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…

Selective hydrodeoxygenation of biomass-derived oxygenates to unsaturated hydrocarbons using molybdenum carbide catalysts.

PubMed

Ren, Hui; Yu, Weiting; Salciccioli, Michael; Chen, Ying; Huang, Yulin; Xiong, Ke; Vlachos, Dionisios G; Chen, Jingguang G

2013-05-01

Which cleavage do you prefer? With a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluations, Mo(2)C is identified as a highly selective HDO catalyst to selectively convert biomass-derived oxygenates to unsaturated hydrocarbons through selective C-O bond scissions without C-C bond cleavage. This provides high-value HDO products for utilization as feedstocks for chemicals and fuels; this also reduces the overall consumption of H2 . Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Compounds and methods for the production of long chain hydrocarbons from biological sources

DOEpatents

Gordon, John Cameron; Silks, Louis A; Sutton, Andrew D; Wu, Ruilian; Schlaf, Marcel; Waldie, Fraser; West, Ryan; Collias, Dimitris Ioannis

2016-08-23

The present invention is directed to the preparation of oxygenated, unsaturated hydrocarbon compounds, such as derivatives of furfural or hydroxymethyl furfural produced by aldol condensation with a ketone or a ketoester, as well as methods of deoxidatively reducing those compounds with hydrogen under acidic conditions to provide saturated hydrocarbons useful as fuels.

Feasibility of oxidation-biodegradation serial foam spraying for total petroleum hydrocarbon removal without soil disturbance.

PubMed

Bajagain, Rishikesh; Park, Yoonsu; Jeong, Seung-Woo

2018-06-01

This study evaluated surface foam spraying technology, which avoids disturbing the soil, to deliver chemical oxidant and oil-degrading microbes to unsaturated soil for 30 days. Hydrogen peroxide foam was sprayed once onto diesel contaminated soil for oxidation of soil total petroleum hydrocarbon (TPH). Periodic bioaugmentation foam was sprayed every three days for biodegradation of soil TPH. Foam spraying employing oxidation-bioaugmentation serial application significantly reduced soil TPH concentrations to 550 mg·kg -1 from an initial 7470 mg·kg -1 . This study selected an optimal hydrogen peroxide concentration of 5%, which is capable of treating diesel oil contaminated soil following biodegradation without supplementary iron. Application of hydrogen peroxide by foam spraying increased the infiltration of hydrogen peroxide into the unsaturated soil. Surface foam spraying provided the aqueous phase of remediation agents evenly to the unsaturated soil and resulted in relatively similar soil water content throughout the soil. The easy and even infiltration of remediation reagents increased their contact with contaminants, resulting in enhanced oxidation and biodegradation. Fractional analysis of TPH showed C18-C22 present in diesel as biodegradation recalcitrant hydrocarbons. Recalcitrant hydrocarbons were reduced by 92% using oxidation-biodegradation serial foam, while biodegradation alone only reduced the recalcitrant fraction by 25%. Copyright © 2018 Elsevier B.V. All rights reserved.

Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

DOE R&D Accomplishments Database

Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

1982-04-01

From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

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.

An Approach that Uses the Concentrations of Hydrocarbon Compounds in Soil Gas at the Source of Contamination to Evaluate the Potential for Intrusion of Petroleum Vapors into Buildings (PVI)

EPA Science Inventory

If motor fuels are spilled from underground storage tanks, petroleum hydrocarbons can vaporize from the spill and move as a vapor through the unsaturated zone. If a building is sited above or near the spill, the hydrocarbons may intrude into the air space of the building. This ...

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.

Fast-quench reactor for hydrogen and elemental carbon production from natural gas and other hydrocarbons

DOEpatents

Detering, Brent A.; Kong, Peter C.

2006-08-29

A fast-quench reactor for production of diatomic hydrogen and unsaturated carbons is provided. During the fast quench in the downstream diverging section of the nozzle, such as in a free expansion chamber, the unsaturated hydrocarbons are further decomposed by reheating the reactor gases. More diatomic hydrogen is produced, along with elemental carbon. Other gas may be added at different stages in the process to form a desired end product and prevent back reactions. The product is a substantially clean-burning hydrogen fuel that leaves no greenhouse gas emissions, and elemental carbon that may be used in powder form as a commodity for several processes.

Long-term evolution of biodegradation and volatilization rates in a crude oil-contaminated aquifer

USGS Publications Warehouse

Chaplin, B.P.; Delin, G.N.; Baker, R.J.; Lahvis, M.A.

2002-01-01

Volatilization and subsequent biodegradation near the water Table make up a coupled natural attenuation pathway that results in significant mass loss of hydrocarbons. Rates of biodegradation and volatilization were documented twice 12 years apart at a crude-oil spill site near Bemidji, Minnesota. Biodegradation rates were determined by calibrating a gas transport model to O2, CO2, and CH4 gas-concentration data in the unsaturated zone. Reaction stoichiometry was assumed in converting O2 and CO2 gas-flux estimates to rates of aerobic biodegradation and CH4 gas-flux estimates to rates of methanogenesis. Model results indicate that the coupled pathway has resulted in significant hydrocarbon mass loss at the site, and it was estimated that approximately 10.52 kg/day were lost in 1985 and 1.99 kg/day in 1997. In 1985 3% of total volatile hydrocarbons diffusing from the floating oil were biodegraded in the lower 1 m of the unsaturated zone and increased to 52% by 1997. Rates of hydrocarbon biodegradation above the center of the floating oil were relatively stable from 1985 to 1997, as the primary metabolic pathway shifted from aerobic to methanogenic biodegradation. Model results indicate that in 1997 biodegradation under methanogenenic conditions represented approximately one-half of total hydrocarbon biodegradation in the lower 1 m of the unsaturated zone. Further downgradient, where substrate concentrations have greatly increased, total biodegradation rates increased by greater than an order of magnitude from 0.04 to 0.43 g/m2-day. It appears that volatilization is the primary mechanism for attenuation in early stages of plume evolution, while biodegradation dominates in later stages.

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

Total OH reactivity measurements for the OH-initiated oxidation of aromatic hydrocarbons in the presence of NOx

NASA Astrophysics Data System (ADS)

Sato, Kei; Nakashima, Yoshihiro; Morino, Yu; Imamura, Takashi; Kurokawa, Jun-ichi; Kajii, Yoshizumi

2017-12-01

The total OH reactivity of the secondary products formed from the OH-initiated oxidation of toluene, p-xylene, and 1,3,5-trimethylbenzene was directly measured in the presence of NOx using a laboratory environmental chamber in order to investigate unidentified reactive species in urban air. The total OH reactivity was also calculated from the concentrations of the reactants and products, which were monitored by Fourier-transform infrared spectroscopy. The difference between the measured and calculated OH reactivity, the so-called missing OH reactivity, comprised 58-81% of the total OH reactivity of the secondary products. These results suggest that the secondary products formed from the oxidation of aromatic hydrocarbons may be important candidates in accounting for the missing OH reactivity in the analyses of urban environments. The Master Chemical Mechanism (MCM) calculations were performed to predict the temporal variation in the total OH reactivity for the oxidation of aromatic hydrocarbons. The MCM calculations successfully reproduced the observed total OH reactivity when the particle and semi-volatile product concentrations were negligibly low. The MCM calculations were used to identify the missing secondary products. The results suggest that important components of the missing OH reactivity are unsaturated multifunctional products such as unsaturated dicarbonyls, unsaturated epoxydicarbonyls, and furanones.

Variation in the chemical composition of cone volatiles within the African cycad genus Encephalartos.

PubMed

Suinyuy, Terence N; Donaldson, John S; Johnson, Steven D

2013-01-01

Volatiles play a key role in attraction of pollinators to cycad cones, but the extent to which volatile chemistry varies among cycad species is still poorly documented. Volatile composition of male and female cones of nineteen African cycad species (Encephalartos; Zamiaceae) was analysed using headspace technique and gas chromatography-mass spectrometry (GC-MS). A total of 152 compounds were identified among the species included in this study, the most common of which were monoterpenes, nitrogen-containing compounds and unsaturated hydrocarbons. Male and female cones emitted similar volatile compounds which varied in relative amounts with two unsaturated hydrocarbons (3E)-1,3-octadiene and (3E,5Z)-1,3,5-octatriene present in the volatile profile of most species. In a multivariate analysis of volatile profiles using non-metric multidimensional scaling (NMDS), a number of species clusters were identified according to shared emission of unsaturated hydrocarbons, pyrazines, benzenoids, aldehydes, alkanes and terpenoids. In comparison, terpenoids are common in Zamia and dominant in Macrozamia species (both in the family Zamiaceae) while benzenoids, esters, and alcohols are dominant in Cycas (Cycadaceae) and in Stangeria (Stangeriaceae). It is likely that volatile variation among Encephalartos species reflects both phylogeny and adaptations to specific beetle pollinators. Copyright © 2012 Elsevier Ltd. All rights reserved.

CO- and HCl-free synthesis of acid chlorides from unsaturated hydrocarbons via shuttle catalysis

NASA Astrophysics Data System (ADS)

Fang, Xianjie; Cacherat, Bastien; Morandi, Bill

2017-11-01

The synthesis of carboxylic acid derivatives from unsaturated hydrocarbons is an important process for the preparation of polymers, pharmaceuticals, cosmetics and agrochemicals. Despite its industrial relevance, the traditional Reppe-type carbonylation reaction using pressurized CO is of limited applicability to laboratory-scale synthesis because of: (1) the safety hazards associated with the use of CO, (2) the need for special equipment to handle pressurized gas, (3) the low reactivity of several relevant nucleophiles and (4) the necessity to employ different, often tailor-made, catalytic systems for each nucleophile. Herein we demonstrate that a shuttle-catalysis approach enables a CO- and HCl-free transfer process between an inexpensive reagent, butyryl chloride, and a wide range of unsaturated substrates to access the corresponding acid chlorides in good yields. This new transformation provides access to a broad range of carbonyl-containing products through the in situ transformation of the reactive acid chloride intermediate. In a broader context, this work demonstrates that isodesmic shuttle-catalysis reactions can unlock elusive catalytic reactions.

Quantification of aerobic biodegradation and volatilization rates of gasoline hydrocarbons near the water table under natural attenuation conditions

USGS Publications Warehouse

Lahvis, Matthew A.; Baehr, Arthur L.; Baker, Ronald J.

1999-01-01

Aerobic biodegradation and volatilization near the water table constitute a coupled pathway that contributes significantly to the natural attenuation of hydrocarbons at gasoline spill sites. Rates of hydrocarbon biodegradation and volatilization were quantified by analyzing vapor transport in the unsaturated zone at a gasoline spill site in Beaufort, South Carolina. Aerobic biodgradation rates decreased with distance above the water table, ranging from 0.20 to 1.5 g m−3 d−1 for toluene, from 0.24 to 0.38 g m−3 d−1for xylene, from 0.09 to 0.24 g m−3 d−1 for cyclohexene, from 0.05 to 0.22 g m−3 d−1 for ethylbenzene, and from 0.02 to 0.08 g m−3 d−1 for benzene. Rates were highest in the capillary zone, where 68% of the total hydrocarbon mass that volatilized from the water table was estimated to have been biodegraded. Hydrocarbons were nearly completely degraded within 1m above the water table. This large loss underscores the importance of aerobic biodradation in limiting the transport of hydrocarbon vapors in the unsaturated zone and implies that vapor‐plume migration to basements and other points of contact may only be significant if a source of free product is present. Furthermore, because transport of the hydrocarbon in the unsaturated zone can be limited relative to that of oxygen and carbon dioxide, soil‐gas surveys conducted at hydrocarbon‐spill sites would benefit by the inclusion of oxygen‐ and carbon‐dioxide‐gas concentration measurements. Aerobic degradation kinetics in the unsaturated zone were approximately first‐order. First‐order rate constants near the water table were highest for cyclohexene (0.21–0.65 d−1) and nearly equivalent for ethylbenzene (0.11–0.31 d−1), xylenes (0.10–0.31 d−1), toluene (0.09–0.30 d−1), and benzene (0.07–0.31 d−1). Hydrocarbon mass loss rates at the water table resulting from the coupled aerobic biodgradation and volatilization process were determined by extrapolating gas transport rates through the capillary zone. Mass loss rates from groundwater were highest for toluene (0.20–0.84 g m−2 d−1), followed by xylenes (0.12–0.69 g m−2 d−1), cyclohexene (0.05–0.15 g m−2 d−1), ethylbenzene (0.02–0.12 g m−2 d−1), and benzene (0.01–0.04 g m−2 d−1). These rates exceed predicted rates of solubilization to groundwater, demonstrating the effectiveness of aerobic biodgradation and volatilization as a combined natural attenuation pathway.

Pi Bond Orders and Bond Lengths

ERIC Educational Resources Information Center

Herndon, William C.; Parkanyi, Cyril

1976-01-01

Discusses three methods of correlating bond orders and bond lengths in unsaturated hydrocarbons: the Pauling theory, the Huckel molecular orbital technique, and self-consistent-field techniques. (MLH)

Intramolecular homolytic displacements. 30. Functional decarbonylative transformations of aldehydes via homolytically induced decomposition of unsaturated peroxyacetals

PubMed

Degueil-Castaing; Moutet; Maillard

2000-06-30

Homolytically induced decompositions of unsaturated peroxyacetals, synthesized from aldehydes, gave alkoxyalkoxyl radicals that yielded alkyl radicals by rapid beta-scission. The latter radicals could react with several types of "transfer agents" to smoothly bring about homolytic decarbonylative functional group transformations of aldehydes into halides, hydrocarbons, xanthates, alkanenitriles, 2-alkyl-3-chloromaleic anhydrides, 1-phenylalk-1-ynes, and ethyl 2-alkylpropenoates.

Denatured ethanol release into gasoline residuals, Part 1: source behaviour.

PubMed

Freitas, Juliana G; Barker, James F

2013-05-01

With the increasing use of ethanol in fuels, it is important to evaluate its fate when released into the environment. While ethanol is less toxic than other organic compounds present in fuels, one of the concerns is the impact ethanol might have on the fate of gasoline hydrocarbons in groundwater. One possible concern is the spill of denatured ethanol (E95: ethanol containing 5% denaturants, usually hydrocarbons) in sites with pre-existing gasoline contamination. In that scenario, ethanol is expected to increase the mobility of the NAPL phase by acting as a cosolvent and decreasing interfacial tension. To evaluate the E95 behaviour and its impacts on pre-existing gasoline, a field test was performed at the CFB-Borden aquifer. Initially gasoline contamination was created releasing 200 L of E10 (gasoline with 10% ethanol) into the unsaturated zone. One year later, 184 L of E95 was released on top of the gasoline contamination. The site was monitored using soil cores, multilevel wells and one glass access tube. At the end of the test, the source zone was excavated and the compounds remaining were quantified. E95 ethanol accumulated and remained within the capillary fringe and unsaturated zone for more than 200 days, despite ~1m oscillations in the water table. The gasoline mobility increased and it was redistributed in the source zone. Gasoline NAPL saturations in the soil increased two fold in the source zone. However, water table oscillations caused a separation between the NAPL and ethanol: NAPL was smeared and remained in deeper positions while ethanol moved upwards following the water table rise. Similarly, the E95 denaturants that initially were within the ethanol-rich phase became separated from ethanol after the water table oscillation, remaining below the ethanol rich zone. The separation between ethanol and hydrocarbons in the source after water table oscillation indicates that ethanol's impact on hydrocarbon residuals is likely limited to early times. Copyright © 2013 Elsevier B.V. All rights reserved.

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

PubMed

Rayne, Sierra; Forest, Kaya

2016-09-18

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

Reverse osmosis membrane of high urea rejection properties. [water purification

NASA Technical Reports Server (NTRS)

Johnson, C. C.; Wydeven, T. J. (Inventor)

1980-01-01

Polymeric membranes suitable for use in reverse osmosis water purification because of their high urea and salt rejection properties are prepared by generating a plasma of an unsaturated hydrocarbon monomer and nitrogen gas from an electrical source. A polymeric membrane is formed by depositing a polymer of the unsaturated monomer from the plasma onto a substrate, so that nitrogen from the nitrogen gas is incorporated within the polymer in a chemically combined form.

Molecular dynamics simulation of unsaturated lipid bilayers at low hydration: parameterization and comparison with diffraction studies.

PubMed Central

Feller, S E; Yin, D; Pastor, R W; MacKerell, A D

1997-01-01

A potential energy function for unsaturated hydrocarbons is proposed and is shown to agree well with experiment, using molecular dynamics simulations of a water/octene interface and a dioleoyl phosphatidylcholine (DOPC) bilayer. The simulation results verify most of the assumptions used in interpreting the DOPC experiments, but suggest a few that should be reconsidered. Comparisons with recent results of a simulation of a dipalmitoyl phosphatidylcholine (DPPC) lipid bilayer show that disorder is comparable, even though the temperature, hydration level, and surface area/lipid for DOPC are lower. These observations highlight the dramatic effects of unsaturation on bilayer structure. Images FIGURE 3 PMID:9370424

Natural attenuation of chlorinated-hydrocarbon contamination at Fort Wainwright, Alaska; a hydrogeochemical and microbiological investigation workplan

USGS Publications Warehouse

McCarthy, Kathleen A.; Lilly, Michael R.; Braddock, Joan F.; Hinzman, Larry D.

1998-01-01

Natural attenuation processes include biological degradation, by which microorganisms break down contaminants into simpler product compounds; adsorption of contaminants to soil particles, which decreases the mass of contaminants dissolved in ground water; and dispersion, which decreases dissolved contaminant concentrations through dilution. The primary objectives of this study are to (1) assess the degree to which such natural processes are attenuating chlorinated-hydrocarbon contamination in ground water, and (2) evaluate the effects of ground-water/surface-water interactions on natural-attenuation processes in the area of the former East and West Quartermasters Fueling Systems for Fort Wainwright, Alaska. The study will include investigations of the hydrologic, geochemical, and microbiological processes occurring at this site that influence the transport and fate of chlorinated hydrocarbons in ground water. To accomplish these objectives, a data-collection program has been initiated that includes measurements of water-table elevations and the stage of the Chena River; measurements of vertical temperature profiles within the subsurface; characterization of moisture distribution and movement in the unsaturated zone; collection of ground-water samples for determination of both organic and inorganic chemical constituents; and collection of ground-water samples for enumeration of microorganisms and determination of their potential to mineralize contaminants. We will use results from the data-collection program described above to refine our conceptual model of hydrology and contaminant attenuation at this site. Measurements of water-table elevations and river stage will help us to understand the magnitude and direction of ground-water flow and how changes in the stage of the Chena River affect ground-water flow. Because ambient ground water and surface water typically have different temperature characteristics, temperature monitoring will likely provide further insight into ground-water/surface-water interactions in the subsurface. Characterization of the unsaturated zone will improve our understanding of interactions among ground water, the unsaturated zone, and the atmosphere. The interactions likely of importance to this study include the migration of water, dissolved contaminants, nutrients, and gases (oxygen, carbon dioxide, and methane) between the saturated and unsaturated zones. We will use the results of ground-water chemical analyses to determine the spatial and temporal distribution of (1) chlorinated-hydrocarbon contaminants and their degradation products, (2) oxidation-reduction indicators, (3) nutrients, and (4) major ground-water ions. These water-quality data will provide insight into ground-water flow directions, interactions between ground water and surface water, attenuation of contaminant concentrations caused by dispersion, and intrinsic microbiological processes. Microbiological analyses will indicate whether microorganisms at the site are capable of degrading the contaminants of interest, and will allow us to estimate their potential to attenuate existing contamination. Physical and chemical data interpreted as part of the analysis of ground water and surface water mixing will improve our understanding of the relationship between water quality and contaminant source mixing.

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.

Crossed Molecular Beams Investigations on the Dynamics and Energetics of Elementary Boron Reactions with Unsaturated Hydrocarbons

DTIC Science & Technology

2005-03-17

Is1 maglev pump (Osaka Vacuum; TG2003 and TG430) to the low 10. torr region; the operation of pulsed and continuous sources increases the pressure to...about 10-5 torr and 10.4 torr, respectively. All maglev pumps require no maintenance and are hydrocarbon free. A dry roots pump (Leybold WS505; 140 s

Thermophysical Properties of Matter - the TPRC Data Series. Volume 11. Viscosity

DTIC Science & Technology

1975-01-01

he monumental accomplishment in themselves, re- has spent enough time looking. Now with the quiring for their production the combined knowledge...Thodos for naphthenic hydrocarbons Thodos [1201] have represented the reduced viscosity (701], aromatic hydrocarbons (702], and unsaturated integral by...thefluidatoneatmospherepressureat thetemperature mixtures of liquids, and examined the case of caustic of interest, and p, is the value of p at the critical soda

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.

Review of unsaturated-zone transport and attenuation of volatile organic compound (VOC) plumes leached from shallow source zones

NASA Astrophysics Data System (ADS)

Rivett, Michael O.; Wealthall, Gary P.; Dearden, Rachel A.; McAlary, Todd A.

2011-04-01

Reliable prediction of the unsaturated zone transport and attenuation of dissolved-phase VOC (volatile organic compound) plumes leached from shallow source zones is a complex, multi-process, environmental problem. It is an important problem as sources, which include solid-waste landfills, aqueous-phase liquid discharge lagoons and NAPL releases partially penetrating the unsaturated zone, may persist for decades. Natural attenuation processes operating in the unsaturated zone that, uniquely for VOCs includes volatilisation, may, however, serve to protect underlying groundwater and potentially reduce the need for expensive remedial actions. Review of the literature indicates that only a few studies have focused upon the overall leached VOC source and plume scenario as a whole. These are mostly modelling studies that often involve high strength, non-aqueous phase liquid (NAPL) sources for which density-induced and diffusive vapour transport is significant. Occasional dissolved-phase aromatic hydrocarbon controlled infiltration field studies also exist. Despite this lack of focus on the overall problem, a wide range of process-based unsaturated zone — VOC research has been conducted that may be collated to build good conceptual model understanding of the scenario, particularly for the much studied aromatic hydrocarbons and chlorinated aliphatic hydrocarbons (CAHs). In general, the former group is likely to be attenuated in the unsaturated zone due to their ready aerobic biodegradation, albeit with rate variability across the literature, whereas the fate of the latter is far less likely to be dominated by a single mechanism and dependent upon the relative importance of the various attenuation processes within individual site — VOC scenarios. Analytical and numerical modelling tools permit effective process representation of the whole scenario, albeit with potential for inclusion of additional processes — e.g., multi-mechanistic sorption phase partitioning, and provide good opportunity for further sensitivity analysis and development to practitioner use. There remains a significant need to obtain intermediate laboratory-scale and particularly field-scale (actual site and controlled release) datasets that address the scenario as a whole and permit validation of the available models. Integrated assessment of the range of simultaneous processes that combine to influence leached plume generation, transport and attenuation in the unsaturated zone is required. Component process research needs are required across the problem scenario and include: the simultaneous volatilisation and dissolution of source zones; development of appropriate field-scale dispersion estimates for the unsaturated zone; assessment of transient VOC exchanges between aqueous, vapour and sorbed phases and their influence upon plume attenuation; development of improved field methods to recognise and quantify biodegradation of CAHs; establishment of the influence of co-contaminants; and, finally, translation of research findings into more robust practitioner practice.

Can conventional bases and unsaturated hydrocarbons be converted into gas-phase superacids that are stronger than most of the known oxyacids? The role of beryllium bonds.

PubMed

Yáñez, Manuel; Mó, Otilia; Alkorta, Ibon; Elguero, José

2013-08-26

The association of BeX2 (X: H, F, Cl) derivatives with azoles leads to a dramatic increase of their intrinsic acidity. Hence, whereas 1H-tetrazole can be considered as a typical N base in the gas phase, the complex 1H-tetrazole-BeCl2 is predicted to be, through the use of high-level G4 ab initio calculations, a nitrogen acid stronger than perchloric acid. This acidity enhancement is due to a more favorable stabilization of the deprotonated species after the beryllium bond is formed, because the deprotonated anion is a much better electron donor than the neutral species. Consequently, this is a general phenomenon that should be observed for any Lewis base, including those in which the basic site is a hydroxy group, an amino group, a carbonyl group, an aromatic N atom, a second-row atom, or the π system of unsaturated hydrocarbons. The consequence is that typical bases like aniline or formamide lead to BeX2 complexes that are stronger acids than phosphoric or chloric acids. Similarly, water, methanol, and SH2 become stronger acids than sulfuric acid, pyridine becomes a C acid almost as strong as acetic acid, and unsaturated hydrocarbons such as ethylene and acetylene become acids as strong as nitric and sulfuric acids, respectively. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic matter in meteorites and comets - Possible origins

NASA Technical Reports Server (NTRS)

Anders, Edward

1991-01-01

At least six extraterrestrial environments may have contributed organic compounds to meteorites and comets: solar nebula, giant-planet subnebulae, asteroid interiors containing liquid water, carbon star atmospheres, and diffuse or dark interstellar clouds. The record in meteorites is partly obscured by pervasive reheating that transformed much of the organic matter to kerogen; nonetheless, it seems that all six formation sites contributed. For comets, the large abundance of HCHO, HCN, and unsaturated hydrocarbons suggests an interstellar component of 50 percent or more, but the contributions of various interstellar processes, and of a solar-nebula component, are hard to quantify. A research program is outlined that may help reduce these uncertainties.

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)

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

Fundamental Flame Velocities of Pure Hydrocarbons I : Alkanes, Alkenes, Alkynes Benzene, and Cyclohexane

NASA Technical Reports Server (NTRS)

Gerstein, Melvin; Levine, Oscar; Wong, Edgar L

1950-01-01

The flame velocities of 37 pure hydrocarbons including normal and branched alkanes, alkenes, and alkynes; as well as benzene and cyclohexane, together with the experimental technique employed are presented. The normal alkanes have about the same flame velocity from ethane through heptane with methane being about 16 percent lower. Unsaturation increases the flame velocity in the order of alkanes, alkenes, and alkynes. Branching reduces the flame velocity.

[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.

Isolation and antiproliferative activity of chemical constituents from Asystasia buettneri Lindau.

PubMed

Hamid, Abdulmumeen A; Aiyelaagbe, Olapeju O; Negi, Arvind S; Luqman, Suaib; Kaneez, Fatima

2017-08-03

N-hexane and methanol extracts of Asystasia buettneri Lindau aerial parts exhibited antiproliferative activity on leukaemia blood carcinoma, K-562. Hexadecane (1), 1,3-propan-2-ol (9Z,12'Z,15″Z)-bis(doeicos-9,12,15-trienoate) (2), hydrocarbon, 2,3,3,10,23-pentamethyl tetraeicos-10,13,16-trien-1-ol (3), hexadecanoic acid (4) and taraxerol (5) were isolated from n-hexane extract; stigmasterol (6) and (Z)-9-octadecenoic acid (7) were isolated from ethyl acetate extract; while unsaturated hydrocarbons, octadecene (8), 8-methyl tetradec-6-ene (9) and 19-methyl eicos-1-ene (10), fatty acids, (Z)-5-hexadecenoic acid (11), 11,22-dimethyl ethyltrieicos-11-enoate (12) and taraxasterol (13) were isolated from methanol extract of the plant. Compounds 4, 5, 7, 11, 12 and 13 exhibited antiproliferative activity against K-562, while compounds 5, 6, 7 and 9 revealed antiproliferative activity by inhibiting hepatic liver (WRL68) cell lines.

Photosensitized oxidation of unsaturated polymers

NASA Technical Reports Server (NTRS)

Golub, M. A.

1979-01-01

The photosensitized oxidation or singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds was reviewed. Emphasis was on cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene), and on 1,4-poly(2,3-dimethyl-1,3-butadiene). The microstructural changes which occur in these polymers on reaction with O2-1 in solution were investigated by infrared H-1 and C-13 NMR spectroscopy. The polymers were shown to yield allylic hydroperoxides with shifted double bonds according to the ene mechanism established for simple olefins. The photosensitized oxidation of the above unsaturated polymer exhibited zero order kinetics, the relative rates paralleling the reactivities of the corresponding simple olefins towards O2-1.

PRODUCTION OF FLUORINE-CONTAINING HYDROCARBON

DOEpatents

Sarsfield, N.F.

1949-08-01

This patent relates to improvements in the production of fluorine- containing hydrocarbon derivatives. The process for increasing the degree of fluorination of a fluorochlorohydrocarbon comprises subjecting a highly fluorinated fluorochlorohydrocarbon to the action of a dehydrochlorinating agent, and treating the resulting unsaturated body with fluorine, cobalt trifluoride, or silver difluoride. A number of reagents are known as dehydrochlorinaling agents, including, for example, the caustic alkalies, either in an anhydrous condition or dissolved in water or a lower aliphatic alcohol.

Nonsaponifiable lipid components of the pollen of elder (Sambucus nigra L.).

PubMed

Stránsky, K; Valterová, I; Fiedler, P

2001-11-30

Pollen of the elder (Sambucus nigra L.) was extracted with chloroform-methanol. The extract was separated by column chromatography into the following groups of compounds: hydrocarbons (8.7%). polycyclic aromatic hydrocarbons (0.2%), complex esters (5.2%), triglycerides (18.7%), hydroxy esters (27.9%), free fatty acids and alcohols (16.8%), free sterols (6.8%), and triterpenic alcohols (4.0%). The nonsaponifiable components (hydrocarbons, fatty acids, alcohols, and sterols) were examined in detail using spectroscopic and chromatographic methods (IR spectroscopy, GC, and GC-MS). The identified compounds were characterized by their mass spectra and Kováts retention indices. The double bond positions and their configurations in unsaturated compounds are also reported.

Part 1: Vadose-zone column studies of toluene (enhanced bioremediation) in a shallow unconfined aquifer

USGS Publications Warehouse

Tindall, J.A.; Friedel, M.J.; Szmajter, R.J.; Cuffin, S.M.

2005-01-01

The objectives of the laboratory study described in this paper were (1) to determine the effectiveness of four nutrient solutions and a control in stimulating the microbial degradation of toluene in the unsaturated zone as an alternative to bioremediation methodologies such as air sparging, in situ vitrification, or others (Part I), and (2) to compare the effectiveness of the addition of the most effective nutrient solution from Part I (modified Hoagland type, nitrate-rich) and hydrogen peroxide (H2O2) on microbial degradation of toluene for repeated, simulated spills in the unsaturated zone (Part II). For Part 1, fifteen columns (30-cm diameter by 150-cm height), packed with air-dried, 0.25-mm, medium-fine sand, were prepared to simulate shallow unconfined aquifer conditions. Toluene (10 mL) was added to the surface of each column, and soil solution and soil gas samples were collected from the columns every third day for 21 days. On day 21, a second application of toluene (10 mL) was made, and the experiment was run for another 21 days. Solution 4 was the most effective for microbial degradation in Part I. For Part II, three columns were designated nutrient-rich 3-day toluene columns and received toluene injections every 3 days; three columns were designated as nutrient-rich 7-day columns and received toluene injections every 7 days; and two columns were used as controls to which no nutrient was added. As measured by CO2 respiration, the initial benefits for aerobic organisms from the O2 enhancement were sustained by the bacteria for only a short period of time (about 8 days). Degradation benefits from the nutrient solution were sustained throughout the experiment. The O2 and nutrient-enhanced columns degraded significantly more toluene than the control columns when simulating repeated spills onto the unsaturated zone, and demonstrated a potentially effective in situ bioremediation technology when used immediately or within days after a spill. The combined usage of H 2O2 and nitrate-rich nutrients served to effectively maximize natural aerobic and anaerobic metabolic processes that biodegrade hydrocarbons in petroleum-contaminated media. Applications of this technology in the field may offer economical advantages to other, more intrusive abatement technologies. ?? Springer 2005.

