, P. R.

2012-12-01

Global geochemical analyses suggest that C2-C4 short chain alkanes are a common component of the utilizable carbon pool in deep-sea sediments worldwide and have been found in diverse ecosystems. From a thermodynamic standpoint, the anaerobic microbial oxidation of these aliphatic hydrocarbons is more energetically yielding than the anaerobic oxidation of methane (AOM). Therefore, the preferential degradation of these hydrocarbons may compete with AOM for the use of oxidants such as sulfate, or other potential oxidants. Such processes could influence the fate of methane in the deep-sea. Sulfate-reducing bacteria (SRB) from hydrocarbon seep sediments of the Gulf of Mexico and Guaymas Basin have previously been enriched that anaerobically oxidize short chain alkanes to generate CO2 with the preferential utilization of 12C-enriched alkanes (Kniemeyer et al. 2007). Different temperature regimens along with multiple substrates were tested and a pure culture (deemed BuS5) was isolated from mesophilic enrichments with propane or n-butane as the sole carbon source. Through comparative sequence analysis, strain BuS5 was determined to cluster with the metabolically diverse Desulfosarcina / Desulfococcus cluster, which also contains the SRB found in consortia with anaerobic, methane-oxidizing archaea in seep sediments. Enrichments from a terrestrial, low temperature sulfidic hydrocarbon seep also corroborated that propane degradation occurred with most bacterial phylotypes surveyed belonging to the Deltaproteobacteria, particularly Desulfobacteraceae (Savage et al. 2011). To date, no microbes capable of ethane oxidation or anaerobic C2-C4 alkane oxidation at thermophilic temperature have been isolated. The sediment-covered, hydrothermal vent systems found at Middle Valley (Juan de Fuca Ridge, eastern Pacific Ocean) are a prime environment for investigating mesophilic to thermophilic anaerobic oxidation of short-chain alkanes, given the elevated temperatures and dissolved hydrocarbon species characteristic of these metalliferous sediments. These systems are also characterized by sharp physicochemical gradients that have been shown to have a pronounced effect on microbial ecology and activity. Sediments were collected from a Middle Valley field with relatively high concentrations of short-chain alkanes and incubated in anaerobic batch reactors with each individual alkane (C1, C2, C3 and C4, respectively) at a range of temperatures (25, 55 and 75 °C) to mimic environmental physico-chemical conditions in a closed system. Stable carbon isotope ratios and radiotracer incubations provide clear evidence for C2-C4 alkane oxidation in the sediments over time. Upon identifying sediments with anaerobic alkane oxidation activity, microbial communities were screened via 16S rRNA pyrosequencing, and key phylotypes were then quantified using both molecular and microscopic methods. There were shifts in overall community composition and putative alkane-oxidizing phylotypes after the incubation period with the alkane substrates. These are the first evidence to date indicating that anaerobic C2-C4 alkane oxidation occurs across a broad range of temperatures in metalliferous sediments.

Considering the Specific Impact of Harsh Conditions and Oil Weathering on Diversity, Adaptation, and Activity of Hydrocarbon-Degrading Bacteria in Strategies of Bioremediation of Harsh Oily-Polluted Soils

PubMed Central

Al Disi, Zulfa; Jaoua, Samir; Al-Thani, Dhabia; Al-Meer, Saeed

2017-01-01

Weathering processes change properties and composition of spilled oil, representing the main reason of failure of bioaugmentation strategies. Our purpose was to investigate the metabolic adaptation of hydrocarbon-degrading bacteria at harsh conditions to be considered to overcome the limitations of bioaugmentation strategies at harsh conditions. Polluted soils, exposed for prolonged periods to weathered oil in harsh soils and weather conditions, were used. Two types of enrichment cultures were employed using 5% and 10% oil or diesel as sole carbon sources with varying the mineral nitrogen sources and C/N ratios. The most effective isolates were obtained based on growth, tolerance to toxicity, and removal efficiency of diesel hydrocarbons. Activities of the newly isolated bacteria, in relation to the microenvironment from where they were isoalted and their interaction with the weathered oil, showed individual specific ability to adapt when exposed to such factors, to acquire metabolic potentialities. Among 39 isolates, ten identified ones by 16S rDNA genes similarities, including special two Pseudomonas isolates and one Citrobacter isolate, showed particularity of shifting hydrocarbon-degrading ability from short chain n-alkanes (n-C12–n-C16) to longer chain n-alkanes (n-C21–n-C25) and vice versa by alternating nitrogen source compositions and C/N ratios. This is shown for the first time. PMID:28243605

Organic geochemistry of the 9.6 km Bertha Rogers No. 1. well, Oklahoma

USGS Publications Warehouse

Price, L.C.; Clayton, J.L.; Rumen, L.L.

1981-01-01

Organic geochemical analyses of fine-grained rocks from the 9.590 km Bertha Rogers No. 1 well have been carried out: total organic carbon, Soxhlet extraction and silica gel chromatography, C15+ saturated and aromatic hydrocarbon gas chromatography and mass spectrometry, pyrolysis, kerogen analysis, X-ray diffraction and visual kerogen analysis. Rocks ranged in age from Permian to Ordovician; the well has an estimated bottom hole temperature of 225??C. Some data from this study are inconsistent with conventional theories concerning the generation and thermal destruction of hydrocarbons. For example, appreciable amounts of C15+ gas-condensate-like hydrocarbons are present in very old rocks currently at temperatures where current theory predicts that only methane and graphite should remain. Also, substantial amounts of pyrolyzable C15+ hydrocarbons remain on the kerogen in these deeply buried Paleozoic rocks. This suggests, at least in somes cases, that temperatures much higher than those predicted by current theory are required for generation and thermal destruction of hydrocarbons. The data from this well also suggest that original composition of organic matter and environment of deposition may have a much stronger influence on the organic geochemical characteristics of fine-grained sediments than has previously been ascribed to them. The results from this well, from other deep hot wells in which temperatures exceed 200??C, and from laboratory experiments, suggest that some of the basic concepts of the generation and maturation of petroleum hydrocarbons may be in error and perhaps should be reexamined. ?? 1981.

Predictable weathering of puparial hydrocarbons of necrophagous flies for determining the postmortem interval: a field experiment using Chrysomya rufifacies.

PubMed

Zhu, Guang-Hui; Jia, Zheng-Jun; Yu, Xiao-Jun; Wu, Ku-Sheng; Chen, Lu-Shi; Lv, Jun-Yao; Eric Benbow, M

2017-05-01

Preadult development of necrophagous flies is commonly recognized as an accurate method for estimating the minimum postmortem interval (PMImin). However, once the PMImin exceeds the duration of preadult development, the method is less accurate. Recently, fly puparial hydrocarbons were found to significantly change with weathering time in the field, indicating their potential use for PMImin estimates. However, additional studies are required to demonstrate how the weathering varies among species. In this study, the puparia of Chrysomya rufifacies were placed in the field to experience natural weathering to characterize hydrocarbon composition change over time. We found that weathering of the puparial hydrocarbons was regular and highly predictable in the field. For most of the hydrocarbons, the abundance decreased significantly and could be modeled using a modified exponent function. In addition, the weathering rate was significantly correlated with the hydrocarbon classes. The weathering rate of 2-methyl alkanes was significantly lower than that of alkenes and internal methyl alkanes, and alkenes were higher than the other two classes. For mono-methyl alkanes, the rate was significantly and positively associated with carbon chain length and branch position. These results indicate that puparial hydrocarbon weathering is highly predictable and can be used for estimating long-term PMImin.

Degradation of halogenated aliphatic compounds by Xanthobacter autotrophicus GJ10.

PubMed Central

Janssen, D B; Scheper, A; Dijkhuizen, L; Witholt, B

1985-01-01

A bacterium that is able to utilize a number of halogenated short-chain hydrocarbons and halogenated carboxylic acids as sole carbon source for growth was identified as a strain of Xanthobacter autotrophicus. The organism constitutively produces two different dehalogenases. One enzyme is specific for halogenated alkanes, whereas the other, which is more heat stable and has a higher pH optimum, is specific for halogenated carboxylic acids. Haloalkanes were hydrolyzed in cell extracts to produce alcohols and halide ions, and a route for the metabolism of 1,2-dichlorethane is proposed. Both dehalogenases show a broad substrate specificity, allowing the degradation of bromine- and chlorine-substituted organic compounds. The results show that X. autotrophicus may play a role in the degradation of organochlorine compounds and that hydrolytic dehalogenases may be involved in the microbial metabolism of short-chain halogenated hydrocarbons in microorganisms. Images PMID:3994371

Producing carbon-based boundary films from catalytically active lubricant additives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erdemir, Ali; Mane, Anil U.; Elam, Jeffrey W.

A lubricant composition includes an oil including a plurality of long-chain hydrocarbon molecules. A quantity of a catalytically active metal-organic additive is mixed with the oil. The metal-organic additive is formulated to fragment the long-chain hydrocarbon molecules of the oil into at least one of dimers and trimers under the influence of at least one of a mechanical loading and a thermal loading. In some embodiments, the metal-organic additive includes a compound of formula II: ##STR00001## where: X is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf,more » Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg or Cn, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are alkyl or alkyl halide.« less

pi-Selective stationary phases: (II) Adsorption behavior of substituted aromatic compounds on n-alkyl-phenyl stationary phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gritti, Fabrice; Guiochon, Georges A; Mayfield, Kirsty

2010-01-01

The frontal analysis method was used to measure the adsorption isotherms of phenol, 4-chlorophenol, p-cresol, 4-methoxyphenol and caffeine on a series of columns packed with home-made alkyl-phenyl bonded silica particles. These ligands consist of a phenyl ring tethered to the silica support via a carbon chain of length ranging from 0 to 4 atoms. The adsorption isotherm models that fit best to the data account for solute-solute interactions that are likely caused by p-p interactions occurring between aromatic compounds and the phenyl group of the ligand. These interactions are the dominant factor responsible for the separation of low molecular weightmore » aromatic compounds on these phenyl-type stationary phases. The saturation capacities depend on whether the spacer of the ligands have an even or an odd number of carbon atoms, with the even alkyl chain lengths having a greater saturation capacity than the odd alkyl chain lengths. The trends in the adsorption equilibrium constant are also significantly different for the even and the odd chain length ligands.« less

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

DOE PAGES

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; ...

2017-11-14

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4, Ln(OTf) 3, In(OTf) 3, Al(OTf) 3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt %more » of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.« less

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4, Ln(OTf) 3, In(OTf) 3, Al(OTf) 3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt %more » of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.« less

Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

NASA Technical Reports Server (NTRS)

Borsdorf, H.; Nazarov, E. G.; Eiceman, G. A.

2002-01-01

The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. c. 2002 American Society for Mass Spectrometry.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

PubMed

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

2018-01-10

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sustained deposition of contaminants from the Deepwater Horizon spill.

PubMed

Yan, Beizhan; Passow, Uta; Chanton, Jeffrey P; Nöthig, Eva-Maria; Asper, Vernon; Sweet, Julia; Pitiranggon, Masha; Diercks, Arne; Pak, Dorothy

2016-06-14

The 2010 Deepwater Horizon oil spill resulted in 1.6-2.6 × 10(10) grams of petrocarbon accumulation on the seafloor. Data from a deep sediment trap, deployed 7.4 km SW of the well between August 2010 and October 2011, disclose that the sinking of spill-associated substances, mediated by marine particles, especially phytoplankton, continued at least 5 mo following the capping of the well. In August/September 2010, an exceptionally large diatom bloom sedimentation event coincided with elevated sinking rates of oil-derived hydrocarbons, black carbon, and two key components of drilling mud, barium and olefins. Barium remained in the water column for months and even entered pelagic food webs. Both saturated and polycyclic aromatic hydrocarbon source indicators corroborate a predominant contribution of crude oil to the sinking hydrocarbons. Cosedimentation with diatoms accumulated contaminants that were dispersed in the water column and transported them downward, where they were concentrated into the upper centimeters of the seafloor, potentially leading to sustained impact on benthic ecosystems.

Sustained deposition of contaminants from the Deepwater Horizon spill

PubMed Central

Yan, Beizhan; Passow, Uta; Chanton, Jeffrey P.; Nöthig, Eva-Maria; Asper, Vernon; Sweet, Julia; Pitiranggon, Masha; Diercks, Arne; Pak, Dorothy

2016-01-01

The 2010 Deepwater Horizon oil spill resulted in 1.6–2.6 × 1010 grams of petrocarbon accumulation on the seafloor. Data from a deep sediment trap, deployed 7.4 km SW of the well between August 2010 and October 2011, disclose that the sinking of spill-associated substances, mediated by marine particles, especially phytoplankton, continued at least 5 mo following the capping of the well. In August/September 2010, an exceptionally large diatom bloom sedimentation event coincided with elevated sinking rates of oil-derived hydrocarbons, black carbon, and two key components of drilling mud, barium and olefins. Barium remained in the water column for months and even entered pelagic food webs. Both saturated and polycyclic aromatic hydrocarbon source indicators corroborate a predominant contribution of crude oil to the sinking hydrocarbons. Cosedimentation with diatoms accumulated contaminants that were dispersed in the water column and transported them downward, where they were concentrated into the upper centimeters of the seafloor, potentially leading to sustained impact on benthic ecosystems. PMID:27247393

Long-wave equivalent viscoelastic solids for porous rocks saturated by two-phase fluids

NASA Astrophysics Data System (ADS)

Santos, J. E.; Savioli, G. B.

2018-04-01

Seismic waves traveling across fluid-saturated poroelastic materials with mesoscopic-scale heterogeneities induce fluid flow and Biot's slow waves generating energy loss and velocity dispersion. Using Biot's equations of motion to model these type of heterogeneities would require extremely fine meshes. We propose a numerical upscaling procedure to determine the complex and frequency dependent P-wave and shear moduli of an effective viscoelastic medium long-wave equivalent to a poroelastic solid saturated by a two-phase fluid. The two-phase fluid is defined in terms of capillary pressure and relative permeability flow functions. The P-wave and shear effective moduli are determined using harmonic compressibility and shear experiments applied on representative samples of the bulk material. Each experiment is associated with a boundary value problem that is solved using the finite element method. Since a poroelastic solid saturated by a two-phase fluid supports the existence of two slow waves, this upscaling procedure allows to analyze their effect on the mesoscopic-loss mechanism in hydrocarbon reservoir formations. Numerical results show that a two-phase Biot medium model predicts higher attenuation than classic Biot models.

Silica phase changes: Diagenetic agent for oil entrapment, Lost Hills field, California

DOE Office of Scientific and Technical Information (OSTI.GOV)

Julander, D.R.; Szymanski, D.L.

1991-02-01

The siliceous shales of the Monterey Group are the primary development target at Lost Hills. Silica phase changes have influenced the distribution and entrapment of hydrocarbons. With increasing temperature, opal A phase diatomite is converted to opal CT and finally quartz phase rock. All phases are low in permeability. The opal A diatomite is characteristically high in oil saturation and productive saturation. Productivity from this phase is dependent on structural position and fieldwide variations in oil viscosity and biodegradation. The deeper chert reservoir coincides with the opal CT to quartz phase transition. Porosity is again reduced in this transition, butmore » saturations in the quartz phase rocks increase. Tests in the chert reservoir indicate a single, low-permeability system, suggesting the importance of matric contribution. resistivity and porosity in the diatomite, and resistivity and velocity in the chert, are the physical properties which best reflect saturation. Methods exploiting these properties (FMS, BHTV, borehole, and surface shear wave studies) should be helpful in further characterizing the reservoirs and identifying future pay.« less

Long-wave equivalent viscoelastic solids for porous rocks saturated by two-phase fluids

NASA Astrophysics Data System (ADS)

Santos, J. E.; Savioli, G. B.

2018-07-01

Seismic waves travelling across fluid-saturated poroelastic materials with mesoscopic-scale heterogeneities induce fluid flow and Biot's slow waves generating energy loss and velocity dispersion. Using Biot's equations of motion to model these type of heterogeneities would require extremely fine meshes. We propose a numerical upscaling procedure to determine the complex and frequency-dependent Pwave and shear moduli of an effective viscoelastic medium long-wave equivalent to a poroelastic solid saturated by a two-phase fluid. The two-phase fluid is defined in terms of capillary pressure and relative permeability flow functions. The Pwave and shear effective moduli are determined using harmonic compressibility and shear experiments applied on representative samples of the bulk material. Each experiment is associated with a boundary value problem that is solved using the finite element method. Since a poroelastic solid saturated by a two-phase fluid supports the existence of two slow waves, this upscaling procedure allows to analyse their effect on the mesoscopic loss mechanism in hydrocarbon reservoir formations. Numerical results show that a two-phase Biot medium model predicts higher attenuation than classic Biot models.

Male-Specific Transfer and Fine Scale Spatial Differences of Newly Identified Cuticular Hydrocarbons and Triacylglycerides in a Drosophila Species Pair

PubMed Central

Yew, Joanne Y.; Dreisewerd, Klaus; de Oliveira, Cássia Cardoso; Etges, William J.

2011-01-01

We analyzed epicuticular hydrocarbon variation in geographically isolated populations of D. mojavensis cultured on different rearing substrates and a sibling species, D. arizonae, with ultraviolet laser desorption/ionization mass spectrometry (UV-LDI MS). Different body parts, i.e. legs, proboscis, and abdomens, of both species showed qualitatively similar hydrocarbon profiles consisting mainly of long-chain monoenes, dienes, trienes, and tetraenes. However, D. arizonae had higher amounts of most hydrocarbons than D. mojavensis and females of both species exhibited greater hydrocarbon amounts than males. Hydrocarbon profiles of D. mojavensis populations were significantly influenced by sex and rearing substrates, and differed between body parts. Lab food–reared flies had lower amounts of most hydrocarbons than flies reared on fermenting cactus substrates. We discovered 48 male- and species-specific hydrocarbons ranging in size from C22 to C50 in the male anogenital region of both species, most not described before. These included several oxygen-containing hydrocarbons in addition to high intensity signals corresponding to putative triacylglycerides, amounts of which were influenced by larval rearing substrates. Some of these compounds were transferred to female cuticles in high amounts during copulation. This is the first study showing that triacylglycerides may be a separate class of courtship-related signaling molecules in drosophilids. This study also extends the kind and number of epicuticular hydrocarbons in these species and emphasizes the role of larval ecology in influencing amounts of these compounds, many of which mediate courtship success within and between species. PMID:21369358

Hydrocarbon polymeric binder for advanced solid propellant

NASA Technical Reports Server (NTRS)

Potts, J. E. (Editor); Ashcraft, A. C., Jr.; Wise, E. W.

1971-01-01

The results of curing vinyl alcohol terpolymers of ethylene, propylene and vinyl acetate are reported for an average functionality of 1.24 when reacted with an equivalent amount of diisocynate, and saturated polyisoprene derivative is described having terminal methyl ester functionality. The development is reported of two hydroxy-telechelic polyisoprenes prepared by DEAB initiated free radical polymerization followed by LiAlH4 reduction of the end groups.

Effect of fatty acids on self-assembly of soybean lecithin systems.

PubMed

Godoy, C A; Valiente, M; Pons, R; Montalvo, G

2015-07-01

With the increasing interest in natural formulations for drug administration and functional foods, it is desirable a good knowledge of the phase behavior of lecithin/fatty acid formulations. Phase structure and properties of ternary lecithin/fatty acids/water systems are studied at 37°C, making emphasis in regions with relatively low water and fatty acid content. The effect of fatty acid saturation degree on the phase microstructure is studied by comparing a fully saturated (palmitic acid, C16:0), monounsaturated (oleic acid, C18:1), and diunsaturated (linoleic acid, C18:2) fatty acids. Phase determinations are based on a combination of polarized light microscopy and small-angle X-ray scattering measurements. Interestingly, unsaturated (oleic acid and linoleic acid) fatty acid destabilizes the lamellar bilayer. Slight differences are observed between the phase diagrams produced by the unsaturated ones: small lamellar, medium cubic and large hexagonal regions. A narrow isotropic fluid region also appears on the lecithin-fatty acid axis, up to 8wt% water. In contrast, a marked difference in phase microsctructure was observed between unsaturated and saturated systems in which the cubic and isotropic fluid phases are not formed. These differences are, probably, a consequence of the high Krafft point of the C16 saturated chains that imply rather rigid chains. However, unsaturated fatty acids result in more flexible tails. The frequent presence of, at least, one unsaturated chain in phospholipids makes it very likely a better mixing situation than in the case of more rigid chains. This swelling potential favors the formation of reverse hexagonal, cubic, and micellar phases. Both unsaturated fatty acid systems evolve by aging, with a reduction of the extension of reverse hexagonal phase and migration of the cubic phase to lower fatty acid and water contents. The kinetic stability of the systems seems to be controlled by the unsaturation of fatty acids. Copyright © 2015 Elsevier B.V. All rights reserved.

Nile Red Detection of Bacterial Hydrocarbons and Ketones in a High-Throughput Format

PubMed Central

Pinzon, Neissa M.; Aukema, Kelly G.; Gralnick, Jeffrey A.; Wackett, Lawrence P.

2011-01-01

ABSTRACT A method for use in high-throughput screening of bacteria for the production of long-chain hydrocarbons and ketones by monitoring fluorescent light emission in the presence of Nile red is described. Nile red has previously been used to screen for polyhydroxybutyrate (PHB) and fatty acid esters, but this is the first report of screening for recombinant bacteria making hydrocarbons or ketones. The microtiter plate assay was evaluated using wild-type and recombinant strains of Shewanella oneidensis and Escherichia coli expressing the enzyme OleA, previously shown to initiate hydrocarbon biosynthesis. The strains expressing exogenous Stenotrophomonas maltophilia oleA, with increased levels of ketone production as determined by gas chromatography-mass spectrometry, were distinguished with Nile red fluorescence. Confocal microscopy images of S. oneidensis oleA-expressing strains stained with Nile red were consistent with a membrane localization of the ketones. This differed from Nile red staining of bacterial PHB or algal lipid droplets that showed intracellular inclusion bodies. These results demonstrated the applicability of Nile red in a high-throughput technique for the detection of bacterial hydrocarbons and ketones. PMID:21712420

New iron catalyst for preparation of polymethylene from synthesis gas

DOEpatents

Sapienza, R.S.; Slegeir, W.A.

1988-03-31

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Iron catalyst for preparation of polymethylene from synthesis gas

DOEpatents

Sapienza, Richard S.; Slegeir, William A.

1990-01-01

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a cabon monoxide containing gas to a product which could substitute for high density polyethylene.

Metabolism and nephrotoxicity of indan in male Fischer 344 rats.

PubMed

Servé, M P; Ferry, M J; Yu, K O; Olson, C T; Hobson, D W

1990-01-01

Indan, a component of fuels, solvents, and varnishes, is metabolized in male Fischer 344 rats to 1-indanol, 2-indanol, 5-indanol, 1-indanone, 2-indanone, 2-hydroxy-1-indanone, cis-1,2-indandiol, and trans-1,2-indandiol. The metabolites were identified using the techniques of gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). The rats treated with indan demonstrated the classic lesions of hydrocarbon-induced nephropathy. The kidney damage produced was less than that found for tetralin and other branched-chain acyclic hydrocarbons.

Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

NASA Astrophysics Data System (ADS)

Dunmore, R. E.; Hopkins, J. R.; Lidster, R. T.; Lee, J. D.; Evans, M. J.; Rickard, A. R.; Lewis, A. C.; Hamilton, J. F.

2015-09-01

Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London), which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20-30 % of the total hydrocarbon mixing ratio but comprise more than 50 % of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that 60 % of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50 % of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for, but very significant, under-reporting of diesel-related hydrocarbons; an underestimation of a factor ~4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide.

Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

NASA Astrophysics Data System (ADS)

Dunmore, R. E.; Hopkins, J. R.; Lidster, R. T.; Lee, J. D.; Evans, M. J.; Rickard, A. R.; Lewis, A. C.; Hamilton, J. F.

2015-03-01

Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London), which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20-30% of the total hydrocarbon mixing ratio but comprise more than 50% of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that, 60% of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50% of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for but, very significant under-reporting of diesel related hydrocarbons; an underestimation of a factor ~ 4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide.

Nutritional adequacy of meals from an independent catering facility versus chain restaurants for young adults.

PubMed

Nikolaou, Charoula Konstantia; Hankey, Catherine Ruth; Lean, Michael Ernest John

2017-03-01

Eating out of home has been associated with the increasing prevalence of obesity. While some chain restaurants provide nutritional information for their products, smaller independent catering facilities may not provide such information. The aim of this study was to assess the nutritional adequacy of meals provided to young adults at an independent catering facility and compare them with meals provided by chain restaurants. Meals were analysed in 2014 in the UK in relation of nutrient provision to targets for macro- and micro-nutrients. One-way ANOVA was performed to compare menus between the restaurants included in the analyses. 2056 meal combinations were analysed, 210 from the student accommodation and 1,846 from five largest national chain restaurants. Mean (SD) nutritional content was: student accommodation: 1193(269)kcal, fat 52.0(22)g, saturated fat 24.5(14.5)g, protein 42.4(28.5)g, carbohydrate 117.0(30)g; chain restaurants: 922(160)kcal, fat 40.0(9.7)g, saturated fat 14.5(5.8)g, protein 31.2(6.5)g, carbohydrate 104.2(16.6)g. Meals from the student accommodation presented significantly more calories than the meals in all five chain restaurants ( p = 0.0015). Meal provision in the student accommodation was in excess of energy requirements and higher than the meals offered in chain restaurants. Regulating or setting nutritional standards for all places that provide food is essential as current food provision may favour unwanted weight gain and diet-related diseases.

Smart Application of Direct Gas Injection using a new conceptual model on Coherent and Incoherent Flow: From Bench Scale to Field Scale.

NASA Astrophysics Data System (ADS)

Geistlinger, H.; Samani, S.; Pohlert, M.; Martienssen, M.; Engelmann, F.; Hüttmann, S.

2008-12-01

Within the framework of the OXYWALL field experiment we developed the direct gas injection (DGI) of oxygen as a remediation technology, which allows the cost-efficient and large-scale cleaning of groundwater contaminated with organic contaminants. That technology can be used as wide-banded, unselective remediation method for complex contaminant mixtures. Particularly, it could be proofed in field experiments that mineral oil hydrocarbons, aromatic hydrocarbons (BTEX), the rather persistent gasoline component Methyl tertiary-butyl ether (MTBE), and chlorinated aliphatic and aromatic hydrocarbons, like Trichloroethene and Monochlorobenzene, can be aerobically metabolized by autochthon microorganisms. Over the last 8 years the field site was investigated and a dense monitoring network was installed using Geoprobe direct- push technology and standard hydrogeological investigations were conducted, like EC-Logs, Injections-Logs, Gamma-Logs, TDR-probes, oxygen measurements with in-situ optodes, and tracer test with test gases SF6, Ar, and Oxygen. The key parameter for controling and regulating the DGI is the spatial and temporal distribution of the gas phase. High-resolution optical bench scale experiments were conducted in order to investigate local gas flow pattern and integral flow properties caused by point-like gas injection into water-saturated glass beads and natural sands. We observed a grain-size (dk)- and flow-rate (Q) dependent transition from incoherent to coherent flow. Conceptualizing the stationary tortuous gas flow as core-annulus flow and applying Hagen- Poiseuille flow for a straight capillary, we propose a flow-rate- and grain-size dependent stability criterion that could describe our experimental results and was used for classifying the experiments in a dk-Q-diagram (flow chart). Since DGI simulations are mainly based on continuum models, we also test the validity of the continuum approach for two-fluid flow in macroscopic homogeneous media by comparing our experimental flow pattern with the theoretical ones. It was found that a pulse-like function yields the best fit for the lateral gas saturation profile. This strange behaviour of a relatively sharp saturation transition is in contradiction to the widely anticipated picture of a smooth Gaussian-like transition, which is obtained by the continuum approach. Based on lab experiments, the proposed flow chart, and computer simulations the DGI-technology will be advanced and optimized at the field scale. A proper application of continuum models to direct gas injection should check, whether stable coherent flow is achieved; estimate the coherence length, and account for the channelized flow pattern by a realistic capillary pressure - saturation relationship. Further research is needed for modeling of direct gas injection to include appropriate stability criteria, the transition from coherent to incoherent flow, and bubble trapping. Geistlinger, H., Krauss, G., Lazik, D., and Luckner, L. (2006) Direct gas injection into saturated glass beads: transition from incoherent to coherent gas flow pattern. Water Resour. Res., 42 (7) W07403. Lazik, D., G. Krauss, H. Geistlinger, and H.-J. Vogel (2008) Multi-scale optical analyses of dynamic gas saturation during air sparging into glass beads, Transp. Porous Media. 74, 87-104.

Change in trans fatty acid content of fast-food purchases associated with New York City's restaurant regulation: a pre-post study.

PubMed

Angell, Sonia Y; Cobb, Laura K; Curtis, Christine J; Konty, Kevin J; Silver, Lynn D

2012-07-17

Dietary trans fat increases risk for coronary heart disease. In 2006, New York City (NYC) passed the first regulation in the United States restricting trans fat use in restaurants. To assess the effect of the NYC regulation on the trans and saturated fat content of fast-food purchases. Cross-sectional study that included purchase receipts matched to available nutritional information and brief surveys of adult lunchtime restaurant customers conducted in 2007 and 2009, before and after implementation of the regulation. 168 randomly selected NYC restaurant locations of 11 fast-food chains. Adult restaurant customers interviewed in 2007 and 2009. Change in mean grams of trans fat, saturated fat, trans plus saturated fat, and trans fat per 1000 kcal per purchase, overall and by chain type. The final sample included 6969 purchases in 2007 and 7885 purchases in 2009. Overall, mean trans fat per purchase decreased by 2.4 g (95% CI, -2.8 to -2.0 g; P < 0.001), whereas saturated fat showed a slight increase of 0.55 g (CI, 0.1 to 1.0 g; P = 0.011). Mean trans plus saturated fat content decreased by 1.9 g overall (CI, -2.5 to -1.2 g; P < 0.001). Mean trans fat per 1000 kcal decreased by 2.7 g per 1000 kcal (CI, -3.1 to -2.3 g per 1000 kcal; P < 0.001). Purchases with zero grams of trans fat increased from 32% to 59%. In a multivariate analysis, the poverty rate of the neighborhood in which the restaurant was located was not associated with changes. Fast-food restaurants that were included may not be representative of all NYC restaurants. The introduction of a local restaurant regulation was associated with a substantial and statistically significant decrease in the trans fat content of purchases at fast-food chains, without a commensurate increase in saturated fat. Restaurant patrons from high- and low-poverty neighborhoods benefited equally. However, federal regulation will be necessary to fully eliminate population exposure to industrial trans fat sources. City of New York and the Robert Wood Johnson Foundation Healthy Eating Research program.

Synthesis and surface activities of a novel di-hydroxyl-sulfate-betaine-type zwitterionic gemini surfactants

NASA Astrophysics Data System (ADS)

Geng, Xiang F.; Hu, Xing Q.; Xia, Ji J.; Jia, Xue C.

2013-04-01

A series of novel di-hydroxyl-sulfate-betaine-type zwitterionic gemini surfactants of 1,2-bis[N-ethyl-N-(2-hydroxyl-3-sulfopropyl)-alkylammonium] alkyl betaines (DBAs-n, where s and n represent the spacer length of 2, 4 and 6 and the hydrocarbon chain length of 8, 12, 14, 16 and 18, respectively) were synthesized by reacting alkylamine with sodium 3-chloro-2-hydroxypropanesulfonate (the alternative sulphonated agent), followed by the reactions with а,ω-dibromoalkyl and then ethyl bromide. Their adsorption and aggregation properties were investigated by means of equilibrium surface tension, dynamic light-scattering (DLS) and transmission electron microscopy (TEM). DBAs-n gemini surfactants showed excellent surface activities and packed tightly at the interface. For example, the minimum CMC value for DBAs-n series was of the order of 10-5 M and the surface tension of water can be decreased as low as 22.2 mN/m. It was also found that the aggregates of DBAs-n solutions were significantly dependent on their hydrocarbon chain lengths. The aggregates changed from vesicles to entangled fiber-like micelles as the chain length increased from dodecyl to tetradecyl.

Gum and deposit formation from jet-turbine and diesel fuels at 100 C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayo, F.R.; Lan, B.Y.

1987-01-01

Rates of oxidation and gum formation for six hydrocarbons, three jet-turbine fuels and three diesel fuels have been measured at 100 C in the presence of t-Bu2O2 tert-butyl-peroxide as initiator. Four of six fuels oxidize faster at 100 C than in previous work at 130 C with initiator. Four any single substrate, the amount of gum produced for the oxygen absorbed is similar at 100 and 130 C even with large changes in rates and t-Bu2O2 concentrations. Thus, one mechanism of gum formation is intimately associated with oxidation. The effects of t-Bu2O2 concentration on the rates of oxygen absorption andmore » gum formation show that gum formation is associated with chain termination by two peroxy radicals. In general, the pure hydrocarbons have long kinetic chains and give good yields of hydroperoxides. The fuels give short kinetic chains and produce little hydroperoxide but but much more gum formation is the coupling of substrates by peroxides in the absence of oxygen. The mechanism, condensation of oxidation products from alkylnaphthalenes, is also proposed.« less

Glycosyl-Nucleolipids as new bioinspired amphiphiles.

PubMed

Latxague, Laurent; Patwa, Amit; Amigues, Eric; Barthélémy, Philippe

2013-09-30

Four new Glycosyl-NucleoLipid (GNL) analogs featuring either a single fluorocarbon or double hydrocarbon chains were synthesized in good yields from azido thymidine as starting material. Physicochemical studies (surface tension measurements, differential scanning calorimetry) indicate that hydroxybutanamide-based GNLs feature endothermic phase transition temperatures like the previously reported double chain glycerol-based GNLs. The second generation of GNFs featuring a free nucleobase reported here presents a better surface activity (lower glim) compared to the first generation of GNFs.

Mono-, di- and trimethylated homologues of isoprenoid tetraether lipid cores in archaea and environmental samples: mass spectrometric identification and significance.

PubMed

Knappy, Chris; Barillà, Daniela; Chong, James; Hodgson, Dominic; Morgan, Hugh; Suleman, Muhammad; Tan, Christine; Yao, Peng; Keely, Brendan

2015-12-01

Higher homologues of widely reported C(86) isoprenoid diglycerol tetraether lipid cores, containing 0-6 cyclopentyl rings, have been identified in (hyper)thermophilic archaea, representing up to 21% of total tetraether lipids in the cells. Liquid chromatography-tandem mass spectrometry confirms that the additional carbon atoms in the C(87-88) homologues are located in the etherified chains. Structures identified include dialkyl and monoalkyl ('H-shaped') tetraethers containing C(40-42) or C(81-82) hydrocarbons, respectively, many representing novel compounds. Gas chromatography-mass spectrometric analysis of hydrocarbons released from the lipid cores by ether cleavage suggests that the C(40) chains are biphytanes and the C(41) chains 13-methylbiphytanes. Multiple isomers, having different chain combinations, were recognised among the dialkyl lipids. Methylated tetraethers are produced by Methanothermobacter thermautotrophicus in varying proportions depending on growth conditions, suggesting that methylation may be an adaptive mechanism to regulate cellular function. The detection of methylated lipids in Pyrobaculum sp. AQ1.S2 and Sulfolobus acidocaldarius represents the first reported occurrences in Crenarchaeota. Soils and aquatic sediments from geographically distinct mesotemperate environments that were screened for homologues contained monomethylated tetraethers, with di- and trimethylated structures being detected occasionally. The structural diversity and range of occurrences of the C(87-89) tetraethers highlight their potential as complementary biomarkers for archaea in natural environments. Copyright © 2015 John Wiley & Sons, Ltd.

Long Chain Saturated and Unsaturated Carboxylic Acids: Filling a Large Gap of Knowledge in Their Enthalpies of Formation.

PubMed

Rogers, Donald W; Zavitsas, Andreas A

2017-01-06

Despite their abundance in nature and their importance in biology, medicine, nutrition, and in industry, gas phase enthalpies of formation of many long chain saturated and unsaturated fatty acids and of dicarboxylic acids are either unavailable or have been estimated with large uncertainties. Available experimental values for stearic acid show a spread of 68 kJ mol -1 . This work fills the knowledge gap by obtaining reliable values by quantum theoretical calculations using G4 model chemistry. Compounds with up to 20 carbon atoms are treated. The theoretical results are in excellent agreement with well established experimental values when such values exist, and they provide a large number of previously unavailable values.

Carbon Dioxide Hydrogenation into Higher Hydrocarbons and Oxygenates: Thermodynamic and Kinetic Bounds and Progress with Heterogeneous and Homogeneous Catalysis.

PubMed

Prieto, Gonzalo

2017-03-22

Under specific scenarios, the catalytic hydrogenation of CO 2 with renewable hydrogen is considered a suitable route for the chemical recycling of this environmentally harmful and chemically refractory molecule into added-value energy carriers and chemicals. The hydrogenation of CO 2 into C 1 products, such as methane and methanol, can be achieved with high selectivities towards the corresponding hydrogenation product. More challenging, however, is the selective production of high (C 2+ ) hydrocarbons and oxygenates. These products are desired as energy vectors, owing to their higher volumetric energy density and compatibility with the current fuel infrastructure than C 1 compounds, and as entry platform chemicals for existing value chains. The major challenge is the optimal integration of catalytic functionalities for both reductive and chain-growth steps. This Minireview summarizes the progress achieved towards the hydrogenation of CO 2 to C 2+ hydrocarbons and oxygenates, covering both solid and molecular catalysts and processes in the gas and liquid phases. Mechanistic aspects are discussed with emphasis on intrinsic kinetic limitations, in some cases inevitably linked to thermodynamic bounds through the concomitant reverse water-gas-shift reaction, which should be considered in the development of advanced catalysts and processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fatty acid and hydrocarbon composition in tropical marine Shewanella amazonensis strain SB2B(T).

PubMed

Motoigi, Taro; Okuyama, Hidetoshi

2011-10-01

Shewanella amazonensis strain SB2B(T) is an isolate from shallow-water marine sediments derived from the Amazon River delta. This bacterium contained a long-chain polyunsaturated hydrocarbon, all-cis -3,6,9,12,16,19,22,25,28 hentriacontanonaene (C31:9), constituting 1-2% of the total fatty acid methyl ester and hydrocarbon fraction, which was produced dependently of decreased growth temperature. Analysis of its cellular fatty acid composition demonstrated that isopentadecanoic acid was the major fatty acid component and that all the main monounsaturated fatty acids had straight chains with a cis configuration. However, monoenoic cyclopropyl fatty acids, which were previously reported to be present in this bacterium, were not detected by mass spectrometric analysis. The growth temperature affected the content of Δ9-cis -hexadecenoic [16:1(Δ9c)], palmitic, and heptadecanoic acids. These results suggest that C31:9, as well as 16:1(Δ9c) might be involved in adaptation to low temperature in S. amazonensis strain SB2B(T) . Our result suggests that polyunsaturated fatty acid synthase protein complex may be involved in synthesis of C31:9 but not in production of eicosapentaenoic acid. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Comparison of the Microbial Production and Combustion Characteristics of Three Alcohol Biofuels: Ethanol, 1-Butanol, and 1-Octanol.

PubMed

Kremer, Florian; Blank, Lars M; Jones, Patrik R; Akhtar, M Kalim

2015-01-01

Over the last decade, microbes have been engineered for the manufacture of a variety of biofuels. Saturated linear-chain alcohols have great potential as transport biofuels. Their hydrocarbon backbones, as well as oxygenated content, confer combustive properties that make it suitable for use in internal combustion engines. Herein, we compared the microbial production and combustion characteristics of ethanol, 1-butanol, and 1-octanol. In terms of productivity and efficiency, current microbial platforms favor the production of ethanol. From a combustion standpoint, the most suitable fuel for spark-ignition engines would be ethanol, while for compression-ignition engines it would be 1-octanol. However, any general conclusions drawn at this stage regarding the most superior biofuel would be premature, as there are still many areas that need to be addressed, such as large-scale purification and pipeline compatibility. So far, the difficulties in developing and optimizing microbial platforms for fuel production, particularly for newer fuel candidates, stem from our poor understanding of the myriad biological factors underpinning them. A great deal of attention therefore needs to be given to the fundamental mechanisms that govern biological processes. Additionally, research needs to be undertaken across a wide range of disciplines to overcome issues of sustainability and commercial viability.

A Comparison of the Microbial Production and Combustion Characteristics of Three Alcohol Biofuels: Ethanol, 1-Butanol, and 1-Octanol

PubMed Central

Kremer, Florian; Blank, Lars M.; Jones, Patrik R.; Akhtar, M. Kalim

2015-01-01

Over the last decade, microbes have been engineered for the manufacture of a variety of biofuels. Saturated linear-chain alcohols have great potential as transport biofuels. Their hydrocarbon backbones, as well as oxygenated content, confer combustive properties that make it suitable for use in internal combustion engines. Herein, we compared the microbial production and combustion characteristics of ethanol, 1-butanol, and 1-octanol. In terms of productivity and efficiency, current microbial platforms favor the production of ethanol. From a combustion standpoint, the most suitable fuel for spark-ignition engines would be ethanol, while for compression-ignition engines it would be 1-octanol. However, any general conclusions drawn at this stage regarding the most superior biofuel would be premature, as there are still many areas that need to be addressed, such as large-scale purification and pipeline compatibility. So far, the difficulties in developing and optimizing microbial platforms for fuel production, particularly for newer fuel candidates, stem from our poor understanding of the myriad biological factors underpinning them. A great deal of attention therefore needs to be given to the fundamental mechanisms that govern biological processes. Additionally, research needs to be undertaken across a wide range of disciplines to overcome issues of sustainability and commercial viability. PMID:26301219

Chemical recognition of kingsnakes by crotalines: effects of size on the ophiophage defensive response.

PubMed

Gutzke, W H; Tucker, C; Mason, R T

1993-01-01

When confronted by an ophiophagous (snake-eating) kingsnake, venomous snakes of the subfamily Crotalinae exhibit a suite of defensive responses including head hiding, thrashing, and an unusual response termed 'body bridging'. Other responses observed, such as biting and 'freezing', are more general in nature and can occur in a variety of contexts. Various crotalines of differing sizes were tested for their responses to kingsnakes (Lampropeltis getulus). Responses of individuals were recorded for up to 18 months. The results indicate that, if habituation can be overcome by periodically allowing a kingsnake to confront but not harm the crotaline, the response is dependent on the size of the crotaline, in that smaller specimens (< 0.9 m) respond readily, while larger snakes (> 1.0 m) tend not to respond. The size of the kingsnake apparently does not have an effect on the crotaline response. These data appear to resolve apparent conflicts in the literature regarding whether certain species respond to ophidian ophiophages. In addition, hexane extracts of kingsnake skin were fractionated using an alumina column. The various fractions obtained were tested to determine which elicited the defensive response. Activity was found only in the most non-polar fraction. Preliminary analysis by gas chromatography/mass spectrometry indicated that this fraction contained straight and branched, saturated and polyunsaturated long-chain hydrocarbons.

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis*

PubMed Central

Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.; Wackett, Lawrence P.; Wilmot, Carrie M.

2016-01-01

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. PMID:27815501

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry aremore » precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation.« less

Effects of Chain Length and Saturability of Fatty Acids on Phospholipids and Proteins in Plasma Membranes of Bovine Mammary Gland.

PubMed

Yan, Qiongxian; Tang, Shaoxun; Han, Xuefeng; Bamikole, Musibau Adungbe; Zhou, Chuanshe; Kang, Jinhe; Wang, Min; Tan, Zhiliang

2016-12-01

Free fatty acids (FFAs) in plasma are essential substrates for de novo synthesis of milk fat, or directly import into mammary cells. The physico-chemical properties of mammary cells membrane composition affected by FFAs with different chain lengths and saturability are unclear yet. Employing GC, FTIR and fluorescence spectroscopy, the adsorption capacity, phospholipids content, membrane proteins conformation, lipid peroxidation product, and free sulfhydryl of plasma membranes (PMs) interacted with different FFAs were determined. The mammary cells PMs at 38 and 39.5 °C showed different adsorption capacities: acetic acid (Ac) > stearic acid (SA) > β-hydroxybutyric acid (BHBA) > trans10, cis12 CLA. In the FTIR spectrum, the major adsorption peaks appeared at 2920 and 2850 cm -1 for phospholipids, and at 1628 and 1560 cm -1 for membrane proteins. The intensities of PMs-FFAs complexes were varied with the FFAs species and their initial concentrations. The β-sheet and turn structures of membrane proteins were transferred into random coil and α-helix after BHBA, SA and trans10, cis12 CLA treatments compared with Ac treatment. The quenching effects on the fluorescence of endogenous membrane protein, 1, 8-ANS, NBD-PE, and DHPE entrapped in PMs by LCFA were different from those of short chain FFAs. These results indicate that the adsorption of FFAs could change membrane protein conformation and polarity of head group in phospholipids. This variation of the mammary cells PMs was regulated by carbon chain length and saturability of FFAs.