A compositional multiphase model for groundwater contamination by petroleum products: 2. Numerical solution

USGS Publications Warehouse

Baehr, Arthur L.; Corapcioglu, M. Yavuz

1987-01-01

In this paper we develop a numerical solution to equations developed in part 1 (M. Y. Corapcioglu and A. L. Baehr, this issue) to predict the fate of an immiscible organic contaminant such as gasoline in the unsaturated zone subsequent to plume establishment. This solution, obtained by using a finite difference scheme and a method of forward projection to evaluate nonlinear coefficients, provides estimates of the flux of solubilized hydrocarbon constituents to groundwater from the portion of a spill which remains trapped in a soil after routine remedial efforts to recover the product have ceased. The procedure was used to solve the one-dimensional (vertical) form of the system of nonlinear partial differential equations defining the transport for each constituent of the product. Additionally, a homogeneous, isothermal soil with constant water content was assumed. An equilibrium assumption partitions the constituents between air, water, adsorbed, and immiscible phases. Free oxygen transport in the soil was also simulated to provide an upper bound estimate of aerobic biodgradation rates. Results are presented for a hypothetical gasoline consisting of eight groups of hydrocarbon constituents. Rates at which hydrocarbon mass is removed from the soil, entering either the atmosphere or groundwater, or is biodegraded are presented. A significant sensitivity to model parameters, particularly the parameters characterizing diffusive vapor transport, was discovered. We conclude that hydrocarbon solute composition in groundwater beneath a gasoline contaminated soil would be heavily weighted toward aromatic constituents like benzene, toluene, and xylene.

Catalysis beyond frontier molecular orbitals: Selectivity in partial hydrogenation of multi-unsaturated hydrocarbons on metal catalysts

PubMed Central

Liu, Wei; Jiang, Yingda; Dostert, Karl-Heinz; O’Brien, Casey P.; Riedel, Wiebke; Savara, Aditya; Schauermann, Swetlana; Tkatchenko, Alexandre

2017-01-01

The mechanistic understanding and control over transformations of multi-unsaturated hydrocarbons on transition metal surfaces remains one of the major challenges of hydrogenation catalysis. To reveal the microscopic origins of hydrogenation chemoselectivity, we performed a comprehensive theoretical investigation on the reactivity of two α,β-unsaturated carbonyls—isophorone and acrolein—on seven (111) metal surfaces: Pd, Pt, Rh, Ir, Cu, Ag, and Au. In doing so, we uncover a general mechanism that goes beyond the celebrated frontier molecular orbital theory, rationalizing the C═C bond activation in isophorone and acrolein as a result of significant surface-induced broadening of high-energy inner molecular orbitals. By extending our calculations to hydrogen-precovered surface and higher adsorbate surface coverage, we further confirm the validity of the “inner orbital broadening mechanism” under realistic catalytic conditions. The proposed mechanism is fully supported by our experimental reaction studies for isophorone and acrolein over Pd nanoparticles terminated with (111) facets. Although the position of the frontier molecular orbitals in these molecules, which are commonly considered to be responsible for chemical interactions, suggests preferential hydrogenation of the C═O double bond, experiments show that hydrogenation occurs at the C═C bond on Pd catalysts. The extent of broadening of inner molecular orbitals might be used as a guiding principle to predict the chemoselectivity for a wide class of catalytic reactions at metal surfaces. PMID:28782033

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.

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.

FATE OF PAH COMPOUNDS IN TWO SOIL TYPES: INFLUENCE OF VOLATILIZATION, ABIOTIC LOSS, AND BIOLOGICAL ACTIVITY

EPA Science Inventory

The fate of 14 polycyclic aromatic hydrocarbon (PAH) compounds was evaluated with regard to interphase transfer potential and mechanisms of treatment in soil under unsaturated conditions. Volatilization and abiotic and biotic fate of the PAHs were determined using two soils not p...

Ethanol Conversion to Hydrocarbons on HZSM-5: Effect of Reaction Conditions and Si/Al Ratio on the Product Distributions

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

Ramasamy, Karthikeyan K.; Wang, Yong

2014-11-17

The Conversion of ethanol to hydrocarbon over HZSM-5 zeolite with different Si/Al ratios was investigated under various reaction conditions. The catalyst with a higher Si/Al ratio (low acid density) deactivated faster and generated more unsaturated compounds at a similar time-on-stream. Temperature affects the catalytic activity with respect to liquid hydrocarbon generation and the hydrocarbon product composition. At lower temperatures (~300°C), the catalyst deactivated faster with respect to the liquid hydrocarbon formation. Higher temperatures (~400°C) reduced the formation of liquid range hydrocarbons and formed more gaseous fractions. Weight hourly space velocity was also found to affect product selectivity with higher weightmore » hourly space velocity leading to a higher extent of ethylene formation. The experimental results were analyzed in terms of the product composition and the coke content with respect to catalyst time-on-stream and compared with the catalyst lifetime with respect to the variables tested on the conversion of ethanol to hydrocarbon.« less

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.

Carbamate-linked cationic lipids with different hydrocarbon chains for gene delivery.

PubMed

Shi, Jia; Yu, Shijun; Zhu, Jie; Zhi, Defu; Zhao, Yinan; Cui, Shaohui; Zhang, Shubiao

2016-05-01

A series of carbamate-linked cationic lipids containing saturated or unsaturated hydrocarbon chains and quaternary ammonium head were designed and synthesized. After recrystallization, carbamate-linked cationic lipids with high purity (over 95%) were obtained. The structures of these lipids were proved by IR spectrum, HR-ESI-MS, HPLC, (1)H NMR and (13)C NMR. The liposomes were prepared by using these cationic lipids and neutral lipid DOPE. Particle size and zeta-potential were studied to show that they were suitable for gene transfection. The DNA-bonding ability of C12:0, C14:0 and C18:1 cationic liposomes was much better than others. The results of transfection showed that hydrophobic chains of these lipids have great effects on their transfection activity. The lipids bearing C12:0, C14:0 saturated chains or C18:1 unsaturated chain showed relatively higher transfection efficiency and lower cytotoxicity. So these cationic lipids could be used as non-viral gene carriers for further studies. Copyright © 2016 Elsevier B.V. All rights reserved.

Thermocatalytic process for CO.sub.2-free production of hydrogen and carbon from hydrocarbons

DOEpatents

Muradov, Nazim Z [Melbourne, FL

2011-08-23

A novel process and apparatus are disclosed for sustainable CO.sub.2-free production of hydrogen and carbon by thermocatalytic decomposition (dissociation, pyrolysis, cracking) of hydrocarbon fuels over carbon-based catalysts in the absence of air and/or water. The apparatus and thermocatalytic process improve the activity and stability of carbon catalysts during the thermocatalytic process and produce both high purity hydrogen (at least, 99.0 volume %) and carbon, from any hydrocarbon fuel, including sulfurous fuels. In a preferred embodiment, production of hydrogen and carbon is achieved by both internal and external activation of carbon catalysts. Internal activation of carbon catalyst is accomplished by recycling of hydrogen-depleted gas containing unsaturated and aromatic hydrocarbons back to the reactor. External activation of the catalyst can be achieved via surface gasification with hot combustion gases during catalyst heating. The process and apparatus can be conveniently integrated with any type of fuel cell to generate electricity.

Anode material for lithium batteries

DOEpatents

Belharouak, Ilias [Westmont, IL; Amine, Khalil [Downers Grove, IL

2012-01-31

Primary and secondary Li-ion and lithium-metal based electrochemical cell systems. The suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of respective cell, or to the cell itself whether it be a liquid, a solid- or plasticized polymer electrolyte system. The gas suppression additives are primarily based on unsaturated hydrocarbons.

Anode material for lithium batteries

DOEpatents

Belharouak, Ilias [Bolingbrook, IL; Amine, Khalil [Downers Grove, IL

2008-06-24

Primary and secondary Li-ion and lithium-metal based electrochemical cell system. The suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of respective cell, or to the cell itself whether it be a liquid, a solid- or plastized polymer electrolyte system. The gas suppression additives are primarily based on unsaturated hydrocarbons.

Anode material for lithium batteries

DOEpatents

Belharouak, Ilias [Bolingbrook, IL; Amine, Khalil [Oak Brook, IL

2011-04-05

Primary and secondary Li-ion and lithium-metal based electrochemical cell systems. The suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of respective cell, or to the cell itself whether it be a liquid, a solid- or plasticized polymer electrolyte system. The gas suppression additives are primarily based on unsaturated hydrocarbons.

Stabilized sulfur binding using activated fillers

DOEpatents

Kalb, Paul D.; Vagin, Vyacheslav P.; Vagin, Sergey P.

2015-07-21

A method of making a stable, sulfur binding composite comprising impregnating a solid aggregate with an organic modifier comprising unsaturated hydrocarbons with at least one double or triple covalent bond between adjacent carbon atoms to create a modifier-impregnated aggregate; heating and drying the modifier-impregnated aggregate to activate the surface of the modifier-impregnated aggregate for reaction with sulfur.

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

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.

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.

An Approach for Developing Site-Specific Lateral and Vertical Inclusion Zones within which Structures Should be Evaluated for Petroleum Vapor Intrusion due to Releases of Motor Fuel from Underground Storage Tanks

EPA Science Inventory

Buildings may be at risk from Petroleum Vapor Intrusion (PVI) when they overlie petroleum hydrocarbon contamination in the unsaturated zone or dissolved in groundwater. The U.S. EPA Office of Underground Storage Tanks (OUST) is preparing Guidance for Addressing Petroleum Vapor I...

Crossed Molecular Beams Investigations on the Dynamics and Energetics of Elementary Boron Reactions with Unsaturated Hydrocarbons

DTIC Science & Technology

2006-03-17

perpendicularly. Each source chamber is pumped by a 2000 ls-1 and a 430 ls-1 maglev pump (Osaka Vacuum; TG2003 and TG430) to the low 10-8 torr region...the operation of pulsed and continuous sources increases the pressure to about 10-5 torr and 10-4 torr, respectively. All maglev pumps require no

Removing volatile contaminants from the unsaturated zone by inducing advective air-phase transport

USGS Publications Warehouse

Baehr, A.L.; Hoag, G.E.; Marley, M.C.

1989-01-01

Organic liquids inadvertently spilled and then distributed in the unsaturated zone can pose a long-term threat to ground water. Many of these substances have significant volatility, and thereby establish a premise for contaminant removal from the unsaturated zone by inducing advective air-phase transport with wells screened in the unsaturated zone. In order to focus attention on the rates of mass transfer from liquid to vapour phases, sand columns were partially saturated with gasoline and vented under steady air-flow conditions. The ability of an equilibrium-based transport model to predict the hydrocarbon vapor flux from the columns implies an efficient rate of local phase transfer for reasonably high air-phase velocities. Thus the success of venting remediations will depend primarily on the ability to induce an air-flow field in a heterogeneous unsaturated zone that will intersect the distributed contaminant. To analyze this aspect of the technique, a mathematical model was developed to predict radially symmetric air flow induced by venting from a single well. This model allows for in-situ determinations of air-phase permeability, which is the fundamental design parameter, and for the analysis of the limitations of a single well design. A successful application of the technique at a site once contaminated by gasoline supports the optimism derived from the experimental and modeliing phases of this study, and illustrates the well construction and field methods used to document the volatile contaminant recovery. ?? 1989.

Futuristic isotope hydrology in the Gulf region

NASA Astrophysics Data System (ADS)

Saravana Kumar, U.; Hadi, Khaled

2018-03-01

The Gulf region is one of the most water-stressed parts in the world. Water in the region is very scarce, shortage of supply and lacking of renewable water resources, while the demand for water is growing day by day. It is thus essential to implement modern approaches and technologies in addressing water-related issues. In this context, isotope hydrology will provide invaluable aid. Some of the most important areas of futuristic applications of isotope hydrology include evaluation of aquifer recharge, storage and their recovery system, understanding of dynamic changes due to long-term exploitation of the groundwater, development and management of shared groundwater aquifers, fresh groundwater discharge along the Arabian Gulf, identification and quantification of hydrocarbon contamination in groundwater; soil moisture and solute movement in unsaturated zone, paleoclimate reconstruction, etc. Literature survey suggests, in general, not many isotope studies on the above have been reported.

Effects of double and triple bonds on the spatial representations of odorants in the rat olfactory bulb.

PubMed

Johnson, Brett A; Ong, Joan; Lee, Kaman; Ho, Sabrina L; Arguello, Spart; Leon, Michael

2007-02-01

Many naturally occurring volatile chemicals that are detected through the sense of smell contain unsaturated (double or triple) carbon-carbon bonds. These bonds can affect odors perceived by humans, yet in a prior study of unsaturated hydrocarbons we found only very minor effects of unsaturated bonds. In the present study, we tested the possibility that unsaturated bonds affect the recognition of oxygen-containing functional groups, because humans perceive odor differences between such molecules. We therefore compared spatial activity patterns across the entire glomerular layer of the rat olfactory bulb evoked by oxygen-containing odorants differing systematically in the presence, position, number, and stereochemistry of unsaturated bonds. We quantified activity patterns by mapping [(14)C]2-deoxyglucose uptake into anatomically standardized data matrices, which we compared statistically. We found that the presence and number of unsaturated bonds consistently affected activity patterns, with the largest effect related to the presence of a triple bond. Effects of bond saturation included a loss of activity in glomeruli strongly activated by the corresponding saturated odorants and/or the presence of activity in areas not stimulated by the corresponding saturated compounds. The position of double bonds also affected patterns of activity, but cis vs. trans configuration had no measurable impact in all five sets of stereoisomers that we studied. These results simultaneously indicate the importance of interactions between carbon-carbon bond types and functional groups in the neural coding of odorant chemical information and highlight the emerging concept that the rat olfactory system is more sensitive to certain types of chemical differences than others. (c) 2006 Wiley-Liss, Inc.

New hits as phase II enzymes inducers from a focused library with heteroatom-heteroatom and Michael-acceptor motives.

PubMed

Cabrera, Mauricio; de Ovalle, Stefani; Bollati-Fogolín, Mariela; Nascimento, Fabiana; Corbelini, Patrícia; Janarelli, Fernanda; Kawano, Daniel; Eifler-Lima, Vera Lucia; González, Mercedes; Cerecetto, Hugo

2015-11-01

The increased activity of phase-II-detoxification enzymes, such as quinone reductase (QR) and glutation S -transferase (GST), correlates with protection against chemically induced carcinogenesis. Herein we studied 11 different chemotypes, pyrazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiazole, 1,3,4-oxathiazole, thienyl hydrazone, α,β-unsaturated-oxime, α,β-unsaturated- N -oxide, coumarin and α,β-unsaturated-carbonyl, as phase-II enzymes inducers in order to identify new pharmacophores with chemopreventive activity. Fifty-four compounds were analyzed on wild-type mouse-hepatoma Hepa-1c1c7 and on the aryl-hydrocarbon-nuclear-translocator (Arnt)-defective mutant BpRc1 cells. New monofunctional inducers of QR and GST were identified, the 1,2,5-oxadiazol-2-oxide (3) , the 1,2,4-triazine-4-oxides (23) and (32) and the tetrahydropyrimidinones (28) and (49) . It was confirmed that Nrf2 nuclear translocation is the operative molecular mechanism that allows compound (3) to exert protective effects via expression of downstream phase-II enzymes.

New hits as phase II enzymes inducers from a focused library with heteroatom–heteroatom and Michael-acceptor motives

PubMed Central

Cabrera, Mauricio; de Ovalle, Stefani; Bollati-Fogolín, Mariela; Nascimento, Fabiana; Corbelini, Patrícia; Janarelli, Fernanda; Kawano, Daniel; Eifler-Lima, Vera Lucia; González, Mercedes; Cerecetto, Hugo

2015-01-01

The increased activity of phase-II-detoxification enzymes, such as quinone reductase (QR) and glutation S-transferase (GST), correlates with protection against chemically induced carcinogenesis. Herein we studied 11 different chemotypes, pyrazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiazole, 1,3,4-oxathiazole, thienyl hydrazone, α,β-unsaturated-oxime, α,β-unsaturated-N-oxide, coumarin and α,β-unsaturated-carbonyl, as phase-II enzymes inducers in order to identify new pharmacophores with chemopreventive activity. Fifty-four compounds were analyzed on wild-type mouse-hepatoma Hepa-1c1c7 and on the aryl-hydrocarbon-nuclear-translocator (Arnt)-defective mutant BpRc1 cells. New monofunctional inducers of QR and GST were identified, the 1,2,5-oxadiazol-2-oxide (3), the 1,2,4-triazine-4-oxides (23) and (32) and the tetrahydropyrimidinones (28) and (49). It was confirmed that Nrf2 nuclear translocation is the operative molecular mechanism that allows compound (3) to exert protective effects via expression of downstream phase-II enzymes. PMID:28031894

Production of fullerenic nanostructures in flames

DOEpatents

Howard, Jack B.; Vander Sande, John B.; Chowdhury, K. Das

1999-01-01

A method for the production of fullerenic nanostructures is described in which unsaturated hydrocarbon fuel and oxygen are combusted in a burner chamber at a sub-atmospheric pressure, thereby establishing a flame. The condensibles of the flame are collected at a post-flame location. The condensibles contain fullerenic nanostructures, such as single and nested nanotubes, single and nested nanoparticles and giant fullerenes. The method of producing fullerenic soot from flames is also described.

Production Of Fullerenic Soot In Flames

DOEpatents

Howard, Jack B.; Vander Sande, John B.; Chowdhury, K. Das

2000-12-19

A method for the production of fullerenic nanostructures is described in which unsaturated hydrocarbon fuel and oxygen are combusted in a burner chamber at a sub-atmospheric pressure, thereby establishing a flame. The condensibles of the flame are collected at a post-flame location. The condensibles contain fullerenic nanostructures, such as single and nested nanotubes, single and nested nanoparticles and giant fullerenes. The method of producing fullerenic soot from flames is also described.

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

Investigating the scale of structural controls on chlorinated hydrocarbon distributions in the fractured-porous unsaturated zone of a sandstone aquifer in the UK

NASA Astrophysics Data System (ADS)

Lawrence, Adrian; Stuart, Marianne; Cheney, Colin; Jones, Neil; Moss, Richard

2006-12-01

Contaminant migration behaviour in the unsaturated zone of a fractured porous aquifer is discussed in the context of a study site in Cheshire, UK. The site is situated on gently dipping sandstones, adjacent to a linear lagoon historically used to dispose of industrial wastes containing chlorinated solvents. Two cores of more than 100 m length were recovered and measurements of chlorinated hydrocarbons (CHCs), inorganic chemistry, lithology, fracturing and aquifer properties were made. The results show that selecting an appropriate vertical sampling density is crucial both to providing an understanding of contaminant pathways and distinguishing whether CHCs are present in the aqueous or non-aqueous phase. The spacing of such sampling should be on a similar scale to the heterogeneity that controls water and contaminant movement. For some sections of the Permo-Triassic aquifer, significant changes in lithology and permeability occur over vertical distances of less than 1 m and samples need to be collected at this interval, otherwise considerable resolution is lost, potentially leading to erroneous interpretation of data. At this site, although CHC concentrations were high, the consistent ratio of the two main components of the plume (tetrachloroethene and trichloroethene) provided evidence of movement in the aqueous phase rather than in dense non-aqueous phase liquid (DNAPL).

Unique distributions of hydrocarbons and sulphur compounds released by flash pyrolysis from the fossilised alga Gloeocapsomorpha prisca , a major constituent in one of four Ordovician kerogens

NASA Astrophysics Data System (ADS)

Douglas, A. G.; Damsté, J. S. Sinninghe; Fowler, M. G.; Eglinton, T. I.; de Leeuw, J. W.

1991-01-01

Kerogens isolated from four rocks of Ordovician age from North America have been analysed by combined pyrolysis-gas chromatography-mass spectrometry to compare and contrast the type and distribution of sulphur-containing compounds and aromatic and aliphatic hydrocarbons present in the pyrolysates. When pyrolysed, all of the kerogens released several series of heterocyclic sulphur compounds including alkylthiophenes, alkylthiolanes, alkylthianes and alkylbenzothiophenes together with n-alkanes, n-alklenes and alkylcyclohexanes as well as alkyl-substituted benzenes and naphthalenes. One of the kerogens, isolated from the Guttenberg oil rock, consisted predominantly of the alga Gloeocapsomorpha prisca, which produced sulphur compounds and hydrocarbons with fingerprint pyrograms that were different from those of the other three kerogens. The data provide prima facie evidence that these distributions may act as pseudo "biological markers" for this species of alga, namely that unsaturated kerogen moieties available for the uptake of sulphur, or which can cyclise to form hydrocarbons, distinguish Gloeocapsomorpha prisca from the contributing organisms of the other kerogens analysed.

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.

(Bio-)remediation of VCHC contaminants in a Technosol under unsaturated conditions.

PubMed

Baumgarten, W; Fleige, H; Peth, S; Horn, R

2013-07-01

The remediation of dense non-aqueous phase liquids has always been a concern of both public and scientific interest groups. In this research work a modified physical concept of (bio)remediation of a volatile chlorinated hydrocarbon (VCHC) contamination was elaborated under laboratory conditions and modeled with HYDRUS-2D. In field dechlorination is influenced by both physicochemical and hydraulic properties of the substrate, e.g. texture, pore size distribution, pore liquid characteristics, e.g. viscosity, pH, surface tension, and dependent on the degree of saturation of the vadose zone. Undisturbed soil cores (100 cm³) were sampled from a Spolic Technosol. Considering hydraulic properties and functions, unsaturated percolation was performed with vertically and horizontally structured samples. VCHC concentrations were calculated prior, during, and after each percolation cycle. According to laboratory findings, microemulsion showed the most efficient results with regard to flow behavior in the unsaturated porous media and its accessibility for bacteria as nutrient. The efficiency of VCHC remediation could be increased by the application of a modified pump-and-treat system: the injection of bacteria Dehalococcoides ethanogenes with microemulsion, and extraction at a constant matric potential level of -6 kPa. Achieved data was used for HYDRUS-2D simulations, modeling in situ conditions, demonstrating the practical relevance (field scale) of performed unsaturated percolation (core scale), and in order to exclude capillary barrier effects.

Adsorption of small hydrocarbons on rutile TiO2(110)

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

Chen, Long; Smith, R. Scott; Kay, Bruce D.

2016-08-01

Temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes with 1 - 4 carbon atoms of C1-C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of an additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar tomore » previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2-C4 hydrocarbons are found nearly independent of the chain length with values of ~1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

Adsorption of small hydrocarbons on rutile TiO 2(110)

DOE PAGES

Chen, Long; Smith, R. Scott; Kay, Bruce D.; ...

2015-11-21

Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C 1–C 4) on rutile TiO 2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti 5c sites. Similar to previous studiesmore » on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti 5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti 5c sites were also determined. The saturation coverage of CH 4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C 2–C 4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

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

In situ bioremediation of an underground diesel fuel spill: A case history

NASA Astrophysics Data System (ADS)

Frankenberger, W. T.; Emerson, K. D.; Turner, D. W.

1989-05-01

In the winter months of 1983, approximately 1000 gallons of diesel fuel had flowed along an asphalt parking lot of a commercial establishment towards a surface drain near an open creek. Investigations led to the discovery of an underground storage tank leaking diesel fuel. Exploratory borings showed that contamination was near the surface horizon and the capillary zone of the water table. Hydrocarbon quantities ranged up to 1500 mg/kg of soil. The plume continued to move in an eastward direction toward the surface water of the creek. A laboratory study indicated relatively high numbers of hydrocarbon-oxidizing organisms relative to glucose-utilizing microorganisms in the unsaturated vadose zone. Bioreclamation was initiated in April 1984 by injecting nutrients (nitrogen and phosphorus) and hydrogen peroxide and terminated in October 1984 upon no detection (<1 mg/kg) of hydrocarbons. A verification boring within the vicinity of the contaminated plume confirmed that residual contamination had attained background levels. The monitoring program was terminated in January 1987.

The diffuse interstellar bands: a tracer for organics in the diffuse interstellar medium?

NASA Technical Reports Server (NTRS)

Salama, F.

1998-01-01

The diffuse interstellar bands (DIBs) are absorption bands seen in the spectra of stars obscured by interstellar dust. DIBs are recognized as a tracer for free, organic molecules in the diffuse interstellar medium (ISM). The potential molecular carriers for the DIBs are discussed with an emphasis on neutral and ionized polycyclic aromatic hydrocarbons (PAHs) for which the most focused effort has been made to date. From the combined astronomical, laboratory and theoretical study, it is concluded that a distribution of free neutral and ionized complex organics (PAHs, fullerenes, unsaturated hydrocarbons) represents the most promising class of candidates to account for the DIBs. The case for aromatic hydrocarbons appears particularly strong. The implied widespread distribution of complex organics in the diffuse ISM bears profound implications for our understanding of the chemical complexity of the ISM, the evolution of prebiotic molecules and its impact on the origin and the evolution of life on early Earth through the exogenous delivery (cometary encounters and metoritic bombardments) of prebiotic organics.

Application of persulfate-oxidation foam spraying as a bioremediation pretreatment for diesel oil-contaminated soil.

PubMed

Bajagain, Rishikesh; Lee, Sojin; Jeong, Seung-Woo

2018-09-01

This study investigated a persulfate-bioaugmentation serial foam spraying technique to remove total petroleum hydrocarbons (TPHs) present in diesel-contaminated unsaturated soil. Feeding of remedial agents by foam spraying increased the infiltration/unsaturated hydraulic conductivity of reagents into the unsaturated soil. Persulfate mixed with a surfactant solution infiltrated the soil faster than peroxide, resulting in relatively even soil moisture content. Persulfate had a higher soil infiltration tendency, which would facilitate its distribution over a wide soil area, thereby enhancing subsequent biodegradation efficiency. Nearly 80% of soil-TPHs were degraded by combined persulfate-bioaugmentation foam spraying, while bioaugmentation foam spraying alone removed 52%. TPH fraction analysis revealed that the removal rate for the biodegradation recalcitrant fraction (C 18 to C 22 ) in deeper soil regions was higher for persulfate-bioaugmentation serial foam application than for peroxide-bioaugmentation foam application. Persulfate-foam spraying may be superior to peroxide for TPH removal even at a low concentration (50 mN) because persulfate-foam is more permeable, persistent, and does not change soil pH in the subsurface. Although the number of soil microbes declines by oxidation pretreatment, bioaugmentation-foam alters the microbial population exponentially. Copyright © 2018 Elsevier Ltd. All rights reserved.

Untangling the Energetics and Dynamics of Boron Monoxide Radical Reactions (11BO; X2Sigma+)

DTIC Science & Technology

2015-04-15

Reaction products of isoelectronic boron monoxide (BO), cyano (CN), ethynyl (CCH), and silicon nitride (SiN) radicals with acetylene and ethylene. 3.10...Isoelectronicity in the Reactions of the Cyano (CN), Boron Monoxide (BO), Silicon Nitride (SiN), and Ethynyl (C2H) Radicals with Unsaturated Hydrocarbons...AFRL-OSR-VA-TR-2015-0111 Untangling the Energetics and Dynamics of Boron Monoxide Radical Reactions Ralf Kaiser UNIVERSITY OF HAWAII SYSTEMS HONOLULU

Bioenvironmental Engineer’s Guide to TVA-1000B Toxic Vapor Analyzer

DTIC Science & Technology

2014-01-01

chemicals including aromatics, unsaturated chlorinated hydrocarbons, aldehydes , ketones , ethylene oxide, hydrogen sulfide, and glycol ether solvents. The...Dimethoxyethane 9.65 Diethyl ketone 9.32 Ethyl amine 8.86 1,1-Dimethylhydrazine 7.28 Diethyl sulfide 8.43 Ethyl benzene 8.76 1,2-Dibromoethene 9.45...Chemical IP (eV) Chemical IP (eV) Chemical IP (eV) Freon 13 (chlorotrifluoromethane) 12.91 Isobutyric acid 10.02 Methyl butyl ketone 9.34

Nickel-catalyzed cycloadditions of unsaturated hydrocarbons, aldehydes, and ketones.

PubMed

Tekavec, Thomas N; Louie, Janis

2008-04-04

The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3,3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon-carbon bond is formed, prior to a competitive beta-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No beta-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C-O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon-carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr).

Nickel-Catalyzed Cycloadditions of Unsaturated Hydrocarbons, Aldehydes, and Ketones

PubMed Central

Tekavec, Thomas N.

2014-01-01

The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3, 3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon–carbon bond is formed, prior to a competitive β-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No β-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C–O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon–carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr). PMID:18318544

Tri- and tetraterpenoid hydrocarbons in the Messel oil shale

NASA Technical Reports Server (NTRS)

Kimble, B. J.; Maxwell, J. R.; Philp, R. P.; Eglinton, G.; Albrecht, P.; Ensminger, A.; Arpino, P.; Ourisson, G.

1974-01-01

The high-molecular-weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high-resolution gas chromatography and combined gas chromatography/mass spectrometry. The following compounds are present: perhydrolycopene, together with one or more unsaturated analogs with the same skeleton; a series of 4-methylsteranes in higher abundance than their 4-desmethyl analogs; two series of pentacyclic triterpanes, one series based on the hopane structure, and the other based on the 17 alpha-H hopane structure; and an intact triterpene hop-17(21)-ene. Only two additional triterpanes were detected in minor concentrations - namely, 30-normoretane and a C31 triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment.

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.

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

Fluoralkenyl nortropanes

DOEpatents

Goodman, Mark M.; Chen, Ping

2002-02-05

Provided are compounds of the following formula: ##STR1## wherein R is C2-C6 mono- or multi-unsaturated hydrocarbon having one or more ethylene, acetylene or allene groups, A is 18 or 19, and X is H or halogen. The compounds of the invention bind to dopamine transporter with high affinity and selectivity and are thus useful as diagnostic and therapeutic agents for diseases associated with dopamine transporter dysfunction. The radiolabeled compounds are useful as imaging agents for visualizing the location and density of dopamine transporter by PET imaging.

Mechanisms of Cellular Membrane Effects of TCDD (2,3,7,8-Tetrachlorodibenzo-p-Dioxin) Selected Perfluorinated Acids and Polyhalogenated Aromatic Hydrocarbons.