Evaluation of certain food additives.

PubMed

2012-01-01

This report represents the conclusions of a Joint FAO/WHO Expert Committee convened to evaluate the safety of various food additives, including flavouring agents, with a view to concluding as to safety concerns and to preparing specifications for identity and purity. The first part of the report contains a general discussion of the principles governing the toxicological evaluation of and assessment of dietary exposure to food additives, including flavouring agents. A summary follows of the Committee's evaluations of technical, toxicological and dietary exposure data for five food additives (magnesium dihydrogen diphosphate; mineral oil (medium and low viscosity) classes II and III; 3-phytase from Aspergillus niger expressed in Aspergillus niger; serine protease (chymotrypsin) from Nocardiopsis prasina expressed in Bacillus licheniformis; and serine protease (trypsin) from Fusarium oxysporum expressed in Fusarium venenatum) and 16 groups of flavouring agents (aliphatic and aromatic amines and amides; aliphatic and aromatic ethers; aliphatic hydrocarbons, alcohols, aldehydes, ketones, carboxylic acids and related esters, sulfides, disulfides and ethers containing furan substitution; aliphatic linear alpha,beta-unsaturated aldehydes, acids and related alcohols, acetals and esters; amino acids and related substances; epoxides; furfuryl alcohol and related substances; linear and branched-chain aliphatic, unsaturated, unconjugated alcohols, aldehydes, acids and related esters; miscellaneous nitrogen-containing substances; phenol and phenol derivatives; pyrazine derivatives; pyridine, pyrrole and quinoline derivatives; saturated aliphatic acyclic branched-chain primary alcohols, aldehydes and acids; simple aliphatic and aromatic sulfides and thiols; sulfur-containing heterocyclic compounds; and sulfur-substituted furan derivatives). Specifications for the following food additives were revised: ethyl cellulose, mineral oil (medium viscosity), modified starches and titanium dioxide. Annexed to the report are tables summarizing the Committee's recommendations for dietary exposures to and toxicological evaluations of the food additives and flavouring agents considered.

Comprehensive analytical methodology to determine hydrocarbons in marine waters using extraction disks coupled to glass fiber filters and compound-specific isotope analyses.

PubMed

Ternon, Eva; Tolosa, Imma

2015-07-24

Solid-phase extraction of both aliphatic (AHs) and aromatic polycyclic hydrocarbons (PAHs) from seawater samples was evaluated using a GFF filter stacked upon an octadecyl bonded silica (C18) disk. Stable-isotope measurements were developed on hydrocarbons extracted from both GFF and C18-disks in order to characterize the source of hydrocarbons. A clear partition of hydrocarbon compounds between the dissolved and the particulate phase was highlighted. PAHs showed a higher affinity with the dissolved phase (recoveries efficiency of 48-71%) whereas AHs presented strong affinity with the particulate phase (up to 76% of extraction efficiency). Medium volumes of seawater samples were tested and no breakthrough was observed for a 5L sample. Isotopic fractionation was investigated within all analytical steps but none was evidenced. This method has been applied to harbor seawater samples and very low AH and PAH concentrations were achieved. Due to the low concentration levels of hydrocarbons in the samples, the source of hydrocarbons was determined by molecular indices rather than isotopic measurements and a pyrolytic origin was evidenced. The aliphatic profile also revealed the presence of long-chain linear alkylbenzenes (LABs). The methodology presented here would better fit to polluted coastal environments affected by recent oil spills. Copyright © 2015 Elsevier B.V. All rights reserved.

Stress corrosion behavior of Ru-enhanced alpha-beta titanium alloys in methanol solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schutz, R.W.; Horrigan, J.M.; Bednarowicz, T.A.

1998-12-31

Conservative, practical guidelines for the minimum water content required to prevent methanolic stress corrosion cracking (SCC) of Ti-6Al-4V-Ru and Ti-3Al-2.5V-Ru alloy tubulars have been developed from slow strain rate testing in plain and acidified NaCl-saturated methanol-water solutions at 25 C. A minimum methanol water content of 10 wt.% is proposed for Ti-6Al-4V-Ru, whereas 2-3 wt.% is sufficient for the lower strength Ti-3Al-2.5V-Ru alloy. Although HCl-acidification aggravated methanolic SCC, intermixing of methanol with crude oil or pure hydrocarbons, H{sub 2}S gas saturation, and/or increasing temperature diminished cracking susceptibility in these alloy tubulars.

Gas Hydrate Characterization from a 3D Seismic Dataset in the Eastern Deepwater Gulf of Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnell, Dan

The presence of a gas hydrate petroleum system and seismic attributes derived from 3D seismic data are used for the identification and characterization of gas hydrate deposits in the deepwater eastern Gulf of Mexico. In the central deepwater Gulf of Mexico (GoM), logging while drilling (LWD) data provided insight to the amplitude response of gas hydrate saturation in sands, which could be used to characterize complex gas hydrate deposits in other sandy deposits. In this study, a large 3D seismic data set from equivalent and distal Plio-Pleistocene sandy channel deposits in the deepwater eastern Gulf of Mexico is screened formore » direct hydrocarbon indicators for gas hydrate saturated sands.« less

High performance liquid chromatographic hydrocarbon group-type analyses of mid-distillates employing fuel-derived fractions as standards

NASA Technical Reports Server (NTRS)

Seng, G. T.; Otterson, D. A.

1983-01-01

Two high performance liquid chromatographic (HPLC) methods have been developed for the determination of saturates, olefins and aromatics in petroleum and shale derived mid-distillate fuels. In one method the fuel to be analyzed is reacted with sulfuric acid, to remove a substantial portion of the aromatics, which provides a reacted fuel fraction for use in group type quantitation. The second involves the removal of a substantial portion of the saturates fraction from the HPLC system to permit the determination of olefin concentrations as low as 0.3 volume percent, and to improve the accuracy and precision of olefins determinations. Each method was evaluated using model compound mixtures and real fuel samples.

Modeling of cobalt-based catalyst use during CSS for low-temperature heavy oil upgrading

NASA Astrophysics Data System (ADS)

Kadyrov, R.; Sitnov, S.; Gareev, B.; Batalin, G.

2018-05-01

One of the methods, which is actively used on deposits of heavy oils of the Upper Kungurian (Ufimian) sandstones of the Republic of Tatarstan, is cyclic steam simulation (CSS). This method consists of 3 stages: injection, soaking, and production. Steam is injected into a well at a temperature of 300 to 340° C for a period of weeks to months. Then, the well is allowed to sit for days to weeks to allow heat to soak into the formation. Finally, the hot oil is pumped out of the well for a period of weeks or months. Once the production rate falls off, the well is put through another cycle. The injection of the catalyst solution before the injection of steam opens the possibility for upgrading the heavy oil in the process of aquathermolysis directly in the reservoir. In this paper, the possibility of using a catalyst precursor based on cobalt for upgrading the hydrocarbons of this field in the process of their extraction is represented. SARA analysis on oil saturated sandstones shows an increase in the proportion of saturated hydrocarbons by 11.1% due to the hydrogenation of aromatic hydrocarbons and their derivatives, the content of resins and asphaltenes are remained practically unchanged. A new method for estimating the adsorption of a catalyst based on taking into account the change in the concentration of the base metal before and after simulation of catalyst injection in the thermobaric conditions of the reservoir is proposed. During the study of catalyst adsorption in the rock, when simulating the CSS process, it is found that almost 28% of the cobalt, which is the main element of the catalyst precursor, is retained in the rock.

Mineral-assisted production of benzene under hydrothermal conditions: Insights from experimental studies on C6 cyclic hydrocarbons

NASA Astrophysics Data System (ADS)

Venturi, Stefania; Tassi, Franco; Gould, Ian R.; Shock, Everett L.; Hartnett, Hilairy E.; Lorance, Edward D.; Bockisch, Christiana; Fecteau, Kristopher M.; Capecchiacci, Francesco; Vaselli, Orlando

2017-10-01

Volatile Organic Compounds (VOCs) are ubiquitously present at low but detectable concentrations in hydrothermal fluids from volcanic and geothermal systems. Although their behavior is strictly controlled by physical and chemical parameters, the mechanisms responsible for the production of most VOCs in natural environments are poorly understood. Among them, benzene, whose abundances were found to be relatively high in hydrothermal gases, can theoretically be originated from reversible catalytic reforming processes, i.e. multi-step dehydrogenation reactions, involving saturated hydrocarbons. However, this hypothesis and other hypotheses are difficult to definitively prove on the basis of compositional data obtained by natural gas discharges only. In this study, therefore, laboratory experiments were carried out to investigate the production of benzene from cyclic hydrocarbons at hydrothermal conditions, specifically 300 °C and 85 bar. The results of experiments carried out in the presence of water and selected powdered minerals, suggest that cyclohexane undergoes dehydrogenation to form benzene, with cyclohexene and cyclohexadiene as by-products, and also as likely reaction intermediates. This reaction is slow when carried out in water alone and competes with isomerization and hydration pathways. However, benzene formation was increased compared to these competing reactions in the presence of sulfide (sphalerite and pyrite) and iron oxide (magnetite and hematite) minerals, whereas no enhancement of any reaction products was observed in the presence of quartz. The production of thiols was observed in experiments involving sphalerite and pyrite, suggesting that sulfide minerals may act both to enhance reactivity and also as reactants after dissolution. These experiments demonstrate that benzene can be effectively produced at hydrothermal conditions through dehydrogenation of saturated cyclic organic structures and highlight the crucial role played by minerals in this process.

Poster 4: Investigating the first steps of hydrocarbon condensation in the laboratory and in Titan's atmosphere

NASA Astrophysics Data System (ADS)

Biennier, Ludovic; Bourgalais, Jeremy; Benidar, Abdessamad; Le Picard, Sebastien

2016-06-01

Hydrocarbons formed in Titan's cold atmosphere, starting with ethane C2H6, ethylene C2H4, acetylene C2H2, propane C3H8,... up to benzene C6H6, play some role in aerosol production, cloud processes, rain generation and Titan's lakes formation. We have started to study in the laboratory the kinetics of the first steps of condensation of these hydrocarbons. Rate coefficients are very sensitive to the description of the potential interaction surfaces of the molecules involved. Combined theoretical and experimental studies at the molecular level of the homogenous nucleation of various small molecules should improve greatly our fundamental understanding. This knowledge will serve as a model for studying more complex nucleation processes actually taking places in planetary atmospheres. Here we present the first experimental kinetic study of the dimerization of two small hydrocarbons: ethane C2H6 and propane C3H8. We have performed experiments to identify the temperature and partial densities ranges over which small hydrocarbon clusters form in saturated uniform supersonic flows. Using our unique reactor based on a Laval nozzle expansions, the kinetics of the formation has also been investigated down to 23 K. The chemical species present in the reactor are probed by a time of flight mass spectrometer equipped with an electron gun for soft ionization of the neutral reagents and products. This work aims at putting some constraints on the role of small hydrocarbon condensation in the formation of haze particles in the dense atmosphere of Titan.

Degradation of hydrocarbons in crude oil by the ascomycete Pseudallescheria boydii (Microascaceae).

PubMed

April, T M; Abbott, S P; Foght, J M; Currah, R S

1998-03-01

Four unique strains of Pseudallescheria boydii were isolated from oil-soaked soils in British Columbia and Alberta and compared to strains from cattle dung and raw sewage. Considerable variability in morphology, colony appearance, colony diameter, and temperature tolerance occurred among the strains. They also varied in the sporogenous states produced in culture; all strains had a Scedosporium anamorph and either the Graphium anamorph or cleistothecial teleomorph. Conspecificity of the six isolates was inferred from their morphology and supported by restriction fragment length polymorphism profiles of the internally transcribed spacer region of rDNA and comparing these to Petriella sordida, a similar taxon in the Microascaceae. Three of the strains isolated from oil-contaminated soil and the strain from sewage were tested for their ability to utilize hydrocarbons by incubation with Prudhoe Bay Crude oil as the sole carbon source. Gas chromatographic analysis of the residual oil revealed that the strains isolated from oil-contaminated soil degraded the linear aliphatics. The strain from sewage, previously shown by others to utilize the volatile n-alkanes (i.e., ethane, propane, and butane), did not utilize the liquid saturate compounds. None of the strains was observed to degrade compounds in the aromatic fraction. Pseudallescheria boydii may be an important agent for in situ bioremediation of saturates in oil-contaminated sites.

Towards Carbon-Neutral CO2 Conversion to Hydrocarbons.

PubMed

Mattia, Davide; Jones, Matthew D; O'Byrne, Justin P; Griffiths, Owen G; Owen, Rhodri E; Sackville, Emma; McManus, Marcelle; Plucinski, Pawel

2015-12-07

With fossil fuels still predicted to contribute close to 80 % of the primary energy consumption by 2040, methods to limit further CO2 emissions in the atmosphere are urgently needed to avoid the catastrophic scenarios associated with global warming. In parallel with improvements in energy efficiency and CO2 storage, the conversion of CO2 has emerged as a complementary route with significant potential. In this work we present the direct thermo-catalytic conversion of CO2 to hydrocarbons using a novel iron nanoparticle-carbon nanotube (Fe@CNT) catalyst. We adopted a holistic and systematic approach to CO2 conversion by integrating process optimization-identifying reaction conditions to maximize conversion and selectivity towards long chain hydrocarbons and/or short olefins-with catalyst optimization through the addition of promoters. The result is the production of valuable hydrocarbons in a manner that can approach carbon neutrality under realistic industrial process conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrocarbon Degradation Pathways used by Coastal Sediment Microbial Communities exposed to Crude Oil

NASA Astrophysics Data System (ADS)

Spaulding-Astudillo, F.; Sharrar, A.; Orcutt, B.

2016-02-01

The site-specific microbial community response to crude oil exposure in marine environments is not well described. Moreover, the abundance of genes implicated in long-chain alkane (LCA) and polycyclic aromatic hydrocarbon (PAH) degradation are not well understood. Coastal sediments from the Beaufort Sea, Gulf of Alaska, and Portland Harbor were treated with crude oil and incubated aerobically. Deep-sea sediments from the Gulf of Mexico were treated with the same crude oil and anaerobically incubated in situ for five months before recovery. Cycloclasticus, a known hydrocarbon-degrader, was abundant in all oiled, aerobic samples regardless of temperature, demonstrating a generalist oil-response strategy. Other hydrocarbon degrading bacteria showed differential response to either site or temperature. Primers for alkB, assA, bssA, and ncr, catabolic gene markers for aerobic LCA degradation, anaerobic LCA degradation, anaerobic LCA & PAH degradation, and anaerobic PAH degradation, respectively, were found in literature and tested on DNA extracts in a QPCR-based assay. Gene abundance was site and condition variable.

Anesthetic-dependent changes in the chain-melting phase transition of DPPG liposomes studied using near-infrared spectroscopy supported by PCA

NASA Astrophysics Data System (ADS)

Kuć, Marta; Cieślik-Boczula, Katarzyna; Rospenk, Maria

2017-11-01

The effect of inhalation anesthetics (enflurane, isoflurane, sevoflurane or halothane) on the lipid chain-melting phase transition of negatively charged phospholipid membranes was studied using near-infrared (NIR) spectroscopy supported by Principal Component Analysis (PCA). NIR spectra of anesthetics-mixed dipalmitoylphosphatidylglycerol (DPPG) membranes were recorded in a range of the first overtone of the symmetric and antisymmetric stretching vibrations of CH2 groups of lipid aliphatic chains as a function of increasing temperature. Anesthetic-dependent changes in the trans to gauche conformers ratio of CH2 groups in the hydrocarbon lipid chains were characterized in detail and compared with the zwitterionic lipid membranes, which were built of dipalmitoylphosphatidylcholine (DPPC) molecules.

Coliform Bacteria for Bioremediation of Waste Hydrocarbons

PubMed Central

2017-01-01

Raw, domestic sewage of Kuwait City contained about 106 ml−1 colony forming units of Enterobacter hormaechei subsp. oharae (56.6%), Klebsiella spp. (36%), and Escherichia coli (7.4%), as characterized by their 16S rRNA-gene sequences. The isolated coliforms grew successfully on a mineral medium with crude oil vapor as a sole source of carbon and energy. Those strains also grew, albeit to different degrees, on individual n-alkanes with carbon chains between C9 and C36 and on the individual aromatic hydrocarbons, toluene, naphthalene, phenanthrene, and biphenyl as sole sources of carbon and energy. These results imply that coliforms, like other hydrocarbonoclastic microorganisms, oxidize hydrocarbons to the corresponding alcohols and then to aldehydes and fatty acids which are biodegraded by β-oxidation to acetyl CoA. The latter is a well-known key intermediate in cell material and energy production. E. coli cells grown in the presence of n-hexadecane (but not in its absence) exhibited typical intracellular hydrocarbon inclusions, as revealed by transmission electron microscopy. Raw sewage samples amended with crude oil, n-hexadecane, or phenanthrene lost these hydrocarbons gradually with time. Meanwhile, the numbers of total and individual coliforms, particularly Enterobacter, increased. It was concluded that coliform bacteria in domestic sewage, probably in other environmental materials too, are effective hydrocarbon-biodegrading microorganisms. PMID:29082238

Comparison of forcefields for molecular dynamics simulations of hydrocarbon phase diagrams

NASA Astrophysics Data System (ADS)

Pisarev, V. V.; Zakharov, S. A.

2018-01-01

Molecular dynamics calculations of vapor-liquid equilibrium of methane-n-butane mixture are performed. Three force-field models are tested: the TraPPE-UA united-atom forcefield, LOPLS-AA all-atom forcefield and a fully flexible version of the TraPPE-EH all-atom forcefield. All those forcefields reproduce well the composition of liquid phase in the mixture as a function of pressure at the 300 K isotherm, while significant discrepancies from experimental data are observed in the saturated vapor compositions with OPLS-AA and TraPPE-UA forcefields. The best agreement with the experimental phase diagram is found with TraPPE-EH forcefield which accurately reproduces compositions of both liquid and vapor phase. This forcefield can be recommended for simulation of two-phase hydrocarbon systems.

Accessibility of Nitroxide Side Chains: Absolute Heisenberg Exchange Rates from Power Saturation EPR

PubMed Central

Altenbach, Christian; Froncisz, Wojciech; Hemker, Roy; Mchaourab, Hassane; Hubbell, Wayne L.

2005-01-01

In site-directed spin labeling, the relative solvent accessibility of spin-labeled side chains is taken to be proportional to the Heisenberg exchange rate (Wex) of the nitroxide with a paramagnetic reagent in solution. In turn, relative values of Wex are determined by continuous wave power saturation methods and expressed as a proportional and dimensionless parameter Π. In the experiments presented here, NiEDDA is characterized as a paramagnetic reagent for solvent accessibility studies, and it is shown that absolute values of Wex can be determined from Π, and that the proportionality constant relating them is independent of the paramagnetic reagent and mobility of the nitroxide. Based on absolute exchange rates, an accessibility factor is defined (0 < ρ < 1) that serves as a quantitative measure of side-chain solvent accessibility. The accessibility factors for a nitroxide side chain at 14 different sites in T4 lysozyme are shown to correlate with a structure-based accessibility parameter derived from the crystal structure of the protein. These results provide a useful means for relating crystallographic and site-directed spin labeling data, and hence comparing crystal and solution structures. PMID:15994891

Dietary intake and food sources of fatty acids in Australian adolescents.

PubMed

O'Sullivan, Therese A; Ambrosini, Gina; Beilin, Lawrie J; Mori, Trevor A; Oddy, Wendy H

2011-02-01

Dietary fat consumed during childhood and adolescence may be related to the development of cardiovascular and other chronic diseases in adulthood; however, there is a lack of information on specific fatty acid intakes and food sources in these populations. Our study aimed to assess fatty acid intakes in Australian adolescents, compare intakes with national guidelines, and identify major food sources of fatty acids. Dietary intake was assessed using measured 3-d records in 822 adolescents aged 13-15 y participating in The Western Australian Pregnancy Cohort (Raine) Study, Australia. Mean daily total fat intakes were 90 ± 25 g for boys and 73 ± 20 g for girls, with saturated fat contributing 14% of total energy intake. Mean contribution to daily energy intake for linoleic, alpha-linolenic, eicosapentaenoic, docosapentaenoic, and docosahexaenoic acids were 3.0%, 0.40%, 0.02%, 0.01%, and 0.04%, respectively, for boys, and 3.3%, 0.42%, 0.02%, 0.01%, and 0.05% for girls. To meet guidelines for chronic disease prevention, consumption of long-chain omega-3 fatty acids in this population may need to increase up to three-fold and the proportion of saturated fat decrease by one-third. Girls were more likely to achieve the guidelines. Major food sources were dairy products for total fat, saturated fat and alpha-linolenic acid, margarines for linoleic acid, and fish for long-chain omega-3 fatty acids. Results suggest that for this population, a higher dietary intake of long-chain omega-3 fatty acids, particularly for boys, and lower proportion of saturated fat is required to meet recommendations for prevention of chronic disease. Copyright © 2011 Elsevier Inc. All rights reserved.

Self-assembly of phosphate fluorosurfactants in carbon dioxide.

PubMed

Keiper, Jason S; Behles, Jacqueline A; Bucholz, Tracy L; Simhan, Ruma; DeSimone, Joseph M; Lynn, Gary W; Wignall, George D; Melnichenko, Yuri B; Frielinghaus, Henrich

2004-02-17

Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and H/F types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scatteringwas used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions.

Multinuclear metal-binding ability of a carotene

PubMed Central

Horiuchi, Shinnosuke; Tachibana, Yuki; Yamashita, Mitsuki; Yamamoto, Koji; Masai, Kohei; Takase, Kohei; Matsutani, Teruo; Kawamata, Shiori; Kurashige, Yuki; Yanai, Takeshi; Murahashi, Tetsuro

2015-01-01

Carotenes are naturally abundant unsaturated hydrocarbon pigments, and their fascinating physical and chemical properties have been studied intensively not only for better understanding of the roles in biological processes but also for the use in artificial chemical systems. However, their metal-binding ability has been virtually unexplored. Here we report that β-carotene has the ability to assemble and align ten metal atoms to afford decanuclear homo- and heterometal chain complexes. The metallo–carotenoid framework shows reversible metalation–demetalation reactivity with multiple metals, which allows us to control the size of metal chains as well as the heterobimetallic composition and arrangement of the carotene-supported metal chains. PMID:25857402

Chemical Characterization of Dissolved Organic Matter (DOM) in Seawater: Structure, Cycling and the Role of Biology

DTIC Science & Technology

2005-02-01

concentration, excluding hydrocarbons , was less than 2% of the total organic carbon present in the samples, and the samples had not been pre-extracted to...carbon chains that make up the separation phase of the C18 134 column. This carbon chain was most likely generated from petroleum products, and had a...produced, bioaccumulating halogenated organic compound. Environmental Science and Technology 38: 1992-1997. Silfer, J. A., M. H. Engel and S. A

Analyses of barley spike mutant waxes identify alkenes, cyclopropanes and internally branched alkanes with dominating isomers at carbon 9.

PubMed

von Wettstein-Knowles, Penny

2007-01-01

About 15% of the epidermal wax on Hordeum vulgare cv. Bonus barley spikes is n-alkanes. Longer homologues are greatly reduced in the eceriferum mutants, cer-a(6), cer-e(8), cer-n(26), cer-n(53), cer-n(985), cer-x(60), cer-yc(135) and cer-yl(187). Simultaneously hydrocarbons accounting for only traces in the wild-type become prominent in the mutants, although their chain-length distributions remain unchanged. Accordingly several new hydrocarbon series were identified. The two major ones were C(23)-C(35)cis monoenoic alkenes (the major 9-ene isomer was part of a homologous series including 11, 13 and 15-enes), and the novel C(27)-C(31) cyclopropanes (the ring carbons of major isomers were 9,10 and 11,12 with lesser amounts of 13,14). Three minor series included 2- and 3-methylalkanes plus C(25)-C(33) internally branched alkanes (methyls on carbons 9, 11, 13, 15 or 17; shorter homologues dominated by the 9 isomer, longer homologues by 11, 13 or 15 isomers). Acyl chains destined for spike waxes are synthesized via acyl and polyketide elongase systems plus associated reductive and decarbonylative/decarboxylative enzyme systems. Both elongation systems are defective in synthesizing C(32) acyl chains in all nine mutants. The similarities in the position of the chemical groups (primarily on carbon 9, secondarily on carbon 11) of the alkenes, cyclopropanes and internally branched methyl alkanes imply an origin from a common, hitherto unrecognized associated pathway in barley, designated the enoic pathway. The elongation system leading to the enoic derived hydrocarbons differs from the known elongation systems by inclusion of a mechanism for introducing a double bond.

Hydrous pyrolysis of crude oil in gold-plated reactors

USGS Publications Warehouse

Curiale, J.A.; Lundegard, P.D.; Kharaka, Y.K.

1992-01-01

Crude oils from Iraq and California have been pyrolyzed under hydrous conditions at 200 and 300??C for time periods up to 210 days, in gold-plated reactors. Elemental (vanadium, nickel), stable isotopic (carbon), and molecular (n-alkanes, acyclic isoprenoids, steranes, terpanes and aromatic steroid hydrocarbons) analyses were made on the original and pyrolyzed oils. Various conventional crude oil maturity parameters, including 20S/(20S + 20R)-24-ethylcholestane ratios and the side-chain-length distribution of aliphatic and aromatic steroidal hydrocarbons, were measured in an effort to assess the modification of molecular maturity parameters in clay-free settings, similar to those encountered in "clean" reservoirs. Concentrations of vanadium and nickel in the Iraq oil decrease significantly and the V/(V + Ni) ratio decreases slightly, with increasing pyrolysis time/temperature. Whole oil carbon isotope ratios remain fairly constant during pyrolysis, as do hopane/sterane ratios and carbon number distribution of 5??(H),14??(H),17??(H),20R steranes. These latter three parameters are considered maturity-invariant. The ratios of short side-chain components to long side-chain components of the regular steranes [C21/(C21 + C29R)] and the triaromatic steroid hydrocarbons [C21/(C21 + C28)] vary systematically with increasing pyrolysis time, indicating that these parameters may be useful as molecular maturity parameters for crude oils in clay-free reservoir rocks. In addition, decreases in bisnorhopane/hopane ratio with increasing pyrolysis time, in a clay-free and kerogen-free environment, suggest that the distribution of these compounds is controlled by either differential thermal stabilities or preferential release from a higher-molecular weight portion of the oil. ?? 1992.

Phase behavior of fluorocarbon and hydrocarbon double-chain hydroxylated and galactosylated amphiphiles and bolaamphiphiles. Long-term shelf-stability of their liposomes.

PubMed

Clary, L; Gadras, C; Greiner, J; Rolland, J P; Santaella, C; Vierling, P; Gulik, A

1999-06-01

This paper describes the morphological characterization, by freeze-fracture electron microscopy, and the thermotropic phase behavior, by differential scanning calorimetry and/or X-ray scattering, of aqueous dispersions of various hydroxylated and galactosylated double-chain amphiphiles and bolaamphiphiles, several of them containing one or two hydrophobic fluorocarbon chains. Colloidal systems are observed in water with the hydroxylated hydrocarbon or fluorocarbon bolaamphiphiles only when they are dispersed with a co-amphiphile such as rac-1,2-dimyristoylphosphatidylcholine (DMPC) or rac-1,2-distearoylphosphatidylcholine (DSPC). Liposomes are formed providing the relative content of bolaamphiphiles does not exceed 20% mol. Most of these liposomes can be thermally sterilized and stored at room temperature for several months without any significant modification of their size and size distribution. The hydrocarbon galactosylated bolaamphiphile HO[C24][C12]Gal forms in water a lamellar phase (the gel to liquid-crystal phase transition is complete at 45 degrees C) and a Im3m cubic phase above 47 degrees C. The fluorocarbon HO[C24][F6C5]Gal analog displays a more complex and metastable phase behavior. The fluorinated non-bolaform galactosylated [F8C7][C16]AEGal and SerGal amphiphiles form lamellar phases in water. Low amounts (10% molar ratio) of the HO[C24][F6C5]Gal or HO[C24][C12]Gal bolaamphiphiles or of the single-headed [F8C7][C16]AEGal improve substantially the shelf-stability of reference phospholipon/cholesterol 2/1 liposomes. These liposomes when co-formulated with a single-headed amphiphile from the SerGal series are by far less stable.

Reconstruction of anthropogenic activities on the excavations of a fireplace sequence from the Krems-Wachtberg site (Austria) using molecular proxies

NASA Astrophysics Data System (ADS)

Wiesenberg, Guido; Hambach, Ulrich

2010-05-01

The well investigated Krems-Wachtberg excavation yielded a broad variety of anthropogenic artefacts and thus enables a proper reconstruction of an ancient settlement of Upper-Palaeolithic age. Despite these artefacts, some questions cannot be answered by sedimentologic and archaeologic approaches. Molecular fossils like lipids including aliphatic hydrocarbons are suitable to improve understanding of e.g. paleoclimatic, pedogenetic, and archaeologic contexts. Especially aliphatic hydrocarbons including straight-chain and branched alkanes yield potential to elucidate biogenic sources of soil and loess organic matter and to assess degradation conditions of primary organic matter. To improve understanding on the terms the fireplaces at the Krems-Wachtberg site are used, aliphatic hydrocarbons are investigated on a set of samples covering several horizons in the context of one fireplace, which was part of the excavation. Horizons above and below the fireplace as well as the fireplace itself were investigated for lipids. Additionally, reference loess samples from a similar age like the fireplace and a pit filling were investigated. Two replicates were available for most samples except for the pit filling. Two distinct fireplace series have been studies. All samples were extracted for lipids using Soxhlet extraction followed by column chromatography in order to separate the aliphatic hydrocarbon fraction from other lipids. Thereafter, aliphatic hydrocarbons were quantified using gas chromatography. The total amounts of extractable organic compounds in the whole sample set from the Krems-Wachtberg site were in the range of usual loess deposits and accounted for 30-80 mg kg-1 loess. The largest contents were observed in reference loess samples and decreased within the excavation from fireplaces > sediments covering fireplace > basement of fireplace > pit. The lower the extract yields, the stronger was the degradation of organic matter. In this context, the pit yielded either organic matter that was strongly degraded during rotting process of organic material after burial or incorporation of already strongly degraded organic matter like ash from fireplaces. The basement of the fireplace was exposed to high temperature for the whole usage of the place, resulting in a modification in the structure of the sediments and a degradation of organic matter within the sediments. The material from the fireplace itself probably was not completely burned and thus yielded comparatively large amounts of extractable components. The sediments covering the fireplace were potentially used to extinguish the fire and hence received a thermal alteration of the organic matter within the sediment under oxygen limiting conditions. Hence, the amount of extractable organic compounds can be used to reconstruct the firing process in the Krems-Wachtberg excavation. The amount of individual aliphatic hydrocarbons parallels the content of all extractable compounds and thus confirms the findings explained above. The aliphatic hydrocarbons reveal typical distribution patterns for grassland vegetation as indicated by a strong predomination of odd long chain alkanes and n-C31 as the most abundant homologue for most samples. Only sediments covering the fireplaces are dominated by n-C29 alkane. The different alkane distribution pattern for these sediments compared to all other samples including reference loess indicates a different biogenic source of the covering sediment than for all other samples. Probably, the covering sediments yield organic matter incorporated under forest or different grassland vegetation than the other sediments. In this study, several molecular markers have been tested for aliphatic hydrocarbons in order to elucidate their sources and to identify degradation effects responsible for the determined distribution patterns. The ratio of long chain vs. short chain alkanes enables the differentiation of plant-derived organic matter characterized by high ratios (>10) and organic matter derived from microbial biomass or degradation (<10). The reference loess samples were characterized by very high values (>50), which indicates plant biomass as the predominant source of loess organic matter. All other samples were characterized by low values (<10), which is due to degradation effects. Microbial alkanes as second potential source of short chain n-alkanes are not likely as odd homologues did not predominate over even homologues, which is typical for microbial alkanes. Furthermore even alkanes dominated in most samples, which can be related to thermal alteration of organic matter as common in fireplaces. Other degradation markers like n-alkanes vs. isoprenoid alkanes (n-C18/phytane) revealed values between 2-4.5. The fireplace samples were characterized by lowest values whereas the reference samples yielded highest values. Hence degradation increased from loess towards fireplace with an intermediate degradation of most other samples. Aliphatic hydrocarbon biomarkers like alkanes were found useful to reconstruct degradation intensity in ancient sediments and to elucidate anthropogenic activities like extinguishing of fire. Hence, organic geochemical investigations can be useful techniques to complement standard archaeological techniques.

Effect of concentration gradients on biodegradation in bench-scale sand columns with HYDRUS modeling of hydrocarbon transport and degradation.

PubMed

Horel, Agota; Schiewer, Silke; Misra, Debasmita

2015-09-01

The present research investigated to what extent results obtained in small microcosm experiments can be extrapolated to larger settings with non-uniform concentrations. Microbial hydrocarbon degradation in sandy sediments was compared for column experiments versus homogenized microcosms with varying concentrations of diesel, Syntroleum, and fish biodiesel as contaminants. Syntroleum and fish biodiesel had higher degradation rates than diesel fuel. Microcosms showed significantly higher overall hydrocarbon mineralization percentages (p < 0.006) than columns. Oxygen levels and moisture content were likely not responsible for that difference, which could, however, be explained by a strong gradient of fuel and nutrient concentrations through the column. The mineralization percentage in the columns was similar to small-scale microcosms at high fuel concentrations. While absolute hydrocarbon degradation increased, mineralization percentages decreased with increasing fuel concentration which was corroborated by saturation kinetics; the absolute CO2 production reached a steady plateau value at high substrate concentrations. Numerical modeling using HYDRUS 2D/3D simulated the transport and degradation of the investigated fuels in vadose zone conditions similar to those in laboratory column experiments. The numerical model was used to evaluate the impact of different degradation rate constants from microcosm versus column experiments.

Phytoremediation of petroleum hydrocarbon-contaminated saline-alkali soil by wild ornamental Iridaceae species.

PubMed

Cheng, Lijuan; Wang, Yanan; Cai, Zhang; Liu, Jie; Yu, Binbin; Zhou, Qixing

2017-03-04

As a green remediation technology, phytoremediation is becoming one of the most promising methods for treating petroleum hydrocarbons (PHCs)-contaminated soil. Pot culture experiments were conducted in this study to investigate phytoremediation potential of two representative Iridaceae species (Iris dichotoma Pall. and Iris lactea Pall.) in remediation of petroleum hydrocarbon-contaminated saline-alkali soil from the Dagang Oilfield in Tianjin, China. The results showed that I. lactea was more endurable to extremely high concentration of PHCs (about 40,000 mg/kg), with a relatively high degradation rate of 20.68%.The degradation rate of total petroleum hydrocarbons (TPHs) in soils contaminated with 10,000 and 20,000 mg/kg of PHCs was 30.79% and 19.36% by I. dichotoma, and 25.02% and 19.35% by I. lactea, respectively, which improved by 10-60% than the unplanted controls. The presence of I. dichotoma and I. lactea promoted degradation of PHCs fractions, among which saturates were more biodegradable than aromatics. Adaptive specialization was observed within the bacterial community. In conclusion, phytoremediation by I. dichotoma should be limited to soils contaminated with ≤20,000 mg/kg of PHCs, while I. lactea could be effectively applied to phytoremediation of contaminated soils by PHCs with at least 40,000 mg/kg.

Method for inverting reflection trace data from 3-D and 4-D seismic surveys and identifying subsurface fluid and pathways in and among hydrocarbon reservoirs based on impedance models

DOEpatents

He, W.; Anderson, R.N.

1998-08-25

A method is disclosed for inverting 3-D seismic reflection data obtained from seismic surveys to derive impedance models for a subsurface region, and for inversion of multiple 3-D seismic surveys (i.e., 4-D seismic surveys) of the same subsurface volume, separated in time to allow for dynamic fluid migration, such that small scale structure and regions of fluid and dynamic fluid flow within the subsurface volume being studied can be identified. The method allows for the mapping and quantification of available hydrocarbons within a reservoir and is thus useful for hydrocarbon prospecting and reservoir management. An iterative seismic inversion scheme constrained by actual well log data which uses a time/depth dependent seismic source function is employed to derive impedance models from 3-D and 4-D seismic datasets. The impedance values can be region grown to better isolate the low impedance hydrocarbon bearing regions. Impedance data derived from multiple 3-D seismic surveys of the same volume can be compared to identify regions of dynamic evolution and bypassed pay. Effective Oil Saturation or net oil thickness can also be derived from the impedance data and used for quantitative assessment of prospective drilling targets and reservoir management. 20 figs.

Method for inverting reflection trace data from 3-D and 4-D seismic surveys and identifying subsurface fluid and pathways in and among hydrocarbon reservoirs based on impedance models

DOEpatents

He, Wei; Anderson, Roger N.

1998-01-01

A method is disclosed for inverting 3-D seismic reflection data obtained from seismic surveys to derive impedance models for a subsurface region, and for inversion of multiple 3-D seismic surveys (i.e., 4-D seismic surveys) of the same subsurface volume, separated in time to allow for dynamic fluid migration, such that small scale structure and regions of fluid and dynamic fluid flow within the subsurface volume being studied can be identified. The method allows for the mapping and quantification of available hydrocarbons within a reservoir and is thus useful for hydrocarbon prospecting and reservoir management. An iterative seismic inversion scheme constrained by actual well log data which uses a time/depth dependent seismic source function is employed to derive impedance models from 3-D and 4-D seismic datasets. The impedance values can be region grown to better isolate the low impedance hydrocarbon bearing regions. Impedance data derived from multiple 3-D seismic surveys of the same volume can be compared to identify regions of dynamic evolution and bypassed pay. Effective Oil Saturation or net oil thickness can also be derived from the impedance data and used for quantitative assessment of prospective drilling targets and reservoir management.

Morphology, Chemistry and Function of the Postpharyngeal Gland in the South American Digger Wasps Trachypus boharti and Trachypus elongatus

PubMed Central

Herzner, Gudrun; Kaltenpoth, Martin; Poettinger, Theodor; Weiss, Katharina; Koedam, Dirk; Kroiss, Johannes; Strohm, Erhard

2013-01-01

Microbes pose severe threats to animals as competitors or pathogens and strongly affect the evolution of life history traits like parental care. Females of the European beewolf Philanthus triangulum, a solitary digger wasp, provision their offspring with paralyzed honeybees and embalm them with the secretion from large postpharyngeal glands (PPG) that contain mainly unsaturated hydrocarbons. This coating changes the physico-chemical properties of the prey surface, causes a reduction of water condensation and retards growth of mold fungi. Here we examined the closely related South American genus Trachypus, which shows a life-history similar to Philanthus. We investigated whether Trachypus spp. also possess PPGs and embalm larval provisions. Using histological methods and 3D reconstructions we show that Trachypus boharti and T. elongatus possess PPGs that are similar to P. triangulum but somewhat smaller. The ultrastructure of the gland epithelium suggests that the gland content is at least partly sequestered from the hemolymph. Chemical analyses using gas chromatography / mass spectrometry revealed that both the cuticle and PPGs of Trachypus contain mainly unsaturated long-chain hydrocarbons. The gland of T. boharti additionally contains long-chain ketones. The hydrocarbons from the PPG of T. elongatus occurred on prey bees excavated from nests in the field but not on conspecific control bees. While the embalming only slightly elevated the amount of hydrocarbons on prey bees, the proportion of unsaturated hydrocarbons, which is crucial for the antifungal effect, was significantly increased. The Trachypus species under study possess PPGs that are very similar to the PPG of P. triangulum with regard to morphology, ultrastructure and chemistry. Moreover, we provide clear evidence that T. elongatus females embalm their prey, presumably as a means of prey preservation. The observed differences among Trachypus and Philanthus in gland size and prey embalming may have evolved in response to divergent ecological conditions. PMID:24324830

Citrate and malonate increase microbial activity and alter microbial community composition in uncontaminated and diesel-contaminated soil microcosms

NASA Astrophysics Data System (ADS)

Martin, Belinda C.; George, Suman J.; Price, Charles A.; Shahsavari, Esmaeil; Ball, Andrew S.; Tibbett, Mark; Ryan, Megan H.

2016-09-01

Petroleum hydrocarbons (PHCs) are among the most prevalent sources of environmental contamination. It has been hypothesized that plant root exudation of low molecular weight organic acid anions (carboxylates) may aid degradation of PHCs by stimulating heterotrophic microbial activity. To test their potential implication for bioremediation, we applied two commonly exuded carboxylates (citrate and malonate) to uncontaminated and diesel-contaminated microcosms (10 000 mg kg-1; aged 40 days) and determined their impact on the microbial community and PHC degradation. Every 48 h for 18 days, soil received 5 µmol g-1 of (i) citrate, (ii) malonate, (iii) citrate + malonate or (iv) water. Microbial activity was measured daily as the flux of CO2. After 18 days, changes in the microbial community were assessed by a community-level physiological profile (CLPP) and 16S rRNA bacterial community profiles determined by denaturing gradient gel electrophoresis (DGGE). Saturated PHCs remaining in the soil were assessed by gas chromatography-mass spectrometry (GC-MS). Cumulative soil respiration increased 4- to 6-fold with the addition of carboxylates, while diesel contamination resulted in a small, but similar, increase across all carboxylate treatments. The addition of carboxylates resulted in distinct changes to the microbial community in both contaminated and uncontaminated soils but only a small increase in the biodegradation of saturated PHCs as measured by the n-C17 : pristane biomarker. We conclude that while the addition of citrate and malonate had little direct effect on the biodegradation of saturated hydrocarbons present in diesel, their effect on the microbial community leads us to suggest further studies using a variety of soils and organic acids, and linked to in situ studies of plants, to investigate the role of carboxylates in microbial community dynamics.

Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

DOEpatents

Sapienza, R.S.; Slegeir, W.A.

1990-05-15

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

DOEpatents

Sapienza, Richard S.; Slegeir, William A.

1990-01-01

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Hawaii Algal Biofuel

DTIC Science & Technology

2013-03-01

155 Figure 56. Ring heater. ....................................................................................................155 Figure 57...structure, the straight chain paraffins are first combined with high pressure hydrogen. The reaction converts them into a hydrogenated ring -like...bonds in the hydrogenated ring -like molecular structure to form many small olefinic double bonds of unsaturated hydrocarbons. The unsaturated

Elastohydrodynamics of farm-based blends comprising amphiphilic oils

USDA-ARS?s Scientific Manuscript database

Vegetable oils contain non-polar hydrocarbon chains and polar ester groups (and possibly also other functional groups such as hydroxyl groups in castor oil). The presence of polar and non-polar groups within the same molecule gives vegetable oil amphiphilic character. The density, refractive index, ...

Identifying the Interaction of Vancomycin With Novel pH-Responsive Lipids as Antibacterial Biomaterials Via Accelerated Molecular Dynamics and Binding Free Energy Calculations.

PubMed

Ahmed, Shaimaa; Vepuri, Suresh B; Jadhav, Mahantesh; Kalhapure, Rahul S; Govender, Thirumala

2018-06-01

Nano-drug delivery systems have proven to be an efficient formulation tool to overcome the challenges with current antibiotics therapy and resistance. A series of pH-responsive lipid molecules were designed and synthesized for future liposomal formulation as a nano-drug delivery system for vancomycin at the infection site. The structures of these lipids differ from each other in respect of hydrocarbon tails: Lipid1, 2, 3 and 4 have stearic, oleic, linoleic, and linolenic acid hydrocarbon chains, respectively. The impact of variation in the hydrocarbon chain in the lipid structure on drug encapsulation and release profile, as well as mode of drug interaction, was investigated using molecular modeling analyses. A wide range of computational tools, including accelerated molecular dynamics, normal molecular dynamics, binding free energy calculations and principle component analysis, were applied to provide comprehensive insight into the interaction landscape between vancomycin and the designed lipid molecules. Interestingly, both MM-GBSA and MM-PBSA binding affinity calculations using normal molecular dynamics and accelerated molecular dynamics trajectories showed a very consistent trend, where the order of binding affinity towards vancomycin was lipid4 > lipid1 > lipid2 > lipid3. From both normal molecular dynamics and accelerated molecular dynamics, the interaction of lipid3 with vancomycin is demonstrated to be the weakest (∆G binding  = -2.17 and -11.57, for normal molecular dynamics and accelerated molecular dynamics, respectively) when compared to other complexes. We believe that the degree of unsaturation of the hydrocarbon chain in the lipid molecules may impact on the overall conformational behavior, interaction mode and encapsulation (wrapping) of the lipid molecules around the vancomycin molecule. This thorough computational analysis prior to the experimental investigation is a valuable approach to guide for predicting the encapsulation ability, drug release and further development of novel liposome-based pH-responsive nano-drug delivery system with refined structural and chemical features of potential lipid molecule for formulation development.