DTIC Science & Technology

1986-10-15

tetrachloro dibenzo-p-dioxin (TCDD); dioxin; perfluoro -n-decanoic acid ( PFDA ); perfluoro -n-octanoic acid ( PFOA ); 3,31,4,41,5,51 hexachlorobiphenyl (345PCB) and...analysis of livers from rats treated with perfluoro -n-decanoic acid ( PFDA ) showed a decrease in stearic acid and an increase in 18 carbon unsaturates...effects of TCDD, PHAH and perfluorinated acids ( PFA ) on mammalian cell membrane function by examing the phenomenon of metabolic cooperation. Metabolic

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.

Prospects of pyrolysis oil from plastic waste as fuel for diesel engines: A review

NASA Astrophysics Data System (ADS)

Mangesh, V. L.; Padmanabhan, S.; Ganesan, S.; PrabhudevRahul, D.; Reddy, T. Dinesh Kumar

2017-05-01

The purpose ofthis study is to review the existing literature about chemical recycling of plastic waste and its potential as fuel for diesel engines. This is a review covering on the field of converting waste plastics into liquid hydrocarbon fuels for diesel engines. Disposal and recycling of waste plastics have become an incremental problem and environmental threat with increasing demand for plastics. One of the effective measures is by converting waste plastic into combustible hydrocarbon liquid as an alternative fuel for running diesel engines. Continued research efforts have been taken by researchers to convert waste plastic in to combustible pyrolysis oil as alternate fuel for diesel engines. An existing literature focuses on the study of chemical structure of the waste plastic pyrolysis compared with diesel oil. Converting waste plastics into fuel oil by different catalysts in catalytic pyrolysis process also reviewed in this paper. The methodology with subsequent hydro treating and hydrocracking of waste plastic pyrolysis oil can reduce unsaturated hydrocarbon bonds which would improve the combustion performance in diesel engines as an alternate fuel.

Cavity Ring Down and Thermal Lens Techniques Applied to Vibrational Spectroscopy of Gases and Liquids

NASA Astrophysics Data System (ADS)

Nyaupane, Parashu Ram

Infrared (IR) and near-infrared (NIR) region gas temperature sensors have been used in the past because of its non-intrusive character and fast time response. In this dissertation cavity ring down (CRD) absorption of oxygen around the region 760 nm has been used to measure the temperature of flowing air in an open optical cavity. This sensor could be a convenient method for measuring the temperature at the input (cold air) and output (hot air) after cooling the blades of a gas turbine. The results could contribute to improvements in turbine blade cooling designs. Additionally, it could be helpful for high temperature measurement in harsh conditions like flames, boilers, and industrial pyrolysis ovens as well as remote sensing. We are interested in experiments that simulate the liquid methane and ethane lakes on Titan which is around the temperature of 94 K. Our specific goal is to quantify the solubility of unsaturated hydrocarbons in liquid ethane and methane. However, it is rather complicated to do so because of the low temperatures, low solubility and solvent effects. So, it is wise to do the experiments at higher temperature and test the suitability of the techniques. In these projects, we were trying to explore if our existing laboratory techniques were sensitive enough to obtain the solubility of unsaturated hydrocarbons in liquid ethane. First, we studied the thermal lens spectroscopy (TLS) of the (Deltav = 6) C-H overtone of benzene and naphthalene in hexane and CCl4 at room temperature.

A compositional multiphase model for groundwater contamination by petroleum products: 1. Theoretical considerations

USGS Publications Warehouse

Corapcioglu, M. Yavuz; Baehr, Arthur L.

1987-01-01

A mathematical model is developed to describe the fate of hydrocarbon constituents of petroleum products introduced to soils as an immiscible liquid from sources such as leaking underground storage tanks and ruptured pipelines. The problem is one of multiphase transport (oil (immiscible), air, and water phases) of a reactive contaminant with constituents such as benzene, toluene, and xylene found in refined petroleum products like gasoline. In the unsaturated zone, transport of each constituent can occur as a solute in the water phase, vapor in the air phase, and as an unaltered constituent in the oil phase. Additionally, the model allows for adsorption. Molecular transformations, microbially mediated or abiotic, are incorporated as sink terms in the conservation of mass equations. An equilibrium approximation, applicable to any immiscible organic contaminant is applied to partition constituent mass between the air, oil, water, and adsorbed phases for points in the region where the oil phase exists. Outside the oil plume the equilibrium approximation takes on a simpler form to partition constituent mass between the air, water, and adsorbed phases only. Microbial degradation of petroleum products is first discussed in a general model, then the conservation of mass equation for oxygen is incorporated into the analysis which takes advantage of the key role played by oxygen in the metabolism of hydrocarbon utilizing microbes in soil environments. Approximations to two subproblems, oil plume establishment in the unsaturated zone, and solute and vapor transport subsequent to immiscible plume establishment are then developed from the general model.

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

Ford, JP; Thapaliya, N; Kelly, MJ

Fatty acids (FAs) derived via thermal hydrolysis of food-grade lard and canola oil were deoxygenated in the liquid phase using a commercially available 5 wt % Pd/C catalyst. Online quadrupole mass spectrometry and gas chromatography were used to monitor the effluent gases from the semi-batch stirred autoclave reactors. Stearic, oleic, and palmitic acids were employed as model compounds. A catalyst lifetime exceeding 2200 turnovers for oleic acid deoxygenation was demonstrated at 300 degrees C and 15 atm under 10% H-2. The initial decarboxylation rate of palmitic acid under 5% H-2 decreases sharply with increasing initial concentration; in contrast, the initialmore » decarbonylation rate increases linearly, indicative of first-order kinetics. Scale-up of diesel-range hydrocarbon production was investigated by increasing the reactor vessel size, initial FA concentration, and FA/catalyst mass ratio. Lower CO2 selectivity and batch productivity were observed at the larger scales (600 and 5000 mL), primarily because of the higher initial FA concentration (67 wt %) employed. Because unsaturated FAs must be hydrogenated before deoxygenation can proceed at an appreciable rate, the additional batch time required for FA hydrogenation reduces the batch productivity for unsaturated feedstocks. Low-temperature hydrogenation of unsaturated feedstocks (using Pd/C or another less-expensive catalyst) prior to deoxygenation is recommended.« less

Development of radiation indicators to distinguish between irradiated and non-irradiated herbal medicines using HPLC and GC-MS.

PubMed

Kim, Min Jung; Ki, Hyeon A; Kim, Won Young; Pal, Sukdeb; Kim, Byeong Keun; Kang, Woo Suk; Song, Joon Myong

2010-09-01

The effects of high dose γ-irradiation on six herbal medicines were investigated using gas chromatography-mass spectrometry (GC/MS) and high-performance liquid chromatography (HPLC). Herbal medicines were irradiated at 0-50 kGy with (60)Co irradiator. HPLC was used to quantify changes of major components including glycyrrhizin, cinnamic acid, poncirin, hesperidin, berberine, and amygdalin in licorice, cinnamon bark, poncirin immature fruit, citrus unshiu peel, coptis rhizome, and apricot kernel. No significant differences were found between gamma-irradiated and non-irradiated samples with regard to the amounts of glycyrrhizin, berberine, and amygdalin. However, the contents of cinnamic acid, poncirin, and hesperidin were increased after irradiation. Volatile compounds were analyzed by GC/MS. The relative proportion of ketone in licorice was diminished after irradiation. The relative amount of hydrocarbons in irradiated cinnamon bark and apricot kernel was higher than that in non-irradiated samples. Therefore, ketone in licorice and hydrocarbons in cinnamon bark and apricot kernel can be considered radiolytic markers. Three unsaturated hydrocarbons, i.e., 1,7,10-hexadecatriene, 6,9-heptadecadiene, and 8-heptadecene, were detected only in apricot kernels irradiated at 25 and 50 kGy. These three hydrocarbons could be used as radiolytic markers to distinguish between irradiated (>25 kGy) and non-irradiated apricot kernels.

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.

Visualizing and Quantifying Bioaccessible Pores in Field-Aged Petroleum Hydrocarbon-Contaminated Clay Soils Using Synchrotron-based X-ray Computed Tomography

NASA Astrophysics Data System (ADS)

Chang, W.; Kim, J.; Zhu, N.; McBeth, J. M.

2015-12-01

Microbial hydrocarbon degradation is environmentally significant and applicable to contaminated site remediation practices only when hydrocarbons (substrates) are physically bioaccessible to bacteria in soil matrices. Powerful X-rays are produced by synchrotron radiation, allowing for bioaccessible pores in soil (larger than 4 microns), where bacteria can be accommodated, colonize and remain active, can be visualized at a much higher resolution. This study visualized and quantified such bioaccessible pores in intact field-aged, oil-contaminated unsaturated soil fractions, and examined the relationship between the abundance of bioaccessible pores and hydrocarbon biodegradation. Using synchrotron-based X-ray Computed Tomography (CT) at the Canadian Light Source, a large dataset of soil particle characteristics, such as pore volumes, surface areas, number of pores and pore size distribution, was generated. Duplicate samples of five different soil fractions with different soil aggregate sizes and water contents (13, 18 and 25%) were examined. The method for calculating the number and distribution of bioaccessible pores using CT images was validated using the known porosity of Ottawa sand. This study indicated that the distribution of bioaccessible pore sizes in soil fractions are very closely related to microbial enhancement. A follow-up aerobic biodegradation experiment for the soils at 17 °C (average site temperature) over 90 days confirmed that a notable decrease in hydrocarbon concentrations occurred in soils fractions with abundant bioaccessible pores and with a larger number of pores between 10 and 100 μm. The hydrocarbon degradation in bioactive soil fractions was extended to relatively high-molecular-weight hydrocarbons (C16-C34). This study provides quantitative information about how internal soil pore characteristics can influence bioremediation performance.

The C-H Stretching Features at 3.2--3.5 μm of Polycyclic Aromatic Hydrocarbons with Aliphatic Sidegroups

NASA Astrophysics Data System (ADS)

Yang, X. J.; Li, Aigen; Glaser, R.; Zhong, J. X.

2016-07-01

The so-called “unidentified” infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μm are ubiquitously seen in a wide variety of astrophysical regions. The UIE features are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, e.g., polycyclic aromatic hydrocarbon (PAH) molecules. The 3.3 μm aromatic C-H stretching feature is often accompanied by a weaker feature at 3.4 μm. The latter is generally thought to result from the C-H stretch of aliphatic groups attached to the aromatic systems. The ratio of the observed intensity of the 3.3 μm aromatic C-H feature to that of the 3.4 μm aliphatic C-H feature allows one to estimate the aliphatic fraction of the UIE carriers, provided that the intrinsic oscillator strengths of the 3.3 μm aromatic C-H stretch ({A}3.3) and the 3.4 μm aliphatic C-H stretch ({A}3.4) are known. While previous studies on the aliphatic fraction of the UIE carriers were mostly based on the {A}3.4/{A}3.3 ratios derived from the mono-methyl derivatives of small PAH molecules, in this work we employ density functional theory to compute the infrared vibrational spectra of PAH molecules with a wide range of sidegroups including ethyl, propyl, butyl, and several unsaturated alkyl chains, as well as all the isomers of dimethyl-substituted pyrene. We find that, except for PAHs with unsaturated alkyl chains, the corresponding {A}3.4/{A}3.3 ratios are close to that of mono-methyl PAHs. This confirms the predominantly aromatic nature of the UIE carriers previously inferred from the {A}3.4/{A}3.3 ratio derived from mono-methyl PAHs.

Tunable recognition of the steroid α-face by adjacent π-electron density

PubMed Central

Friščić, T.; Lancaster, R. W.; Fábián, L.; Karamertzanis, P. G.

2010-01-01

We report a previously unknown recognition motif between the α-face of the steroid hydrocarbon backbone and π-electron-rich aromatic substrates. Our study is based on a systematic and comparative analysis of the solid-state complexation of four steroids with 24 aromatic molecules. By using the solid state as a medium for complexation, we circumvent solubility and solvent competition problems that are inherent to the liquid phase. Characterization is performed using powder and single crystal X-ray diffraction, infrared solid-state spectroscopy and is complemented by a comprehensive cocrystal structure prediction methodology that surpasses earlier computational approaches in terms of realism and complexity. Our combined experimental and theoretical approach reveals that the α⋯π stacking is of electrostatic origin and is highly dependent on the steroid backbone’s unsaturated and conjugated character. We demonstrate that the α⋯π stacking interaction can drive the assembly of molecules, in particular progesterone, into solid-state complexes without the need for additional strong interactions. It results in a marked difference in the solid-state complexation propensities of different steroids with aromatic molecules, suggesting a strong dependence of the steroid-binding affinity and even physicochemical properties on the steroid’s A-ring structure. Hence, the hydrocarbon part of the steroid is a potentially important variable in structure-activity relationships for establishing the binding and signaling properties of steroids, and in the manufacture of pharmaceutical cocrystals. PMID:20624985

The chemistry of gamete attraction: chemical structures, biosynthesis, and (a)biotic degradation of algal pheromones.

PubMed Central

Boland, W

1995-01-01

Female gametes of marine brown algae release and/or attract their conspecific males by chemical signals. The majority of these compounds are unsaturated, nonfunctionalized acyclic, and/or alicyclic C11 hydrocarbons. Threshold concentrations for release and attraction are generally observed in the range of 1-1000 pmol. The blends may contain various configurational isomers of the genuine pheromones as well as mixtures of enantiomers. Higher plants produce the C11 hydrocarbons from dodeca-3,6,9-trienoic acid; brown algae exploit the family of icosanoids for biosynthesis of the same compounds. The biosynthetic routes comprise several spontaneously occurring pericyclic reactions such as [3.3]-sigmatropic rearrangements, [1.7]-hydrogen shifts, and electrocyclic ring closures. All pheromones are (a)biotically degraded by ubiquitous oxidative pathways involving singlet oxygen or hydroxyl radicals, which may be produced through the agency of heavy metals, huminic acids, or light. PMID:7816845

Ordered Structure Formed by Biologically Related Molecules

NASA Astrophysics Data System (ADS)

Hatta, Ichiro; Nishino, Junichiro; Sumi, Akinori; Hibino, Masahiro

1995-07-01

The two-dimensional arrangement of biologically related molecules was studied by means of scanning probe microscopy. For monolayers of fatty acid molecules with a saturated hydrocarbon chain adsorbed on a graphite substrate, in the scanning tunneling microscope image, the position associated with the carbon atoms was clearly distinguished. In addition, based on the image for fatty acid molecules with an unsaturated hydrocarbon chain, at the position of a double bond, local electrical conductance was found to increase. Based on the images, it was pointed out that not the position of each carbon but the interaction between a graphite substrate and an alkyl chain plays an important role in imaging. On the other hand, for the surface of Langmuir-Blodgett films composed of phosphatidic acids with cations, the scanning force microscope image shows, for the first time, evidence of the methyl ends in the arrangement of phospholipid molecules.

Light hydrocarbons vertical profiles and fluxes in a french rural area

NASA Astrophysics Data System (ADS)

Kanakidou, M.; Bonsang, B.; Lambert, G.

By means of manned hot air balloon flights, in July 1986, an experiment was conducted in a rural area of southwest France in order to determine the production at ground level of non-methane hydrocarbons in the C 2-C 6 range. Flux determinations were based on vertical profiles before and after the development of a temperature inversion layer which allowed the measurement of the NMHC accumulation close to ground level. The main species produced in the late afternoon were acetylene, propane, ethene, propene and ethane with production rates of the order of 0.5 to 2 × 10 -4g of C m -2 h -1. Isoprene was found to be the main other unsaturated species also produced. The fluxes and the atmospheric content of the air column before the inversion are consistent with an average OH radical concentration of 2 × 10 6 cm -3.

Microbial ecology of a crude oil contaminated aquifer

USGS Publications Warehouse

Bekins, B.A.; Cozzarelli, I.M.; Warren, E.; Godsy, E.M.

2002-01-01

Detailed microbial analyses of a glacial outwash aquifer contaminated by crude oil provide insights into the pattern of microbial succession from iron reducing to methanogenic in the anaerobic portion of the contaminant plume. We analysed sediments from this area for populations of aerobes, iron reducers, fermenters and methanogens, using the most probable number method. On the basis of the microbial data the anaerobic area can be divided into distinct physiological zones dominated by either iron-reducers or a consortium of fermenters and methanogens. Chemistry and permeability data show that methanogenic conditions develop first in areas of high hydrocarbon flux. Thus, we find methanogens both in high permeability horizons and also where separate-phase crude oil is present in either the saturated or unsaturated zone. Microbial numbers peak at the top of the separate-phase oil suggesting that growth is most rapid in locations with access to both hydrocarbons and nutrients infiltrating from the surface.

Investigation of hydrocarbon oil transformation by gliding arc discharge: comparison of batch and recirculated configurations

NASA Astrophysics Data System (ADS)

Whitehead, J. Christopher; Prantsidou, Maria

2016-04-01

The degradation of liquid dodecane was studied in a gliding arc discharge (GAD) of humid argon or nitrogen. A batch or recirculating configuration was used. The products in the gaseous and liquid phase were analysed by infrared and chromatography and optical emission spectroscopy was used to identify the excited species in the discharge. The best degradation performance comes from the use of humid N2 but a GAD of humid argon produces fewer gas-phase products but more liquid-phase end-products. A wide range of products such as heavier saturated or unsaturated hydrocarbons both aliphatic and aromatic, and oxidation products mainly alcohols, but also aldehydes, ketones and esters are produced in the liquid-phase. The recirculating treatment mode is more effective than the batch mode increasing the reactivity and changing the product selectivities. Overall, the study shows promising results for the organic liquid waste treatment, especially in the recirculating mode.

Applied remediation of petroleum hydrocarbons 3(6)

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

Hinchee, R.E.; Kittel, J.A.; Reisinger, H.J.

1995-12-31

This volume provides sound scientific and engineering approaches. Sections of this volume cover bioremediation markets, general technology overviews, and selected case studies of crude oil spills in marine environments, heavy-metal co-contamination, steam injection, nitrate-based bioremediation, land farming, nutrient addition, confined aquifers, anaerobic biodegradation, free-product recovery technologies, bioremediation in low permeability soils and rock, biopile treatment, field-scale studies, oily waste organics as soil amendments, BTEX degradation in a biofilter, surfactant-aided recovery, mass transport in BTEX removal, electron acceptor selection and delivery strategies, and electrokinetic moisture and nutrient control in unsaturated soils.

Alkoxide-based magnesium electrolyte compositions for magnesium batteries

DOEpatents

Dai, Sheng; Sun, Xiao-Guang; Liao, Chen; Guo, Bingkun

2018-01-30

Alkoxide magnesium halide compounds having the formula: RO--Mg--X (1) wherein R is a saturated or unsaturated hydrocarbon group that is unsubstituted, or alternatively, substituted with one or more heteroatom linkers and/or one or more heteroatom-containing groups comprising at least one heteroatom selected from fluorine, nitrogen, oxygen, sulfur, and silicon; and X is a halide atom. Also described are electrolyte compositions containing a compound of Formula (1) in a suitable polar aprotic or ionic solvent, as well as magnesium batteries in which such electrolytes are incorporated.

Analysis of the Control Factors of Groundwater Petroleum Hydrocarbons Contamination in a City’s West Part

NASA Astrophysics Data System (ADS)

Sun, L. H.; Ma, Z. M.; Liu, Z. W.

2018-05-01

Based on study of the hydrogeological condition and the characteristics of petroleum hydrocarbons pollution in karst groundwater, an oil refinery located in western part of a certain city is chosen as the study site to have an analysis on the control factors of groundwater petroleum hydrocarbons contamination. The study result shows that the control factors of groundwater petroleum hydrocarbons contamination are hydrogeological condition and biodegradation. The soil layer of Quaternary is very thin, the limestone is exposed in the surface, which makes the petroleum hydrocarbons easy to permeate into the water bearing layer. Karst-fractured zone in aquifer determines the migration way of petroleum hydrocarbons to be convection, but the magmatic rock in northern part has certain blocking effect on the migration of petroleum hydrocarbons. Biodegradation makes both the contamination plume area of petroleum hydrocarbons and the content of petroleum hydrocarbons decreased.

Pore-water extraction from unsaturated tuff by triaxial and one-dimensional compression methods, Nevada Test Site, Nevada

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

Mower, T.E.; Higgins, J.D.; Yang, In C.

1994-07-01

The hydrologic system in the unsaturated tuff at Yucca Mountain, Nevada, is being evaluated for the US Department of Energy by the Yucca Mountain Project Branch of the US Geological Survey as a potential site for a high-level radioactive-waste repository. Part of this investigation includes a hydrochemical study that is being made to assess characteristics of the hydrologic system such as: traveltime, direction of flow, recharge and source relations, and types and magnitudes of chemical reactions in the unsaturated tuff. In addition, this hydrochemical information will be used in the study of the dispersive and corrosive effects of unsaturated-zone watermore » on the radioactive-waste storage canisters. This report describes the design and validation of laboratory experimental procedures for extracting representative samples of uncontaminated pore water from welded and nonwelded, unsaturated tuffs from the Nevada Test Site.« less

Milk fatty acid unsaturation: genetic parameters and effects of stearoyl-CoA desaturase (SCD1) and acyl CoA: diacylglycerol acyltransferase 1 (DGAT1).

PubMed

Schennink, A; Heck, J M L; Bovenhuis, H; Visker, M H P W; van Valenberg, H J F; van Arendonk, J A M

2008-05-01

With regard to human health aspects of milk fat, increasing the amount of unsaturated fatty acids in milk is an important selection objective. The cow's diet has an influence on the degree of unsaturation, but literature suggests that genetics also plays a role. To estimate genetic variation in milk fatty acid unsaturation indices, milk fatty acid composition of 1,933 Dutch Holstein Friesian heifers was measured and unsaturation indices were calculated. An unsaturation index represents the concentration of the unsaturated product proportional to the sum of the unsaturated product and the saturated substrate. Intraherd heritabilities were moderate, ranging from 0.23 +/- 0.07 for conjugated linoleic acid (CLA) index to 0.46 +/- 0.09 for C16 index. We genotyped the cows for the SCD1 A293V and DGAT1 K232A polymorphisms, which are known to alter milk fatty acid composition. Both genes explain part of the genetic variation in unsaturation indices. The SCD1 V allele is associated with lower C10, C12, and C14 indices, and with higher C16, C18, and CLA indices in comparison to the SCD1 A allele, with no differences in total unsaturation index. In comparison to the DGAT1 K allele, the DGAT1 A allele is associated with lower C10, C12, C14, and C16 indices and with higher C18, CLA, and total indices. We conclude that selective breeding can contribute to higher unsaturation indices, and that selective breeding can capitalize on genotypic information of both the SCD1 A293V and the DGAT1 K232A polymorphism.

Reconnaissance investigation of petroleum products in soil and ground water at Longmire, Mount Rainier National Park, Washington, 1990

USGS Publications Warehouse

Sumioka, S.S.

1995-01-01

The removal of an underground waste-oil storage tank in Mount Rainier National Park, at Longmire, Washington, led to the discovery that soil surrounding the tank was saturated with unidentified petroleum hydrocarbons. Subsequent investigations by the National Park Service indicated that a petroleum product smelling like diesel oil was present in the unsaturated zone as far as 120 feet from the tank site. A study was conducted by the U.S. Geological Survey in cooperation with the National Park Service to determine the extent to which the petroleum hydrocarbons have affected the unsaturated zone and ground water in the Longmire area. Measurements of water levels in wells and of water-surface elevations of the Nisqually River and a wetland west of Longmire indicate that ground water does not flow from the maintenance area to the river or to the wetland. Waste oil and diesel oil were detected in soil samples from the site closest to the waste-oil storage-tank site. Diesel oil was also detected in samples from a site about 200 feet northwest of the storage-tank site. Organic compounds of undetermined origin were detected in soil samples from all of the other sites. Waste oil was not conclusively detected in any of the ground-water samples. Diesel oil was detected in water samples from the well closest to the storage tank and from a well about 200 feet west of the storage-tank site. Ground-water samples from all of the other wells contained organic compounds of undetermined origin.

Storage and mobilization of natural and septic nitrate in thick unsaturated zones, California

USGS Publications Warehouse

Izbicki, John A.; Flint, Alan L.; O'Leary, David R.; Nishikawa, Tracy; Martin, Peter; Johnson, Russell D.; Clark, Dennis A.

2015-01-01

Mobilization of natural and septic nitrate from the unsaturated zone as a result of managed aquifer recharge has degraded water quality from public-supply wells near Yucca Valley in the western Mojave Desert, California. The effect of nitrate storage and potential for denitrification in the unsaturated zone to mitigate increasing nitrate concentrations were investigated. Storage of water extractable nitrate in unsaturated alluvium up to 160 meters (m) thick, ranged from 420 to 6600 kilograms per hectare (kg/ha) as nitrogen (N) beneath undeveloped sites, from 6100 to 9200 kg/ha as N beneath unsewered sites. Nitrate reducing and denitrifying bacteria were less abundant under undeveloped sites and more abundant under unsewered sites; however, δ15N–NO3, and δ18O–NO3 data show only about 5–10% denitrification of septic nitrate in most samples—although as much as 40% denitrification occurred in some parts the unsaturated zone and near the top of the water table. Storage of nitrate in thick unsaturated zones and dilution with low-nitrate groundwater are the primary attenuation mechanisms for nitrate from septic discharges in the study area. Numerical simulations of unsaturated flow, using the computer program TOUGH2, showed septic effluent movement through the unsaturated zone increased as the number and density of the septic tanks increased, and decreased with increased layering, and increased slope of layers, within the unsaturated zone. Managing housing density can delay arrival of septic discharges at the water table, especially in layered unsaturated alluvium, allowing time for development of strategies to address future water-quality issues.

Storage and mobilization of natural and septic nitrate in thick unsaturated zones, California

NASA Astrophysics Data System (ADS)

Izbicki, John A.; Flint, Alan L.; O'Leary, David R.; Nishikawa, Tracy; Martin, Peter; Johnson, Russell D.; Clark, Dennis A.

2015-05-01

Mobilization of natural and septic nitrate from the unsaturated zone as a result of managed aquifer recharge has degraded water quality from public-supply wells near Yucca Valley in the western Mojave Desert, California. The effect of nitrate storage and potential for denitrification in the unsaturated zone to mitigate increasing nitrate concentrations were investigated. Storage of water extractable nitrate in unsaturated alluvium up to 160 meters (m) thick, ranged from 420 to 6600 kilograms per hectare (kg/ha) as nitrogen (N) beneath undeveloped sites, from 6100 to 9200 kg/ha as N beneath unsewered sites. Nitrate reducing and denitrifying bacteria were less abundant under undeveloped sites and more abundant under unsewered sites; however, δ15N-NO3, and δ18O-NO3 data show only about 5-10% denitrification of septic nitrate in most samples-although as much as 40% denitrification occurred in some parts the unsaturated zone and near the top of the water table. Storage of nitrate in thick unsaturated zones and dilution with low-nitrate groundwater are the primary attenuation mechanisms for nitrate from septic discharges in the study area. Numerical simulations of unsaturated flow, using the computer program TOUGH2, showed septic effluent movement through the unsaturated zone increased as the number and density of the septic tanks increased, and decreased with increased layering, and increased slope of layers, within the unsaturated zone. Managing housing density can delay arrival of septic discharges at the water table, especially in layered unsaturated alluvium, allowing time for development of strategies to address future water-quality issues.

Petroleum hydrocarbon biodegradation under seasonal freeze-thaw soil temperature regimes in contaminated soils from a sub-Arctic site.

PubMed

Chang, Wonjae; Klemm, Sara; Beaulieu, Chantale; Hawari, Jalal; Whyte, Lyle; Ghoshal, Subhasis

2011-02-01

Several studies have shown that biostimulation in ex situ systems such as landfarms and biopiles can facilitate remediation of petroleum hydrocarbon contaminated soils at sub-Arctic sites during summers when temperatures are above freezing. In this study, we examine the biodegradation of semivolatile (F2: C10-C16) and nonvolatile (F3: C16-C34) petroleum hydrocarbons and microbial respiration and population dynamics at post- and presummer temperatures ranging from -5 to 14 °C. The studies were conducted in pilot-scale tanks with soils obtained from a historically contaminated sub-Arctic site in Resolution Island (RI), Canada. In aerobic, nutrient-amended, unsaturated soils, the F2 hydrocarbons decreased by 32% during the seasonal freeze-thaw phase where soils were cooled from 2 to -5 °C at a freezing rate of -0.12 °C d(-1) and then thawed from -5 to 4 °C at a thawing rate of +0.16 °C d(-1). In the unamended (control) tank, the F2 fraction only decreased by 14% during the same period. Biodegradation of individual hydrocarbon compounds in the nutrient-amended soils was also confirmed by comparing their abundance over time to that of the conserved diesel biomarker, bicyclic sesquiterpanes (BS). During this period, microbial respiration was observed, even at subzero temperatures when unfrozen liquid water was detected during the freeze-thaw period. An increase in culturable heterotrophs and 16S rDNA copy numbers was noted during the freezing phase, and the (14)C-hexadecane mineralization in soil samples obtained from the nutrient-amended tank steadily increased. Hydrocarbon degrading bacterial populations identified as Corynebacterineae- and Alkanindiges-related strains emerged during the freezing and thawing phases, respectively, indicating there were temperature-based microbial community shifts.

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.

Relative stability and proton transfer reactions of unsaturated isocyanides and cyanides

NASA Astrophysics Data System (ADS)

Adamson, Aiko; Kaljurand, Ivari; Guillemin, Jean-Claude; Burk, Peeter

2016-09-01

The typical Gibbs free energy difference between hydrocarbon substituted isocyanides and the corresponding cyanides is 25 to 28 kcal/mol in favor of the cyanides and is mostly independent of the substituent. Triple bonded species with a -C ≡ C-RN,C (RN,C = CN, NC) structure can be considered as exceptions. Because isocyanide and cyanide species have very similar structures, the relative energy is independent of the pressure and temperature conditions. Theoretical and experimental gas-phase investigations show that basicity of isocyanides ranges from 182.1 to 198.2 kcal/mol which is 14.0 to 19.7 kcal/mol higher than the basicity of respective cyanides. The most favored protonation centers are located on isocyanide or cyanide group depending on the species. The biggest increase of basicity was caused by bulkier substituents. The substitutions have greater influence on the basicity of cyanides than on the basicity of isocyanides. In regard to deprotonation, the cyanides are more acidic than the corresponding isocyanides. For most of the unsaturated cyanide and isocyanide species the (N,C)-CHR' hydrogen (the one connected to the carbon next to cyanide/isocyanide group) is the most acidic. Our work suggests that for derivatives bearing unsaturated substituent the favored deprotonation center may be different and some cyanides and isocyanides are unstable towards gas-phase deprotonation equilibrium as the formed anion tends to isomerize.

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.

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.

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

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

Mechanical Properties of Unsaturated Polyester / Montmorillonite Composites

DTIC Science & Technology

2001-11-01

Montmorillonite Composites DISTRIBUTION: Approved for public release, distribution unlimited This paper is part of the following report: TITLE: Nanophase and...Mechanical Properties of Unsaturated Polyester / Montmorillonite Composites A. Baran Inceoglu and Ulku Yilmazer Middle East Technical University, Chemical...analysed the nature of the curing agent on structure. Kornmann, Berglund and Giannelis [8] studied nanocomposites based on montmorillonite modified

Percoll gradient-centrifuged capacitated mouse sperm have increased fertilizing ability and higher contents of sulfogalactosylglycerolipid and docosahexaenoic acid-containing phosphatidylcholine compared to washed capacitated mouse sperm.

PubMed

Furimsky, Anna; Vuong, Ngoc; Xu, Hongbin; Kumarathasan, Premkumari; Xu, Min; Weerachatyanukul, Wattana; Bou Khalil, Maroun; Kates, Morris; Tanphaichitr, Nongnuj

2005-03-01

Although Percoll gradient centrifugation has been used routinely to prepare motile human sperm, its use in preparing motile mouse sperm has been limited. Here, we showed that Percoll gradient-centrifuged (PGC) capacitated mouse sperm had markedly higher fertilizing ability (sperm-zona pellucida [ZP] binding and in vitro fertilization) than washed capacitated mouse sperm. We also showed that the lipid profiles of PGC capacitated sperm and washed capacitated sperm differed significantly. The PGC sperm had much lower contents of cholesterol and phospholipids. This resulted in relative enrichment of male germ cell-specific sulfogalactosylglycerolipid (SGG), a ZP-binding ligand, in PGC capacitated sperm, and this would explain, in part, their increased ZP-binding ability compared with that of washed capacitated sperm. Analyses of phospholipid fatty acyl chains revealed that PGC capacitated sperm were enriched in phosphatidylcholine (PC) molecular species containing highly unsaturated fatty acids (HUFAs), with docosahexaenoic acid (DHA; C22: 6n-3) being the predominant HUFA (42% of total hydrocarbon chains of PC). In contrast, the level of PC-HUFAs comprising arachidonic acid (20:4n-6), docosapentaenoic acid (C22:5n-6), and DHA in washed capacitated sperm was only 27%. Having the highest unsaturation degree among all HUFAs in PC, DHA would enhance membrane fluidity to the uppermost. Therefore, membranes of PGC capacitated sperm would undergo fertilization-related fusion events at higher rates than washed capacitated sperm. These results suggested that PGC mouse sperm should be used in fertilization experiments and that SGG and DHA should be considered to be important biomarkers for sperm fertilizing ability.

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.

MEANS FOR SHIELDING REACTORS

DOEpatents

Garrison, W.M.; McClinton, L.T.; Burton, M.

1959-03-10

A reactor of the heterageneous, heavy water moderated type is described. The reactor is comprised of a plurality of vertically disposed fuel element tubes extending through a tank of heavy water moderator and adapted to accommodate a flow of coolant water in contact with the fuel elements. A tank containing outgoing coolant water is disposed above the core to function is a radiation shield. Unsaturated liquid hydrocarbon is floated on top of the water in the shield tank to reduce to a minimum the possibility of the occurrence of explosive gaseous mixtures resulting from the neutron bombardment of the water in the shield tank.

Highly Unsaturated Platinum and Palladium Carbenes PtC 3 and PdC 3 Isolated and Characterized in the Gas Phase

DOE PAGES

Bittner, Dror M.; Zaleski, Daniel P.; Tew, David P.; ...

2016-02-16

Carbenes of platinum and palladium, PtC 3 and PdC 3 , were generated in the gas phase through laser vaporization of a metal target in the presence of a low concentration of a hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy and abinitio calculations confirm that both molecules are linear. The geometry of PtC 3 was accurately determined by fitting to the experimental moments of inertia of twenty-six isotopologues. In conclusion, the results are consistent with the proposal of an autogenic isolobal relationship between O, Au + , and Ptatoms.

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.

n-Nonacosadienes from the marine haptophytes Emiliania huxleyi and Gephyrocapsa oceanica.

PubMed

Nakamura, Hideto; Sawada, Ken; Araie, Hiroya; Suzuki, Iwane; Shiraiwa, Yoshihiro

2015-03-01

The hydrocarbons in cultures of marine haptophytes Emiliania huxleyi NIES837 and Gephyrocapsa oceanica NIES1315 were analyzed, and nonacosadienes and hentriacontadienes were detected as the major compounds in both strains. C29 and C31 monoenes and di-, tri- and tetra-unsaturated C33 alkenes were also detected as minor compounds but not C37 and C38 alkenes. The positions of the double bonds in the C29 and C31 alkenes were determined by mass spectrometry of their dimethyl disulfide (DMDS) adducts. Among the four C29 alkenes identified, the most abundant isomer was 2,20-nonacosadiene, and the other three compounds were 1,20-nonacosadiene, 3,20-nonacosadiene and 9-nonacosene, respectively. Hitherto, 2,20-nonacosadiene and 3,20-nonacosadiene were unknown to be natural products. The double bond at the n-9 (ω9) position in these C29 alkenes is hypothesized to be derived from precursors of unsaturated fatty acids possessing an n-9 double bond, such as (9Z)-9-octadecenoic acid. Nonacosadienes have the potential for being used as distinct haptophyte biomarkers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Investigations of the unsaturated zone at two radioactive waste disposal sites in Lithuania.

PubMed

Skuratovič, Žana; Mažeika, Jonas; Petrošius, Rimantas; Martma, Tõnu

2016-01-01

The unsaturated zone is an important part of the water cycle, governed by many hydrological and hydrogeological factors and processes and provide water and nutrients to the terrestrial ecosystem. Besides, the soils of the unsaturated zone are regarded as the first natural barrier to a large extent and are able to limit the spread of contaminants depending on their properties. The unsaturated zone provides a linkage between atmospheric moisture, groundwater, and seepage of groundwater to streams, lakes, or other surface water bodies. The major difference between water flow in saturated and unsaturated soils is that the hydraulic conductivity, which is conventionally assumed to be a constant in saturated soils, is a function of the degree of saturation or matrix suction in the unsaturated soils. In Lithuania, low and intermediate level radioactive wastes generated from medicine, industry and research were accumulated at the Maisiagala radioactive waste repository. Short-lived low and intermediate levels radioactive waste, generated during the operation of the Ignalina Nuclear Power Plant (INPP) and arising after the INPP decommissioning will be disposed of in the near surface repository close to the INPP (Stabatiske site). Extensive data sets of the hydraulic properties and water content attributed to unsaturated zone soil profiles of the two radioactive waste disposal sites have been collected and summarized. Globally widespread radionuclide tritium ((3)H) and stable isotope ratio ((18)O/(16)O and (2)H/(1)H) distribution features were determined in precipitation, unsaturated zone soil moisture profiles and groundwater.

Electronic Absorption Spectra of Mass-Selected Hydrocarbon Cations in Solid Neon: C_nH_4+ (n=5-8,10,12)

NASA Astrophysics Data System (ADS)

Nagy, A.; Fulara, J.; Garkusha, I.; Maier, J. P.

2011-05-01

Small, unsaturated hydrocarbons, C_nH_m (n,m≤6), play an important role in astrochemical models as they have been detected in various space objects such as the interstellar medium or envelopes of carbon-rich stars. Although identification of most of these species was based on rotational studies, they are candidate carriers of the infamous diffuse interstellar bands. It has been proposed that corresponding cationic species formed upon UV radiation may also be of astrophysical relevance; therefore, their optical spectra need to be determined. In this contribution, electronic absorption spectra of mass-selected C_nH_4+ (n=5-8,10,12) ions trapped in neon matrices are presented. The cations were produced in a hot-cathode discharge source, guided through a series of electrostatic lenses, mass filtered and co-deposited with excess of neon onto a rhodium-coated sapphire plate held at 6 K. In the same experiments, neutral species were generated from the cations by a photobleaching procedure.

Chemical Composition of Microbe-Derived Dissolved Organic Matter in Cryoconite in Tibetan Plateau Glaciers: Insights from Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Analysis.

PubMed

Feng, Lin; Xu, Jianzhong; Kang, Shichang; Li, Xiaofei; Li, Yang; Jiang, Bin; Shi, Quan

2016-12-20

Cryoconite in mountain glaciers plays important roles in glacial ablation and biogeochemical cycles. In this study, the composition and sources of dissolved organic matter (DOM) in cryoconite from the ablation regions of two Tibetan Plateau glaciers were determined using electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and fluorescence spectrometry. A marked absorbance between 300 and 350 nm in the DOM absorption spectra was observed which was consistent with microbe-derived mycosporine-like amino acids. Fluorescence excitation-emission matrices showed that DOM had intense signals at protein-like substance peaks and weak signals at humic-like substance peaks. The high-resolution mass spectra of FT-ICR-MS showed cryoconite DOM from both glaciers contained diverse lignins, lipids, proteins, and unsaturated hydrocarbons. The lipids and proteins were consistent with material from microbial sources, and the lignins and unsaturated hydrocarbons were probably from vascular plant material supplied in atmospheric aerosols and debris from around the glaciers. Almost one-third of the identified DOM molecules had low C/N ratios (≤20), indicating their high bioavailability. Using a conservative cryoconite distribution on Chinese mountain glacier surfaces (6%) and an average debris mass per square meter of cryoconite (292 ± 196 g m -2 ), we found that the amount of DOC produced in cryoconite on Chinese glaciers as much as 0.23 ± 0.1 Gg per cryoconite formation process. This dissolved organic carbon may absorb solar radiation, accelerate glacial melting, and be an important source of bioavailable DOM to proglacial and downstream aquatic ecosystems.

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.

A pollinators' eye view of a shelter mimicry system.

PubMed

Vereecken, Nicolas J; Dorchin, Achik; Dafni, Amots; Hötling, Susann; Schulz, Stefan; Watts, Stella

2013-06-01

'Human-red' flowers are traditionally considered to be rather unpopular with bees, yet some allogamous species in the section Oncocyclus (genus Iris, Iridaceae) have evolved specialized interactions with their pollinators, a narrow taxonomic range of male solitary bees. The dark-red, tubular flowers of these irises are nectarless but provide protective shelters (i.e. a non-nutritive form of reward) primarily to male solitary bees (Apidae, Eucerini) that pollinate the flowers while looking for a shelter. An earlier study on orchids suggested that species pollinated predominantly by male solitary bees produce significantly larger amounts and larger numbers of different n-alkenes (unsaturated cuticular hydrocarbons). Whether or not this also applies to the Oncocyclus irises and whether pollinators are attracted by specific colours or scents of these flowers is unknown. Using Iris atropurpurea, recording of pollinator preferences for shelters with different spatial parameters was combined with analyses of floral colours (by spectrophotometry) and scents (by gas chromatography-mass spectrometry) to test the hypotheses that (a) pollinators significantly prefer floral tunnels facing the rising sun (floral heat-reward hypothesis), and that (b) flowers pollinated predominantly by male solitary bees produce significantly larger amounts and larger numbers of unsaturated cuticular hydrocarbons (n-alkenes) in their floral scent (preadaptation to sexual-deception hypothesis). Male bees do not significantly prefer shelters facing the rising sun or with the presence of high absolute/relative amounts and numbers of n-alkenes in the floral scent. The results suggest that the flowers of I. atropurpurea probably evolved by pollinator-mediated selection acting primarily on floral colours to mimic large achromatic ('bee-black') protective shelters used preferentially by male solitary bees, and that pollinator visits are presumably not the result of an odour-based sexual stimulation or motivated by an increased morning floral heat reward in tunnels facing the rising sun.

Acetylene and Ethylene Adsorption on a β-Mo 2C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactions

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

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres

Mo 2C catalysts are widely used in hydrogenation reactions; however, the role of the C and Mo terminations in these catalysts is not clear. Understanding the binding of adsorbates is key for explaining the activity of Mo 2C. The adsorption of acetylene and ethylene, probe molecules representing alkynes and olefins, respectively, was studied in this paper on a β-Mo 2C(100) surface with C and Mo terminations using calculations based on periodic density functional theory. Moreover, the role of the C/Mo molar ratio was investigated to compare the catalytic potential of cubic (δ-MoC) and orthorhombic (β-Mo 2C) surfaces. The geometry andmore » electronic properties of the clean δ-MoC(001) and β-Mo 2C(100) surfaces have a strong influence on the binding of unsaturated hydrocarbons. The adsorption of ethylene is weaker than that of acetylene on the surfaces of the cubic and orthorhombic systems; adsorption of the hydrocarbons was stronger on β-Mo 2C(100) than on δ-MoC(001). The C termination in β-Mo 2C(100) actively participates in both acetylene and ethylene adsorption and is not merely a spectator. Finally, the results of this work suggest that the β-Mo 2C(100)-C surface could be the one responsible for the catalytic activity during the hydrogenation of unsaturated C≡C and C=C bonds, while the Mo-terminated surface could be poisoned or transformed by the strong adsorption of C and CH x fragments.« less

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.

Acetylene and Ethylene Adsorption on a β-Mo 2C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactions

DOE PAGES

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres; ...

2017-08-18

Mo 2C catalysts are widely used in hydrogenation reactions; however, the role of the C and Mo terminations in these catalysts is not clear. Understanding the binding of adsorbates is key for explaining the activity of Mo 2C. The adsorption of acetylene and ethylene, probe molecules representing alkynes and olefins, respectively, was studied in this paper on a β-Mo 2C(100) surface with C and Mo terminations using calculations based on periodic density functional theory. Moreover, the role of the C/Mo molar ratio was investigated to compare the catalytic potential of cubic (δ-MoC) and orthorhombic (β-Mo 2C) surfaces. The geometry andmore » electronic properties of the clean δ-MoC(001) and β-Mo 2C(100) surfaces have a strong influence on the binding of unsaturated hydrocarbons. The adsorption of ethylene is weaker than that of acetylene on the surfaces of the cubic and orthorhombic systems; adsorption of the hydrocarbons was stronger on β-Mo 2C(100) than on δ-MoC(001). The C termination in β-Mo 2C(100) actively participates in both acetylene and ethylene adsorption and is not merely a spectator. Finally, the results of this work suggest that the β-Mo 2C(100)-C surface could be the one responsible for the catalytic activity during the hydrogenation of unsaturated C≡C and C=C bonds, while the Mo-terminated surface could be poisoned or transformed by the strong adsorption of C and CH x fragments.« less

Rate coefficients for the reactions of C2(a(3)Pi(u)) and C2(X(1)Sigma(g)(+)) with various hydrocarbons (CH4, C2H2, C2H4, C2H6, and C3H8): a gas-phase experimental study over the temperature range 24-300 K.

PubMed

Páramo, Alejandra; Canosa, André; Le Picard, Sébastien D; Sims, Ian R

2008-10-02

The kinetics of reactions of C2(a(3)Pi(u)) and C2(X(1)Sigma(g)(+)) with various hydrocarbons (CH4, C2H2, C2H4, C2H6, and C3H8) have been studied in a uniform supersonic flow expansion over the temperature range 24-300 K. Rate coefficients have been obtained by using the pulsed laser photolysis-laser induced fluorescence technique, where both radicals were produced at the same time but detected separately. The reactivity of the triplet state was found to be significantly lower than that of the singlet ground state for all reactants over the whole temperature range of the study. Whereas C2(X(1)Sigma(g)(+)) reacts with a rate coefficient close to the gas kinetic limit with all hydrocarbons studied apart from CH4, C2(a(3)Pi(u)) appears to be more sensitive to the molecular and electronic structure of the reactant partners. The latter reacts at least one order of magnitude faster with unsaturated hydrocarbons than with alkanes, and the rate coefficients increase very significantly with the size of the alkane. Results are briefly discussed in terms of their potential astrophysical impact.

Reservoir simulation with the cubic plus (cross-) association equation of state for water, CO2, hydrocarbons, and tracers

NASA Astrophysics Data System (ADS)

Moortgat, Joachim

2018-04-01

This work presents an efficient reservoir simulation framework for multicomponent, multiphase, compressible flow, based on the cubic-plus-association (CPA) equation of state (EOS). CPA is an accurate EOS for mixtures that contain non-polar hydrocarbons, self-associating polar water, and cross-associating molecules like methane, ethane, unsaturated hydrocarbons, CO2, and H2S. While CPA is accurate, its mathematical formulation is highly non-linear, resulting in excessive computational costs that have made the EOS unfeasible for large scale reservoir simulations. This work presents algorithms that overcome these bottlenecks and achieve an efficiency comparable to the much simpler cubic EOS approach. The main applications that require such accurate phase behavior modeling are 1) the study of methane leakage from high-pressure production wells and its potential impact on groundwater resources, 2) modeling of geological CO2 sequestration in brine aquifers when one is interested in more than the CO2 and H2O components, e.g. methane, other light hydrocarbons, and various tracers, and 3) enhanced oil recovery by CO2 injection in reservoirs that have previously been waterflooded or contain connate water. We present numerical examples of all those scenarios, extensive validation of the CPA EOS with experimental data, and analyses of the efficiency of our proposed numerical schemes. The accuracy, efficiency, and robustness of the presented phase split computations pave the way to more widespread adoption of CPA in reservoir simulators.

Three phase heat and mass transfer model for unsaturated soil freezing process: Part 2 - model validation

NASA Astrophysics Data System (ADS)

Zhang, Yaning; Xu, Fei; Li, Bingxi; Kim, Yong-Song; Zhao, Wenke; Xie, Gongnan; Fu, Zhongbin

2018-04-01

This study aims to validate the three-phase heat and mass transfer model developed in the first part (Three phase heat and mass transfer model for unsaturated soil freezing process: Part 1 - model development). Experimental results from studies and experiments were used for the validation. The results showed that the correlation coefficients for the simulated and experimental water contents at different soil depths were between 0.83 and 0.92. The correlation coefficients for the simulated and experimental liquid water contents at different soil temperatures were between 0.95 and 0.99. With these high accuracies, the developed model can be well used to predict the water contents at different soil depths and temperatures.

Sedimentary organic biomarkers suggest detrimental effects of PAHs on estuarine microbial biomass during the 20th century in San Francisco Bay, CA, USA

USGS Publications Warehouse

Nilsen, Elena B.; Rosenbauer, Robert J.; Fuller, Christopher C.; Jaffe, Bruce E.

2014-01-01

Hydrocarbon contaminants are ubiquitous in urban aquatic ecosystems, and the ability of some microbial strains to degrade certain polycyclic aromatic hydrocarbons (PAHs) is well established. However, detrimental effects of petroleum hydrocarbon contamination on nondegrader microbial populations and photosynthetic organisms have not often been considered. In the current study, fatty acid methyl ester (FAME) biomarkers in the sediment record were used to assess historical impacts of petroleum contamination on microbial and/or algal biomass in South San Francisco Bay, CA, USA. Profiles of saturated, branched, and monounsaturated fatty acids had similar concentrations and patterns downcore. Total PAHs in a sediment core were on average greater than 20× higher above ∼200 cm than below, which corresponds roughly to the year 1900. Isomer ratios were consistent with a predominant petroleum combustion source for PAHs. Several individual PAHs exceeded sediment quality screening values. Negative correlations between petroleum contaminants and microbial and algal biomarkers – along with high trans/cis ratios of unsaturated FA, and principle component analysis of the PAH and fatty acid records – suggest a negative impacts of petroleum contamination, appearing early in the 20th century, on microbial and/or algal ecology at the site.

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

Degree of fatty acyl chain unsaturation in biliary lecithin dictates cholesterol nucleation and crystal growth.

PubMed

Tazuma, S; Ochi, H; Teramen, K; Yamashita, Y; Horikawa, K; Miura, H; Hirano, N; Sasaki, M; Aihara, N; Hatsushika, S

1994-11-17

To clarify factors involved in the formation of cholesterol gallstones, we studied the relationship between the degree of fatty acyl chain unsaturation of biliary lecithin and bile metastability. We used supersaturated model bile solutions (molar taurocholate/lecithin/cholesterol ratio (73:19.5:7.5), total lipid concentration 9 g/dl) that contained equimolar egg yolk or soybean lecithins or a sn-1 palmitoyl, sn-2 linoleoyl phosphatidylcholine. Gel permeation chromatographic studies showed that the vesicular cholesterol distribution and dimension were inversely related to the degree of unsaturation of the lecithin species, estimated by reverse phase, high-performance liquid chromatography. Differential interference contrast microscopy and assay of cholesterol crystal growth showed that a higher degree of fatty acyl chain unsaturation of the lecithin species was associated with a faster nucleation time and rate of crystal growth. Our results suggest that vesicular lecithins containing more unsaturated fatty acyl chains bind less tightly to cholesterol than lecithins containing predominantly saturated fatty acids, and that the biliary lecithin species dictates, in part, the nucleation and growth of cholesterol crystals in bile.

Data from a Thick Unsaturated Zone Underlying Two Artificial Recharge Sites along Oro Grande Wash in the Western Part of the Mojave Desert, near Victorville, San Bernardino County, California, 2001-2006

USGS Publications Warehouse

Clark, Dennis A.; Izbicki, John A.; Johnson, Russell D.; Land, Michael

2009-01-01

This report presents data on the physical and hydraulic properties of unsaturated alluvial deposits and on the chemical and isotopic composition of water collected at two recharge sites in the western part of the Mojave Desert, near Victorville, California, from 2001 to 2006. Unsaturated-zone monitoring sites were installed adjacent to the two recharge ponds using the ODEX air-hammer and air rotary method to depths of about 460 feet and 269 feet below land surface. Each of the two unsaturated-zone monitoring sites included a water-table well, matric-potential sensors, and suction-cup lysimeters installed in a single bore hole. Drilling procedures, lithologic and geophysical data, and site construction and instrumentation are described. Core material was analyzed for water content, bulk density, water potential, particle size, and water retention. The chemical composition of leachate from almost 400 samples of cores and cuttings was determined. Water from suction-cup lysimeters also was analyzed for chemical and isotopic composition. In addition, data on the chemical and isotopic composition of groundwater from the two water-table wells are reported along with chemical and isotopic composition of the surface water in the recharge ponds.

Highly Unsaturated Platinum and Palladium Carbenes PtC3 and PdC3 Isolated and Characterized in the Gas Phase

PubMed Central

Bittner, Dror M.; Zaleski, Daniel P.; Tew, David P.

2016-01-01

Abstract Carbenes of platinum and palladium, PtC3 and PdC3, were generated in the gas phase through laser vaporization of a metal target in the presence of a low concentration of a hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy and ab initio calculations confirm that both molecules are linear. The geometry of PtC3 was accurately determined by fitting to the experimental moments of inertia of twenty‐six isotopologues. The results are consistent with the proposal of an autogenic isolobal relationship between O, Au+, and Pt atoms. PMID:26879473

[Branched alkanes and other apolar compounds produced by the cyanobacterium Microcoleus vaginatus from the Negev desert].

PubMed

Dembitskiĭ, V M; Dor, I; Shkrob, I; Aki, M

2001-01-01

Gas chromatography-mass spectrometry on serially coupled capillary columns with different polarity of stationary phases showed that the soil cyanobacterium Microcoleus vaginatus from the Negev desert produces an unusual mixture of 4 normal and more than 60 branched alkanes, as well as a number of fatty acids, cyclic and unsaturated hydrocarbons, aldehydes, alcohols, and ketones. The dominant compounds were heptadecane (12%), 7-methylheptadecane (7.8%), hexadecanoic acid (6.5%), (Z)-9-hexadecenoic acid (5.6%), 4-ethyl-2,2,6,6-tetramethylheptane (2.8%), (Z)-9-octadecenoic acid (2.8%), and 4-methyl-5-propylnonane (2.7%).

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

40 CFR 1039.805 - What symbols, acronyms, and abbreviations does this part use?

Code of Federal Regulations, 2010 CFR

2010-07-01

... oxide. NISTNational Institute of Standards and Technology. NMHCnonmethane hydrocarbons. NOXoxides of... Automotive Engineers. SEASelective enforcement audit. THCtotal hydrocarbon. THCEtotal hydrocarbon equivalent...

40 CFR 1039.805 - What symbols, acronyms, and abbreviations does this part use?

Code of Federal Regulations, 2011 CFR

2011-07-01

... oxide. NISTNational Institute of Standards and Technology. NMHCnonmethane hydrocarbons. NOXoxides of... Automotive Engineers. SEASelective enforcement audit. THCtotal hydrocarbon. THCEtotal hydrocarbon equivalent...

Infrared and reflectron time-of-flight mass spectroscopic analysis of methane (CH4)-carbon monoxide (CO) ices exposed to ionization radiation--toward the formation of carbonyl-bearing molecules in extraterrestrial ices.

PubMed

Kaiser, Ralf I; Maity, Surajit; Jones, Brant M

2014-02-28

Ice mixtures of methane and carbon monoxide were exposed to ionizing radiation in the form of energetic electrons at 5.5 K to investigate the formation of carbonyl bearing molecules in extraterrestrial ices. The radiation induced chemical processing of the mixed ices along with their isotopically labeled counterparts was probed online and in situ via infrared spectroscopy (solid state) aided with reflectron time-of-flight mass spectrometry (ReTOFMS) coupled to single photon photoionization (PI) at 10.49 eV (gas phase). Deconvolution of the carbonyl absorption feature centered at 1727 cm(-1) in the processed ices and subsequent kinetic fitting to the temporal growth of the newly formed species suggests the formation of acetaldehyde (CH3CHO) together with four key classes of carbonyl-bearing molecules: (i) alkyl aldehydes, (ii) alkyl ketones, (iii) α,β-unsaturated ketones/aldehydes and (iv) α,β,γ,δ-unsaturated ketones/α,β-dicarbonyl compounds in keto-enol form. The mechanistical studies indicate that acetaldehyde acts as the key building block of higher aldehydes (i) and ketones (ii) with unsaturated ketones/aldehydes (iii) and/or α,β-dicarbonyl compounds (iv) formed from the latter. Upon sublimation of the newly synthesized molecules, ReTOFMS together with isotopic shifts of the mass-to-charge ratios was exploited to identify eleven product classes containing molecules with up to six carbon atoms, which can be formally derived from C1-C5 hydrocarbons incorporating up to three carbon monoxide building blocks. The classes are (i) saturated aldehydes/ketones, (ii) unsaturated aldehydes/ketones, (iii) doubly unsaturated aldehydes/ketones, (iv) saturated dicarbonyls (aldehydes/ketones), (v) unsaturated dicarbonyls (aldehydes/ketones), (vi) saturated tricarbonyls (aldehydes/ketones), molecules containing (vii) one carbonyl - one alcohol (viii), two carbonyls - one alcohol, (ix) one carbonyl - two alcohol groups along with (x) alcohols and (xi) diols. Reaction pathways to synthesize these classes were derived as well. The present experiments provide clear evidence for the formation of key organic molecules--acetaldehyde, acetone, and potentially vinylalcohol--which are among the 15 carbonyl containing organic molecules detected in the interstellar medium. Despite numerous previous experimental investigations probing the effect of ionizing radiation on simple astrophysical ice representatives, our results suggest that more complex organic molecules can be formed in extraterrestrial ices than previously suggested. An outlook on further identification of individual isomers is also presented.

Reconstructing the pollinator community and predicting seed set from hydrocarbon footprints on flowers.

PubMed

Witjes, Sebastian; Witsch, Kristian; Eltz, Thomas

2011-04-01

The measurement of insect visits to flowers is essential for basic and applied pollination ecology, but is often fraught with difficulty. Floral visitation is highly variable and observational studies are limited in scope due to the considerable time needed to acquire reliable data. Our study investigates whether the analysis of hydrocarbon residues (footprints) deposited by insects during flower visits allows the reconstruction of the visitor community and the prediction of seed set for large numbers of plants. In three consecutive years we recorded bumblebee visitation to wild plants of comfrey, Symphytum officinale, and later used gas chromatography/mass spectrometry (GC/MS) to quantify bumblebee-derived unsaturated hydrocarbons (UHCs) extracted from flowers. The UHCs washed from corollae were most similar to the tarsal UHC profile of the most abundant bumblebee species, Bombus pascuorum, in all 3 years. The species compositions of the bumblebee communities estimated from UHCs on flowers were also similar to those actually observed. There was a significant positive correlation between the observed number of visits by each of three bumblebee species (contributing 3-68% of the flower visits) and the estimated number of visits based on UHC profiles. Furthermore, significant correlations were obtained separately for workers and drones of two species. Seed set of comfrey plants was positively correlated with overall bumblebee visitation and the total amount of UHCs on flowers, suggesting the potential for pollen limitation. We suggest that quantifying cumulative footprint hydrocarbons provides a novel way to assess floral visitation by insects, and that this method can be used to predict seed set in pollen-limited plants.

Diesel particle filter and fuel effects on heavy-duty diesel engine emissions.

PubMed

Ratcliff, Matthew A; Dane, A John; Williams, Aaron; Ireland, John; Luecke, Jon; McCormick, Robert L; Voorhees, Kent J

2010-11-01

The impacts of biodiesel and a continuously regenerated (catalyzed) diesel particle filter (DPF) on the emissions of volatile unburned hydrocarbons, carbonyls, and particle associated polycyclic aromatic hydrocarbons (PAH) and nitro-PAH, were investigated. Experiments were conducted on a 5.9 L Cummins ISB, heavy-duty diesel engine using certification ultra-low-sulfur diesel (ULSD, S ≤ 15 ppm), soy biodiesel (B100), and a 20% blend thereof (B20). Against the ULSD baseline, B20 and B100 reduced engine-out emissions of measured unburned volatile hydrocarbons and PM associated PAH and nitro-PAH by significant percentages (40% or more for B20 and higher percentage for B100). However, emissions of benzene were unaffected by the presence of biodiesel and emissions of naphthalene actually increased for B100. This suggests that the unsaturated FAME in soy-biodiesel can react to form aromatic rings in the diesel combustion environment. Methyl acrylate and methyl 3-butanoate were observed as significant species in the exhaust for B20 and B100 and may serve as markers of the presence of biodiesel in the fuel. The DPF was highly effective at converting gaseous hydrocarbons and PM associated PAH and total nitro-PAH. However, conversion of 1-nitropyrene by the DPF was less than 50% for all fuels. Blending of biodiesel caused a slight reduction in engine-out emissions of acrolein, but otherwise had little effect on carbonyl emissions. The DPF was highly effective for conversion of carbonyls, with the exception of formaldehyde. Formaldehyde emissions were increased by the DPF for ULSD and B20.

Catalytic properties of volcanic rocks in the synthesis of hydrocarbons from carbon monoxide and hydrogen

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

Taran, Yu.A.; Novak, F.I.; Antoshchuk, I.A.