Hydrocarbon activation under sulfate-reducing and methanogenic conditions proceeds by different mechanisms.

NASA Astrophysics Data System (ADS)

Head, Ian; Gray, Neil; Aitken, Caroline; Sherry, Angela; Jones, Martin; Larter, Stephen

2010-05-01

Microbial degradation of alkanes typically involves their conversion to fatty acids which are then catabolised by beta-oxidation. The critical step in this process is activation of the hydrocarbon. Under oxic conditions this is catalyzed by monooxygenase enzymes with the formation of long chain alcohols. In the absence of oxygen alternative alkane activation mechanisms have been observed or proposed. Fumarate addition to alkanes to form alkyl succinates is considered a central process in anaerobic hydrocarbon degradation. Comparative studies of crude oil degradation under sulphate-reducing and methanogenic conditions revealed distinctive patterns of compound class removal and metabolite formation. Alkyl succinates derived from C7 to C26 n-alkanes and branched chain alkanes were found in abundance in sulfate-reducing systems but these were not detected during methanogenic crude oil degradation. Only one other mechanism of alkane activation has been elucidated to date. This involves addition of carbon derived from bicarbonate/CO2 to C-3 of an alkane chain to form a 2-ethylalkane with subsequent removal of the ethyl group leading to the formation of a fatty acid 1 carbon shorter than the original alkane. 2-ethylalkanes have never been detected as metabolites of anaerobic alkane degradation and were not detected in crude oil-degrading methanogenic systems. Due to the range of alkanes present in crude oil it was not possible to infer the generation of C-odd acids from C-even alkanes which is characteristic of the C-3 carboxylation mechanism. Furthermore genes homologous to alkysuccinate synthetases were not detected in the methanogenic hydrocarbon degrading community by pyrosequencing of total DNA extracted from methanogenic enrichments cultures. beta-oxidation genes were detected and intriguingly, alcohol and aldehyde dehydrogenase genes were present. This offers the possibility that alkane activation in the methanogenic system does not proceed via acid metabolites, but may be initiated by an anaerobic hydroxylation reaction. This is not unprecedented and hydroxylation of ethylbenzene has been demonstrated. However the C-H bond dissociation energy of alkanes is typically considered too high to readily permit alkane hydroxylation. It is however clear that alkane activation in these methanogenic crude oil-degrading systems involves mechanisms other than the well-known fumarate-addition reactions.

Nonionic diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behaviour

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena

2014-09-24

The thermotropic and lyotropic liquid crystalline phase behaviour of a series of diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains (geranoyl, H-farnesoyl, and phytanoyl) has been investigated. When neat, both H-farnesoyl and phytanoyl diethanolamide form a smectic liquid crystalline structure at sub-zero temperatures. In addition, all three diethanolamides exhibit a glass transition temperature at around -73 C. Geranoyl diethanolamide forms a lamellar crystalline phase with a lattice parameter of 17.4 {angstrom} following long term storage accompanied by the loss of the glass transition. In the presence of water, H-farnesoyl and phytanoyl diethanolamide form lyotropic liquid crystalline phases, whilst geranoyl diethanolamide forms anmore » L{sub 2} phase. H-farnesoyl diethanolamide forms a fluid lamellar phase (L{sub {alpha}}) at room temperature and up to {approx} 40 C. Phytanoyl diethanolamide displays a rich mesomorphism forming the inverse diamond (Q{sub II}{sup D}) and gyroid (Q{sub II}{sup G}) bicontinuous cubic phases in addition to an L{sub {alpha}} phase.« less

End product yields from the extraruminal fermentation of various polysaccharide, protein and nucleic acid components of biofuels feedstocks.

PubMed

Weimer, Paul J

2011-02-01

"Extraruminal" fermentations employing in vitro incubation of mixed ruminal bacterial consortia, are capable of converting a complex array of biomass materials to mixtures of volatile fatty acids (VFA), methane, and carbon dioxide. Most of the potential energy in the biomass feedstock is retained in the VFA products, which are potential reactants for electrochemical conversion to hydrocarbon fuels. Quantitative data on VFA yields and proportions from biomass components are necessary for determining industrial feasibility, but such measurements have not been systematically reported. VFA yields and proportions were determined for a variety of carbohydrates, proteins and nucleic acids. Carbohydrates yielded primarily acetic and propionic acids, while proteins also yielded a more favorable product mix (longer average chain length and branched chain VFAs). Addition of certain co-substrates (e.g., glycerol) favorably improved the VFA product mix. The results have implications for hydrocarbon fuel generation from biomass materials by hybrid fermentation/chemical processes. Published by Elsevier Ltd.

Effects of a meal rich in medium-chain saturated fat on postprandial lipemia in relatives of type 2 diabetics.

PubMed

Pietraszek, Anna; Hermansen, Kjeld; Pedersen, Steen B; Langdahl, Bente L; Holst, Jens J; Gregersen, Søren

2013-01-01

Patients with type 2 diabetes and their relatives (REL) have increased risk for cardiovascular disease (CVD). Postprandial triglyceridemia (PPL), which is influenced by diet, is an independent risk factor for CVD. Little is known about the effects of medium-chain saturated fatty acids (medium-chain SFA) on PPL and gene expression in REL. The objective of this study was to test the hypothesis that medium-chain SFA cause larger PPL response in REL compared with controls (CON) and have a differential effect on circulating incretins and ghrelin and gene expression in muscle and adipose tissue in REL and CON. Seventeen REL and 17 CON received a fat-rich meal (79 energy percent from fat) based on medium-chain SFA (coconut oil). Plasma concentrations of triglycerides (TG), free-fatty acids, insulin, glucose, glucagon-like peptide-1, glucose-dependent insulintropic peptide, and ghrelin were measured before and during 240 min postprandially. Muscle and adipose tissue biopsies were taken at baseline and after the test meal. After the test meal, REL had a higher plasma TG response (P = 0.002) and a tendency toward higher insulin response (P = 0.100). A number of genes were upregulated in response to the meal rich in medium-chain SFA in CON, but not in REL. A meal high in medium-chain SFA resulted in larger PPL response in REL than in CON. It remains to be clarified whether this can be reproduced by a pure medium-chain fat (MCT) load. The meal exerted a differential effect on gene expression in muscle, but not adipose tissue, of REL compared with CON. Copyright © 2013 Elsevier Inc. All rights reserved.

Effect of medium-chain triglycerides on calbindin-D9k expression in the intestine.

PubMed

Devlin, A; Innis, S M; Wall, K; Krisinger, J

1996-05-01

These studies determined the effect of the saturated fat source in infant formula on the expression of calbindin-D9k (CaBP-9k). Piglets were fed from birth to 8 d with milk or formula containing saturated fatty acids as medium-chain triglycerides (MCT), coconut oil, palm oil (Palm 1), or synthesized triglycerides with 16:0 directed to the sn-2 position (Palm 2). Levels of intestinal CaBP-9k mRNA were significantly (P < 0.01) higher in piglets fed formula with MCT than in piglets fed the other formula or milk; and higher in piglets fed the Palm-1 than in piglets fed Palm-2 formula. This is the first evidence that MCT alter piglet intestinal CaBP-9k mRNA.

Impact of Branched-Chain Amino Acid Catabolism on Fatty Acid and Alkene Biosynthesis in Micrococcus luteus.

PubMed

Surger, Maximilian J; Angelov, Angel; Stier, Philipp; Übelacker, Maria; Liebl, Wolfgang

2018-01-01

Micrococcus luteus naturally produces alkenes, unsaturated aliphatic hydrocarbons, and represents a promising host to produce hydrocarbons as constituents of biofuels and lubricants. In this work, we identify the genes for key enzymes of the branched-chain amino acid catabolism in M. luteus , whose first metabolic steps lead also to the formation of primer molecules for branched-chain fatty acid and olefin biosynthesis, and demonstrate how these genes can be used to manipulate the production of specific olefins in this organism. We constructed mutants of several gene candidates involved in the branched-chain amino acid metabolism or its regulation and investigated the resulting changes in the cellular fatty acid and olefin profiles by GC/MS. The gene cluster encoding the components of the branched-chain α-keto acid dehydrogenase (BCKD) complex was identified by deletion and promoter exchange mutagenesis. Overexpression of the BCKD gene cluster resulted in about threefold increased olefin production whereas deletion of the cluster led to a drastic reduction in branched-chain fatty acid content and a complete loss of olefin production. The specificities of the acyl-CoA dehydrogenases of the branched amino acid degradation pathways were deduced from the fatty acid and olefin profiles of the respective deletion mutant strains. In addition, growth experiments with branched amino acids as the only nitrogen source were carried out with the mutants in order to confirm our annotations. Both the deletion mutant of the BCKD complex, responsible for the further degradation of all three branched-chain amino acids, as well as the deletion mutant of the proposed isovaleryl-CoA dehydrogenase (specific for leucine degradation) were not able to grow on leucine in contrast to the parental strain. In conclusion, our experiments allow the unambigous assignment of specific functions to the genes for key enzymes of the branched-chain amino acid metabolism of M. luteus . We also show how this knowledge can be used to engineer the isomeric composition and the chain lengths of the olefins produced by this organism.

Dissolved oxygen saturation controls PAH biodegradation in freshwater estuary sediments.

PubMed

Boyd, T J; Montgomery, M T; Steele, J K; Pohlman, J W; Reatherford, S R; Spargo, B J; Smith, D C

2005-02-01

Polycyclic aromatic hydrocarbons (PAHs) are common contaminants in terrestrial and aquatic environments and can represent a significant constituent of the carbon pool in coastal sediments. We report here the results of an 18-month seasonal study of PAH biodegradation and heterotrophic bacterial production and their controlling biogeochemical factors from 186 sediment samples taken in a tidally influenced freshwater estuary. For each sampling event, measurements were averaged from 25-45 stations covering approximately 250 km(2). There was a clear relationship between bacterial production and ambient temperature, but none between production and bottom water dissolved oxygen (DO) % saturation or PAH concentrations. In contrast with other studies, we found no effect of temperature on the biodegradation of naphthalene, phenanthrene, or fluoranthene. PAH mineralization correlated with bottom water DO saturation above 70% (r(2) > 0.99). These results suggest that the proportional utilization of PAH carbon to natural organic carbon is as much as three orders of magnitude higher during cooler months, when water temperatures are lower and DO % saturation is higher. Infusion of cooler, well-oxygenated water to the water column overlying contaminated sediments during the summer months may stimulate PAH metabolism preferentially over non-PAH organic matter.

Tidal river sediments in the Washington, D.C. area. 11. Distribution and sources of organic containmants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wade, T.L.; Velinsky, D.J.; Reinharz, E.

1994-06-01

Concentrations of aliphatic, aromatic, and chlorinated hydrocarbons were determined from 33 surface-sediment samples taken from the Tidal Basin, Washington Ship Channel, and the Anacostia and Potomac rivers in Washington, D.C. In conjunction with these samples, selected storm sewers and outfalls also were sampled to help elucidate general sources of contamination to the area. All of the sediments contained detectable concentrations of aliphatic and aromatic hydrocarbons, DDT (total dichlorodiphenytrichloroethande), DDE (dichlorodiphenyldichloroethene), DDD (dichlorodiphenyldichloroethane), PCBx (total polychlorinated biphenyls) and total chlordanes (oxy-, {alpha}-, and {gamma}-chlordane and cis + trans-nonachlor). Sediment concentrations of most contaminants were highest in the Anacostia River just downstreammore » of the Washington Navy Yard, except for total chlordane, which appeared to have upstream sources in addition to storm and combined sewer runoff. This area has the highest number of storm and combined sewer outfalls in the river. Potomac River stations had lower concentrations than other stations. Polycyclic aromatic hydrocarbons, saturated hydrocarbons, and the unresolved complex mixture (UCM) distributions reflect mixtures of combustion products and direct discharges of petroleum products. Sources of PCBs appear to be related to specific outfalls, while hydrocarbon inputs, especially PAHs, are diffuse, and may be related to street runoff. This study indicates that in large urban areas, nonpoint sources deliver substantial amounts of contaminants to ecosystems through storm and combined sewer systems, and control of these inputs must be addressed. 33 refs., 6 figs., 3 tabs.« less

C-H bond activation of hydrocarbons by an imidozirconocene complex.

PubMed

Hoyt, Helen M; Michael, Forrest E; Bergman, Robert G

2004-02-04

Monomeric imidozirconocene complexes of the type Cp2(L)Zr=NCMe3 (Cp = cyclopentadienyl, L = Lewis base) have been shown to activate the carbon-hydrogen bonds of benzene, but not the C-H bonds of saturated hydrocarbons. To our knowledge, this singularly important class of C-H activation reactions has heretofore not been observed in imidometallocene systems. The M=NR bond formed on heating the racemic ethylenebis(tetrahydro)indenyl methyl tert-butyl amide complex, however, cleanly and quantitatively activates a wide range of n-alkane, alkene, and arene C-H bonds. Mechanistic experiments support the proposal of intramolecular elimination of methane followed by a concerted addition of the hydrocarbon C-H bond. Products formed by activation of sp2 C-H bonds are generally more thermodynamically stable than those formed by activation of sp3 C-H bonds, and those resulting from reaction at primary C-H bonds are preferred over secondary sp3 C-H activation products. There is also evidence that thermodynamic selectivity among C-H bonds is sterically rather than electronically controlled.

Conserved queen pheromones in bumblebees: a reply to Amsalem et al.

PubMed

Holman, Luke; van Zweden, Jelle S; Oliveira, Ricardo C; van Oystaeyen, Annette; Wenseleers, Tom

2017-01-01

In a recent study, Amsalem, Orlova & Grozinger (2015) performed experiments with Bombus impatiens bumblebees to test the hypothesis that saturated cuticular hydrocarbons are evolutionarily conserved signals used to regulate reproductive division of labor in many Hymenopteran social insects. They concluded that the cuticular hydrocarbon pentacosane (C 25 ), previously identified as a queen pheromone in a congeneric bumblebee, does not affect worker reproduction in B. impatiens . Here we discuss some shortcomings of Amsalem et al.'s study that make its conclusions unreliable. In particular, several confounding effects may have affected the results of both experimental manipulations in the study. Additionally, the study's low sample sizes (mean n per treatment = 13.6, range: 4-23) give it low power, not 96-99% power as claimed, such that its conclusions may be false negatives. Inappropriate statistical tests were also used, and our reanalysis found that C 25 substantially reduced and delayed worker egg laying in B. impatiens . We review the evidence that cuticular hydrocarbons act as queen pheromones, and offer some recommendations for future queen pheromone experiments.

Does bioavailability limit biodegradation? A comparison of hydrocarbon biodegradation and desorption rates in aged soils.

PubMed

Huesemann, Michael H; Hausmann, Tom S; Fortman, Tim J

2004-08-01

In order to determine whether bioavailability limits the biodegradability of petroleum hydrocarbons in aged soils, both the biodegradation and abiotic desorption rates of PAHs and n-alkanes were measured at various time points in six different aged soils undergoing slurry bioremediation treatment. Alkane biodegradation rates were always much greater than the respective desorption rates, indicating that these saturated hydrocarbons apparently do not need to be dissolved into the aqueous phase prior to metabolism by soil microorganisms. The biodegradation of PAHs was generally not mass-transfer rate limited during the initial phase, while it often became so at the end of the treatment period when biodegradation rates equaled abiotic desorption rates. However, in all cases where PAH biodegradation was not observed or PAH removal temporarily stalled, bioavailability limitations were not deemed responsible for this recalcitrance since these PAHs desorbed rapidly from the soil into the aqueous phase. Consequently, aged PAHs that are often thought to be recalcitrant due to bioavailability limitations may not be so and therefore may pose a greater risk to environmental receptors than previously thought.

Does Bioavailability Limit Biodegradability? A Comparison of Hydrocarbon Biodegradation and Desorption Rates in Aged Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huesemann, Michael H.; Hausmann, Tom S.; Fortman, Timothy J.

In order to determine whether bioavailability limits the biodegradability of petroleum hydrocarbons in aged soils, both the biodegradation and abiotic desorption rates of PAHs and n-alkanes were measured at various time points in six different aged soils undergoing slurry bioremediation treatment. Alkane biodegradation rates were always much greater than the respective desorption rates, indicating that these saturated hydrocarbons do not need to be transferred into the aqueous phase prior to metabolism by soil microorganisms. The biodegradation of PAHs was generally not mass-transfer rate limited during the initial phase, while it often became so at the end of the treatment periodmore » when biodegradation rates equaled abiotic desorption rates. However, in all cases where PAH biodegradation was not observed or PAH removal temporarily stalled, bioavailability limitations were not deemed responsible for this recalcitrance since these PAHs desorbed rapidly from the soil into the aqueous phase. Consequently, aged PAHs that are often thought to be recalcitrant due to bioavailability limitations may not be so and therefore may pose a greater risk to environmental receptors than previously thought.« less

Accumulation of medium-chain, saturated fatty acyl moieties in seed oils of transgenic Camelina sativa.

PubMed

Hu, Zhaohui; Wu, Qian; Dalal, Jyoti; Vasani, Naresh; Lopez, Harry O; Sederoff, Heike W; Qu, Rongda

2017-01-01

With its high seed oil content, the mustard family plant Camelina sativa has gained attention as a potential biofuel source. As a bioenergy crop, camelina has many advantages. It grows on marginal land with low demand for water and fertilizer, has a relatively short life cycle, and is stress tolerant. As most other crop seed oils, camelina seed triacylglycerols (TAGs) consist of mostly long, unsaturated fatty acyl moieties, which is not desirable for biofuel processing. In our efforts to produce shorter, saturated chain fatty acyl moieties in camelina seed oil for conversion to jet fuel, a 12:0-acyl-carrier thioesterase gene, UcFATB1, from California bay (Umbellularia californica Nutt.) was expressed in camelina seeds. Up to 40% of short chain laurate (C12:0) and myristate (C14:0) were present in TAGs of the seed oil of the transgenics. The total oil content and germination rate of the transgenic seeds were not affected. Analysis of positions of these two fatty acyl moieties in TAGs indicated that they were present at the sn-1 and sn-3 positions, but not sn-2, on the TAGs. Suppression of the camelina KASII genes by RNAi constructs led to higher accumulation of palmitate (C16:0), from 7.5% up to 28.5%, and further reduction of longer, unsaturated fatty acids in seed TAGs. Co-transformation of camelina with both constructs resulted in enhanced accumulation of all three medium-chain, saturated fatty acids in camelina seed oils. Our results show that a California bay gene can be successfully used to modify the oil composition in camelina seed and present a new biological alternative for jet fuel production.

Accumulation of medium-chain, saturated fatty acyl moieties in seed oils of transgenic Camelina sativa

PubMed Central

Dalal, Jyoti; Vasani, Naresh; Lopez, Harry O.; Sederoff, Heike W.

2017-01-01

With its high seed oil content, the mustard family plant Camelina sativa has gained attention as a potential biofuel source. As a bioenergy crop, camelina has many advantages. It grows on marginal land with low demand for water and fertilizer, has a relatively short life cycle, and is stress tolerant. As most other crop seed oils, camelina seed triacylglycerols (TAGs) consist of mostly long, unsaturated fatty acyl moieties, which is not desirable for biofuel processing. In our efforts to produce shorter, saturated chain fatty acyl moieties in camelina seed oil for conversion to jet fuel, a 12:0-acyl-carrier thioesterase gene, UcFATB1, from California bay (Umbellularia californica Nutt.) was expressed in camelina seeds. Up to 40% of short chain laurate (C12:0) and myristate (C14:0) were present in TAGs of the seed oil of the transgenics. The total oil content and germination rate of the transgenic seeds were not affected. Analysis of positions of these two fatty acyl moieties in TAGs indicated that they were present at the sn-1 and sn-3 positions, but not sn-2, on the TAGs. Suppression of the camelina KASII genes by RNAi constructs led to higher accumulation of palmitate (C16:0), from 7.5% up to 28.5%, and further reduction of longer, unsaturated fatty acids in seed TAGs. Co-transformation of camelina with both constructs resulted in enhanced accumulation of all three medium-chain, saturated fatty acids in camelina seed oils. Our results show that a California bay gene can be successfully used to modify the oil composition in camelina seed and present a new biological alternative for jet fuel production. PMID:28212406

Composition of plasma and atheromatous plaque among coronary artery disease subjects consuming coconut oil or sunflower oil as the cooking medium.

PubMed

Palazhy, Sabitha; Kamath, Prakash; Rajesh, P C; Vaidyanathan, Kannan; Nair, Shiv K; Vasudevan, D M

2012-12-01

Coconut oil, which is rich in medium-chain saturated fatty acids, is the principal cooking medium of the people of Kerala, India. Replacement of saturated fat with polyunsaturated fat is effective in reducing serum cholesterol levels. However, the effect of substituting coconut oil with sunflower oil on the fatty acid composition of plaque has not been thoroughly investigated. We therefore evaluated and compared the fatty acid composition of plasma and plaque among subjects consuming coconut oil or sunflower oil as the cooking medium. Endarterectomy samples and plasma samples were obtained from subjects who underwent coronary artery bypass grafts (n = 71). The subjects were grouped based on the type of oil they were using as their cooking medium (coconut oil or sunflower oil). The fatty acid composition in the plaques and the plasma was determined by HPLC and the data were analyzed statistically. Sunflower oil consumers had elevated concentrations of linoleic acid (p = 0.001) in plasma, while coconut oil users had higher myristic acid levels (p = 0.011) in plasma. Medium-chain fatty acids did not differ significantly between the two groups in the plasma. Medium-chain fatty acids were detected in the plaques in both groups of subjects. In contrast to previous reports, long-chain saturated fatty acids dominated the lipid content of plaque in this population, and the fatty acid composition of plaque was not significantly different between the two groups. No correlation between fatty acids of plasma and plaque was observed in either group. A change in cooking medium, although it altered the plasma fatty acid composition, was not reflected in the plaque composition.