1981-10-01

Results obtained from studying the catalytic properties of effusive rocks of various chemical compositions, extracted from lava flows of several Kamchatka volcanos, in the process of synthesis from carbon monoxide and hydrogen, are presented. It was evident that samples of volcanic rock display catalytic properties in the process of synthesis from CO and H/sub 2/ in which liquid and gaseous hydrocarbons and an insignificant amount of oxygen-containing compounds are formed as products of the reactions. At a synthesis temperature of 350/sup 0/C the catalytic activity of the samples is characterized by the conversion of CO at a level of 70more » to 80%, and H/sub 2/ at 50 to 60%. The yield of oil, gasoline, and natural gas reached 40, 11, and 3 ml/m/sup 3/, respectively. The light synthetic products were presented based on saturated hydrocarbons of an aliphatic series with significant contents of olefins and insignificant quantities of alcohols and carbonyl compounds. The composition of gaseous products is characterized by significant unsaturation (approx. 33%) and a high content of butane-butylenic fractions (to approx. 55%). The data obtained showed that volcanic rocks were able to catalyze the synthesis of hydrocarbons from CO and H/sub 2/. The sources of the catalytic properties of the rocks shown are evidently iron compounds, and the remaining ingredients of the rocks are able to fulfill the role of structural or chemical promoters influencing the properties of the catalysts and the composition of the reaction products formed. 2 tables. (DP)« less

Experimental and modeling study of the thermal decomposition of methyl decanoate

PubMed Central

Herbinet, Olivier; Glaude, Pierre-Alexandre; Warth, Valérie; Battin-Leclerc, Frédérique

2013-01-01

The experimental study of the thermal decomposition of methyl decanoate was performed in a jet-stirred reactor at temperatures ranging from 773 to 1123 K, at residence times between 1 and 4 s, at a pressure of 800 Torr (106.6 kPa) and at high dilution in helium (fuel inlet mole fraction of 0.0218). Species leaving the reactor were analyzed by gas chromatography. Main reaction products were hydrogen, carbon oxides, small hydrocarbons from C1 to C3, large 1-olefins from 1-butene to 1-nonene, and unsaturated esters with one double bond at the end of the alkyl chain from methyl-2-propenoate to methyl-8-nonenoate. At the highest temperatures, the formation of polyunsaturated species was observed: 1,3-butadiene, 1,3-cyclopentadiene, benzene, toluene, indene, and naphthalene. These results were compared with previous ones about the pyrolysis of n-dodecane, an n-alkane of similar size. The reactivity of both molecules was found to be very close. The alkane produces more olefins while the ester yields unsaturated oxygenated compounds. A detailed kinetic model for the thermal decomposition of methyl decanoate has been generated using the version of software EXGAS which was updated to take into account the specific chemistry involved in the oxidation of methyl esters. This model contains 324 species and 3231 reactions. It provided a very good prediction of the experimental data obtained in jet-stirred reactor. The formation of the major products was analyzed. The kinetic analysis showed that the retro-ene reactions of intermediate unsaturated methyl esters are of importance in low reactivity systems. PMID:23710078

The effects of diet and breed on the volatile compounds of cooked lamb.

PubMed

Elmore, J S; Mottram, D S; Enser, M; Wood, J D

2000-06-01

The effect of varying the n-3 polyunsaturated fatty acid (PUFA) composition of lamb muscle on the formation of aroma volatiles during cooking has been examined. The meat was obtained from four groups of Suffolk and Soay lambs fed different supplementary fats: a palm-oil based control; bruised whole linseed, which increased muscle levels of α-linolenic acid (C18:3 n-3); fish oil, which increased eicosapentaenoic acid (EPA, C20:5 n-3) and docosahexaenoic acid (DHA, C22:6 n-3); and equal quantities of linseed and fish oil (fat basis). Higher quantities of lipid oxidation products were found in the aroma volatiles of lamb muscle from animals fed fish oil, compared to the control. In particular, unsaturated aldehydes, unsaturated hydrocarbons and alkylfurans increased up to fourfold. These compounds derived from the autoxidation of PUFAs during cooking. Although some of these volatiles were increased in meat from animals fed the linseed supplement, the effect was not as great as with the fish oil fed lambs. Levels of volatiles derived from the Maillard reaction, such as pyrazines and sulfur compounds, were up to four times higher in Soays than Suffolks.

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

Deuterium isotope effects in polymerization of benzene under pressure

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

Cai, Weizhao; Dunuwille, Mihindra; He, Jiangang

The enormous versatility in the properties of carbon materials depends on the content of the sp 2 and sp 3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C 6H 6 and C 6D 6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures showmore » the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C 6D 6 shed light on the mechanism of polymerization of benzene. Lastly, we find that C 6D 6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp 3 hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C 6D 6 is observed.« less

Deuterium isotope effects in polymerization of benzene under pressure

DOE PAGES

Cai, Weizhao; Dunuwille, Mihindra; He, Jiangang; ...

2017-04-10

The enormous versatility in the properties of carbon materials depends on the content of the sp 2 and sp 3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C 6H 6 and C 6D 6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures showmore » the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C 6D 6 shed light on the mechanism of polymerization of benzene. Lastly, we find that C 6D 6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp 3 hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C 6D 6 is observed.« less

Production and characterization of biodiesel from carbon dioxide concentrating chemolithotrophic bacteria, Serratia sp. ISTD04.

PubMed

Bharti, Randhir K; Srivastava, Shaili; Thakur, Indu Shekhar

2014-02-01

A chemolithotrophic bacterium, Serratia sp. ISTD04, enriched in the chemostat in presence of sodium bicarbonate as sole carbon source was evaluated for potential of carbon dioxide (CO2) sequestration and biofuel production. CO2 sequestration efficiency of the bacterium was determined by enzymatic activity of carbonic anhydrase and ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO). Further, Western blot analysis confirmed presence of RuBisCO. The bacterium produced 0.487 and 0.647mgmg(-1) per unit cell dry weight of hydrocarbons and lipids respectively. The hydrocarbons were within the range of C13-C24 making it equivalent to light oil. GC-MS analysis of lipids produced by the bacterium indicated presence of C15-C20 organic compounds that made it potential source of biodiesel after transesterification. GC-MS, FTIR and NMR spectroscopic characterization of the fatty acid methyl esters revealed the presence of 55% and 45% of unsaturated and saturated organic compounds respectively, thus making it a balanced biodiesel composition. Copyright © 2013 Elsevier Ltd. All rights reserved.

40 CFR 1045.805 - What symbols, acronyms, and abbreviations does this part use?

Code of Federal Regulations, 2011 CFR

2011-07-01

.... NARANational Archives and Records Administration. NMHCnonmethane hydrocarbons. NOXoxides of nitrogen (NO and.... SAESociety of Automotive Engineers. THCtotal hydrocarbon. THCEtotal hydrocarbon equivalent. U.S.C.United...

40 CFR 1045.805 - What symbols, acronyms, and abbreviations does this part use?

Code of Federal Regulations, 2010 CFR

2010-07-01

.... NARANational Archives and Records Administration. NMHCnonmethane hydrocarbons. NOXoxides of nitrogen (NO and.... SAESociety of Automotive Engineers. THCtotal hydrocarbon. THCEtotal hydrocarbon equivalent. U.S.C.United...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2010 CFR

2010-07-01

... Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Averageboiling point * (degrees F) Criteria Reactivityfactor 1 80-205 Alkanes... + Dry Point) / 2 (b) Aromatic Hydrocarbon Solvents ...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2011 CFR

2011-07-01

... Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Averageboiling point * (degrees F) Criteria Reactivityfactor 1 80-205 Alkanes... + Dry Point) / 2 (b) Aromatic Hydrocarbon Solvents ...

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.

Extending the basic function of lattice oxygen in lepidocrocite titanate - The conversion of intercalated fatty acid to liquid hydrocarbon fuels

NASA Astrophysics Data System (ADS)

Maluangnont, Tosapol; Arsa, Pornanan; Sooknoi, Tawan

2017-12-01

We report herein the basicity of the external and internal lattice oxygen (OL) in lepidocrocite titanates with respect to CO2 and palmitic acid, respectively. Several compositions have been tested with different types of the metal M aliovalently (co)substituted for Ti, K0.8[MyTi2-y]O4 (M = Li, Mg, Fe, Co, Ni, Cu, Zn, Cu/Ni and Cu/Zn). The low CO2 desorption peak temperature (70-100 °C) suggests that the external OL sites are weakly basic similar to TiO2. However, the internal OL sites are sufficiently basic to deprotonate palmitic acid, forming the intercalated potassium palmitate at the interlayer spaces. The latter serves as a two-dimensional (2D) molecular reactor for the production of liquid hydrocarbon fuels via deoxygenation under atmospheric N2. A relationship has been observed between the yield of the liquid products vs the partial charge of the lattice oxygen (δO). Since the deoxygenation pathway is highly dependent on the metal substitution, the redox-active sites might also play some roles. The co-substituted K0.8[Cu0.2Ni0.2]Ti1.6O4 produced 68.0% yield of the liquid products, with 51% saturated and 15% unsaturated C15 hydrocarbons at 350 °C.

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.

On the formation of polyacetylenes and cyanopolyacetylenes in Titan's atmosphere and their role in astrobiology.

PubMed

Kaiser, Ralf I; Mebel, Alexander M

2012-08-21

This tutorial review compiles recent experimental and theoretical studies on the formation of polyacetylenes (H(C≡C)(n)H) and cyanopolyacetylenes (H(C≡C)(n)CN) together with their methyl-substituted counterparts (CH(3)(C≡C)(n)H, CH(3)(C≡C)(n)CN) as probed under single collision conditions in crossed beam studies via the elementary reactions of ethynyl (CCH) and cyano radicals (CN) with unsaturated hydrocarbons. The role of these key reaction classes in the chemical evolution of Titan's orange-brownish haze layers is also discussed. We further comment on astrobiological implications of our findings with respect to proto-Earth and present a brief outlook on future research directions.

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).

Pyrolysis-mass spectrometry/pattern recognition on a well-characterized suite of humic samples

USGS Publications Warehouse

MacCarthy, P.; DeLuca, S.J.; Voorhees, K.J.; Malcolm, R.L.; Thurman, E.M.

1985-01-01

A suite of well-characterized humic and fulvic acids of freshwater, soil and plant origin was subjected to pyrolysis-mass spectrometry and the resulting data were analyzed by pattern recognition and factor analysis. A factor analysis plot of the data shows that the humic acids and fulvic acids can be segregated into two distinct classes. Carbohydrate and phenolic components are more pronounced in the pyrolysis products of the fulvic acids, and saturated and unsaturated hydrocarbons contribute more to the humic acid pyrolysis products. A second factor analysis plot shows a separation which appears to be based primarily on whether the samples are of aquatic or soil origin. ?? 1985.

Biochemical characterization of blood orange, sweet orange, lemon, bergamot and bitter orange.

PubMed

Moufida, Saïdani; Marzouk, Brahim

2003-04-01

This paper reports on the composition of aroma compounds and fatty acids and some physico-chemical parameters (juice percentage, acidity and total sugars) in five varieties of citrus: blood orange, sweet orange, lemon, bergamot and bitter orange. Volatile compounds and methyl esters have been analyzed by gas chromatography. Limonene is the most abundant compound of monoterpene hydrocarbons for all of the examined juices. Eighteen fatty acids have been identified in the studied citrus juices, their quantification points out that unsaturated acids predominate over the saturated ones. Mean concentration of fatty acids varies from 311.8 mg/l in blood orange juice to 678 mg/l in bitter orange juice. Copyright 2003 Elsevier Science Ltd.

Ozone Modulation/Membrane Introduction Mass Spectrometry for Analysis of Hydrocarbon Pollutants in Air

NASA Astrophysics Data System (ADS)

Atkinson, D. B.

2001-12-01

Modulation of volatile hydrocarbons in two-component mixtures is demonstrated using an ozonolysis pretreatment with membrane introduction mass spectrometry (MIMS). The MIMS technique allows selective introduction of volatile and semivolatile analytes into a mass spectrometer via processes known collectively as pervaporation [Kotiaho and Cooks, 1992]. A semipermeable polymer membrane acts as an interface between the sample (vapor or solution) and the vacuum of the mass spectrometer. This technique has been demonstrated to allow for sensitive analysis of hydrocarbons and other non-polar volatile organic compounds (VOC`s) in air samples[Cisper et al., 1995] . The methodology has the advantages of no sample pretreatment and short analysis time, which are promising for online monitoring applications but the chief disadvantage of lack of a separation step for the different analytes in a mixture. Several approaches have been investigated to overcome this problem including use of selective chemical ionization [Bier and Cooks, 1987] and multivariate calibration techniques[Ketola et al., 1999] . A new approach is reported for the quantitative measurement of VOCs in complex matrices. The method seeks to reduce the complexity of mass spectra observed in hydrocarbon mixture analysis by selective pretreatment of the analyte mixture. In the current investigation, the rapid reaction of ozone with alkenes is used, producing oxygenated compounds which are suppressed by the MIMS system. This has the effect of removing signals due to unsaturated analytes from the compound mass spectra, and comparison of the spectra before and after the ozone treatment reveals the nature of the parent compounds. In preliminary investigations, ozone reacted completely with cyclohexene from a mixture of cylohexene and cyclohexane, and with β -pinene from a mixture of toluene and β -pinene, suppressing the ion signals from the olefins. A slight attenuation of the cyclohexane and toluene in those mixtures was also observed. Despite this problem, the hydrocarbon signal response can be calibrated and the method can be used for quantitative analysis of volatile hydrocarbon compounds in air samples. This methodology should augment the efficiency of the MIMS approach in online and onsite monitoring of VOC emissions. Bier, M.R., and R.G. Cooks, Membrane Interface for Selective Introduction of Volatile Compounds Directly into The Ionization Chamber of a Mass Spectrometer, Anal. Chem., 59 (4), 597, 1987. Cisper, M.E., C.G. Gill, L.E. Townsend, and P.H. Hemberger, On-Line Detection of Volatile Organic Compounds in Air at Parts-per-Trillion Levels by Membrane Introduction Mass Spectrometry, Anal. Chem., 67 (8), 1413-1417, 1995. Ketola, R.A., M. Ojala, and J. Heikkonen, A Non-linear Asymmetric Error Function-based Least Mean Square Approach for the Analysis of Multicomponent Mass Spectra Measured by Membrane Inlet Mass Spectrometry, Rapid Commun. Mass Spectrom., 13 (8), 654, 1999. Kotiaho, T., and R.G. Cooks, Membrane Introduction Mass Spectrometry in Environmental Analysis, in: J.J. Breen, M. J. Dellarco, (Eds), Pollution in Industrial processes, 126 pp., ACS Symp. Ser., Washington, D.C. 508, 1992.

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.

Theoretical Studies of Elementary Hydrocarbon Species and Their Reactions

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

Allen, Wesley D.; Schaefer, III, Henry F.

2015-11-14

This is the final report of the theoretical studies of elementary hydrocarbon species and their reactions. Part A has a bibliography of publications supported by DOE from 2010 to 2016 and Part B goes into recent research highlights.

Effect of Unsaturated Flow on Delayed Response of Unconfined Aquifiers to Pumping

NASA Astrophysics Data System (ADS)

Tartakovsky, G.; Neuman, S. P.

2005-12-01

A new analytical solution is presented for the delayed response process characterizing flow to a partially penetrating well in an unconfined aquifer. The new solution generalizes that of Neuman [1972, 1974] by accounting for unsaturated flow above the water table. Axially symmetric three-dimensional flow in the unsaturated zone is described by a linearized version of Richards' equation in which hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value (defining the interface between the saturated and unsaturated zones). Unsaturated soil properties are characterized by an exponent κ having the dimension of inverse length and a dimensionless exponent κD = κb where b is initial saturated thickness. Our treatment of the unsaturated zone is similar to that of Kroszynski and Dagan [1975] who however have ignored internal (artesian) aquifer storage. It has been suggested by Boulton [1954, 1963, 1970] and Neuman [1972, 1974], and is confirmed by our solution, that internal storage is required to reproduce the early increase in drawdown characterizing delayed response to pumping in typical aquifers. According to our new solution such aquifers are characterized by relatively large κ_ D values, typically 10 or larger; in the limit as κD tends to infinity (the soil unsaturated water retention capacity becomes insignificant and/or aquifer thickness become large), unsaturated flow becomes unimportant and our solution reduces to that of Neuman. In typical cases corresponding to κD larger than or equal to 10, unsaturated flow is found to have little impact on early and late dimensionless time behaviors of drawdown measured wholly or in part at some distance below the water table; unsaturated flow causes drawdown to increase slightly at intermediate dimensionless time values that represent transition from an early artesian dominated to a late water-table dominated flow regime. The increase in drawdown during this transition period is caused by delayed drainage from the unsaturated zone, whose relatively small effect is superimposed on the more pronounced phenomenon of delay in water table decline relative to artesian head drops below it. Delayed drainage from the unsaturated zone becomes less and less important as κD increases; as it approaches infinity, this effect dies out completely and drawdown is controlled entirely by delayed decline in the water table. The unsaturated zone has major impact on drawdown at intermediate time, and significant impact at early and late times, in the atypical case of small κD values (1 or less), becoming the dominant factor as κD approaches zero (the soil water retention capacity becomes very large and/or saturated thickness becomes insignificant).

Decomposition of groundwater level fluctuations using transfer modelling in an area with shallow to deep unsaturated zones

NASA Astrophysics Data System (ADS)

Gehrels, J. C.; van Geer, F. C.; de Vries, J. J.

1994-05-01

Time series analysis of the fluctuations in shallow groundwater levels in the Netherlands lowlands have revealed a large-scale decline in head during recent decades as a result of an increase in land drainage and groundwater withdrawal. The situation is more ambiguous in large groundwater bodies located in the eastern part of the country, where the unsaturated zone increases from near zero along the edges to about 40 m in the centre of the area. As depth of the unsaturated zone increases, groundwater level reacts with an increasing delay to fluctuations in climate and influences of human activities. The aim of the present paper is to model groundwater level fluctuations in these areas using a linear stochastic transfer function model, relating groundwater levels to estimated precipitation excess, and to separate artificial components from the natural groundwater regime. In this way, the impact of groundwater withdrawal and the reclamation of a 1000 km 2 polder area on the groundwater levels in the adjoining higher ground could be assessed. It became evident that the linearity assumption of the transfer functions becomes a serious drawback in areas with the deepest groundwater levels, because of non-linear processes in the deep unsaturated zone and the non-synchronous arrival of recharge in the saturated zone. Comparison of the results from modelling the influence of reclamation with an analytical solution showed that the lowering of groundwater level is partly compensated by reduced discharge and therefore is less than expected.

Cation-exchanged SAPO-34 for adsorption-based hydrocarbon separations: predictions from dispersion-corrected DFT calculations.

PubMed

Fischer, Michael; Bell, Robert G

2014-10-21

The influence of the nature of the cation on the interaction of the silicoaluminophosphate SAPO-34 with small hydrocarbons (ethane, ethylene, acetylene, propane, propylene) is investigated using periodic density-functional theory calculations including a semi-empirical dispersion correction (DFT-D). Initial calculations are used to evaluate which of the guest-accessible cation sites in the chabazite-type structure is energetically preferred for a set of ten cations, which comprises four alkali metals (Li(+), Na(+), K(+), Rb(+)), three alkaline earth metals (Mg(2+), Ca(2+), Sr(2+)), and three transition metals (Cu(+), Ag(+), Fe(2+)). All eight cations that are likely to be found at the SII site (centre of a six-ring) are then included in the following investigation, which studies the interaction with the hydrocarbon guest molecules. In addition to the interaction energies, some trends and peculiarities regarding the adsorption geometries are analysed, and electron density difference plots obtained from the calculations are used to gain insights into the dominant interaction types. In addition to dispersion interactions, electrostatic and polarisation effects dominate for the main group cations, whereas significant orbital interactions are observed for unsaturated hydrocarbons interacting with transition metal (TM) cations. The differences between the interaction energies obtained for pairs of hydrocarbons of interest (such as ethylene-ethane and propylene-propane) deliver some qualitative insights: if this energy difference is large, it can be expected that the material will exhibit a high selectivity in the adsorption-based separation of alkene-alkane mixtures, which constitutes a problem of considerable industrial relevance. While the calculations show that TM-exchanged SAPO-34 materials are likely to exhibit a very high preference for alkenes over alkanes, the strong interaction may render an application in industrial processes impractical due to the large amount of energy required for regeneration. In this respect, SAPOs exchanged with alkaline earth cations could provide a better balance between selectivity and energy cost of regeneration.

Simulating the Atmospheric Impact of Criegee Intermediates: Implementation of new understanding in atmospheric chemical mechanisms

NASA Astrophysics Data System (ADS)

Bloss, William; Newland, Mike; Rickard, Andrew; Vereecken, Luc; Evans, Mathew; Munoz, Amalia; Rodenas, Mila

2016-04-01

Unsaturated hydrocarbons - alkenes - account for about 90% of global VOC. Stabilized Criegee Intermediates (SCI) are thought to be formed in the atmosphere mainly from reactions of unsaturated hydrocarbons with ozone. SCI have been shown in laboratory and chamber experiments to rapidly oxidise SO2 and NO2, providing a potentially important gas phase oxidation route for these species in the atmosphere. They have also been implicated in the formation of aerosol and organic acids. However, the importance of SCI reactions with traces gases is critically dependent on the relative ratio of the rate constants for the reactions of the SCI with these and other trace gases, with H2O, and for unimolecular decomposition, which vary between SCIs, and between geometric isomers. The selection of reactions and rate constants is critically important in determining the calculated impact of SCI processes upon atmospheric composition and chemistry. Since the recent resurgence in interest in this chemistry, a number of model studies have been performed, with SCI mechanisms of varying comprehensiveness and accuracy, as the understanding of the community has evolved from new laboratory, theoretical and chamber studies, and field observations. Here we present an assessment of the dependence of modelled SCI abundance, behaviour and impacts upon the Criegee mechanism adopted, in the context of (a) the accepted status quo prior to the laboratory and field studies of Welz et al. and Mauldin et al., (b) changes to the SCI mechanism reflecting new kinetics for key bimolecular reactions, e.g. with SO2 and NO2; (c) emerging understanding of the interactions of SCI with water vapour and their unimolecular decomposition and (d) reactions with other atmospheric trace gases. The modelled SCI behaviour is compared with the results from recent chamber studies, and the resulting calculated SCI abundance and impacts evaluated for urban and forested atmospheric boundary layer scenarios.

A pollinators' eye view of a shelter mimicry system

PubMed Central

Vereecken, Nicolas J.; Dorchin, Achik; Dafni, Amots; Hötling, Susann; Schulz, Stefan; Watts, Stella

2013-01-01

Background and Aims ‘Human-red’ flowers are traditionally considered to be rather unpopular with bees, yet some allogamous species in the section Oncocyclus (genus Iris, Iridaceae) have evolved specialized interactions with their pollinators, a narrow taxonomic range of male solitary bees. The dark-red, tubular flowers of these irises are nectarless but provide protective shelters (i.e. a non-nutritive form of reward) primarily to male solitary bees (Apidae, Eucerini) that pollinate the flowers while looking for a shelter. An earlier study on orchids suggested that species pollinated predominantly by male solitary bees produce significantly larger amounts and larger numbers of different n-alkenes (unsaturated cuticular hydrocarbons). Whether or not this also applies to the Oncocyclus irises and whether pollinators are attracted by specific colours or scents of these flowers is unknown. Methods Using Iris atropurpurea, recording of pollinator preferences for shelters with different spatial parameters was combined with analyses of floral colours (by spectrophotometry) and scents (by gas chromatography–mass spectrometry) to test the hypotheses that (a) pollinators significantly prefer floral tunnels facing the rising sun (floral heat-reward hypothesis), and that (b) flowers pollinated predominantly by male solitary bees produce significantly larger amounts and larger numbers of unsaturated cuticular hydrocarbons (n-alkenes) in their floral scent (preadaptation to sexual-deception hypothesis). Key Results Male bees do not significantly prefer shelters facing the rising sun or with the presence of high absolute/relative amounts and numbers of n-alkenes in the floral scent. Conclusions The results suggest that the flowers of I. atropurpurea probably evolved by pollinator-mediated selection acting primarily on floral colours to mimic large achromatic (‘bee-black’) protective shelters used preferentially by male solitary bees, and that pollinator visits are presumably not the result of an odour-based sexual stimulation or motivated by an increased morning floral heat reward in tunnels facing the rising sun. PMID:23599249

Physiology of deletion mutants in the anaerobic β-myrcene degradation pathway in Castellaniella defragrans

PubMed Central

2012-01-01

Background Monoterpenes present a large and versatile group of unsaturated hydrocarbons of plant origin with widespread use in the fragrance as well as food industry. The anaerobic β-myrcene degradation pathway in Castellaniella defragrans strain 65Phen differs from well known aerobic, monooxygenase-containing pathways. The initial enzyme linalool dehydratase-isomerase ldi/LDI catalyzes the hydration of β-myrcene to (S)-(+)-linalool and its isomerization to geraniol. A high-affinity geraniol dehydrogenase geoA/GeDH and a geranial dehydrogenase geoB/GaDH contribute to the formation of geranic acid. A genetic system was for the first time applied for the betaproteobacterium to prove in vivo the relevance of the linalool dehydratase-isomerase and the geraniol dehydrogenase. In-frame deletion cassettes were introduced by conjugation and two homologous recombination events. Results Polar effects were absent in the in-frame deletion mutants C. defragrans Δldi and C. defragrans ΔgeoA. The physiological characterization of the strains demonstrated a requirement of the linalool dehydratase-isomerase for growth on acyclic monoterpenes, but not on cyclic monoterpenes. The deletion of geoA resulted in a phenotype with hampered growth rate on monoterpenes as sole carbon and energy source as well as reduced biomass yields. Enzyme assays revealed the presence of a second geraniol dehydrogenase. The deletion mutants were in trans complemented with the broad-host range expression vector pBBR1MCS-4ldi and pBBR1MCS-2geoA, restoring in both cases the wild type phenotype. Conclusions In-frame deletion mutants of genes in the anaerobic β-myrcene degradation revealed novel insights in the in vivo function. The deletion of a high-affinity geraniol dehydrogenase hampered, but did not preclude growth on monoterpenes. A second geraniol dehydrogenase activity was present that contributes to the β-myrcene degradation pathway. Growth on cyclic monoterpenes independent of the initial enzyme LDI suggests the presence of a second enzyme system activating unsaturated hydrocarbons. PMID:22947208

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.

METHOD FOR RECOVERING URANIUM FROM OILS

DOEpatents

Gooch, L.H.

1959-07-14

A method is presented for recovering uranium from hydrocarbon oils, wherein the uranium is principally present as UF/sub 4/. According to the invention, substantially complete removal of the uranium from the hydrocarbon oil may be effected by intimately mixing one part of acetone to about 2 to 12 parts of the hydrocarbon oil containing uranium and separating the resulting cake of uranium from the resulting mixture. The uranium in the cake may be readily recovered by burning to the oxide.

Pronounced occurrence of long-chain alkenones and dinosterol in a 25,000-year lipid molecular fossil record from Lake Titicaca, South America

NASA Astrophysics Data System (ADS)

Theissen, Kevin M.; Zinniker, David A.; Moldowan, J. Michael; Dunbar, Robert B.; Rowe, Harold D.

2005-02-01

Our analysis of lipid molecular fossils from a Lake Titicaca (16° S, 69° W) sediment core reveals distinct changes in the ecology of the lake over an ˜25,000-yr period spanning latest Pleistocene to late Holocene time. Previous investigations have shown that over this time period Lake Titicaca was subject to large changes in lake level in response to regional climatic variability. Our results indicate that lake algal populations were greatly affected by the changing physical and chemical conditions in Lake Titicaca. Hydrocarbons are characterized by a combination of odd-numbered, mid- to long-chain (C 21-C 31) normal alkanes and alkenes. During periods when lake level was higher (latest Pleistocene, early Holocene, and late Holocene), the C 21n-alkane, and the C 25 and C 27 alkenes dominate hydrocarbon distributions and indicate contribution from an algal source, potentially the freshwater alga Botryococcus braunii. The C 30 4 α-methyl sterol (dinosterol) increases sharply during the mid-Holocene, suggesting a greatly increased dinoflagellate presence at that time. Long-chain alkenones (LCAs) become significant during the early Holocene and are highly abundant in mid-Holocene samples. There are relatively few published records of LCA detection in lake sediments but their occurrence is geographically widespread (Antarctica, Asia, Europe, North America). Lake Titicaca represents the first South American lake and the first low-latitude lake in which LCAs have been reported. LCA abundance and distribution may be related to the temperature-dependent response of an unidentified algal precursor. Although the LCA unsaturation indices cannot be used to determine absolute Lake Titicaca temperatures, we suspect that the published LCA U37K unsaturation calibrations can be applied to infer relative temperatures for early to mid-Holocene time when LCA concentrations are high. Using these criteria, the U37K unsaturation indices suggest relatively warmer temperatures in the mid-Holocene. In contrast to previous speculation, lipid analysis provides little evidence of a greatly increased presence of aquatic plants during the mid-Holocene. Instead, it appears that a few algal species were dominant in the lake. Based on the dramatic rise in abundances of LCAs and dinosterol during the early to mid-Holocene, we suspect that the algal producers of these compounds rose in response to a combination of physical and chemical changes in the lake. These include temperature, salinity, and alkalinity changes that occurred as lake level dropped sharply during a multi-millennial drought affecting the Central Andean Altiplano.

Polymerisation par plasma a pression atmospherique: Caracterisation des depots et leurs applications en biotechnologies

NASA Astrophysics Data System (ADS)

Girard-Lauriault, Pierre-Luc

Nitrogen (N)-containing polymer surfaces are attractive in numerous technological contexts, for example in biomedical applications. Here, we have used an atmospheric-pressure dielectric barrier discharge (DBD) apparatus to deposit novel families of N-rich plasma polymers, designated PP:N, using mixtures of three different hydrocarbon precursors (methane, ethylene, and acetylene) in nitrogen at varying respective gas flow ratios, typically parts per thousand. In preparation for subsequent cell-surface interaction studies, the first part of this research focuses on the chemical mapping of those materials, with specific attention to (semi)- quantitative analyses of functional groups. Well-established and some lesser-known analytical techniques have been combined to provide the best possible chemical and structural characterisations of these three families of PP:N thin films; namely, X-ray photoelectron spectroscopy (XPS), Near-edge X-ray absorption fine structure (NEXAFS), Fourier transform infrared spectroscopy (FTIR), contact angle goniometry (CAG), and elemental analysis (EA). High, "tunable" total nitrogen content was measured by both XPS and EA (between 6% and 25% by EA, or between 10% and 40% by XPS, which cannot detect hydrogen). Chemical derivatisation with 4-trifluoromethylbenzaldehyde (TFBA) enabled measurements of primary amine concentrations, the functionality of greatest bio-technological interest, which were found to account for 5 % to 20 % of the total bound nitrogen. By combining the above-mentioned complementary methods, we were further able to determine the complete chemical formulae, the degrees of unsaturation, and other major chemical functionalities in PP:N film structures. Several of these features are believed to be without precedents in the literature on hydrocarbon plasma polymers, for example measurements of absolute compositions (including hydrogen), and of unsaturation. It was shown that besides amines, nitriles, isonitriles and imines are the main nitrogenated functional groups in those materials. In a second part of this work, we have studied the interraction of these well-characterised surfaces with living cells. We have first demonstrated the adhesion, on both uniformly coated and micro-patterned PP:N deposits on BOPP, of three different cell types, namely, growth plate and articular chondrocytes, as well as U937 monocytes, the latter of which do not adhere at all to synthetic polymers used in tissue culture. In an effort to gain insight into cell adhesion mechanisms, we conducted a series of experiments where we cultured U937 monocytes on PP:N, as well as on two other families of chemically well-characterised N-rich thin films, the latter deposited by low pressure RF plasma and by vacuum ultra-violet (VUV) photo-polymerisation ("PVP:N" films). It was first shown that there exist sharply-defined ("critical") surface-chemical conditions that are necessary to induce cell adhesion. By comparing the extensively-characterised film chemistries at the " critical " conditions, we have clearly demonstrated the dominant role of primary amines in the cell adhesion mechanism. In the final aspect of this work, quantitative real-time reverse transcription-polymerase chain reaction (real-time RT-PCR) experiments were conducted using U937 cells that had been made to adhere on PP:N and PVP:N materials for up to 24h. We have shown that the adhesion of U937 monocytes to PP:N and PVP:N surfaces induced a transient expression of cytokines, markers of macrophage activation, as well as a sustained expression of PPARgamma and ICAM-I, implicated in the adhesion and retention of monocytes. Keywords: biomaterials; dielectric barrier discharges (DBD); deposition; plasma polymerisation; ESCA/XPS; NEXAFS; FTIR; primary amines; cell adhesion; gene expression.

Method for making hydrogen rich gas from hydrocarbon fuel

DOEpatents

Krumpelt, M.; Ahmed, S.; Kumar, R.; Doshi, R.

1999-07-27

A method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400 C for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide. 4 figs.

Method for making hydrogen rich gas from hydrocarbon fuel

DOEpatents

Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

1999-01-01

A method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

Surface quality of unsaturated polyester resin processed via continuous multi-shot rotational molding

NASA Astrophysics Data System (ADS)

Ogila, K. O.; Yang, W.; Shao, M.; Tan, J.

2017-05-01

Unsaturated Polyester Resin is a versatile and cost efficient thermosetting plastic whose application in rotational molding is currently limited by its relatively high initial viscosity and heat of reaction. These material characteristics result in uneven material distribution, poor surface finish and imperfections in the moldings especially when large wall thicknesses are required. The current work attempts to remedy these shortcomings through the development of a continuous multi-shot system which adds predetermined loads of unsaturated polyester resin into a rotating mold at various intervals. As part of this system, a laboratory-scale uniaxial rotational molding machine was used to produce Unsaturated Polyester Resin moldings in single and double shots. Optimal processing conditions were determined through visual studies, three dimensional microscopic studies, thickness distribution analysis and Fourier Transform Infrared spectroscopy. Volume filling fractions of 0.049-0.065, second shot volumes of 0.5-0.75 from the first shot, rotational speeds of 15-20 rpm and temperatures of 30-50 °C resulted in moldings of suitable quality on both the inner and outer surfaces.

Data from a thick unsaturated zone in Joshua Tree, San Bernardino County, California, 2007--09

USGS Publications Warehouse

Burgess, Matthew; Izbicki, John; Teague, Nicholas; O'Leary, David R.; Clark, Dennis; Land, Michael

2012-01-01

Data were collected on the physical properties of unsaturated alluvial deposits, the chemical composition of leachate extracted from unsaturated alluvial deposits, the chemical and isotopic composition of groundwater and unsaturated-zone water, and the chemical composition of unsaturated-zone gas at four monitoring sites in the southwestern part of the Mojave Desert in the town of Joshua Tree, San Bernardino County, California. The presence of denitrifying and nitrate-reducing bacteria from unsaturated alluvial deposits was evaluated for two of these monitoring sites that underlie unsewered residential development. Four unsaturated-zone monitoring sites were installed in the Joshua Tree area—two in an unsewered residential development and two adjacent to a proposed artificial-recharge site in an undeveloped area. The two boreholes in residential development areas were installed by using the ODEX air-hammer method. One borehole was drilled through the unsaturated zone to a depth of 541 ft (feet) below land surface; a well screened across the water table was installed. Groundwater was sampled from this well. The second borehole was drilled to a depth of 81 ft below land surface. Drilling procedures, lithologic and geophysical data, construction details, and instrumentation placed in these boreholes are described. Core material was analyzed for water content, bulk density, matric potential, particle size, and water retention. The leachate from over 500 subsamples of cores and cuttings was analyzed for soluble anions, including fluoride, sulfate, bromide, chloride, nitrate, nitrite, and orthophosphate. Groundwater was analyzed for major ions, inorganic compounds, select trace elements, and isotopic composition. Unsaturated-zone water from suction-cup lysimeters was analyzed for major ions, inorganic compounds, select trace elements, and isotopic composition. Unsaturated-zone gas samples were analyzed for argon, oxygen, nitrogen, methane, carbon dioxide, ethane, nitrous oxide, and carbon monoxide. Drill cuttings were analyzed for denitrifying and nitrate-reducing bacteria. One of the boreholes installed adjacent to the Joshua Basin Water District proposed groundwater-recharge facility was installed by using the ODEX air-hammer method and the other was installed by using a 7.875-inch hollow-stem auger. Drilling procedures, lithologic and geophysical data, construction details, and instrumentation placed in these boreholes are described; however, geochemical data were not available at the time of publication.

Unveiling chemical defense in the rice stalk stink bug against the entomopathogenic fungus Metarhizium anisopliae.

PubMed

da Silva, Rodrigo Alves; Quintela, Eliane Dias; Mascarin, Gabriel Moura; Pedrini, Nicolás; Lião, Luciano Moraes; Ferri, Pedro Henrique

2015-05-01

Eggs, nymphs (1st-5th instar) and adults of Tibraca limbativentris were challenged by conidial suspensions of its major fungal pathogen Metarhizium anisopliae in order to assess their susceptibility. The role of chemical defensive compounds from exocrine secretions produced by both nymphs and adults were examined for their participation on M. anisopliae infection. Although insect susceptibility to M. anisopliae followed a dose-dependent manner, adults followed by older nymphs displayed the highest resistance. Eggs were highly susceptible showing >96% fungal infection. Crude extracts isolated from metathoracic scent gland and dorsal abdominal glands of adults and nymphs, respectively, showed fungistatic effects by impairing spore germination, vegetative growth and sporulation. Gas chromatography-mass spectrometry analysis of these extracts revealed that the major components were short-chain hydrocarbons (C10-13) and unsaturated aldehydes. In vitro tests with the corresponding synthetic standards indicated compounds with greater antifungal activity including (E)-2-hexenal, (E)-2-octenal, and (E)-2-decenal, with the latter being the most deleterious to fungal fitness. We demonstrated that differential susceptibility of the rice stalk stink bug to M. anisopliae infection is age-specific and partly mediated by fungistatic properties of aldehydes, which are produced by scent glands of both nymphs and adults. Copyright © 2015 Elsevier Inc. All rights reserved.

Hydrocarbons and Air Pollution: An Annotated Bibliography. Part I., Categories A to E and Part II., Categories F to M and Indexes.

ERIC Educational Resources Information Center

National Air Pollution Control Administration (DHEW), Raleigh, NC.

This two-part bibliography represents an effort to collect, condense, and organize the literature on the hydrocarbons in relation to air pollution. The approximately 2,300 documents abstracted are all included in the information storage and retrieval system of the National Air Pollution Control Administration's (NAPCA) Air Pollution Technical…

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

Prospects for applications of electron beams in processing of gas and oil hydrocarbons

NASA Astrophysics Data System (ADS)

Ponomarev, A. V.; Pershukov, V. A.; Smirnov, V. P.

2015-12-01

Waste-free processing of oil and oil gases can be based on electron-beam technologies. Their major advantage is an opportunity of controlled manufacturing of a wide range of products with a higher utility value at moderate temperatures and pressures. The work considers certain key aspects of electron beam technologies applied for the chain cracking of heavy crude oil, for the synthesis of premium gasoline from oil gases, and also for the hydrogenation, alkylation, and isomerization of unsaturated oil products. Electronbeam processing of oil can be embodied via compact mobile modules which are applicable for direct usage at distant oil and gas fields. More cost-effective and reliable electron accelerators should be developed to realize the potential of electron-beam technologies.

Experimental Study on Interactions Between H Atoms and Organic Haze

NASA Technical Reports Server (NTRS)

Sekine, Y.; Imanaka, H.; Khare, B. N.; Bakes, E. L. O.; McKay, C. P.; Sugita, S.; Matsui, T.

2005-01-01

In Titan s atmosphere composed of N2 and CH4, irradiations of both solar ultraviolet light and charged particles induce active chemical reactions. In the processes of these reactions, a large amount of hydrogen (H) atoms are expected to be formed by dissociation of CH4 and other hydrocarbons [e.g., 1, 2]. Theoretical models suggest that these active H atoms need to be converted to stable hydrogen molecules (H2) efficiently to maintain unsaturated hydrocarbons and organic haze in Titan s atmosphere [e.g., 1]. Furthermore, molecular hydrogen is an important greenhouse effect gas in Titan s atmosphere, and small variation in its abundance strongly affects Titan s surface temperature [3]. Thus, the formation of H2 molecules from H atoms is a key reaction for both the atmospheric chemistry and the surface environment of Titan. Although several numerical calculations have been conducted to investigate the atmospheric chemistry of Titan with hypothesized recombination reactions of H atoms, such as catalytic scheme of C4H2 [e.g., 1, 2], it is still unclear what chemical reaction is responsible for the conversion of H atoms to H2 molecules in Titan s atmosphere.

Geochemical characteristics of organic compounds in a permafrost sediment core sample from northeast Siberia, Russia

NASA Technical Reports Server (NTRS)

Matsumoto, G. I.; Friedmann, E. I.; Gilichinsky, D. A.

1995-01-01

We studied total organic carbon (TOC), hydrocarbons and fatty acids in a permafrost sediment core sample (well 6-90, length 32.0 m, 1.5-2.5 Ma BP) from northeast Siberia (approximately 70 degrees N, 158 degrees E), Russia, to elucidate their geochemical features in relation to source organisms and paleoenvironmental conditions. Long-chain n-alkanes and n-alkanoic acids (>C19) were most predominant hydrocarbons and fatty acids, respectively, so organic matter in the sediment core was derived mainly from vascular plants and, to a much smaller extent, from bacteria. Low concentrations of unsaturated fatty acids revealed that organic matter in the sediment core was considerably degraded during and/or after sedimentation. The predominance of vascular plant components, the major ionic components of nonmarine sources, and geological data strongly implied that the sediment layers were formed in shallow lacustrine environments, such as swamp with large influences of tundra or forest-tundra vegetation. Also, no drastic changes in paleoenvironmental conditions for biological activity or geological events, such as sea transgressions or ice-sheet influences, occurred at the sampling site approximately 100 km from the coast of the East Siberian Sea during the late Pliocene an early Pleistocene periods.

Nucleation of Hydrogen Deficient Carbon Clusters in Circumstellar Envelopes of Carbon Stars

NASA Astrophysics Data System (ADS)

Chiong, C. C.; Asvany, O.; Balucani, N.; Lee, Y. T.; Kaiser, R. I.

2001-04-01

Hydrogen deficient carbon clusters HCn and H2Cn are thought to resemble the crucial link between naked carbon clusters such as C2/C3, polycyclic aromatic hydrocarbons, and carbon rich interstellar/circumstellar grains. To fully understand the astrophysical significance of these grain nuclei condensation processes, it is of paramount significance to elucidate first detailed mechanism how these simple precursors are formed in outflow of carbon rich stars. Due to this importance, we initiated in our laboratory a systematic research program to investigate reactions of C2 and C3 clusters in their singlet X1Σg+ ground state with unsaturated hydrocarbons C2H2 and C2H4 employing the crossed molecular beam technique. These experiments yield the first doubly differential reactive cross section on the cluster versus H/H2 exchange and supply valuable information on the stepwise growth of carbon rich structures in extraterrestrial environments. Preliminary data analyses identify the CCCCH, CCCCH, and CCCCH2 isomers which were identified in the circumstellar shell of IRC+10216 together with hitherto unobserved interstellar n-C4H3, n-C5H3, and CCCCCH2 radicals.

Does the volatile hydrocarbon profile differ between the sexes: a case study on five aphidophagous ladybirds.

PubMed

Pattanayak, Rojalin; Mishra, Geetanjali; Omkar; Chanotiya, Chandan Singh; Rout, Prasant Kumar; Mohanty, Chandra Sekhar

2014-11-01

Insect hydrocarbons (HCs) primarily serve as a waterproofing cuticular layer and function extensively in chemical communication by facilitating species, sex, and colony recognition. In this study, headspace solid-phase microextraction is employed for investigating the sex-specific volatile HC profile of five ladybirds collected from Lucknow, India namely, Coccinella septempunctata (L.), Coccinella transversalis (Fabr.), Menochilus sexmaculatus (Fabr.), Propylea dissecta (Mulsant), and Anegleis cardoni (Weise) for the first time. Major compounds reported in C. septempunctata, C. transversalis, and A. cardoni are methyl-branched saturated HCs, whereas in M. sexmaculatus, and P. dissecta, they are unsaturated HCs. Other than A. cardoni, both the sexes of the other four ladybirds had similar compounds at highest peak but with statistically significant differences. However, in A. cardoni, which is a beetle with a narrow niche, the major compound in both male and female was different. The difference in volatile HC profile of the sexes of the five ladybirds indicates that gender-specific differences primarily exist due to quantitative differences in chemicals with only very few chemicals being unique to a gender. This variation in semiochemicals might have a role in behavioral or ecological aspects of the studied ladybirds. © 2014 Wiley Periodicals, Inc.

Identification of the cuticular lipid composition of the Western Flower Thrips Frankliniella occidentalis.

PubMed

Gołebiowski, Marek; Maliński, Edmund; Nawrot, Jan; Szafranek, Janusz; Stepnowski, Piotr

2007-06-01

The Western Flower Thrips Frankliniella occidentalis effectively resists many insecticides, but it can be controlled by the use of bioinsecticides such as entomopathogenic fungi. The epicuticular chemistry of these insects is therefore of great interest, and accordingly, the cuticular lipid composition of F. occidentalis was analysed. It was found that the cuticular lipids of both the adult and larval stages of F. occidentalis consist of two groups of compounds--hydrocarbons and free fatty acids. The same hydrocarbon pattern was found in both adults and larvae, with the exception of n-hentriacontane, which was detected only in adult insects. The following homologous series were identified: n-alkanes from C-25 to C-29 (31) with the marked dominance of odd numbers of carbon atoms, 3-methylalkanes with 26 and 28 carbon atoms, and branched monomethylalkanes (branched at C-9, -11, -13 and -15) with 26, 28 and 30 carbon atoms. The chemical composition of the free fatty acids consists of two homologous series: saturated (C(14:0), C(16:0), C(18:0)) and unsaturated fatty acids (C(16:1) and C(18:1)). This analysis confirmed the lack of potential inhibitors of entomopathogenic fungi in the cuticular lipids of this insect species.

Fast ground-water mixing and basal recharge in an unconfined, alluvial aquifer, Konza LTER Site, Northeastern Kansas

USGS Publications Warehouse

Macpherson, G.L.; Sophocleous, M.

2004-01-01

Ground-water chemistry and water levels at three levels in a well nest were monitored biweekly for two and a half years in a shallow unconfined floodplain aquifer in order to study the dynamics of such shallow aquifers. The aquifer, in northeastern Kansas, consists of high porosity, low hydraulic conductivity fine-grained sediments dominated by silt and bounded by fractured limestone and shale bedrock. Results show that the aquifer underwent chemical stratification followed by homogenization three times during the study period. The length of time between maximum stratification and complete homogenization was 3-5 months. The chemical parameters most useful for demonstrating the mixing trends were dissolved nitrate and sulfate. Higher nitrate concentrations were typical of unsaturated zone water and were sourced from fertilizer applied to the cultivated fields on the floodplain. Variations in sulfate concentrations are attributed to dissolution of rare gypsum in limestone bedrock and variable evapoconcentration in the unsaturated zone. The mixing of three chemically different waters (entrained, unsaturated-zone water; water entering the base of the floodplain aquifer; and water in residence before each mixing event) was simulated. The resident water component for each mixing event was a fixed composition based on measured water chemistry in the intermediate part of the aquifer. The entrained water composition was calculated using a measured composition of the shallow part of the aquifer and measurements of soil-water content in the unsaturated zone. The incoming basal water composition and the fractions of each mixing component were fitted to match the measured chemistry at the three levels in the aquifer. A conceptual model for this site explains: (1) rapid water-level rises, (2) water-chemistry changes at all levels in the aquifer coincident with the water-level rises, (3) low measured hydraulic conductivity of the valley fill and apparent lack of preferential flow pathways, (4) minuscule amounts of unsaturated-zone recharge, and (5) dissolved oxygen peaks in the saturated zone lagging water-level peaks. We postulate that rainfall enters fractures in bedrock adjacent to the floodplain. This recharge water moves rapidly through the fractured bedrock into the base of the floodplain aquifer. The recharge event through the bedrock causes a rapid rise in water level in the floodplain aquifer, and the chemistry of the deepest water in the floodplain aquifer changes at that time. The rising water also entrains slow-moving, nitrate-rich, unsaturated-zone water, altering the chemistry of water in the shallow part of the aquifer. Vertical chemical stratification in the aquifer is thus created by the change in water chemistry in the upper and lower parts of the saturated zone. As the water level begins to decline, the aquifer undergoes mixing that eventually results in homogeneous water chemistry. The rise in water level from the recharge event also displaces gas from the unsaturated zone that is then replaced as the water level declines following the recharge event. This new, oxygen-rich vadose-zone air equilibrates rapidly with saturated-zone water, resulting in a dissolved oxygen pulse in the ground water that peaks one-half to 2 months after the water-level peak. This oxygen pulse subsequently declines over a period of 2-6 months. ?? 2003 Elsevier B.V. All rights reserved.

Soil Iodine Determination in Deccan Syneclise, India: Implications for Near Surface Geochemical Hydrocarbon Prospecting

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

Mani, Devleena, E-mail: devleenatiwari@ngri.res.in; Kumar, T. Satish; Rasheed, M. A.

2011-03-15

The association of iodine with organic matter in sedimentary basins is well documented. High iodine concentration in soils overlying oil and gas fields and areas with hydrocarbon microseepage has been observed and used as a geochemical exploratory tool for hydrocarbons in a few studies. In this study, we measure iodine concentration in soil samples collected from parts of Deccan Syneclise in the west central India to investigate its potential application as a geochemical indicator for hydrocarbons. The Deccan Syneclise consists of rifted depositional sites with Gondwana-Mesozoic sediments up to 3.5 km concealed under the Deccan Traps and is considered prospectivemore » for hydrocarbons. The concentration of iodine in soil samples is determined using ICP-MS and the values range between 1.1 and 19.3 ppm. High iodine values are characteristic of the northern part of the sampled region. The total organic carbon (TOC) content of the soil samples range between 0.1 and 1.3%. The TOC correlates poorly with the soil iodine (r{sup 2} < 1), indicating a lack of association of iodine with the surficial organic matter and the possibility of interaction between the seeping hydrocarbons and soil iodine. Further, the distribution pattern of iodine compares well with two surface geochemical indicators: the adsorbed light gaseous hydrocarbons (methane through butane) and the propane-oxidizing bacterial populations in the soil. The integration of geochemical observations show the occurrence of elevated values in the northern part of the study area, which is also coincident with the presence of exposed dyke swarms that probably serve as conduits for hydrocarbon microseepage. The corroboration of iodine with existing geological, geophysical, and geochemical data suggests its efficacy as one of the potential tool in surface geochemical exploration of hydrocarbons. Our study supports Deccan Syneclise to be promising in terms of its hydrocarbon prospects.« less

Overview of research on water, gas, and radionuclide transport at the Amargosa Desert Research Site, Nevada: A section in U.S. Geological Survey Toxic Substances Hydrology Program: Proceedings of the technical meeting, Charleston, South Carolina, March 8-12, 1999: Volume 3 (Part C) (WRI 99-4018C)

USGS Publications Warehouse

Andraski, Brian J.; Stonestrom, David A.; Morganwalp, David W.; Buxton, Herbert T.

1999-01-01

Studies at the U.S. Geological Survey Amargosa Desert Research Site have focused on characterizing factors and processes that control transport and fate of contaminants in arid environments. This paper summarizes research results that have been published through 1998. Results have improved understanding of water and gas movement through a thick unsaturated zone, including the degree to which features of the natural unsaturated-flow system can be altered by installation of a waste-disposal facility. The study of radioactive-contaminant transport at the site is at an early stage. Field data measured in association with this new component of research have generated speculation regarding the exact mechanisms that control tritium transport in arid unsaturated zones.

Geohydrology, water quality, and nitrogen geochemistry in the saturated and unsaturated zones beneath various land uses, Riverside and San Bernardino counties, California, 1991-93

USGS Publications Warehouse

Rees, Terry F.; Bright, Daniel J.; Fay, Ronald G.; Christensen, Allen H.; Anders, Robert; Baharie, Brian S.; Land, Michael T.

1995-01-01

The U.S. Geological Survey, in cooperation with the Eastern Municipal Water District, the Metropolitan Water District of Southern California, and the Orange County Water District, has completed a detailed study of the Hemet groundwater basin. The quantity of ground water stored in the basin in August 1992 is estimated to be 327,000 acre-feet. Dissolved-solids concentration ranged from 380 to 700 mg/L (milligrams per liter), except in small areas where the concentration exceeded 1,000 mg/L. Nitrate concentrations exceeded the U.S. Environmental Protection Agency Maximum Contaminant Level (MCL) of 10 mg/L nitrate (as nitrogen) in the southeastern part of the basin, in the Domenigoni Valley area, and beneath a dairy in the Diamond Valley area. Seven sites representing selected land uses-- residential, turf grass irrigated with reclaimed water, citrus grove, irrigated farm, poultry farm, and dairy (two sites)--were selected for detailed study of nitrogen geochemistry in the unsaturated zone. For all land uses, nitrate was the dominant nitrogen species in the unsaturated zone.Although nitrate was seasonally present in the shallow unsaturated zone beneath the residential site, it was absent at moderate depths, suggesting negligible migration of nitrate from the surface at this time. Microbial denitrification probably is occurring in the shallow unsaturated zone. High nitrate concentrations in the deep unsaturated zone (greater than 100 ft) suggest either significantly higher nitrate loading at some time in the past, or lateral movement of nitrate at depth. Nitrate also is seasonally present in the shallow unsaturated zone beneath the reclaimed-water site, and (in contrast with the residential site), nitrate is perennially present in the deeper unsaturated zone. Microbial denitrification in the unsaturated zone and in the capillary fringe above the water table decreases the concentrations of nitrate in pore water to below the MCL before reaching the water table.Pore water in the unsaturated zone beneath the citrus grove site contains very high concentrations of nitrate. Even though there are zones of microbial denitrification, nitrate seems to be migrating downward to the water table. The presence of a shallow perched-water zone beneath the irrigated-farm site prevents the vertical movement of nitrate from the surface to the regional water table. Above the perched zone, nitrate concentrations in the unsaturated zone are variable, ranging from below the MCL to four times the MCL. Periodically, nitrate is flushed from the shallow unsaturated zone to the perched-water zone. The unsaturated zone pore-moisture quality could not be adequately addressed because of the very dry conditions in the unsaturated zone beneath the poultry-farm site. Surficial clay deposits prevent water from percolating downward.At the two dairy sites, nitrate loading in pore water at the surface was very high, as great as 7,000 mg/L. Microbial denitrification in the unsaturated zone causes such concentrations to decrease rapidly with depth. At a depth of 20 ft, nitrate concentration was less than 100 mg/L. In areas where the depth to water is less than 20 ft, nitrate loading to ground water can be very high, whereas in areas where depth to water is greater than 100 ft, most of the nitrate is microbially removed before reaching the water table.

Method for producing viscous hydrocarbons

DOEpatents

Poston, Robert S.

1982-01-01

A method for recovering viscous hydrocarbons and synthetic fuels from a subterranean formation by drilling a well bore through the formation and completing the well by cementing a casing means in the upper part of the pay zone. The well is completed as an open hole completion and a superheated thermal vapor stream comprised of steam and combustion gases is injected into the lower part of the pay zone. The combustion gases migrate to the top of the pay zone and form a gas cap which provides formation pressure to produce the viscous hydrocarbons and synthetic fuels.

Implementation of Solute Transport in the Vadose Zone into the `HYDRUS Package for MODFLOW'

NASA Astrophysics Data System (ADS)

Simunek, J.; Beegum, S.; Szymkiewicz, A.; Sudheer, K. P.

2017-12-01

The 'HYDRUS package for MODFLOW' was developed by Seo et al. (2007) and Twarakavi et al. (2008) to simultaneously evaluate transient water flow in both unsaturated and saturated zones. The package, which is based on the HYDRUS-1D model (Šimůnek et al., 2016) simulating unsaturated water flow in the vadose zone, was incorporated into MODFLOW (Harbaugh et al., 2000) simulating saturated groundwater flow. The HYDRUS package in the coupled model can be used to represent the effects of various unsaturated zone processes, including infiltration, evaporation, root water uptake, capillary rise, and recharge in homogeneous or layered soil profiles. The coupled model is effective in addressing spatially-variable saturated-unsaturated hydrological processes at the regional scale, allowing for complex layering in the unsaturated zone, spatially and temporarily variable water fluxes at the soil surface and in the root zone, and with alternating recharge and discharge fluxes (Twarakavi et al., 2008). One of the major limitations of the coupled model was that it could not be used to simulate at the same time solute transport. However, solute transport is highly dependent on water table fluctuations due to temporal and spatial variations in groundwater recharge. This is an important concern when the coupled model is used for analyzing groundwater contamination due to transport through the unsaturated zone. The objective of this study is to integrate the solute transport model (the solute transport part of HYDRUS-1D for the unsaturated zone and MT3DMS (Zheng and Wang, 1999; Zheng, 2009) for the saturated zone) into an existing coupled water flow model. The unsaturated zone component of the coupled model can consider solute transport involving many biogeochemical processes and reactions, including first-order degradation, volatilization, linear or nonlinear sorption, one-site kinetic sorption, two-site sorption, and two-kinetic sites sorption (Šimůnek and van Genuchten, 2008). Due to complex interactions at the groundwater table, certain modifications of the pressure head (compared to the original coupling) and solute concentration profiles were incorporated into the HYDRUS package. The developed integrated model is verified using HYDRUS-2D and analyzed for its computational time requirements.

Lipid engineering reveals regulatory roles for membrane fluidity in yeast flocculation and oxygen-limited growth

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

Degreif, Daniel; de Rond, Tristan; Bertl, Adam

Cells modulate lipid metabolism in order to maintain membrane homeostasis. In this paper, we use a metabolic engineering approach to manipulate the stoichiometry of fatty acid unsaturation, a regulator of cell membrane fluidity, in Saccharomyces cerevisiae. Unexpectedly, reduced lipid unsaturation triggered cell-cell adhesion (flocculation), a phenomenon characteristic of industrial yeast but uncommon in laboratory strains. We find that ER lipid saturation sensors induce expression of FLO1 – encoding a cell wall polysaccharide binding protein – independently of its canonical regulator. In wild-type cells, Flo1p-dependent flocculation occurs under oxygen-limited growth, which reduces unsaturated lipid synthesis and thus serves as the environmentalmore » trigger for flocculation. Transcriptional analysis shows that FLO1 is one of the most highly induced genes in response to changes in lipid unsaturation, and that the set of membrane fluidity-sensitive genes is globally activated as part of the cell's long-term response to hypoxia during fermentation. Finally, our results show how the lipid homeostasis machinery of budding yeast is adapted to carry out a broad response to an environmental stimulus important in biotechnology.« less

Lipid engineering reveals regulatory roles for membrane fluidity in yeast flocculation and oxygen-limited growth.

PubMed

Degreif, Daniel; de Rond, Tristan; Bertl, Adam; Keasling, Jay D; Budin, Itay

2017-05-01

Cells modulate lipid metabolism in order to maintain membrane homeostasis. Here we use a metabolic engineering approach to manipulate the stoichiometry of fatty acid unsaturation, a regulator of cell membrane fluidity, in Saccharomyces cerevisiae. Unexpectedly, reduced lipid unsaturation triggered cell-cell adhesion (flocculation), a phenomenon characteristic of industrial yeast but uncommon in laboratory strains. We find that ER lipid saturation sensors induce expression of FLO1 - encoding a cell wall polysaccharide binding protein - independently of its canonical regulator. In wild-type cells, Flo1p-dependent flocculation occurs under oxygen-limited growth, which reduces unsaturated lipid synthesis and thus serves as the environmental trigger for flocculation. Transcriptional analysis shows that FLO1 is one of the most highly induced genes in response to changes in lipid unsaturation, and that the set of membrane fluidity-sensitive genes is globally activated as part of the cell's long-term response to hypoxia during fermentation. Our results show how the lipid homeostasis machinery of budding yeast is adapted to carry out a broad response to an environmental stimulus important in biotechnology. Copyright © 2017 International Metabolic Engineering Society. All rights reserved.

Asymmetric or symmetric bilayer formation during oblique drop impact depends on rheological properties of saturated and unsaturated lipid monolayers.

PubMed

Vranceanu, Marcel; Terinte, Nicoleta; Nirschl, Hermann; Leneweit, Gero

2011-02-01

Bilayer structures are formed by approaching two liquid surfaces with phospholipid monolayers, which are brought into contact by oblique drop impact on a liquid surface. Asymmetric bilayers can be produced by the coupling of drop and target monolayers. In contrast, symmetric bilayers or multilayers are formed by collapse of the compressed target monolayer. We show that under all studied conditions bilayer/multilayer synthesis takes place. The experimental conditions for the synthesis of asymmetric or symmetric bilayers are described quantitatively in terms of the surface rheological (surface elasticity and dilational viscosity) and the hydrodynamical parameters (Weber number and impact angle). The composition and mechanical properties of the phospholipid monolayers strongly influences the patterns of drop impact and the bilayer/multilayer formation. Cholesterol stiffens unsaturated phospholipid monolayers and fluidifies saturated monolayers. All monolayers form asymmetric vesicle-like structures, which are stable in the aqueous medium. Additionally, unsaturated phospholipid monolayers without cholesterol form symmetric vesicles by folding parts of the target monolayer. Sufficient presence of cholesterol in unsaturated phospholipid monolayers inhibits the folding of the target monolayer and the subsequent formation of symmetric bilayers. The rheological properties of saturated and unsaturated phospholipid monolayers and their mixtures with cholesterol are discussed. Based on drop impact results it is shown that the state of a so far undefined region in the DPPC/cholesterol phase diagram is a fluid phase. Copyright © 2010 Elsevier Inc. All rights reserved.

Organic chemistry of cometary dust as derived from PUMA 1 data

NASA Technical Reports Server (NTRS)

Kissel, J.; Krueger, F. R.

1989-01-01

Onboard the Halley Fly-By spacecrafts Vega 1, Vega 2, and Giotto were the dust impact mass spectrometers PUMA 1, PUMA 2, and PIA respectively. PUMA 1 was the most sensitive instrument among them. From its data the occurrence of masslines greater than 60 Daltons could be shown to be statistically significant. An analysis of these masslines lead to a scenario, which could explain the masslines as fragment ions from larger molecules which characterize the chemical nature of cometary organic matter as: (1) highly unsaturated hydrocarbons; (2) some of them containing oxygen; (3) less containing nitrogen; and (4) a few containing oxygen and nitrogen as heteroatoms. From the properties of the spectrometer, also some physical parameters of the dust particles could be inferred, such as their density and structure.