DFT Modeling of Cross-Linked Polyethylene: Role of Gold Atoms and Dispersion Interactions.

PubMed

Blaško, Martin; Mach, Pavel; Antušek, Andrej; Urban, Miroslav

2018-02-08

Using DFT modeling, we analyze the concerted action of gold atoms and dispersion interactions in cross-linked polyethylene. Our model consists of two oligomer chains (PEn) with 7, 11, 15, 19, or 23 carbon atoms in each oligomer cross-linked with one to three Au atoms through C-Au-C bonds. In structures with a single gold atom the C-Au-C bond is located in the central position of the oligomer. Binding energies (BEs) with respect to two oligomer radical fragments and Au are as high as 362-489 kJ/mol depending on the length of the oligomer chain. When the dispersion contribution in PEn-Au-PEn oligomers is omitted, BE is almost independent of the number of carbon atoms, lying between 293 and 296 kJ/mol. The dispersion energy contributions to BEs in PEn-Au-PEn rise nearly linearly with the number of carbon atoms in the PEn chain. The carbon-carbon distance in the C-Au-C moiety is around 4.1 Å, similar to the bond distance between saturated closed shell chains in the polyethylene crystal. BEs of pure saturated closed shell PEn-PEn oligomers are 51-187 kJ/mol. Both Au atoms and dispersion interactions contribute considerably to the creation of nearly parallel chains of oligomers with reasonably high binding energies.

Modern Processes of Hydrocarbon Migration and Re-Formation of Oil and Gas Fields (Based on the Results of Monitoring and Geochemical Studies)

NASA Astrophysics Data System (ADS)

Plotnikova, Irina; Salakhidinova, Gulmira; Nosova, Fidania; Pronin, Nikita; Ostroukhov, Sergey

2015-04-01

Special geochemical studies of oils allowed to allocate a movable migration component of oils in the industrial oil deposits. In the field the migration component of oils varies in different parts of the field. The largest percentage of the light migration component (gas condensate of the oil) was detected in the central part of the Kama-Kinel troughs system. Monitoring of the composition of water, oil and gas (condensate light oil component) in the sedimentary cover and ni crystalline basement led to the conclusion of modern migration of hydrocarbons in sedimentary cover. This proves the existence of the modern processes of formation and reformation of oil and gas fields. This presentation is dedicated to the problem of definition of geochemical criteria of selection of hydrocarbons deposit reformation zone in the sample wells of Minibaevskaya area of Romashkinskoye field. While carrying out this work we examined 11 samples of oil from the Upper Devonian Pashiysky horizon. Four oil samples were collected from wells reckoned among the "anomalous" zones that were marked out according to the results of geophysical, oil field and geological research. Geochemical studies of oils were conducted in the laboratory of geochemistry of the Kazan (Volga-region) Federal University. The wells where the signs of hydrocarbons influx from the deep zones of the crust were recorded are considered to be "anomalous". A number of scientists connect this fact to the hypothesis about periodic influx of deep hydrocarbons to the oil deposits of Romashkinskoye field. Other researchers believe that the source rocks of the adjacent valleys sedimentary cover generate gases when entering the main zone of gas formation, which then migrate up the section and passing through the previously formed deposits of oil, change and "lighten" their composition. Regardless of the point of view on the source of the hydrocarbons, the study of the process of deposits refilling with light hydrocarbons is an important fundamental task of exceptional practical importance. The reservoir water monitoring has been conducted in five wells that have penetrated the water-saturated, loosely aggregated zones of the South Tatarstan Arch's basement. The long-term testing resulted in the production of reservoir water from the basement. The sedimentary cover in these wells is blocked by the column, which prevents water cross-flowing from the sedimentary cover. The observations have shown that the levels, gas saturation, mineralisation, density, and composition of reservoir waters from the loosely aggregated zones of the basement change with time. The varying characteristics of the water include its component composition, redox potential, and amount of chlorine and some other components and trace elements. Compositional changes in gases of the loosely aggregated zones of the basement, variations in the gas saturation of reservoir waters and of their composition, the decreasing density of oil in the sedimentary cover, - all result from one cause. This cause is the movement of fluids (solutions and gases dissolved in them) through the loosely aggregated zones and faults of the Earth's crust and the sedimentary cover. The fluids mainly move vertically in an upward direction, although their migration through subhorizontal, loosely aggregated zones of the crystalline basement is also possible. Fluid migration still takes place in the Earth's crust of ancient platforms. This phenomenon indicates that some portions of the platforms - primarily, their margins - periodically resume tectonic activities. The fluid dynamic activity of the crust define the processes in the sedimentary cover. It affects the development of the sedimentary basin during the sedimentation period, and the formation of mineral deposits. The monitoring of the present-day movement of fluid systems in the loosely aggregated zones of the basement will permit the more detailed study of the present-day fluid regime in the upper portion of the Earth's crust and the sedimentary cover.

Endophytic Bacteria Associated with Hieracium piloselloides: Their Potential for Hydrocarbon-Utilizing and Plant Growth-Promotion.

PubMed

Pawlik, Małgorzata; Piotrowska-Seget, Zofia

2015-01-01

The aim of this study was to assess the potential of 18 crude-oil-degrading endophytic bacteria for removal of hydrocarbons and promotion of plant growth. Strains were isolated from Hieracium piloselloides (tall hawkweed), which grows in soil heavily polluted with petroleum hydrocarbons. Bacteria from the genus Pseudomonas were abundant among the isolates. The potential for hydrocarbon degradation was evaluated by polymerase chain reaction (PCR) analyses of the genes alkB, alkH, C23O, P450, and pah. It was found that 88.89% of the endophytic bacteria contained gene-encoding polycyclic aromatic hydrocarbon (PAH) initial dioxygenase, 61% possessed the 2,3-catechol dioxygenase gene, and 39% of strains that were tested had the cytochrome P-450 hydroxylase gene. All isolates were capable of producing indole-3-acetic acid (1.8-76.4 μg/ml). Only 17% of them were able to produce siderophores, excrete cellulase, and solubilize phosphate. Hydrogen cyanide synthesis occurred in 33% of endophytic bacteria. The 1-aminocyclopropane-1-carboxylate deaminase activity in isolates that were screened was in the range of 2.6 to 74.1 μmol α-ketobutyrate/mg/h. This feature of the bacteria indicated that isolates may enhance the phytoremediation process. Data suggest that crude-oil-degrading endophytic bacteria possess potential to be promising candidates for enhancement of phytoremediation of hydrocarbon-contaminated soil. Further evaluation of these bacteria is needed in order to assess the role played in the degradation of petroleum hydrocarbons.

Bioaccessible Porosity: A new approach to assess residual contamination after bioremediation of hydrophobic organic compounds in sub-surface microporous environments

NASA Astrophysics Data System (ADS)

Akbari, A.; Ghoshal, S.

2016-12-01

We define a new parameter, "bioaccessible porosity", the fraction of aggregate volume accessible to soil bacteria, towards a priori assessment of hydrocarbon bioremediation end points. Microbial uptake of poorly soluble hydrocarbons occurs through direct uptake or micellar solubilzation/emulsification associated with biosurfactant production, and requires close proximity of bacteria and hydrocarbon phase. In subsurface microporous environments, bioremediation rates are attenuated when residual hydrophobic contamination is entrapped in sterically restrictive environments which is not accessible to soil bacteria. This study presents new approaches for characterization of the microstructure of porous media and as well, the ability of indigenous hydrocarbon degraders to access to a range of pore sizes. Bacterial access to poorly soluble hydrocarbons in soil micro pores were simulated with bioreactors with membranes with different pore sizes containing the hydrocarbon degrading bacteria, Dietzia maris. D. maris is Gram-positive, and nonmotile that we isolated as the major hydrocarbon degrader from a fine-grained, weathered, hydrocarbon-contaminated site soil. Under nutritional stress, planktonic D. maris cells were aggregated and accessed 5 µm but not 3 µm and smaller pores. However, when hexadecane was available at the pore mouth, D. maris colonized the pore mouth, and accessed pores as small as 0.4 µm. This suggests bacterial accessibility to different pore sizes is regulated by nutritional conditions. A combination of X-ray micro-CT scanning, gas adsorption and mercury intrusion porosimetry was used to characterize the range of pore sizes of soil aggregates. In case of the studied contaminated soil, the bioaccessible porosity were determined as 25% , 27% and 29% (assuming 4, 1, 0.4 µm respectively as accessibility criteria), and about 2.7% of aggregate volume was attributed to 0.006-0.4 µm pores. The 2% aggregate volume at an assumed saturation of 10% could accommodate 1000 mg/ kg soil of oil. The remediation endpoint after extended biotreatment was at similar order of magnitude of 600 mg/kg. The approach introduced here could be used for qualitative assessment of attainable bioremediation endpoint in soils with different microstructure and hydrocarbon degrading bacterial community.

Gas hydrate characterization from a 3D seismic dataset in the deepwater eastern Gulf of Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnell, Daniel; Haneberg, William C.

Principal component analysis of spectral decomposition results combined with amplitude and frequency seismic attributes derived from 3D seismic data are used for the identification and characterization of gas hydrate deposits in the deepwater eastern Gulf of Mexico. In the central deepwater Gulf of Mexico (GoM), logging while drilling LWD data provided insight to the amplitude response of gas hydrate saturation in sands, which could be used to characterize complex gas hydrate deposits in other sandy deposits. In this study, a large 3D seismic data set from equivalent and distal Plio Pleistocene sandy channel deposits in the deepwater eastern Gulf ofmore » Mexico is screened for direct hydrocarbon indicators for gas hydrate saturated sands.« less

Cobalt carbide nanoprisms for direct production of lower olefins from syngas

NASA Astrophysics Data System (ADS)

Zhong, Liangshu; Yu, Fei; An, Yunlei; Zhao, Yonghui; Sun, Yuhan; Li, Zhengjia; Lin, Tiejun; Lin, Yanjun; Qi, Xingzhen; Dai, Yuanyuan; Gu, Lin; Hu, Jinsong; Jin, Shifeng; Shen, Qun; Wang, Hui

2016-10-01

Lower olefins—generally referring to ethylene, propylene and butylene—are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The ‘Fischer-Tropsch to olefins’ (FTO) process has long offered a way of producing lower olefins directly from syngas—a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

Time Course-Dependent Methanogenic Crude Oil Biodegradation: Dynamics of Fumarate Addition Metabolites, Biodegradative Genes, and Microbial Community Composition

PubMed Central

Toth, Courtney R. A.; Gieg, Lisa M.

2018-01-01

Biodegradation of crude oil in subsurface petroleum reservoirs has adversely impacted most of the world's oil, converting this resource to heavier forms that are of lower quality and more challenging to recover. Oil degradation in deep reservoir environments has been attributed to methanogenesis over geological time, yet our understanding of the processes and organisms mediating oil transformation in the absence of electron acceptors remains incomplete. Here, we sought to identify hydrocarbon activation mechanisms and reservoir-associated microorganisms that may have helped shape the formation of biodegraded oil by incubating oilfield produced water in the presence of light (°API = 32) or heavy crude oil (°API = 16). Over the course of 17 months, we conducted routine analytical (GC, GC-MS) and molecular (PCR/qPCR of assA and bssA genes, 16S rRNA gene sequencing) surveys to assess microbial community composition and activity changes over time. Over the incubation period, we detected the formation of transient hydrocarbon metabolites indicative of alkane and alkylbenzene addition to fumarate, corresponding with increases in methane production and fumarate addition gene abundance. Chemical and gene-based evidence of hydrocarbon biodegradation under methanogenic conditions was supported by the enrichment of hydrocarbon fermenters known to catalyze fumarate addition reactions (e.g., Desulfotomaculum, Smithella), along with syntrophic bacteria (Syntrophus), methanogenic archaea, and several candidate phyla (e.g., “Atribacteria”, “Cloacimonetes”). Our results reveal that fumarate addition is a possible mechanism for catalyzing the methanogenic biodegradation of susceptible saturates and aromatic hydrocarbons in crude oil, and we propose the roles of community members and candidate phyla in our cultures that may be involved in hydrocarbon transformation to methane in crude oil systems. PMID:29354103

Oxidation of aliphatic, branched chain, and aromatic hydrocarbons by Nocardia cyriacigeorgica isolated from oil-polluted sand samples collected in the Saudi Arabian Desert.

PubMed

Le, Thi Nhi-Cong; Mikolasch, Annett; Awe, Susanne; Sheikhany, Halah; Klenk, Hans-Peter; Schauer, Frieder

2010-06-01

A soil bacterium isolated from oil-polluted sand samples collected in the Saudi Arabian Desert has been determined as Nocardia cyriacigeorgica, which has a high capacity of degrading and utilizing a broad range of hydrocarbons. The metabolic pathways of three classes of hydrocarbons were elucidated by identifying metabolites in cell-free extracts analyzed by GC/MS and HPLC/UV-Vis in comparison with standard compounds. During tetradecane oxidation, tetradecanol; tetradecanoic acid; dodecanoic acid; decanoic acid could be found as metabolites, indicating a monoterminal degradation pathway of n -alkanes. The oxidation of pristane resulted in the presence of pristanoic acid; 2-methylglutaric acid; 4,8-dimethylnonanoic acid; and 2,6-dimethylheptanoic acid, which give rise to a possible mono- and di-terminal oxidation. In case of sec -octylbenzene, eight metabolites were detected including 5-phenylhexanoic acid; 3-phenylbutyric acid; 2-phenylpropionic acid; beta -methylcinnamic acid; acetophenone; beta -hydroxy acetophenone; 2,3-dihydroxy benzoic acid and succinic acid. From these intermediates a new degradation pathway for sec -octylbenzene was investigated. Our results indicate that N. cyriacigeorgica has the ability to degrade aliphatic and branched chain alkanes as well as alkylbenzene effectively and, therefore, N. cyriacigeorgica is probably a suitable bacterium for biodegradation of oil or petroleum products in contaminated soils. ((c) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim).

Sites of intermolecular crosslinking of fatty acyl chains in phospholipids carrying a photoactivable carbene precursor

PubMed Central

Gupta, Chhitar M.; Costello, Catherine E.; Khorana, H. Gobind

1979-01-01

Sonicated vesicles of 1-fatty acyl-2-ω-(2-diazo-3,3,3-trifluoropropionoxy) fatty acyl sn-glycero-3-phosphoryl-cholines were shown recently to form intermolecular crosslinks by insertion of the photogenerated carbene into a C—H bond of a neighboring hydrocarbon chain. We now report that photolysis of multilamellar dispersions gives a second series of products in which carbene insertion is accompanied by elimination of a molecule of hydrogen fluoride. The sites of crosslinking in the latter compounds have been studied by mass spectrometry using phospholipids with varying chain lengths of the fatty acyl groups carrying the carbene precursor. The patterns observed show that the point of maximum crosslinking is consistent with the recent conclusion that in phospholipids the sn-2 fatty acyl chain trails the sn-1 chain by 2-4 atoms. Images PMID:16592675

Use of microresistivity from the dipmeter to improve formation evaluation in thin sands, Northeast Kalimantan, Indonesia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sallee, J.E.; Wood, B.R.

1984-09-01

Estimation of reserves in lenticular reservoirs consisting of many thin-bedded sand/shale sequences is complicated by an overly pessimistic evaluation of sand count and hydrocarbon in place when conventional log interpretation techniques are used. It is probable that thin clean sand lenses have connected permeability. Their contribution to production should be considered in the estimation of reserves. An approach has been devised to improve the evaluation of thin clean sands by introducing accurate bed boundaries between sand and shale laminae as identified clearly on the dipmeter microresistivity curve processing presentation (GEODIP). Dipmeter data are integrated into conventional computer log analyses tomore » yield more realistic estimates of porosity and hydrocarbon saturation throughout the reservoir. The method and the results attained to date are described.« less

Novel hydrocarbon monooxygenase genes in the metatranscriptome of a natural deep-sea hydrocarbon plume.

PubMed

Li, Meng; Jain, Sunit; Baker, Brett J; Taylor, Chris; Dick, Gregory J

2014-01-01

Particulate membrane-associated hydrocarbon monooxygenases (pHMOs) are critical components of the aerobic degradation pathway for low molecular weight hydrocarbons, including the potent greenhouse gas methane. Here, we analysed pHMO gene diversity in metagenomes and metatranscriptomes of hydrocarbon-rich hydrothermal plumes in the Guaymas Basin (GB) and nearby background waters in the deep Gulf of California. Seven distinct phylogenetic groups of pHMO were present and transcriptionally active in both plume and background waters, including several that are undetectable with currently available polymerase chain reaction (PCR) primers. The seven groups of pHMOs included those related to a putative ethane oxidizing Methylococcaceae-like group, a group of the SAR324 Deltaproteobacteria, three deep-sea clades (Deep sea-1/symbiont-like, Deep sea-2/PS-80 and Deep sea-3/OPU3) within gammaproteobacterial methanotrophs, one clade related to Group Z and one unknown group. Differential abundance of pHMO gene transcripts in plume and background suggests niche differentiation between groups. Corresponding 16S rRNA genes reflected similar phylogenetic and transcriptomic abundance trends. The novelty of transcriptionally active pHMOs we recovered from a hydrocarbon-rich hydrothermal plume suggests there are significant gaps in our knowledge of the diversity and function of these enzymes in the environment. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

The Separation and Identification of Straight Chain Hydrocarbons: An Experiment Using Gas-Liquid Chromatography.

ERIC Educational Resources Information Center

Benson, G. A.

1982-01-01

An experiment using gas-liquid chromatography is discussed, introducing the student to concept of dead volume and its measurement, idea and use of an internal reference compound, and to linear relationship existing between measurements of a separation on two different stationary phases. (Author/SK)

A liposomal model that mimics the cutaneous production of vitamin D3. Studies of the mechanism of the membrane-enhanced thermal isomerization of previtamin D3 to vitamin D3

NASA Technical Reports Server (NTRS)

Tian, X. Q.; Holick, M. F.

1999-01-01

We reported previously that the rate of previtamin D3 (preD3) <==> vitamin D3 isomerization was enhanced by about 10 times in the skin compared with that in organic solvents. To elucidate the mechanism by which the rate of this reaction is enhanced in the skin, we developed a liposomal model that mimicked the enhanced isomerization of preD3 to vitamin D3 that was described in human skin. Using this model we studied the effect of changing the polarity of preD3 as well as changing the chain length and the degree of saturation of liposomal phospholipids on the kinetics of preD3 <==> vitamin D3 isomerization. We found that a decrease in the hydrophilic interaction of the preD3 with liposomal phospholipids by an esterification of the 3beta-hydroxy of preD3 (previtamin D3-3beta-acetate) reduced the rate of the isomerization by 67%. The addition of a hydroxyl on C-25 of the hydrophobic side chain (25-hydroxyprevitamin D3), which decreased the hydrophobic interaction of preD3 with the phospholipids, reduced the rate by 87%. In contrast, in an isotropic n-hexane solution, there was little difference among the rates of the conversion of preD3, its 3beta-acetate, and 25-hydroxy derivatives to their corresponding vitamin D3 compounds. We also determined rate constants (k) of preD3 <==> vitamin D3 isomerization in liposomes containing phosphatidylcholines with different carbon chain lengths. The rates of the reaction were found to be enhanced as the number of carbons (Cn) in the hydrocarbon chain of the phospholipids increased from 10 to 18. In conclusion, these results support our hypothesis that amphipathic interactions between preD3 and membrane phospholipids stabilize preD3 in its "cholesterol like" cZc-conformer, the only conformer of preD3 that can convert to vitamin D3. The stronger these interactions were, the more preD3 was likely in its cZc conformation at any moment and the faster was the rate of its conversion to vitamin D3.

Structural investigation of nonpolar sulfur cross-linked macromolecules in petroleum

NASA Astrophysics Data System (ADS)

Adam, P.; Schmid, J. C.; Mycke, B.; Strazielle, C.; Connan, J.; Huc, A.; Riva, A.; Albrecht, P.

1993-07-01

A novel hexane-soluble nonpolar macromolecular fraction (NPMF) has been found to occur in substantial amounts (up to 32%) in sulfur-rich crude oils and a rock extract. It is highly aliphatic and has a molecular weight culminating at several thousand mass units, as proven by spectroscopic and molecular weight studies. C-S bond hydrogenolysis of NPMF with Raney nickel as a catalyst yields high proportions of aliphatic hydrocarbons in which long linear, acyclic polyisoprenoid and carotenoid chains usually predominate (except in one case) over polycyclic structures, such as steroids and hopanoids. Hence, NPMF consists mainly of macromolecules composed of low molecular weight hydrocarbon subunits cross-linked with sulfide bridges. Use of deuterated Raney nickel indicated in one case (Rozel Point oil) that the long chains and some hopanoids are multiattached to the macromolecular network, whereas other structural subunits, such as steroids or gammacerane, are essentially monoattached. Detailed structural determinations of the hydrocarbon "building blocks" of NPMF give information on their origin and the mode of formation of these macromolecules in the subsurface. Indeed, most of the building blocks can be related to algal (e.g., long linear chains, steroids, β-carotene, and related carotenoids) or bacterial (e.g., acyclic and monocyclic carotenoids, long-chain acyclic isoprenoids) precursors which essentially exist in living organisms as monounsaturated or polyunsaturated species or are easily transformed into such species by diagenetic processes (e.g., steroids). It appears that these alkenes or polyenes become selectively trapped into a macromolecular network by reaction with inorganic sulfur species produced by bacteria in a kind of natural, low-temperature, vulcanization process. This process could start at early diagenesis already in the water column or eventually continue in the bottom sediment. Although its exact nature is yet unknown, it seems likely that the cross-linking reaction can be initiated by the cleavage of sulfur species in a radical type mechanism. The alkanes formed upon desulfurization of NPMF usually represent much higher amounts than the free alkanes of the samples and show a dramatically different composition. They may deliver very useful, complementary information in studies related to source and palaeoenvironment.