Electrophilic activation and cycloisomerization of enynes: a new route to functional cyclopropanes.

PubMed

Bruneau, Christian

2005-04-15

Transformations of enynes in the presence of transition-metal catalysts have played an important role in the preparation of a variety of cyclic compounds. Recent developments in the activation of triple carbon-carbon bonds by electrophilic metal centers have provided a new entry to the selective synthesis of cyclopropane derivatives from enynes. The mechanisms of these reactions involve catalytic species with both ionic and cyclopropylcarbenoid character. This type of activation will undoubtedly be further developed for application to other unsaturated hydrocarbons and inspire new catalytic cascade reaction sequences. This Minireview discusses the recent developments in electrophilic activation of enynes and shows that simple catalysts such as [Ru(3)(CO)(12)], PtCl(2), and cationic gold complexes are efficient precursors to promote the formation of functional polyclic compounds.

Ethenolysis: A Green Catalytic Tool to Cleave Carbon-Carbon Double Bonds.

PubMed

Bidange, Johan; Fischmeister, Cédric; Bruneau, Christian

2016-08-22

Remarkable innovations have been made in the field of olefin metathesis due to the design and preparation of new catalysts. Ethenolysis, which is cross-metathesis with ethylene, represents one catalytic transformation that has been used with the purpose of cleaving internal carbon-carbon double bonds. The objectives were either the ring opening of cyclic olefins to produce dienes or the shortening of unsaturated hydrocarbon chains to degrade polymers or generate valuable shorter terminal olefins in a controlled manner. This Review summarizes several aspects of this reaction: the catalysts, their degradation in the presence of ethylene, some parameters driving their productivity, the side reactions, and the applications of ethenolysis in organic synthesis and in potential industrial applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Characterization of contamination, source and degradation of petroleum between upland and paddy fields based on geochemical characteristics and phospholipid fatty acids.

PubMed

Zhang, Juan; Wang, Renqing; Du, Xiaoming; Li, Fasheng; Dai, Jiulan

2012-01-01

To evaluate contamination caused by petroleum, surface soil samples were collected from both upland and paddy fields along the irrigation canals in the Hunpu wastewater irrigation region in northeast China. N-alkanes, terpanes, steranes, and phospholipid fatty acids (PLFA) in the surface soil samples were analyzed. The aliphatic hydrocarbon concentration was highest in the samples obtained from the upland field near an operational oil well; it was lowest at I-3P where wastewater irrigation promoted the downward movement of hydrocarbons. The Hunpu region was found contaminated by heavy petroleum from oxic lacustrine fresh water or marine deltaic source rocks. Geochemical parameters also indicated significantly heavier contamination and degradation in the upland fields compared with the paddy fields. Principal component analysis based on PLFA showed various microbial communities between petroleum contaminated upland and paddy fields. Gram-negative bacteria indicated by 15:0, 3OH 12:0, and 16:1(9) were significantly higher in the paddy fields, whereas Gram-positive bacteria indicated by i16:0 and 18:1(9)c were significantly higher in the upland fields (p < 0.05). These PLFAs were related to petroleum contamination. Poly-unsaturated PLFA (18:2omega6, 9; indicative of hydrocarbon-degrading bacteria and fungi) was also significantly elevated in the upland fields. This paper recommends more sensitive indicators of contamination and degradation of petroleum in soil. The results also provide guidelines on soil pollution control and remediation in the Hunpu region and other similar regions.

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 5 2011-07-01 2011-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Boiling range (degrees F) Criteria Reactivityfactor 21 280-290 Aromatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 5 2010-07-01 2010-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Boiling range (degrees F) Criteria Reactivityfactor 21 280-290 Aromatic...

Probing and Comparing the Photobromination and Photoiodination of Dissolved Organic Matter by Using Ultra-High-Resolution Mass Spectrometry.

PubMed

Hao, Zhineng; Yin, Yongguang; Cao, Dong; Liu, Jingfu

2017-05-16

Photochemical halogenation of dissolved organic matter (DOM) may represent an important abiotic process for the formation of natural organobromine compounds (OBCs) and natural organoiodine compounds (OICs) within surface waters. Here we report the enhanced formation of OBCs and OICs by photohalogenating DOM in freshwater and seawater, as well as the noticeable difference in the distribution and composition pattern of newly formed OBCs and OICs. By using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry, various OBCs and OICs were identified during the photohalogenation processes in sunlit waters. The respective number of OBCs and OICs formed in artificial seawater (ASW) under light radiation was higher than that in artificial freshwater (AFW), suggesting a possible role of the mixed reactive halogen species. OBCs were formed mainly via substitution reactions and addition reactions accompanied by other reactions and distributed into three classes: unsaturated hydrocarbons with relatively low oxygen content, unsaturated aliphatic compounds, and saturated fatty acids and carbohydrates with relatively high hydrogen content. Unlike the OBCs, OICs were located primarily in the region of carboxylic-rich alicyclic molecules composed of esterified phenolic, carboxylated, and fused alicyclic structures and were generated mainly through electrophilic substitution of the aromatic proton. Our findings call for further investigation on the exact structure and toxicity of the OBCs and OICs generated in the natural environment.

Photochemical reactions of cyanoacetylene and dicyanoacetylene: Possible processes in Titan's atmosphere

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Guillemin, J. C.

1991-01-01

Titan has an atmosphere which is subject to dramatic chemical evolution due mainly to the dramatic effect of the UV flux from the Sun. The energetic solar photons and other particles are converting the methane-nitrogen atmosphere into the unsaturated carbon compounds observed by the Voyager probes. These same solar photons are also converting some of these unsaturated reaction products into the aerosols observed in the atmosphere which obscure the view of the surface of Titan. In particular, the photochemical reactions of cyanoacetylene, dicyanoacetylene, acetylene and ethylene may result in the formation of the higher hydrocarbons and polymers which result in the aerosols observed in Titan's atmosphere. Polymers are the principal reaction products formed by irradiation of cyanoacetylene and dicyanoacetylene. Irradiation of cyanoacetylene with 185 nm of light also yields 1,3,5-tricyanobenzene while irradiation at 254 nm yields 1,2,4-tricyanobenzene and tetracyano cyclooctatetraenes. Photolyses of mixtures of cyanoacetylene and acetylene yields mono- and di- cyanobenzenes. The 1-Cyanocyclobutene is formed from the photochemical addition of cyanoacetylene with ethylene. The photolysis of dicyanoacetylene with acetylene yields 2,3-dicyano-1,3-butadiene and 1,2-dicyanobenzene. Tetracyano cyclooctatetraene products were also observed in the photolysis of mixtures of dicyanoacetylene and acetylene with 254 nm light. The 1,2-Dicyano cyclobutene is obtained from the photolysis dicyanoacetylene and ethylene. Reaction mechanisms will be proposed to explain the observed photoproducts.

Simulation and experimental study of resin flow in fibre fabrics

NASA Astrophysics Data System (ADS)

Yan, Fei; Yan, Shilin; Li, Yongjing

2017-06-01

Liquid Composite Moulding (LCM) is gradually becoming the most competitive manufacturing technology for producing large composite parts with complex geometry with high quality and low cost. These parts include those for airplanes, wind turbine blades and automobile components. Fibre fabrics in liquid composite moulding can be considered as dual-scale porous media. In different gap scales, an unsaturated flow is produced during the mould filling process. This particular flow behaviour deviates from the traditional Darcy’s law, which is used to calculate the filling pressure and will cause errors. According to sink theory, the unsaturated flow characteristics of this dual-scale porous media were studied in this paper, and a FEM solution program was developed. The results showed that the pressure curves against the position which simulated by sink functions were departure from the position of traditional theory. In addition, the simulation results of partially-saturated region were consistent with the experimental data.

Aspects of hysteresis in unsaturated porous media flow

NASA Astrophysics Data System (ADS)

van Duijn, Hans

2016-04-01

About 20 years ago, Peter Raats and I wrote a technical note related to the horizontal redistribution in unsaturated porous media with hysteresis in the capillary pressure (P.A.C. Raats & C.J. van Duijn, A note on horizontal redistribution with capillary hysteresis, WWR 31, p. 231-232, 1995). In the first part of my presentation, I will revisit the results of that paper. In particular the cases of unconventional flow, where the water flows from the dry region to the wet region. A comparison will be made with results obtained with the current interface area models as introduced by Gray & Hassanizadeh. I will explain and outline the differences. In the second part, travelling wave solutions of Richards equation with gravity and with hysteresis in both the capillary pressure and relative permeability will be discussed. It will be explained why such solutions oscillate in space-time and how they behave as the hysteresis regularization vanishes.

Fingerprinting aliphatic hydrocarbon pollutants over agricultural lands surrounding Tehran oil refinery.

PubMed

Bayat, Javad; Hashemi, Seyed Hossein; Khoshbakht, Korros; Deihimfard, Reza

2016-11-01

The analysis of aliphatic hydrocarbons, which are composed of n-alkanes as well as branched and cyclic alkanes, can be used to distinguish between the sources of hydrocarbon contamination. In this study, the concentration of aliphatic hydrocarbons, soil pH, and organic matter in agricultural soils located south of Tehran were monitored. Eighty-three soil samples were taken from two depth ranges of 0-30 and 30-60 cm. The results showed that aliphatic compounds ranged from 0.22-68.11 mg kg -1 at the top to 0.33-53.18 mg kg -1 at subsoil. The amount of hydrocarbons increases from the northern parts toward the south, and hydrocarbon pollutants originated from both petroleum and non-petroleum sources. Higher concentrations of aliphatic compounds in the southern parts indicated that, aside from the practice of irrigating with untreated wastewater, leakage from oil refinery storage tanks possibly contributed to soil pollution. The results also showed that several sources have polluted the agricultural soils. It is necessary to develop a new local pollution criterion as a diagnostic index that includes not only hydrocarbons but also other parameters such as heavy metal content in both soil and untreated wastewater, surface runoff, and other irrigation water resources to determine the exact origin of pollution.

Ground-Water Geochemistry of Kwajalein Island, Republic of the Marshall Islands, 1991

USGS Publications Warehouse

Tribble, Gordon W.

1997-01-01

Ground water on Kwajalein Island is an important source of drinking water, particularly during periods of low rainfall. Fresh ground water is found as a thin lens underlain by saltwater. The concentration of dissolved ions increases with depth below the water table and proximity to the shoreline as high-salinity seawater mixes with fresh ground water. The maximum depth of the freshwater lens is 37 ft. Chloride is assumed to be non-reactive under the range of geochemical conditions on the atoll. The concentration of chloride thus is used as a conservative constituent to evaluate freshwater-saltwater mixing within the aquifer. Concentrations of sodium and for the most part, potassium and sulfate, also appear to be determined by conservative mixing between saltwater and rain. Concentrations of calcium, magnesium, and strontium are higher than expected from conservative mixing; these higher concentrations are a result of the dissolution of carbonate minerals. An excess in dissolved inorganic carbon results from carbonate-mineral dissolution and from the oxidation of organic matter in the aquifer; the stoichiometric difference between excess dissolved inorganic carbon and excess bivalent cations is used as a measure of the amount of organic-matter oxidation. Organic-matter oxidation also is indicated by the low concentration of dissolved oxygen, high concentrations of nutrients, and the presence of hydrogen sulfide in many of the water samples. Low levels of dissolved oxygen indicate oxic respiration, and sulfate reduction is indicated by hydrogen sulfide. The amount of dissolved inorganic carbon released during organic-matter oxidation is nearly equivalent to the amount of carbonate-mineral dissolution. Organic-matter oxidation and carbonate-mineral dissolution seem to be most active either in the unsaturated zone or near the top of the water table. The most plausible explanation is that high amounts of oxic respiration in the unsaturated zone generate carbon dioxide, which causes carbonate minerals to dissolve. Ground water contaminated by petroleum hydrocarbons had the highest levels of mineral dissolution and organic respiration (including sulfate reduction), indicating that bacteria are oxidizing the contaminants.

The organic aerosols of Titan

NASA Technical Reports Server (NTRS)

Khare, B. N.; Sagan, C.; Thompson, W. R.; Arakawa, E. T.; Suits, F.; Calcott, T. A.; Williams, M. W.; Shrader, S.; Ogino, H.; Willingham, T. O.

1986-01-01

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan prepared by continuous dc discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mb is determined from X-ray to microwave frequencies. Values of n (approx. 1.65) and k (approx. 0.004 to 0.08) in the visible are consistent with deductions made by groundbased and spaceborne observations of Titan. Many infrared absorption features are present in k(lambda), including the 4.6 micrometer nitrile band. Molecular analysis of the volatile components of this tholin was performed by sequential and nonsequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycylic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition,acid hydrolysis produces a racemic mixture of biological and nonbiological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.

Selected techniques for monitoring water movement through unsaturated alluvium during managed aquifer recharge

USGS Publications Warehouse

Nawikas, Joseph M.; O'Leary, David R.; Izbicki, John A.; Burgess, Matthew K.

2016-10-21

Managed aquifer recharge is used to augment natural recharge to aquifers. It can be used to replenish aquifers depleted by pumping or to store water during wetter years for withdrawal during drier years. Infiltration from ponds is a commonly used, inexpensive approach for managed aquifer recharge.At some managed aquifer-recharge sites, the time when infiltrated water arrives at the water table is not always clearly shown by water-level data. As part of site characterization and operation, it can be desirable to track downward movement of infiltrated water through the unsaturated zone to identify when it arrives at the water table.

Modeling unsaturated zone flow and runoff processes by integrating MODFLOW-LGR and VSF, and creating the new CFL package

USGS Publications Warehouse

Borsia, I.; Rossetto, R.; Schifani, C.; Hill, Mary C.

2013-01-01

In this paper two modifications to the MODFLOW code are presented. One concerns an extension of Local Grid Refinement (LGR) to Variable Saturated Flow process (VSF) capability. This modification allows the user to solve the 3D Richards’ equation only in selected parts of the model domain. The second modification introduces a new package, named CFL (Cascading Flow), which improves the computation of overland flow when ground surface saturation is simulated using either VSF or the Unsaturated Zone Flow (UZF) package. The modeling concepts are presented and demonstrated. Programmer documentation is included in appendices.

Variability and scaling of hydraulic properties for 200 Area soils, Hanford Site

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

Khaleel, R.; Freeman, E.J.

Over the years, data have been obtained on soil hydraulic properties at the Hanford Site. Much of these data have been obtained as part of recent site characterization activities for the Environmental Restoration Program. The existing data on vadose zone soil properties are, however, fragmented and documented in reports that have not been formally reviewed and released. This study helps to identify, compile, and interpret all available data for the principal soil types in the 200 Areas plateau. Information on particle-size distribution, moisture retention, and saturated hydraulic conductivity (K{sub s}) is available for 183 samples from 12 sites in themore » 200 Areas. Data on moisture retention and K{sub s} are corrected for gravel content. After the data are corrected and cataloged, hydraulic parameters are determined by fitting the van Genuchten soil-moisture retention model to the data. A nonlinear parameter estimation code, RETC, is used. The unsaturated hydraulic conductivity relationship can subsequently be predicted using the van Genuchten parameters, Mualem`s model, and laboratory-measured saturated hydraulic conductivity estimates. Alternatively, provided unsaturated conductivity measurements are available, the moisture retention curve-fitting parameters, Mualem`s model, and a single unsaturated conductivity measurement can be used to predict unsaturated conductivities for the desired range of field moisture regime.« less

Tandem sulfur chemiluminescence and flame ionization detection with planar microfluidic devices for the characterization of sulfur compounds in hydrocarbon matrices.

PubMed

Luong, J; Gras, R; Shellie, R A; Cortes, H J

2013-07-05

The detection of sulfur compounds in different hydrocarbon matrices, from light hydrocarbon feedstocks to medium synthetic crude oil feeds provides meaningful information for optimization of refining processes as well as demonstration of compliance with petroleum product specifications. With the incorporation of planar microfluidic devices in a novel chromatographic configuration, sulfur compounds from hydrogen sulfide to alkyl dibenzothiophenes and heavier distributions of sulfur compounds over a wide range of matrices spanning across a boiling point range of more than 650°C can be characterized, using one single analytical configuration in less than 25min. In tandem with a sulfur chemiluminescence detector for sulfur analysis is a flame ionization detector. The flame ionization detector can be used to establish the boiling point range of the sulfur compounds in various hydrocarbon fractions for elemental specific simulated distillation analysis as well as profiling the hydrocarbon matrices for process optimization. Repeatability of less than 3% RSD (n=20) over a range of 0.5-1000 parts per million (v/v) was obtained with a limit of detection of 50 parts per billion and a linear range of 0.5-1000 parts per million with a correlation co-efficient of 0.998. Copyright © 2013 Elsevier B.V. All rights reserved.

Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst.

PubMed

Senan, Ahmed M; Zhang, Sicheng; Zeng, Miao; Chen, Zhuqi; Yin, Guochuan

2017-08-16

Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu 2+ cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu 2+ , and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.

Correlation of physical properties with molecular structure for some dicyclic hydrocarbons having high thermal-energy release per unit volume

NASA Technical Reports Server (NTRS)

Wise, P H; Serijan, K T; Goodman, I A

1951-01-01

As part of a program to study the correlation between molecular structure and physical properties of high-density hydrocarbons, the net heats of combustion, melting points, boiling points, densities, and kinematic viscosities of some hydrocarbons in the 2-n-alkylbiphenyl, 1,1-diphenylalkane, diphenylalkane, 1,1-dicyclohexylalkane, and dicyclohexylalkane series are presented.

Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

NASA Astrophysics Data System (ADS)

Murillo, Luis E.

Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are also discussed. Chemisorption, TPD, FTIR using a batch reactor for the self-hydrogenation of cyclohexene and CO adsorbed on the bimetallic surfaces were carried out to correlate surface science findings with experiments on supported bimetallic catalysts. To expand the studies on the effect of bimetallic structures on hydrogenation reactions, molecules with multiple functional groups such as alpha,beta-unsaturated aldehydes were also investigated. Studies of selective hydrogenation of a,ss-unsaturated aldehydes toward the desired unsaturated alcohols are of interest for the production of fine chemicals and pharmaceuticals. In these compounds, competitive hydrogenation of the C=C and C=O bonds occurs. TPD and HREELS experiments of acrolein (CH2=CH-CH=O) on Pt-based bimetallic surfaces are performed to investigate their effects on the hydrogenation activity of the C-O bond. The production of the desired unsaturated alcohol, allyl alcohol, has been observed for the first time on Pt-Ni-Pt(111) under UHV conditions. However, the propionaldehyde yield is five times higher than the allyl alcohol yield. Thus, a preferential isomerization reaction of allyl alcohol to propionaldehyde is very likely to occur on the Pt-Ni-Pt(111) surface as observed on the desorption studies of allyl alcohol on this surface. The hydrogenation of acrolein is also carried out under UHV conditions on other 3d-transition metal/Pt(111) surfaces such as Co/Pt(111), Fe/Pt(111), and Cu/Pt(111). So far, the highest activity and allyl alcohol yield are found on the Pt-Ni-Pt(111) surface with pre-adsorbed hydrogen.

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2B Table 2B to Subpart E of Part 59—Reactivity Factors for Aliphatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2C Table 2C to Subpart E of Part 59—Reactivity Factors for Aromatic...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2B Table 2B to Subpart E of Part 59—Reactivity Factors for Aliphatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2C Table 2C to Subpart E of Part 59—Reactivity Factors for Aromatic...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2B Table 2B to Subpart E of Part 59—Reactivity Factors for Aliphatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2C Table 2C to Subpart E of Part 59—Reactivity Factors for Aromatic...

Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

NASA Astrophysics Data System (ADS)

Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.

2017-07-01

The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

The direct aromatization of methane

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

Marcelin, G.; Oukaci, R.; Migone, R.A.

1995-12-31

The thermal decomposition of methane shows significant potential as a process for the production of higher unsaturated and aromatic hydrocarbons when the extent of the reaction is limited. Thermodynamic calculations have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that cooling the product and reacting gases asmore » the reaction proceeds can significantly reduce or eliminate the formation of solid carbon and heavier (C{sub 10+}) materials. Much work remains to be done in optimizing the quenching process and this is one of the goals of this program. Means to lower the temperature of the reaction are being studied as this result in a more feasible commercial process due to savings realized in energy and material of construction costs. The use of free-radical generators and catalysts will be investigated as a means of lowering the reaction temperature thus allowing faster quenching. It is highly likely that such studies will lead to a successful direct methane to higher hydrocarbon process.« less

The effect of clay catalyst on the chemical composition of bio-oil obtained by co-pyrolysis of cellulose and polyethylene.

PubMed

Solak, Agnieszka; Rutkowski, Piotr

2014-02-01

Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 - montmorillonite K10, KSF - montmorillonite KSF, B - Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500°C with heating rate of 100°C/s to produce bio-oil with high yield. The pyrolytic oil yield was in the range of 41.3-79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500°C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

Hydrocarbon fuels from brown grease: Moving from the research laboratory toward an industrial process

NASA Astrophysics Data System (ADS)

Pratt, Lawrence M.; Strothers, Joel; Pinnock, Travis; Hilaire, Dickens Saint; Bacolod, Beatrice; Cai, Zhuo Biao; Sim, Yoke-Leng

2017-04-01

Brown grease is a generic term for the oily solids and semi-solids that accumulate in the sewer system and in sewage treatment plants. It has previously been shown that brown grease undergoes pyrolysis to form a homologous series of alkanes and 1-alkenes between 7 and 17 carbon atoms, with smaller amounts of higher hydrocarbons and ketones up to about 30 carbon atoms. The initial study was performed in batch mode on a scale of up to 50 grams of starting material. However, continuous processes are usually more efficient for large scale production of fuels and commodity chemicals. This work describes the research and development of a continuous process. The first step was to determine the required reactor temperature. Brown grease consists largely of saturated and unsaturated fatty acids, and they react at different rates, and produce different products and intermediates. Intermediates include ketones, alcohols, and aldehydes, and Fe(III) ion catalyzes at least some of the reactions. By monitoring the pyrolysis of brown grease, its individual components, and intermediates, it was determined that a reactor temperature of at least 340 °C is required. A small scale (1 L) continuous stirred tank reactor was built and its performance is described.

Impact of Hydrogeological Uncertainty on Estimation of Environmental Risks Posed by Hydrocarbon Transportation Networks

NASA Astrophysics Data System (ADS)

Ciriello, V.; Lauriola, I.; Bonvicini, S.; Cozzani, V.; Di Federico, V.; Tartakovsky, Daniel M.

2017-11-01

Ubiquitous hydrogeological uncertainty undermines the veracity of quantitative predictions of soil and groundwater contamination due to accidental hydrocarbon spills from onshore pipelines. Such predictions, therefore, must be accompanied by quantification of predictive uncertainty, especially when they are used for environmental risk assessment. We quantify the impact of parametric uncertainty on quantitative forecasting of temporal evolution of two key risk indices, volumes of unsaturated and saturated soil contaminated by a surface spill of light nonaqueous-phase liquids. This is accomplished by treating the relevant uncertain parameters as random variables and deploying two alternative probabilistic models to estimate their effect on predictive uncertainty. A physics-based model is solved with a stochastic collocation method and is supplemented by a global sensitivity analysis. A second model represents the quantities of interest as polynomials of random inputs and has a virtually negligible computational cost, which enables one to explore any number of risk-related contamination scenarios. For a typical oil-spill scenario, our method can be used to identify key flow and transport parameters affecting the risk indices, to elucidate texture-dependent behavior of different soils, and to evaluate, with a degree of confidence specified by the decision-maker, the extent of contamination and the correspondent remediation costs.

Structural analysis of Clostridium acetobutylicum ATCC 824 glycoside hydrolase from CAZy family GH105

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

Germane, Katherine L., E-mail: katherine.germane.civ@mail.mil; Servinsky, Matthew D.; Gerlach, Elliot S.

2015-07-29

The crystal structure of the protein product of the C. acetobutylicum ATCC 824 gene CA-C0359 is structurally similar to YteR, an unsaturated rhamnogalacturonyl hydrolase from B. subtilis strain 168. Substrate modeling and electrostatic studies of the active site of the structure of CA-C0359 suggests that the protein can now be considered to be part of CAZy glycoside hydrolase family 105. Clostridium acetobutylicum ATCC 824 gene CA-C0359 encodes a putative unsaturated rhamnogalacturonyl hydrolase (URH) with distant amino-acid sequence homology to YteR of Bacillus subtilis strain 168. YteR, like other URHs, has core structural homology to unsaturated glucuronyl hydrolases, but hydrolyzes themore » unsaturated disaccharide derivative of rhamnogalacturonan I. The crystal structure of the recombinant CA-C0359 protein was solved to 1.6 Å resolution by molecular replacement using the phase information of the previously reported structure of YteR (PDB entry (http://scripts.iucr.org/cgi-bin/cr.cgi?rm)) from Bacillus subtilis strain 168. The YteR-like protein is a six-α-hairpin barrel with two β-sheet strands and a small helix overlaying the end of the hairpins next to the active site. The protein has low primary protein sequence identity to YteR but is structurally similar. The two tertiary structures align with a root-mean-square deviation of 1.4 Å and contain a highly conserved active pocket. There is a conserved aspartic acid residue in both structures, which has been shown to be important for hydration of the C=C bond during the release of unsaturated galacturonic acid by YteR. A surface electrostatic potential comparison of CA-C0359 and proteins from CAZy families GH88 and GH105 reveals the make-up of the active site to be a combination of the unsaturated rhamnogalacturonyl hydrolase and the unsaturated glucuronyl hydrolase from Bacillus subtilis strain 168. Structural and electrostatic comparisons suggests that the protein may have a slightly different substrate specificity from that of YteR.« less

CO2 dynamics in the Amargosa Desert: Fluxes and isotopic speciation in a deep unsaturated zone

USGS Publications Warehouse

Walvoord, Michelle Ann; Striegl, Robert G.; Prudic, David E.; Stonestrom, David A.

2005-01-01

Natural unsaturated-zone gas profiles at the U.S. Geological Survey's Amargosa Desert Research Site, near Beatty, Nevada, reveal the presence of two physically and isotopically distinct CO2 sources, one shallow and one deep. The shallow source derives from seasonally variable autotrophic and heterotrophic respiration in the root zone. Scanning electron micrograph results indicate that at least part of the deep CO2 source is associated with calcite precipitation at the 110-m-deep water table. We use a geochemical gas-diffusion model to explore processes of CO2 production and behavior in the unsaturated zone. The individual isotopic species 12CO2, 13CO2, and 14CO2 are treated as separate chemical components that diffuse and react independently. Steady state model solutions, constrained by the measured δ13C (in CO2), and δ14C (in CO2) profiles, indicate that the shallow CO2 source from root and microbial respiration composes ∼97% of the annual average total CO2 production at this arid site. Despite the small contribution from deep CO2 production amounting to ∼0.1 mol m−2 yr−1, upward diffusion from depth strongly influences the distribution of CO2 and carbon isotopes in the deep unsaturated zone. In addition to diffusion from deep CO2 production, 14C exchange with a sorbed CO2 phase is indicated by the modeled δ14C profiles, confirming previous work. The new model of carbon-isotopic profiles provides a quantitative approach for evaluating fluxes of carbon under natural conditions in deep unsaturated zones.

40 CFR Appendix F to Part 75 - Conversion Procedures

Code of Federal Regulations, 2010 CFR

2010-07-01

...-00, Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter, or ASTM D4809-00, Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb...

Highlights from the SoilCAM project: Soil Contamination, Advanced integrated characterisation and time-lapse Monitoring

NASA Astrophysics Data System (ADS)

French, H. K.; van der Zee, S. E. A. T. M.; Wehrer, M.; Godio, A.; Pedersen, L. B.; Toscano, G.

2012-04-01

The SoilCAM project (Soil Contamination, Advanced integrated characterisation and time-lapse Monitoring 2008-2012, EU-FP7-212663) is aimed at improving current methods for monitoring contaminant distribution and biodegradation in the subsurface. At two test sites, Oslo airport Gardermoen in Norway and the Trecate site in Italy, a number of geophysical techniques, lysimeter and other soil and water sampling techniques as well as numerical flow and transport modelling have been combined at different scales in order to characterise flow transport processes in the unsaturated and saturated zones. Laboratory experiments have provided data on physical and bio-geo-chemical parameters for use in models and to select remediation methods. The geophysical techniques were used to map geological heterogeneities and also conduct time-lapse measurements of processes in the unsaturated zone. Both cross borehole and surface electrodes were used for electrical resistivity and induced polarisation surveys. The geophysical surveys showed clear indications of areas highly affected by de-icing chemicals along the runway at Oslo airport. The time lapse measurements along the runway at the airport show infiltration patterns during snowmelt and are used to validate 2D unsaturated flow and transport simulations using SUTRA. The Orchestra model is used to describe the complex interaction between bio-geo-chemical processes in a 1D profile along the runway. The presence of installations such as a membrane along the runway highly affects the flow pattern and challenges the capacity of the numerical code. Smaller scale field site measurements have revealed the increase of iron and manganese during degradation of de-icing chemicals. The use of Nitrate to increase red-ox potential was tested, but results have not been analysed yet. So far it cannot be concluded that degradation process can be quantified indirectly by geophysical monitoring. At the Trecate site a combination of georadar, electrical resistivity and radio magneto telluric provided a broad outline of the geology down to 50 m, there is a good consistency in the data in the overlapping part, and more deep samples would be required to validate the geological interpretation of the data. Anomalies in the Induced polarisation and electrical resistivity data from the cross borehole measurements indicate where the remaining crude oil can be found. Water samples from multilevel samplers reveal crude oil present in emulsion in the zone of groundwater fluctuations, highlighting the importance of colloidal transport. Geochemistry of the groundwater clearly indicates degradation of hydrocarbons under iron- and sulphate reducing conditions. Modflow has been used to simulate the regional groundwater flow and transport in the area. An overview of the work that has been conducted and main highlights of the results so far will be presented.

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

Assessing field-scale biogeophysical signatures of bioremediation over a mature crude oil spill

USGS Publications Warehouse

Slater, Lee; Ntarlagiannis, Dimitrios; Atekwana, Estella; Mewafy, Farag; Revil, Andre; Skold, Magnus; Gorby, Yuri; Day-Lewis, Frederick D.; Lane, John W.; Trost, Jared J.; Werkema, Dale D.; Delin, Geoffrey N.; Herkelrath, William N.; Rectanus, H.V.; Sirabian, R.

2011-01-01

We conducted electrical geophysical measurements at the National Crude Oil Spill Fate and Natural Attenuation Research Site (Bemidji, MN). Borehole and surface self-potential measurements do not show evidence for the existence of a biogeobattery mechanism in response to the redox gradient resulting from biodegradation of oil. The relatively small self potentials recorded are instead consistent with an electrodiffusion mechanism driven by differences in the mobility of charge carriers associated with biodegradation byproducts. Complex resistivity measurements reveal elevated electrical conductivity and interfacial polarization at the water table where oil contamination is present, extending into the unsaturated zone. This finding implies that the effect of microbial cell growth/attachment, biofilm formation, and mineral weathering accompanying hydrocarbon biodegradation on complex interfacial conductivity imparts a sufficiently large electrical signal to be measured using field-scale geophysical techniques.