Membrane consisting of polyquaternary amine ion exchange polymer network interpenetrating the chains of thermoplastic matrix polymer

NASA Technical Reports Server (NTRS)

Rembaum, A.; Wallace, C. J. (Inventor)

1978-01-01

An ion exchange membrane was formed from a solution containing dissolved matrix polymer and a set of monomers which are capable of reacting to form a polyquaternary ion exchange material; for example vinyl pyride and a dihalo hydrocarbon. After casting solution and evaporation of the volatile component's, a relatively strong ion exchange membrane was obtained which is capable of removing anions, such as nitrate or chromate from water. The ion exchange polymer forms an interpenetrating network with the chains of the matrix polymer.

Frustrated magnetism in the spin–chain metal Yb 2Fe 12P 7

DOE PAGES

Baumbach, Ryan E.; Hamlin, James J.; Janoschek, Marc; ...

2016-01-08

Here, magnetization measurements for magnetic fieldsmore » $${{\\mu}_{0}}H$$ up to 60 T are reported for the noncentrosymmetric spin–chain metal Yb 2Fe 12P 7. These measurements reveal behavior that is consistent with Ising-like spin chain magnetism that produces pronounced spin degeneracy. In particular, we find that although a Brillouin field dependence is observed in M( H) for $$H\\bot ~c$$ with a saturation moment that is close to the expected value for free ions of Yb 3+, non-Brillouin-like behavior is seen for $$H~\\parallel ~c$$ with an initial saturation moment that is nearly half the free ion value. In addition, hysteretic behavior that extends above the ordering temperature $${{T}_{\\text{M}}}$$ is seen for $$H~\\parallel ~c$$ but not for $$H~\\bot ~c$$ , suggesting out-of-equilibrium physics. This point of view is strengthened by the observation of a spin reconfiguration in the ordered state for $$H~\\parallel ~c$$ which is only seen for $$T\\leqslant {{T}_{\\text{M}}}$$ and after polarizing the spins. Together with the heat capacity data, these results suggest that the anomalous low temperature phenomena that were previously reported are driven by spin degeneracy that is related to the Ising-like one dimensional chain-like configuration of the Yb ions.« less

Effective S =2 antiferromagnetic spin chain in the salt (o -MePy-V)FeCl4

NASA Astrophysics Data System (ADS)

Iwasaki, Y.; Kida, T.; Hagiwara, M.; Kawakami, T.; Hosokoshi, Y.; Tamekuni, Y.; Yamaguchi, H.

2018-02-01

We present a model compound for the S =2 antiferromagnetic (AF) spin chain composed of the salt (o -MePy-V ) FeCl4 . Ab initio molecular-orbital calculations indicate the formation of a partially stacked two-dimensional (2D) spin model comprising five types of exchange interactions between S =1 /2 and S =5 /2 spins, which locate on verdazyl radical and Fe ion, respectively. The magnetic properties of the synthesized crystals indicate that the dominant interaction between the S =1 /2 and S =5 /2 spins stabilizes an S =2 spin in the low-temperature region, and an effective S =2 AF chain is formed for T ≪10 K and H <4 T. We explain the magnetization curve and electron-spin-resonance modes quantitatively based on the S =2 AF chain. At higher fields above quantitatively 4 T, the magnetization curve assumes two-thirds of the full saturation value for fields between 4 and 20 T, and approaches saturation at ˜40 T. The spin model in the high-field region can be considered as a quasi-2D S =1 /2 honeycomb lattice under an effective internal field caused by the fully polarized S =5 /2 spin.

Comparison of the mopping ability of chemically modified and unmodified biological wastes on crude oil and its lower fractions.

PubMed

Nduka, John Kanayochukwu; Ezenweke, Linus Obi; Ezenwa, Emmanuel Tagbo

2008-11-01

Activated and unactivated powders of goat hair and coir (coconut husk) separated into two particle sizes were used to mop up spills of crude oil, diesel, kerosene and petrol. It was observed that the materials (sorbents) mopped up appreciable volumes of the hydrocarbon liquids (sorbates) within 90 min of contact. Activation, particle size of sorbents and molecular weight (chain length) of sorbates (hydrocarbon) are major determining factors. Carbonization and particle size enhanced the mopping ability as follows--carbonized 325 microm > uncarbonized 325 microm > carbonized 625 microm > uncarbonized 625 microm, thus activated sorbents with large surface area (small particle size) mopped more hydrocarbons than unactivated of the same particle size. The sorbates were mopped in the order--crude oil > diesel > kerosene > petrol. It was further observed that goat hair (keratin protein) with oleophilic and aquaphobic properties adsorbed more of all the hydrocarbons than coir at all sizes and treatment. Large quantities of the mopped oils were recovered by mere pressing while the waste sorbents with 0.5-2.0% leachable residual oil could be utilized as alternative to fire wood.

Prebiotic hydrocarbon synthesis in impacting reduced astrophysical icy mixtures

DOE PAGES

Koziol, Lucas; Goldman, Nir

2015-04-21

We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extendedmore » structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Lastly, our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.« less

Prebiotic hydrocarbon synthesis in impacting reduced astrophysical icy mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koziol, Lucas; Goldman, Nir

We present results of prebiotic organic synthesis in shock-compressed reducing mixtures of simple ices from quantum molecular dynamics simulations extended to close to chemical equilibrium timescales. Given the relative abundance of carbon in reduced forms in astrophysical ices as well as the tendency of these mixtures to form complex hydrocarbons under the presence of external stimuli, it is possible that cometary impacts on a planetary surface could have yielded a larger array of prebiotic organic compounds than previously investigated. We find that the high pressures and temperatures due to shock compression yield a large assortment of carbon- and nitrogen-bonded extendedmore » structures that are highly reactive with short molecular lifetimes. Expansion and cooling causes these materials to break apart and form a wide variety of stable, potentially life-building compounds, including long-chain linear and branched hydrocarbons, large heterocyclic compounds, and a variety of different amines and exotic amino acids. Lastly, our results help provide a bottom-up understanding of hydrocarbon impact synthesis on the early Earth and its role in producing life-building molecules from simple starting materials.« less

The aliphatic hydrocarbon distributions of terrestrial plants around an alpine lake: a pilot study from Lake Ximencuo, Eastern Qinghai-Tibet Plateau

NASA Astrophysics Data System (ADS)

Pu, Yang; Jia, Jihong; Cao, Jicheng

2017-12-01

As part of an investigation of the sources of aliphatic hydrocarbons to the sediments of alpine Lake Ximencuo, leaves of the eight dominant vascular plants were collected and their hydrocarbon contents were analyzed. A series of unsaturated aliphatic hydrocarbons were identified in the plant leaves; in particular, Festuca sp. contain a series of n-alkadienes that have rarely been reported in previous studies. The comparison of n-alkane proxies (ACL 27-33, ACL T, P aq, and CPI) and δ13Corg among plant leaves, surface soils, and lake sediments suggests that organic proxies have been altered to varying degrees during the transport and burial process of organic materials. It is believed that microbial reworking and source changes have great impacts on organic proxies in the alpine lake system. In addition, the cluster analysis for plant leaves depending on n-alkane compositions and the ACL T proxy generates similar results. Accordingly, we postulate that the average chain length of plant waxes might be a potential indicator of plant classification in regions such as the Qinghai-Tibet Plateau.

Room temperature ordering of dipalmitoyl phosphatidylserine bilayers induced by short chain alcohols.

PubMed

Wachtel, E; Bach, D; Miller, I R

2013-01-01

Using differential scanning calorimetry and small and wide angle X-ray diffraction, we show that, following extended incubation at room temperature, methanol, propanol, and three of the isomers of butanol can induce ordering in dipalmitoyl phosphatidylserine (DPPS) gel phase bilayers. The organization of the bilayers in the presence of ethanol, described previously, is now observed to be a general effect of short chain alcohols. Evidence is presented for tilting of the acyl chains with respect to the bilayer normal in the presence of ethanol or propanol. However, the different chain lengths of the alcohols, and isomeric form, influence the thermal stability of the ordered gel to different extents. This behavior is unlike that of the gel state phosphatidylcholine analog which, in the presence of short chain alcohols, undergoes hydrocarbon chain interdigitation. Dipalmitoyl phosphatidylcholine added to DPPS in the presence of 20 vol% ethanol, acts to suppress the ordered gel phase. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Photochemical processes on Titan: Irradiation of mixtures of gases that simulate Titan's atmosphere

NASA Astrophysics Data System (ADS)

Tran, Buu N.; Joseph, Jeffrey C.; Force, Michael; Briggs, Robert G.; Vuitton, Veronique; Ferris, James P.

2005-09-01

Photochemical reaction pathways in Titan's atmosphere were investigated by irradiation of the individual components and the mixture containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene. The quantum yields for the loss of the reactants and the formation of products were determined. Photolysis of ethylene yields mainly saturated compounds (ethane, propane, and butane) while photolysis of acetylene yields the same saturated compounds as well as ethylene and diacetylene. Irradiation of cyanoacetylene yields mainly hydrogen cyanide and small amounts of acetonitrile. When an amount of methane corresponding to its mixing ratio on Titan was added to these mixtures the quantum yields for the loss of reactants decreased and the quantum yields for hydrocarbon formation increased indicative of a hydrogen atom abstraction from methane by the photochemically generated radicals. GC/MS analysis of the products formed by irradiation of mixtures of all these gases generated over 120 compounds which were mainly aliphatic hydrocarbons containing double and triple bonds along with much smaller amounts of aromatic compounds like benzene, toluene and phenylacetylene. The reaction pathways were investigated by the use of 13C acetylene in these gas mixtures. No polycyclic aromatic compounds were detected. Vapor pressures of these compounds under conditions present in Titan's atmosphere were calculated. The low molecular weight compounds likely to be present in the atmosphere and aerosols of Titan as a result of photochemical processes are proposed.

Bioremediation of diesel-polluted soil using biostimulation as post-treatment after oxidation with Fenton-like reagents: assays in a pilot plant.

PubMed

Silva-Castro, Gloria Andrea; Rodelas, Belén; Perucha, Carlos; Laguna, Jaime; González-López, Jesús; Calvo, Concepción

2013-02-15

The present study focuses on the remediation of diesel-polluted soil using modified Fenton treatment coupled with inorganic NPK fertilizer ("Fenton+NPK"). Studies were carried out in a pilot plant containing 1 m(3) of sandy soil contaminated with 20,000 mg kg(-1) of diesel, placed outdoors at a temperature ranging between 5 and 10 °C. Results showed that NPK-fertilizer as post-treatment stimulated culturable degrading bacteria and enhanced dehydrogenase activity. Fenton+NPK treatment increased total petroleum hydrocarbon (TPH) removal efficacy. Natural attenuation removed 49% of TPH in the surface layer, 23% of TPH in the non-saturated layer and 4% of the TPH in the saturated layer, while the percentage removed of TPH after Fenton+NPK treatment was 58%, 57% and 32% respectively. The results from our study showed that, immediately after soil contamination, occurred a specialization and differentiation of the bacterial community, but after this initial modification, no significant changes of bacterial diversity was observed under natural attenuation conditions. In contrast, when the Fenton's reagent was applied a reduction of the bacterial biodiversity was observed. However, the post-biostimulation did enhance the degrading microbiota and stimulated their degrading biological activity. In conclusion, biostimulation, as a post-treatment step in chemical oxidation, is an effective solution to remediate hydrocarbon-polluted sites. Copyright © 2012 Elsevier B.V. All rights reserved.

Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light.

PubMed

Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

2015-04-28

Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

Polycyclic aromatic hydrocarbons - Primitive pigment systems in the prebiotic environment

NASA Technical Reports Server (NTRS)

Deamer, D. W.

1992-01-01

The chemical evolution of meteoritic organics in the primitive earth is examined experimentally with attention given to the photochemical effects of hydrocarbon/water mixtures. Also addressed are the generation of amphiphilic products by photochemical reactions and the transduction of light energy into potentially useful forms. Polycyclic aromatic hydrocarbons (PAHs) absorb light and exist in carbonaceous chondrites; PAHs are therefore examined as primitive pigments by means of salt solutions with pyrene, fluoranthene, and pyrene derivatives with hexadecane. The hexadecane undergoes photochemical oxidation and yields long-chain amphiphiles with oxygen supplied by water, and acid pH shifts also occur. PAHs are also tested in lipid bilayer membranes to examine light-energy transduction. Protons are found to accumulate within the membrane-bounded volume to form proton gradients, and this reaction is theorized to be a good model of primitive photochemical reactions that related to the transduction of light energy into useable forms.

Gum and deposit formation from jet-turbine and diesel fuels at 130C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayo, F.R.; Lan, Bosco Y.

1986-01-01

The ultimate objective of this work is to devise an accelerated test to compare rates of soluble gum and deposit formation from jet-turbine and diesel fuels in storage and of hard deposits in engines. This paper describes rates of oxygen absorption and gum formation in air at 130 C. For a single fuel or hydrocarbon, the rate of gum formation is closely proportional to the oxygen absorbed, even when this rate varies with purification and additives. In general, pure hydrocarbons absorb oxygen much faster than the fuels, but the fuels and 2-ethylnaphthalene give more gum for the oxygen absorbed thanmore » the other pure hydrocarbons. Gum has two main sources; one appears to be associated with the chain termination mechanism in oxidation, the other coupling of fuel molecules in the absence of oxygen. Other possibilities are discussed.« less

Hydrocarbon contamination of coastal sediments from the Sfax area (Tunisia), Mediterranean Sea.

PubMed

Louati, A; Elleuch, B; Kallel, M; Saliot, A; Dagaut, J; Oudot, J

2001-06-01

The coastal area off the city of Sfax (730,000 inhabitants), well-known for fisheries and industrial activities, receives high inputs of organic matter mostly anthropogenic. Eighteen stations were selected in the vicinity of the direct discharge of industrial sewage effluents in the sea in order to study the spatial distribution of the organic contamination. Surface sediments sampled in the shallow shelf were analysed for hydrocarbons by Fourier transform infrared spectroscopy, gas chromatography and gas chromatography/mass spectrometry. Total hydrocarbon distributions revealed high contamination as compared to other coastal Mediterranean sites, with an average concentration of 1865 ppm/dry weight sediment. Gas chromatographic distribution patterns, values of unresolved mixture/n-alkane ratio and distributions of steranes and hopanes confirmed a petroleum contamination of the Arabian light crude oil type. Biogenic compounds were also identified with a series of short-chain carbon-numbered n-alkenes in the carbon range 16-24.

Sexual Communication in the Drosophila Genus.

PubMed

Bontonou, Gwénaëlle; Wicker-Thomas, Claude

2014-06-18

In insects, sexual behavior depends on chemical and non-chemical cues that might play an important role in sexual isolation. In this review, we present current knowledge about sexual behavior in the Drosophila genus. We describe courtship and signals involved in sexual communication, with a special focus on sex pheromones. We examine the role of cuticular hydrocarbons as sex pheromones, their implication in sexual isolation, and their evolution. Finally, we discuss the roles of male cuticular non-hydrocarbon pheromones that act after mating: cis-vaccenyl acetate, developing on its controversial role in courtship behavior and long-chain acetyldienylacetates and triacylglycerides, which act as anti-aphrodisiacs in mated females.

Experimental Assessment of Carbon Isotopes of Light Hydrocarbons under Different Redox Conditions

NASA Astrophysics Data System (ADS)

Fu, Q.; Chen, X.

2017-12-01

Hydrocarbons can be derived from a variety of carbon sources, by different processes, and under a wide range of physicochemical conditions. Other than bacterial activities facilitating biogenic hydrocarbon formation at low temperatures, decomposition of complex organic matter in sedimentary rocks at elevated temperatures produce thermogenic hydrocarbons, whereas abiogenic hydrocarbons are mainly generated through Fischer-Tropsch type synthesis with mineral catalysts. The carbon isotope has been used extensively to distinguish hydrocarbons of different origins and their formation conditions. For each type of hydrocarbons, however, environmental conditions may change reaction pathways and corresponding isotope fractionations. To better understand the variation of carbon isotopes caused by environmental variables, mineral constraints in particular, a series of laboratory experiments are conducted. In experiments where thermogenic hydrocarbons are formed, oil shale is the source material with different gypsum contents (0, 0.3, 0.5, and 1 wt.%). The abundance of generated light straight chain hydrocarbons decreases with increasing gypsum content, but their carbon isotopes become heavier. For example, the δ13C value of methane increases from -55.1‰ to -41.4‰ with gypsum varying between 0 and 1 wt.%. In similar experiments with the presence of MnO2, carbon isotope values of light alkanes are also higher, but with limited magnitudes (e.g., 3 to 4‰ for methane). In another experiment with dissolved H2 gas of 100 mmol/kg, light alkanes become depleted in 13C than experiments without H2. For example, there is a depletion of 2.7‰ for methane. The variation of carbon isotope values of light alkanes suggests the redox condition, constrained by mineral assemblage, fluid composition, and physical environment, play an important role in isotope fractionation. The pathway of hydrocarbon generation may be different under oxidized or reducing conditions. A set of experiments, in which abiogenic hydrocarbons are formed, is currently in progress. Combined together, they would facilitate our understanding of carbon isotope fractionation under geological conditions, and effective use of carbon isotopes as a diagnostic tool for hydrocarbons that are poorly understood in terms of origin and evolution.

Properties, performance and associated hazards of state-of-the-art durable water repellent (DWR) chemistry for textile finishing.

PubMed

Holmquist, H; Schellenberger, S; van der Veen, I; Peters, G M; Leonards, P E G; Cousins, I T

2016-05-01

Following the phase-out of long-chain per- and polyfluoroalkyl substances (PFASs), the textile industry had to find alternatives for side-chain fluorinated polymer based durable water repellent (DWR) chemistries that incorporated long perfluoroalkyl side chains. This phase-out and subsequent substitution with alternatives has resulted in a market where both fluorinated and non-fluorinated DWRs are available. These DWR alternatives can be divided into four broad groups that reflect their basic chemistry: side-chain fluorinated polymers, silicones, hydrocarbons and other chemistries (includes dendrimer and inorganic nanoparticle chemistries). In this critical review, the alternative DWRs are assessed with regards to their structural properties and connected performance, loss and degradation processes resulting in diffuse environmental emissions, and hazard profiles for selected emitted substances. Our review shows that there are large differences in performance between the alternative DWRs, most importantly the lack of oil repellence of non-fluorinated alternatives. It also shows that for all alternatives, impurities and/or degradation products of the DWR chemistries are diffusively emitted to the environment. Our hazard ranking suggests that hydrocarbon based DWR is the most environmentally benign, followed by silicone and side-chain fluorinated polymer-based DWR chemistries. Industrial commitments to reduce the levels of impurities in silicone based and side-chain fluorinated polymer based DWR formulations will lower the actual risks. There is a lack of information on the hazards associated with DWRs, in particular for the dendrimer and inorganic nanoparticle chemistries, and these data gaps must be filled. Until environmentally safe alternatives, which provide the required performance, are available our recommendation is to choose DWR chemistry on a case-by-case basis, always weighing the benefits connected to increased performance against the risks to the environment and human health. Copyright © 2016 Elsevier Ltd. All rights reserved.

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis.

PubMed

Goblirsch, Brandon R; Jensen, Matthew R; Mohamed, Fatuma A; Wackett, Lawrence P; Wilmot, Carrie M

2016-12-23

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety-unusual for a thiolase-are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys 143 ) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C 12 and C 14 ) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ 117 ) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Evaluation of certain food additives.

PubMed

2009-01-01

This report represents the conclusions of a Joint FAO/WHO Expert Committee convened to evaluate the safety of various food additives, including flavouring agents, with a view to recommending acceptable daily intakes (ADIs) and to preparing specifications for identity and purity. The first part of the report contains a general discussion of the principles governing the toxicological evaluation and assessment of intake of food additives (in particular, flavouring agents). A summary follows of the Committee's evaluations of technical, toxicological and intake data for certain food additives (asparaginase from Aspergillus niger expressed in A. niger, calcium lignosulfonate (40-65), ethyl lauroyl arginate, paprika extract, phospholipase C expressed in Pichia pastoris, phytosterols, phytostanols and their esters, polydimethylsiloxane, steviol glycosides and sulfites [assessment of dietary exposure]) and 10 groups of related flavouring agents (aliphatic branched-chain saturated and unsaturated alcohols, aldehydes, acids and related esters; aliphatic linear alpha,beta-unsaturated aldehydes, acids and related alcohols, acetals and esters; aliphatic secondary alcohols, ketones and related esters; alkoxy-substituted allylbenzenes present in foods and essential oils and used as flavouring agents; esters of aliphatic acyclic primary alcohols with aliphatic linear saturated carboxylic acids; furan-substituted aliphatic hydrocarbons, alcohols, aldehydes, ketones, carboxylic acids and related esters, sulfides, disulfides and ethers; miscellaneous nitrogen-containing substances; monocyclic and bicyclic secondary alcohols, ketones and related esters; hydroxy- and alkoxy-substituted benzyl derivatives; and substances structurally related to menthol). Specifications for the following food additives were revised: canthaxanthin; carob bean gum and carob bean gum (clarified); chlorophyllin copper complexes, sodium and potassium salts; Fast Green FCF; guar gum and guar gum (clarified); iron oxides; isomalt; monomagnesium phosphate; Patent Blue V; Sunset Yellow FCF; and trisodium diphosphate. Re-evaluation of flavouring agents for which estimated intake was based on anticipated poundage data was carried out for 2-isopropyl- N,2,3-trimethylbutyramide (No. 1595) and L-monomenthyl glutarate (No. 1414). Annexed to the report are tables summarizing the Committee's recommendations for intakes and toxicological evaluations of the food additives considered.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Dongwook; Vardon, Derek R.; Murali, Dheeptha

We demonstrate hydrothermal (300 degrees C, 10 MPa) catalytic conversion of real waste lipids (e.g., waste vegetable oil, sewer trap grease) to liquid hydrocarbon fuels without net need for external chemical inputs (e.g., H2 gas, methanol). A supported bimetallic catalyst (Pt-Re/C; 5 wt % of each metal) previously shown to catalyze both aqueous phase reforming of glycerol (a triacylglyceride lipid hydrolysis coproduct) to H2 gas and conversion of oleic and stearic acid, model unsaturated and saturated fatty acids, to linear alkanes was applied to process real waste lipid feedstocks in water. For reactions conducted with an initially inert headspace gasmore » (N2), waste vegetable oil (WVO) was fully converted into linear hydrocarbons (C15-C17) and other hydrolyzed byproducts within 4.5 h, and H2 gas production was observed. Addition of H2 to the initial reactor headspace accelerated conversion, but net H2 production was still observed, in agreement with results obtained for aqueous mixtures containing model fatty acids and glycerol. Conversion to liquid hydrocarbons with net H2 production was also observed for a range of other waste lipid feedstocks (animal fat residuals, sewer trap grease, dry distiller's grain oil, coffee oil residual). These findings demonstrate potential for valorization of waste lipids through conversion to hydrocarbons that are more compatible with current petroleum-based liquid fuels than the biodiesel and biogas products of conventional waste lipid processing technologies.« less

Migration kinetics of mineral oil hydrocarbons from recycled paperboard to dry food: monitoring of two real cases.

PubMed

Lorenzini, R; Biedermann, M; Grob, K; Garbini, D; Barbanera, M; Braschi, I

2013-01-01

Mineral oil hydrocarbons present in printing inks and recycled paper migrate from paper-based food packaging to foods primarily through the gas phase. Migration from two commercial products packed in recycled paperboard, i.e. muesli and egg pasta, was monitored up to the end of their shelf life (1 year) to study the influence of time, storage conditions, food packaging structure and temperature. Mineral oil saturated and aromatic hydrocarbons (MOSH and MOAH, respectively), and diisopropyl naphthalenes (DIPN) were monitored using online HPLC-GC/FID. Storage conditions were: free standing, shelved, and packed in transport boxes of corrugated board, to represent domestic, supermarket and warehouse storage, respectively. Migration to food whose packs were kept in transport boxes was the highest, especially after prolonged storage, followed by shelved and free-standing packs. Tested temperatures were representative of refrigeration, room temperature, storage in summer months and accelerated migration testing. Migration was strongly influenced by temperature: for egg pasta directly packed in paperboard, around 30 mg kg⁻¹ of MOSH migrated in 8 months at 20°C, but in only 1 week at 40°C. Muesli was contained into an internal polyethylene bag, which firstly adsorbed hydrocarbons and later released them partly towards the food. Differently, the external polypropylene bag, containing pasta and recycled paper tray, strongly limited the migration towards the atmosphere and gave rise to the highest level of food contamination. Tests at increased temperatures not only accelerated migration, but also widened the migration of hydrocarbons to higher molecular masses, highlighting thus a difficult interpretation of data from accelerated simulation.

A simple thermodynamic model useful for calculating gas solubilities in water/brine/hydrocarbon mixtures from 0 to 250 C and 1 to 150 bars

NASA Astrophysics Data System (ADS)

Perez, R. J.; Shevalier, M.; Hutcheon, I.

2004-05-01

Gas solubility is of considerable interest, not only for the theoretical understanding of vapor-liquid equilibria, but also due to extensive applications in combined geochemical, engineering, and environmental problems, such as greenhouse gas sequestration. Reliable models for gas solubility calculations in salt waters and hydrocarbons are also valuable when evaluating fluid inclusions saturated with gas components. We have modeled the solubility of methane, ethane, hydrogen, carbon dioxide, hydrogen sulfide, and five other gases in a water-brine-hydrocarbon system by solving a non-linear system of equations composed by modified Henry's Law Constants (HLC), gas fugacities, and assuming binary mixtures. HLCs are a function of pressure, temperature, brine salinity, and hydrocarbon density. Experimental data of vapor pressures and mutual solubilities of binary mixtures provide the basis for the calibration of the proposed model. It is demonstrated that, by using the Setchenow equation, only a relatively simple modification of the pure water model is required to assess the solubility of gases in brine solutions. Henry's Law constants for gases in hydrocarbons are derived using regular solution theory and Ostwald coefficients available from the literature. We present a set of two-parameter polynomial expressions, which allow simple computation and formulation of the model. Our calculations show that solubility predictions using modified HLCs are acceptable within 0 to 250 C, 1 to 150 bars, salinity up to 5 molar, and gas concentrations up to 4 molar. Our model is currently being used in the IEA Weyburn CO2 monitoring and storage project.

The Pyrolytic Profile of Lyophilized and Deep-Frozen Compact Part of the Human Bone

PubMed Central

Lodowska, Jolanta; Wolny, Daniel; Kurkiewicz, Sławomir; Węglarz, Ludmiła

2012-01-01

Background. Bone grafts are used in the treatment of nonunion of fractures, bone tumors and in arthroplasty. Tissues preserved by lyophilization or deep freezing are used as implants nowadays. Lyophilized grafts are utilized in the therapy of birth defects and bone benign tumors, while deep-frozen ones are applied in orthopedics. The aim of the study was to compare the pyrolytic pattern, as an indirect means of the analysis of organic composition of deep-frozen and lyophilized compact part of the human bone. Methods. Samples of preserved bone tissue were subjected to thermolysis and tetrahydroammonium-hydroxide- (TMAH-) associated thermochemolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS). Results. Derivatives of benzene, pyridine, pyrrole, phenol, sulfur compounds, nitriles, saturated and unsaturated aliphatic hydrocarbons, and fatty acids (C12–C20) were identified in the pyrolytic pattern. The pyrolyzates were the most abundant in derivatives of pyrrole and nitriles originated from proteins. The predominant product in pyrolytic pattern of the investigated bone was pyrrolo[1,2-α]piperazine-3,6-dione derived from collagen. The content of this compound significantly differentiated the lyophilized graft from the deep-frozen one. Oleic and palmitic acid were predominant among fatty acids of the investigated samples. The deep-frozen implants were characterized by higher percentage of long-chain fatty acids than lyophilized grafts. PMID:22619606

Contribution of gustation to the palatability of linoleic acid.

PubMed

Saitou, Katsuyoshi; Yoneda, Takeshi; Mizushige, Takafumi; Asano, Hiroki; Okamura, Maya; Matsumura, Shigenobu; Eguchi, Ai; Manabe, Yasuko; Tsuzuki, Satoshi; Inoue, Kazuo; Fushiki, Tohru

2009-01-08

We investigated the palatability of a low concentration of linoleic acid (LA) in short-term two-bottle choice tests and licking tests. To examine the contribution of gustation, mice were rendered anosmic with olfactory nerve transection surgery and test solutions were prepared using mineral oil (saturated long-chain hydrocarbon) to minimize textural effects. In the two-bottle choice tests between various pairs of different concentrations of corn oil and LA, both anosmic and the sham-operated mice constantly preferred a higher concentration of corn oil and LA. In the licking tests, the initial licking rate for 1% LA was higher than that for mineral oil in anosmic mice. In accordance with the results of the two-bottle choice test, the initial licking rate for corn oil and LA increased in a concentration-dependent manner in both anosmic and sham-operated mice in the licking test, and reached its peak at 100% corn oil and 1% LA. A preference comparison between 1% LA and 100% corn oil showed that anosmic mice preferred 1% LA over 100% corn oil. These results suggest that mice could recognize dietary fat and fatty acid solutions in the oral cavity without any olfactory or textural cues and the fatty acid recognition on their tongues might provide a pivotal cue to how dietary fat is recognized in the oral cavity.

Characterization of Cyanobacterial Hydrocarbon Composition and Distribution of Biosynthetic Pathways

PubMed Central

Coates, R. Cameron; Podell, Sheila; Korobeynikov, Anton; Lapidus, Alla; Pevzner, Pavel; Sherman, David H.; Allen, Eric E.; Gerwick, Lena; Gerwick, William H.

2014-01-01

Cyanobacteria possess the unique capacity to naturally produce hydrocarbons from fatty acids. Hydrocarbon compositions of thirty-two strains of cyanobacteria were characterized to reveal novel structural features and insights into hydrocarbon biosynthesis in cyanobacteria. This investigation revealed new double bond (2- and 3-heptadecene) and methyl group positions (3-, 4- and 5-methylheptadecane) for a variety of strains. Additionally, results from this study and literature reports indicate that hydrocarbon production is a universal phenomenon in cyanobacteria. All cyanobacteria possess the capacity to produce hydrocarbons from fatty acids yet not all accomplish this through the same metabolic pathway. One pathway comprises a two-step conversion of fatty acids first to fatty aldehydes and then alkanes that involves a fatty acyl ACP reductase (FAAR) and aldehyde deformylating oxygenase (ADO). The second involves a polyketide synthase (PKS) pathway that first elongates the acyl chain followed by decarboxylation to produce a terminal alkene (olefin synthase, OLS). Sixty-one strains possessing the FAAR/ADO pathway and twelve strains possessing the OLS pathway were newly identified through bioinformatic analyses. Strains possessing the OLS pathway formed a cohesive phylogenetic clade with the exception of three Moorea strains and Leptolyngbya sp. PCC 6406 which may have acquired the OLS pathway via horizontal gene transfer. Hydrocarbon pathways were identified in one-hundred-forty-two strains of cyanobacteria over a broad phylogenetic range and there were no instances where both the FAAR/ADO and the OLS pathways were found together in the same genome, suggesting an unknown selective pressure maintains one or the other pathway, but not both. PMID:24475038

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

NASA Technical Reports Server (NTRS)

Kumar, Nitin; Couzis, Alex; Maldarelli, Charles; Singh, Bhim S. (Technical Monitor)

2000-01-01

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid/surfaces. At a hydrophobic surface, the air/hydrophobic solid tension is low, and the solid/aqueous tension is high. A large contact angle forms as the aqueous/air tension acts together with the solid/air tension to balance the large solid/aqueous tension. The aqueous phase, instead of spreading, is held in a meniscus by the large angle. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants (i.e. amphiphiles with a hydrophobic chain of methylene groups attached to a large polar group to give aqueous solubility) do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm or polyethylene. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3)) and an extended ethoxylate (-(OCH2CH2)n-) polar group in the form of a chain with seven or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (lermed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread and can be used in microgravity. We propose that the trisiloxane surfactants superspread when the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space filling mat on the surface which removes a significant amount of the surface water. The water adjacent to the hydrophobic solid surface is of high energy due to incomplete hydrogen bonding; its removal significantly lowers the tension and reduces the contact angle. Hydrocarbon surfactants cannot remove as much surface water because their large polar groups prevent the chains from cohering lengthwise. In our report last year we presented a poster describing the preparation of model very hydrophobic surfaces which are homogeneous and atomically smooth using self assembled monolayers of octadecyl trichlorosilane (OTS). In this poster we will use these surfaces as test substrates in developing hydrocarbon based surfactant systems which superspread. We studied a binary hydrocarbon surfactant systems consisting of a very soluble large polar group polyethylene oxide surfactant (C12E6 (CH3(CH2)11(OCH2CH2)6OH) and a long chain alcohol dodecanol. By mixing the alcohol with this soluble surfactant we have found that the contact angle of the mixed system on our test hydrophobic surfaces is very low. We hypothesize that the alcohol fills in the gaps between adjacent adsorbed chains of the large polar group surfactant. This filling in removes the surface water and effects the decrease in contact angle. We confirm this hypothesis by demonstrating that at the air/water interface the mixed layer forms condensed phases while the soluble large polar group surfactant by itself does not. We present drop impact experiments which demonstrate that the dodecanol/C12E6 mixture is effective in causing impacting drops to spread on the very hydrophobic model OTS surfaces.

Ecophysiology of syntrophic communities that degrade saturated and unsaturated long-chain fatty acids.

PubMed

Sousa, Diana Z; Smidt, Hauke; Alves, Maria M; Stams, Alfons J M

2009-06-01

Syntrophic relationships are the key for biodegradation in methanogenic environments. We review the ecological and physiological features of syntrophic communities involved in the degradation of saturated and unsaturated long-chain fatty acids (LCFA), as well as their potential application to convert lipids/fats containing waste to biogas. Presently, about 14 species have been described with the ability to grow on fatty acids in syntrophy with methanogens, all belonging to the families Syntrophomonadaceae and Syntrophaceae. The principle pathway of LCFA degradation is through beta-oxidation, but the initial steps in the conversion of unsaturated LCFA are unclear. Communities enriched on unsaturated LCFA also degrade saturated LCFA, but the opposite generally is not the case. For efficient methane formation, the physical and inhibitory effects of LCFA on methanogenesis need to be considered. LCFA adsorbs strongly to biomass, which causes encapsulation of active syntrophic communities and hampers diffusion of substrate and products in and out of the biomass. Quantification of archaea by real-time PCR analysis suggests that potential LCFA inhibitory effect towards methanogens might be reversible. Rather, the conversion of adsorbed LCFA in batch assays was shown to result in a significant increase of archaeal cell numbers in anaerobic sludge samples.

Saturated fatty acid chain length and positional distribution in infant formula: effects on growth and plasma lipids and ketones in piglets.

PubMed

Innis, S M; Quinlan, P; Diersen-Schade, D

1993-03-01

Human milk contains a large proportion of palmitic acid (16:0) with > 70% esterified to the center sn-2 position of the milk triglyceride. Infant formulas often use 8:0 + 10:0 [medium-chain triglyceride (MCT)] or 12:0 + 14:0 (coconut oil) as the saturated fat. The effect of formula saturated fatty acid composition; 8:0 + 10:0, 12:0 + 14:0, or 16:0 from palm oil or synthesized triglyceride containing predominantly sn-2 16:0 on plasma lipids and fatty acids was studied in piglets. Although the formulas contained similar 18:1 and 18:2n-6, plasma lipid percentages of 18:1 and 18:2n-6 were higher in piglets fed the formula with MCT or coconut oil rather than the formulas with 16:0, or sow milk. The sn-2 16:0 of the synthesized triglyceride had unique properties. Specifically, piglets fed synthesized triglyceride had significantly higher cholesteryl ester 16:0 identical to that in piglets fed sow milk and higher plasma total and high-density-lipoprotein cholesterol than piglets fed the other formulas.

A model of high-affinity antibody binding to type III group B Streptococcus capsular polysaccharide.

PubMed

Wessels, M R; Muñoz, A; Kasper, D L

1987-12-01

We recently reported that the single repeating-unit pentasaccharide of type III group B Streptococcus (GBS) capsular polysaccharide is only weakly reactive with type III GBS antiserum. To further elucidate the relationship between antigen-chain length and antigenicity, tritiated oligosaccharides derived from type III capsular polysaccharide were used to generate detailed saturation binding curves with a fixed concentration of rabbit antiserum in a radioactive antigen-binding assay. A graded increase in affinity of antigen-antibody binding was seen as oligosaccharide size increased from 2.6 repeating units to 92 repeating units. These differences in affinity of antibody binding to oligosaccharides of different molecular size were confirmed by immunoprecipitation and competitive ELISA, two independent assays of antigen-antibody binding. Analysis of the saturation binding experiment indicated a difference of 300-fold in antibody-binding affinity for the largest versus the smallest tested oligosaccharides. Unexpectedly, the saturation binding values approached by the individual curves were inversely related to oligosaccharide chain length on a molar basis but equivalent on a weight basis. This observation is compatible with a model in which binding of an immunoglobulin molecule to an antigenic site on the polysaccharide facilitates subsequent binding of antibody to that antigen.

Effects of crude oil on water and tracer movement in the unsaturated and saturated zones.

PubMed

Delin, Geoffrey N; Herkelrath, William N

2017-05-01

A tracer test was conducted to aid in the investigation of water movement and solute transport at a crude-oil spill site near Bemidji, Minnesota. Time of travel was measured using breakthrough curves for rhodamine WT and bromide tracers moving from the soil surface through oil-contaminated and oil-free unsaturated zones to the saturated zone. Results indicate that the rates of tracer movement were similar in the oil-free unsaturated and saturated zones compared to the oily zones. These results are somewhat surprising given the oil contamination in the unsaturated and saturated zones. Rhodamine tracer breakthrough in the unsaturated and saturated zones in general was delayed in comparison to bromide tracer breakthrough. Peak tracer concentrations for the lysimeters and wells in the oily zone were much greater than at the corresponding depths in the oil-free zone. Water and tracer movement in the oily zone was complicated by soil hydrophobicity and decreased oil saturations toward the periphery of the oil. Preferential flow resulted in reduced tracer interaction with the soil, adsorption, and dispersion and faster tracer movement in the oily zone than expected. Tracers were freely transported through the oily zone to the water table. Recharge calculations support the idea that the oil does not substantially affect recharge in the oily zone. This is an important result indicating that previous model-based assumptions of decreased recharge beneath the oil were incorrect. Results have important implications for modeling the fate and transport of dissolved contaminants at hydrocarbon spill sites. Published by Elsevier B.V.

Angptl4 protects against severe proinflammatory effects of saturated fat by inhibiting fatty acid uptake into mesenteric lymph node macrophages.

PubMed

Lichtenstein, Laeticia; Mattijssen, Frits; de Wit, Nicole J; Georgiadi, Anastasia; Hooiveld, Guido J; van der Meer, Roelof; He, Yin; Qi, Ling; Köster, Anja; Tamsma, Jouke T; Tan, Nguan Soon; Müller, Michael; Kersten, Sander

2010-12-01

Dietary saturated fat is linked to numerous chronic diseases, including cardiovascular disease. Here we study the role of the lipoprotein lipase inhibitor Angptl4 in the response to dietary saturated fat. Strikingly, in mice lacking Angptl4, saturated fat induces a severe and lethal phenotype characterized by fibrinopurulent peritonitis, ascites, intestinal fibrosis, and cachexia. These abnormalities are preceded by a massive acute phase response induced by saturated but not unsaturated fat or medium-chain fat, originating in mesenteric lymph nodes (MLNs). MLNs undergo dramatic expansion and contain numerous lipid-laden macrophages. In peritoneal macrophages incubated with chyle, Angptl4 dramatically reduced foam cell formation, inflammatory gene expression, and chyle-induced activation of ER stress. Induction of macrophage Angptl4 by fatty acids is part of a mechanism that serves to reduce postprandial lipid uptake from chyle into MLN-resident macrophages by inhibiting triglyceride hydrolysis, thereby preventing macrophage activation and foam cell formation and protecting against progressive, uncontrolled saturated fat-induced inflammation. Copyright © 2010 Elsevier Inc. All rights reserved.

Group-type hydrocarbon standards for high-performance liquid chromatographic analysis of middistillate fuels

NASA Technical Reports Server (NTRS)

Otterson, D. A.; Seng, G. T.

1984-01-01

A new high-performance liquid chromatographic (HPLC) method for group-type analysis of middistillate fuels is described. It uses a refractive index detector and standards that are prepared by reacting a portion of the fuel sample with sulfuric acid. A complete analysis of a middistillate fuel for saturates and aromatics (including the preparation of the standard) requires about 15 min if standards for several fuels are prepared simultaneously. From model fuel studies, the method was found to be accurate to within 0.4 vol% saturates or aromatics, and provides a precision of + or - 0.4 vol%. Olefin determinations require an additional 15 min of analysis time. However, this determination is needed only for those fuels displaying a significant olefin response at 200 nm (obtained routinely during the saturated/aromatics analysis procedure). The olefin determination uses the responses of the olefins and the corresponding saturates, as well as the average value of their refractive index sensitivity ratios (1.1). Studied indicated that, although the relative error in the olefins result could reach 10 percent by using this average sensitivity ratio, it was 5 percent for the fuels used in this study. Olefin concentrations as low as 0.1 vol% have been determined using this method.

Novel Structures of Self-Associating Stapled Peptides

PubMed Central

Bhattacharya, Shibani; Zhang, Hongtao; Cowburn, David; Debnath, Asim K.

2012-01-01

Hydrocarbon stapling of peptides is a powerful technique to transform linear peptides into cell-permeable helical structures that can bind to specific biological targets. In this study, we have used high resolution solution NMR techniques complemented by Dynamic Light Scattering to characterize extensively a family of hydrocarbon stapled peptides with known inhibitory activity against HIV-1 capsid assembly to evaluate the various factors that modulate activity. The helical peptides share a common binding motif but differ in charge, the length and position of the staple. An important outcome of the study was to show the peptides share a propensity to self-associate into organized polymeric structures mediated predominantly by hydrophobic interactions between the olefinic chain and the aromatic side-chains from the peptide. We have also investigated in detail the structural significance of the length and position of the staple, and of olefinic bond isomerization in stabilizing the helical conformation of the peptides as potential factors driving polymerization. This study presents the numerous challenges of designing biologically active stapled peptides and the conclusions have broad implications for optimizing a promising new class of compounds in drug discovery. PMID:22170623

Polycyclic aromatic hydrocarbons in the bakery chain.

PubMed

Ciecierska, M; Obiedziński, M W

2013-11-01

The level of polycyclic aromatic hydrocarbons occurrence and the possibility of their formation in the bakery chain, its raw materials and final products, were examined. Experimental bread baking, with different baking temperatures, was performed in the Warsaw bakery, using cyclothermic deck ovens. PAHs determination was performed by high-pressure liquid chromatography with fluorescent and diode array detectors (HPLC-FLD/DAD) and confirmed by gas chromatography coupled with mass spectrometry (GC/MS). Total content of 19 PAHs in the grain, flour and bran varied from 1.07 to 3.65 μg/kg and, in bread, from 1.59 to 13.6 μg/kg depending on the part of bread and baking temperature. Based on the dough's contamination level and the influence of the baking temperature on the bread's PAHs content, it was confirmed that PAHs are formed during baking. Considering the results of the average dietary exposure to PAHs and the MOE (Margin of Exposure) analysis, it could be concluded that analysed bread and cereal products constitute little concern for consumer health. Copyright © 2013 Elsevier Ltd. All rights reserved.

Motor fuels and chemicals from coal via the Sasol Synthol route

NASA Astrophysics Data System (ADS)

Hoogendoorn, J. C.

1981-03-01

The production of synthetic motor fuels and chemicals from coal by the Sasol procedures is discussed. This process is based on the Fischer-Tropsch reaction by passing hydrogen and carbon monoxide in a specific ratio over iron catalysts at elevated temperatures and pressures. Two parallel reactor systems are discussed. The smaller system employs fixed-bed reactors, using a precipitated iron catalyst and produces predominantly heavy hydrocarbons of an aliphatic nature with carbon chains up to 100. These straight-chain hydrocarbons yield excellent waxes and high quality diesel oil. The larger system uses a powdered iron catalyst in a circulating fluid-bed reactor, a concept developed from American catalytic cracker technology. This system has the advantage of high production capacity and scale-up potential, and produces light olefins which can be used either as petrochemical feedstock or refined and added to the motor fuel pool, and ethylene which is augmented by ethane cracking. Analysis of product selectivities and values shows that co-production of chemicals and motor fuels from coal is profitable and efficient.