Problems in Catalytic Oxidation of Hydrocarbons and Detailed Simulation of Combustion Processes

NASA Astrophysics Data System (ADS)

Xin, Yuxuan

This dissertation research consists of two parts, with Part I on the kinetics of catalytic oxidation of hydrocarbons and Part II on aspects on the detailed simulation of combustion processes. In Part I, the catalytic oxidation of C1--C3 hydrocarbons, namely methane, ethane, propane and ethylene, was investigated for lean hydrocarbon-air mixtures over an unsupported Pd-based catalyst, from 600 to 800 K and under atmospheric pressure. In Chapter 2, the experimental facility of wire microcalorimetry and simulation configuration were described in details. In Chapter 3 and 4, the oxidation rate of C1--C 3 hydrocarbons is demonstrated to be determined by the dissociative adsorption of hydrocarbons. A detailed surface kinetics model is proposed with deriving the rate coefficient of hydrocarbon dissociative adsorption from the wire microcalorimetry data. In Part II, four fundamental studies were conducted through detailed combustion simulations. In Chapter 5, self-accelerating hydrogen-air flames are studied via two-dimensional detailed numerical simulation (DNS). The increase in the global flame velocity is shown to be caused by the increase of flame surface area, and the fractal structure of the flame front is demonstrated by the box-counting method. In Chapter 6, skeletal reaction models for butane combustion are derived by using directed relation graph (DRG) and DRG-aided sensitivity analysis (DRGASA), and uncertainty minimization by polynomial chaos expansion (MUM-PCE) mothodes. The dependence of model uncertainty is subjected to the completeness of the model. In Chapter 7, a systematic strategy is proposed to reduce the cost of the multicomponent diffusion model by accurately accounting for the species whose diffusivity is important to the global responses of the combustion systems, and approximating those of less importance by the mixture-averaged model. The reduced model is validated in an n-heptane mechanism with 88 species. In Chapter 8, the influence of Soret diffusion on the n-heptane/air flames is investigated numerically. In the unstretched flames, Soret diffusion primarily affects the chemical kinetics embedded in the flame structure and the net effect is small; while in the stretched flames, its impact is mainly through those of n-heptane and the secondary fuel, H2, in modifying the flame temperature, with substantial effects.

Process to separate alkali metal salts from alkali metal reacted hydrocarbons

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

Gordon, John Howard; Alvare, Javier; Larsen, Dennis

A process to facilitate gravimetric separation of alkali metal salts, such as alkali metal sulfides and polysulfides, from alkali metal reacted hydrocarbons. The disclosed process is part of a method of upgrading a hydrocarbon feedstock by removing heteroatoms and/or one or more heavy metals from the hydrocarbon feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase containing alkali metal salts and reduced heavy metals, and an upgraded hydrocarbon feedstock. The inorganic phasemore » may be gravimetrically separated from the upgraded hydrocarbon feedstock after mixing at a temperature between about 350.degree. C. to 400.degree. C. for a time period between about 15 minutes and 2 hours.« less

Observations of the release of non-methane hydrocarbons from fractured shale.

PubMed

Sommariva, Roberto; Blake, Robert S; Cuss, Robert J; Cordell, Rebecca L; Harrington, Jon F; White, Iain R; Monks, Paul S

2014-01-01

The organic content of shale has become of commercial interest as a source of hydrocarbons, owing to the development of hydraulic fracturing ("fracking"). While the main focus is on the extraction of methane, shale also contains significant amounts of non-methane hydrocarbons (NMHCs). We describe the first real-time observations of the release of NMHCs from a fractured shale. Samples from the Bowland-Hodder formation (England) were analyzed under different conditions using mass spectrometry, with the objective of understanding the dynamic process of gas release upon fracturing of the shale. A wide range of NMHCs (alkanes, cycloalkanes, aromatics, and bicyclic hydrocarbons) are released at parts per million or parts per billion level with temperature- and humidity-dependent release rates, which can be rationalized in terms of the physicochemical characteristics of different hydrocarbon classes. Our results indicate that higher energy inputs (i.e., temperatures) significantly increase the amount of NMHCs released from shale, while humidity tends to suppress it; additionally, a large fraction of the gas is released within the first hour after the shale has been fractured. These findings suggest that other hydrocarbons of commercial interest may be extracted from shale and open the possibility to optimize the "fracking" process, improving gas yields and reducing environmental impacts.

Determination of mineral oil aromatic hydrocarbons in edible oils and fats by online liquid chromatography-gas chromatography-flame ionization detection - Evaluation of automated removal strategies for biogenic olefins.

PubMed

Nestola, Marco; Schmidt, Torsten C

2017-07-07

The determination of mineral oil aromatic hydrocarbons (MOAH) in foodstuffs gained in importance over the last years as carcinogenicity cannot be excluded for certain MOAH. The existence of olefins in foodstuffs, such as edible oils and fats, can be problematic for the determination of MOAH by LC-GC-FID. Removal of these interfering substances by HPLC based on polarity differences is not possible. During gas chromatographic separation heavily overloaded peaks are observed rendering the detection of small mineral oil contaminations almost impossible. Therefore, removal of these olefins is necessary before subjection of the sample to LC-GC-FID. Epoxidation of olefins to increase their polarity proved to be a valuable tool in the past. Precision and trueness of the results as shown in a collaborative trial, however, are relying on exact reaction conditions. Additionally, it is known that certain MOAH are oxidized during epoxidation and therefore get lost. In the scope of this work, hydroboration, bromohydrin reaction, and epoxidation were examined for their potential for derivatization of unsaturated hydrocarbons with increased robustness and higher recovery of MOAH. Epoxidation by meta-chloroperoxybenzoic acid (mCPBA) delivered the best removal of olefins. Factors influencing this reaction were enlightened. Adaption of the reaction conditions and time-controlled automation increased the recovery of polycyclic MOAH. Good precision (RSD r <1.5%) and recovery (95-102%) for MOAH were also observed for sunflower and olive oils spiked with a lubricating mineral oil (at 24.5mg/kg of MOAH). The trueness of the method was verified by analyzing collaborative trial samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical kinetic model uncertainty minimization through laminar flame speed measurements

PubMed Central

Park, Okjoo; Veloo, Peter S.; Sheen, David A.; Tao, Yujie; Egolfopoulos, Fokion N.; Wang, Hai

2016-01-01

Laminar flame speed measurements were carried for mixture of air with eight C3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011, 158, 2358–2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C3 and C4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel. PMID:27890938

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

Chemical kinetic model uncertainty minimization through laminar flame speed measurements.

PubMed

Park, Okjoo; Veloo, Peter S; Sheen, David A; Tao, Yujie; Egolfopoulos, Fokion N; Wang, Hai

2016-10-01

Laminar flame speed measurements were carried for mixture of air with eight C 3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso -butene, n -butane, and iso -butane) at the room temperature and ambient pressure. Along with C 1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011, 158, 2358-2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C 3 and C 4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C 3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C 4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C 4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel.

Effects of temperature on transcriptome and cuticular hydrocarbon expression in ecologically differentiated populations of desert Drosophila.

PubMed

Etges, William J; de Oliveira, Cássia C; Rajpurohit, Subhash; Gibbs, Allen G

2017-01-01

We assessed the effects of temperature differences on gene expression using whole-transcriptome microarrays and cuticular hydrocarbon variation in populations of cactophilic Drosophila mojavensis . Four populations from Baja California and mainland Mexico and Arizona were each reared on two different host cacti, reared to sexual maturity on laboratory media, and adults were exposed for 12 hr to 15, 25, or 35°C. Temperature differences influenced the expression of 3,294 genes, while population differences and host plants affected >2,400 each in adult flies. Enriched, functionally related groups of genes whose expression changed at high temperatures included heat response genes, as well as genes affecting chromatin structure. Gene expression differences between mainland and peninsular populations included genes involved in metabolism of secondary compounds, mitochondrial activity, and tRNA synthases. Flies reared on the ancestral host plant, pitaya agria cactus, showed upregulation of genes involved in metabolism, while flies reared on organ pipe cactus had higher expression of DNA repair and chromatin remodeling genes. Population × environment (G × E) interactions had widespread effects on the transcriptome where population × temperature interactions affected the expression of >5,000 orthologs, and there were >4,000 orthologs that showed temperature × host plant interactions. Adults exposed to 35°C had lower amounts of most cuticular hydrocarbons than those exposed to 15 or 25°C, including abundant unsaturated alkadienes. For insects adapted to different host plants and climatic regimes, our results suggest that temperature shifts associated with climate change have large and significant effects on transcriptomes of genetically differentiated natural populations.

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.

Lipid biomarker and microbial community of 49.6°E hydrothermal field at Southwest Indian Ocean Ridge

NASA Astrophysics Data System (ADS)

Lei, J.; Chu, F.; Yu, X.; Li, X.; Tao, C.

2012-12-01

In 2007, Chinese Research Cruises Discovered the First Active Hydrothermal Vent Field at the Ultraslow Spreading Southwest Indian Ridge. This study intent to get composition, evolution and origin information of lipid compounds in SWIR, and recognize the style of lipid biomarkers which have obviously indicative significance for community structure.Soluble organic matter were extracted from geological samples (including chimney sulfide, oxide, around hydrothermal vents) in Southwest Indian Ridge (SWIR), and divided into hydrocarbon, fatty acid component by column chromatography. GC, GC-MS, HPLC-MS were applied for composition and abundance analysis. Lipid in hydrothermal sulfide contains obvious isoprenoidal hydrocarbon biomarkers (Sq, IS40) and GDGTs (m/z=653) that associated with methanogenic archaea which belongs to Euryarchaeota, and iso /anti-iso fatty acid (iC15:0, aiC15:0, iC17:0, aiC17:0)which may originated from sulfate reducing bacteria (SRB).Lipids extracted from hydrothermal oxide lack isoprenoidal hydrocarbon, and Ph/C18 (0.57) is much lower than sulfide (1.22). Fatty acid compound of oxide include abundant saturated fatty (C16:0, C18:0) acid and mono-unsaturated fatty acids (C16:1n7, C18:1n7), but much less iso/anti-iso was detected. Lipid composition of hydrothermal oxide showed that archaea activity was seldom in hydrothermal oxide, and sulfur-oxidizing bacteria was the main microbial community.Study of Jaeschke (2010) showed that high temperature hydrothermal venting encompassed different microbial community from low temperature hydrothermal venting. Our study showed that in different stage of hydrothermal, microbial community structure may be distinct.

Partial oxidation catalyst

DOEpatents

Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

2000-01-01

A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

Changing rooster sperm membranes to facilitate cryopreservation

USDA-ARS?s Scientific Manuscript database

Cryopreservation damages rooster sperm membranes. Part of this damage is due to membrane transitioning from the fluid to the gel state as temperature is reduced. This damage may be prevented by increasing membrane fluidity at low temperatures by incorporating cholesterol or unsaturated lipids into t...

Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source

NASA Astrophysics Data System (ADS)

Xie, Xiaobo; Wang, Zhenpeng; Li, Yafeng; Zhan, Lingpeng; Nie, Zongxiu

2017-06-01

A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O - 3H]+ was observed in the case of individual alkanes (C5-C19) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. [Figure not available: see fulltext.

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

Tao, Shikang; Lu, Xiaohui; Levac, Nicole

Aerosol samples collected in the urban areas of Shanghai and Los Angeles were analyzed by nanospray-desorption electrospray ionization mass spectrometry (nano-DESI MS) with high mass resolution (m/Δm=100,000). Solvent mixtures of acetonitrile/water and acetonitrile/toluene were used to extract and ionize polar and non-polar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. Majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates in the two samples have distinctly different molecular characteristics. Specifically, organosulfates in the Los Angeles sample were dominated by isoprene- ormore » monoterpene-derived products, while organosulfates of yet unknown origin in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degree of oxidation and unsaturation. The use of acetonitrile/toluene solvent facilitated identification of this type of organosulfates, suggesting they could be missed in previous studies relying on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the organosulfates detected in the Shanghai sample suggest that they may act as surfactants, and plausibly affect the surface tension and hygroscopicity of the atmospheric particulate matter. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in liquid phase could be the formation pathway of these special organosulfates. Finally, long-chain alkanes from vehicle emissions might be their precursors.« less

Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source.

PubMed

Xie, Xiaobo; Wang, Zhenpeng; Li, Yafeng; Zhan, Lingpeng; Nie, Zongxiu

2017-06-01

A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O - 3H] + was observed in the case of individual alkanes (C 5 -C 19 ) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. Graphical Abstract ᅟ.

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.

Thermal capacitator design rationale. Part 1: Thermal and mechanical property data for selected materials potentially useful in thermal capacitor design and construction

NASA Technical Reports Server (NTRS)

Bailey, J. A.; Liao, C. K.

1975-01-01

The thermal properties of paraffin hydrocarbons and hydrocarbon mixtures which may be used as the phase change material (PCM) in thermal capacitors are discussed. The paraffin hydrocarbons selected for consideration are those in the range from C11H24 (n-Undecane) to C20H42 (n-Eicosane). A limited amount of data is included concerning other properties of paraffin hydrocarbons and the thermal and mechanical properties of several aluminum alloys which may find application as constructional materials. Data concerning the melting temperature, transition temperature, latent heat of fusion, heat of transition, specific heat, and thermal conductivity of pure and commercial grades of paraffin hydrocarbons are given. An index of companies capable of producing paraffin hydrocarbons and information concerning the availability of various grades (purity levels) is provided.

Hydrocarbons and heavy metals in the different sewer deposits in the 'Le Marais' catchment (Paris, France): stocks, distributions and origins.

PubMed

Rocher, Vincent; Azimi, Sam; Moilleron, Régis; Chebbo, Ghassan

2004-05-05

The knowledge of the pollution stored in combined sewers is of prime importance in terms of management of wet weather flow pollution since sewer deposits play a significant role as source of pollution in combined sewer overflows. This work, which focused on the hydrocarbon (aliphatic and aromatic hydrocarbons) and metallic (Fe, Zn, Pb, Cu and Cd) pollution fixed to the different kinds of sewer deposits (gross bed sediment [GBS], organic layer [OL] and biofilm), was performed in order to provide a complete overview of the contaminant storage in the 'Le Marais' combined sewer (Central Paris, France). Firstly, our results have shown that, for all kinds of pollutants, a major part was stored in the GBS (87 to 98%), a lesser part in the OL (2 to 13%) and an insignificant part in the biofilm (<1%). These results demonstrated that the potential contribution of biofilm to wet weather pollution was negligible compared to the OL one. Secondly, the investigation of hydrocarbon fingerprints in each deposit has provided relevant information about contamination origins: (1) aliphatic hydrocarbon distributions were indicative of petroleum input in the GBS and reflected a mixture of biogenic and petroleum inputs in the OL and biofilm, (2) aromatic hydrocarbon distributions suggested an important pyrolytic contamination in all the deposits. Finally, the study of pollutant fingerprints in the different deposits and in the suspended solids going through the collector has shown that: (1) the suspended solids were the major component of OL and biofilm while urban runoff seemed to be the main transport mechanism introducing pollutants in the GBS and (2) the residence times in sewer of OL and biofilm were quite short compared to those for GBS.

Genetic variability of milk fatty acids.

PubMed

Arnould, V M-R; Soyeurt, H

2009-01-01

The milk fatty acid (FA) profile is far from the optimal fat composition in regards to human health. The natural sources of variation, such as feeding or genetics, could be used to increase the concentrations of unsaturated fatty acids. The impact of feeding is well described. However, genetic effects on the milk FA composition begin to be extensively studied. This paper summarizes the available information about the genetic variability of FAs. The greatest breed differences in FA composition are observed between Holstein and Jersey milk. Milk fat of the latter breed contains higher concentrations of saturated FAs, especially short-chain FAs. The variation of the delta-9 desaturase activity estimated from specific FA ratios could explain partly these breed differences. The choice of a specific breed seems to be a possibility to improve the nutritional quality of milk fat. Generally, the proportions of FAs in milk are more heritable than the proportions of these same FAs in fat. Heritability estimates range from 0.00 to 0.54. The presence of some single nucleotide polymorphisms could explain partly the observed individual genetic variability. The polymorphisms detected on SCD1 and DGAT1 genes influence the milk FA composition. The SCD1 V allele increases the unsaturation of C16 and C18. The DGAT1 A allele is related to the unsaturation of C18. So, a combination of the molecular and quantitative approaches should be used to develop tools helping farmers in the selection of their animals to improve the nutritional quality of the produced milk fat.

Thermochemistry and Photochemistry in Thick Atmospheres on Super Earths and Mini Neptunes

NASA Astrophysics Data System (ADS)

Hu, R.; Seager, S.

2013-12-01

Dectection and characterization of low-mass exoplanets is poised to accelerate in the coming decade. Some low-mass exoplanets, namely super Earths and some mini Neptunes, will likely have thick atmospheres that are not H2-dominated. We have developed a photochemistry-thermochemistry model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H2-dominated atmospheres and non-H2-dominated atmospheres. Using this model, we have simulated the molecular composition of thick atmospheres on warm and hot super Earths/mini Neptunes, and classified thick atmospheres into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres, depending on the hydrogen abundance and the carbon to oxygen abundance ratio. We find that carbon has to be in the form of CO2 rather than CH4 or CO in an H2-depleted water-dominated thick atmosphere, and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to formation of unsaturated hydrocarbons. For future observations, we find for GJ 1214b that (1) C2H2 features at 1.0 and 1.5 μm in transmission are diagnostic for hydrocarbon-rich atmospheres; (2) a constraint on the thermal emission at 4.5 μm could differentiate water-rich atmospheres versus hydrocarbon-rich atmospheres; (3) a detection of water-vapor features and a confirmation of nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. For a hot super Earth like 55 Cnc e, the diagnostic features of water-rich atmospheres (H2O) and the diagnostic features of hydrocarbon-rich atmospheres (CO and C2H2) are well separated in transmission spectra at 0.6-5 μm, which would enable straightforward characterization. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Theoretical transmission spectra and thermal emission spectra of non-H2-dominated atmospheres on GJ 1214b based on photochemistry-thermochemistry simulations in comparison with current observations. The simulated spectra are for an hydrogen abundance of 0.5 and a variety of carbon to oxygen ratios ranging from oxygen rich to carbon rich. The atmospheric scenarios with different carbon to oxygen ratios can be constrained via the spectral features of their hallmark molecules.

Chemical interactions in complex matrices: Determination of polar impurities in biofuels and fuel contaminants in building materials

NASA Astrophysics Data System (ADS)

Baglayeva, Ganna

The solutions to several real-life analytical and physical chemistry problems, which involve chemical interactions in complex matrices are presented. The possible interferences due to the analyte-analyte and analyte-matrix chemical interactions were minimized on each step of the performed chemical analysis. Concrete and wood, as major construction materials, typically become contaminated with fuel oil hydrocarbons during their spillage. In the catastrophic scenarios (e.g., during floods), fuel oil mixes with water and then becomes entrained within the porous structure of wood or concrete. A strategy was proposed for the efficient extraction of fuel oil hydrocarbons from concrete to enable their monitoring. The impacts of sample aging and inundation with water on the extraction efficiency were investigated to elucidate the nature of analytematrix interactions. Two extraction methods, 4-days cold solvent extraction with shaking and 24-hours Soxhlet extraction with ethylacetate, methanol or acetonitrile yielded 95-100 % recovery of fuel oil hydrocarbons from concrete. A method of concrete remediation after contamination with fuel oil hydrocarbons using activated carbon as an adsorbent was developed. The 14 days remediation was able to achieve ca. 90 % of the contaminant removal even from aged water-submerged concrete samples. The degree of contamination can be qualitatively assessed using transport rates of the contaminants. Two models were developed, Fickian and empirical, to predict long-term transport behavior of fuel oil hydrocarbons under flood representative scenarios into wood. Various sorption parameters, including sorption rate, penetration degree and diffusion coefficients were obtained. The explanations to the observed three sorption phases are provided in terms of analyte-matrix interactions. The detailed simultaneous analysis of intermediate products of the cracking of triacylglycerol oils, namely monocarboxylic acids, triacyl-, diacyl- and monoacylglycerols was developed. The identification and quantification of analytes were performed using a 15-m high temperature capillary column (DB-1HT) with a GC coupled to both flame ionization and mass spectrometric detectors. To eliminate discrimination of low or high molecular weight species, programmed temperature vaporization (PTV) injection parameters were optimized using design of experiments methodology. Evaluation of the column temperature program and MS parameters allowed achieving separation of majority of target compounds based on their total number of carbon atoms, regioisomerization and, to some extent, degree of unsaturation.

Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs.

PubMed

Sherwood Lollar, B; Westgate, T D; Ward, J A; Slater, G F; Lacrampe-Couloume, G

2002-04-04

Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.

PERSONAL EXPOSURES TO POLYCYCLIC AROMATIC HYDROCARBONS ASSOCIATED WITH THE NHEXAS PILOT

EPA Science Inventory

Personal exposure monitoring for select polycyclic aromatic hydrocarbons (PAHs) was performed as part of the National Human Exposure Assessment Survey (NHEXAS) Pilot Study in Baltimore, MD. Twenty-four hour PM10 sample collections (~5.7 m3) were performed using personal envi...

Compound-specific carbon and hydrogen isotope analysis of sub-parts per billion level waterborne petroleum hydrocarbons

USGS Publications Warehouse

Wang, Y.; Huang, Y.; Huckins, J.N.; Petty, J.D.

2004-01-01

Compound-specific carbon and hydrogen isotope analysis (CSCIA and CSHIA) has been increasingly used to study the source, transport, and bioremediation of organic contaminants such as petroleum hydrocarbons. In natural aquatic systems, dissolved contaminants represent the bioavailable fraction that generally is of the greatest toxicological significance. However, determining the isotopic ratios of waterborne hydrophobic contaminants in natural waters is very challenging because of their extremely low concentrations (often at sub-parts ber billion, or even lower). To acquire sufficient quantities of polycyclic aromatic hydrocarbons with 10 ng/L concentration for CSHIA, more than 1000 L of water must be extracted. Conventional liquid/liquid or solid-phase extraction is not suitable for such large volume extractions. We have developed a new approach that is capable of efficiently sampling sub-parts per billion level waterborne petroleum hydrocarbons for CSIA. We use semipermeable membrane devices (SPMDs) to accumulate hydrophobic contaminants from polluted waters and then recover the compounds in the laboratory for CSIA. In this study, we demonstrate, under a variety of experimental conditions (different concentrations, temperatures, and turbulence levels), that SPMD-associated processes do not induce C and H isotopic fractionations. The applicability of SPMD-CSIA technology to natural systems is further demonstrated by determining the ??13C and ??D values of petroleum hydrocarbons present in the Pawtuxet River, RI. Our results show that the combined SPMD-CSIA is an effective tool to investigate the source and fate of hydrophobic contaminants in the aquatic environments.

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.

Purafil-filtration prevents the development of ozone-induced frost injury: A potential role for nitric oxide

NASA Astrophysics Data System (ADS)

Neighbour, E. A.; Pearson, M.; Mehlhorn, H.

The relationship between exposure to ozone in the summer and the subsequent development of frost hardiness in the autumn was evaluated in recent experiments with red spruce ( Picea rubens Sarg. Syn. P. rubra). When O 3 was added to air filtered only through charcoal (contaminated with nitric oxide (NO)), frost sensitivity in late autumn was increased as measured by conductivity from electrocyte leakage. However, when O 3 was added to air filtered through charcoal and Purafil (no NO), no enhancement of frost sensitivity was found. A possible explanation of this difference, involving the chain-propagating property of NO in the O 3-initiated oxidation of unsaturated hydrocarbons (HCs), is proposed and discussed. N 2O 5, which was found to be generated at approximately 0.02 moles per mole of O 3 in the first year's experiment, only marginally modified O 3 toxicity.

Heteroatom-free arene-cobalt and arene-iron catalysts for hydrogenations.

PubMed

Gärtner, Dominik; Welther, Alice; Rad, Babak Rezaei; Wolf, Robert; Jacobi von Wangelin, Axel

2014-04-01

75 years after the discovery of hydroformylation, cobalt catalysts are now undergoing a renaissance in hydrogenation reactions. We have evaluated arene metalates in which the low-valent metal species is--conceptually different from heteroatom-based ligands--stabilized by π coordination to hydrocarbons. Potassium bis(anthracene)cobaltate 1 and -ferrate 2 can be viewed as synthetic precursors of quasi-"naked" anionic metal species; their aggregation is effectively impeded by (labile) coordination to the various π acceptors present in the hydrogenation reactions of unsaturated molecules (alkenes, arenes, carbonyl compounds). Kinetic studies, NMR spectroscopy, and poisoning studies of alkene hydrogenations support the formation of a homogeneous catalyst derived from 1 which is stabilized by the coordination of alkenes. This catalyst concept complements the use of complexes with heteroatom donor ligands for reductive processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct measurements of HOx radicals in the marine boundary layer: testing the current tropospheric chemistry mechanism.

PubMed

Kanaya, Yugo; Akimoto, Hajime

2002-01-01

OH and HO(2) radicals, atmospheric detergents, and the reservoir thereof, play central roles in tropospheric chemistry. In spite of their importance, we had no choice but to trust their concentrations predicted by modeling studies based on known chemical processes. However, recent direct measurements of these radicals have enabled us to test and revise our knowledge of the processes by comparing the predicted and observed values of the radical concentrations. We developed a laser-induced fluorescence (LIF) instrument and successfully observed OH and HO(2) at three remote islands of Japan (Oki Island, Okinawa Island, and Rishiri Island). At Okinawa Island, the observed daytime level of HO(2) agreed closely with the model estimates, suggesting that the photochemistry at Okinawa is well described by the current chemistry mechanism. At Rishiri Island, in contrast, the observed daytime level of HO(2) was consistently much lower than the calculated values. We proposed that iodine chemistry, usually not incorporated into the mechanism, is at least partly responsible for the discrepancy in the results. At night, HO(2) was detected at levels greater than 1 pptv at all three islands, suggesting the presence of processes in the dark that produce radicals. We showed that ozone reactions with unsaturated hydrocarbons, including monoterpenes, could significantly contribute to radical production. Copyright 2002 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 2: 199-211, 2002: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10019

Engineering a Promiscuous Tautomerase into a More Efficient Aldolase for Self-Condensations of Linear Aliphatic Aldehydes.

PubMed

Rahimi, Mehran; van der Meer, Jan-Ytzen; Geertsema, Edzard M; Poelarends, Gerrit J

2017-07-18

The enzyme 4-oxalocrotonate tautomerase (4-OT) from Pseudomonas putida mt-2 takes part in a catabolic pathway for aromatic hydrocarbons, where it catalyzes the conversion of 2hydroxyhexa-2,4-dienedioate into 2-oxohexa-3-enedioate. This tautomerase can also promiscuously catalyze carbon-carbon bond-forming reactions, including various types of aldol reactions, by using its amino-terminal proline as a key catalytic residue. Here, we used systematic mutagenesis to identify two hotspots in 4-OT (Met45 and Phe50) at which single mutations give marked improvements in aldolase activity for the self-condensation of propanal. Activity screening of a focused library in which these two hotspots were varied led to the discovery of a 4-OT variant (M45Y/F50V) with strongly enhanced aldolase activity in the self-condensation of linear aliphatic aldehydes, such as acetaldehyde, propanal, and butanal, to yield α,β-unsaturated aldehydes. With both propanal and benzaldehyde, this double mutant, unlike the previously constructed single mutant F50A, mainly catalyzes the self-condensation of propanal rather than the cross-condensation of propanal and benzaldehyde, thus indicating that it indeed has altered substrate specificity. This variant could serve as a template to create new biocatalysts that lack dehydration activity and possess further enhanced aldolase activity, thus enabling the efficient enzymatic self-coupling of aliphatic aldehydes. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Mechanisms of hydrocarbon migration in Mahakam delta, Kalimantan, Indonesia

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

Durand, B.; Bessereau, G.; Ungerer, P.H.

1986-05-01

In the Mahakam delta, hydrocarbons formed from landplant debris, either dispersed in clays or concentrated in coal levels. The hydrocarbon zone is located partly or entirely in overpressured zones. Hydrocarbon migration is primarily a polyphasic mechanism, i.e., water and hydrocarbons move in separate phases. When hydrocarbon generation occurs in normally pressured zones, hydrocarbons are easily expelled to close carrier beds. Then they migrate toward the top of structures through a network of abundant interconnected sand bodies. However, most hydrocarbons are generated in overpressured zones, in which they move preferentially toward the structural highs. Simultaneously, excess pressure is transmitted to themore » top of the structures because of the sedimentary load in the synclines, which results in a high pressure gradient at the top. This pressure gradient facilitates hydrocarbon filtration from overpressured zones to normally pressured zones, or it may cause hydraulic fracturing, which provides avenues for migration. Gas-rich hydrocarbons formed in deep overpressured zones, probably in a single phase owing to high temperature and pressures. The passage from overpressured zones to normally pressured zones resulted in decreased temperature and pressure, which produced several hydrocarbon phases by retrograde condensation. Finally, lighter hydrocarbons pooled above the heaviest ones. These mechanisms have been simulated by a numerical model of basin evolution, including a two-phase migration modulus, and by a numerical model of retrograde condensation.« less

Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 1. Quantum chemical studies.

PubMed

McIntosh, Grant J; Russell, Douglas K

2013-05-23

Analogues of important aromatic growth mechanisms in hydrocarbon pyrolysis and combustion systems are extended to chlorinated systems. We consider the addition of C2Cl2 to both C4Cl3 and C4Cl5 radicals at the M06-2X/6-311+G(3df,3p)//B3LYP/6-31G(d) level of theory, and we demonstrate that these reaction systems have much in common with those of nonchlorinated species. In particular, we find that these radicals appear to lead preferentially to fulvenes, and not to the observed aromatic products, as is found in nonchlorinated systems. We have therefore also considered nonradical C4/C2 channels by way of Diels-Alder cyclization of C4Cl4/C2Cl2 and C4H2Cl2/C2HCl pairs to describe aromatic formation. While the latter pair readily leads to the formation of partially chlorinated benzenes, the fully chlorinated congeners are sterically prohibited from ring closing directly; this leads to a series of novel rearrangement processes which predict the formation of hexachloro-1,5-diene-3-yne, in addition to hexachlorobenzene, in good agreement with experiment. This suggests, for the first time, that facile nonradical routes to aromatic formation are operative in partially and fully chlorinated pyrolysis and combustion systems.

Cuticular hydrocarbons as sex pheromone of the bee Colletes cunicularius and the key to its mimicry by the sexually deceptive orchid, Ophrys exaltata.

PubMed

Mant, Jim; Brändli, Christoph; Vereecken, Nicolas J; Schulz, Claudia M; Francke, Wittko; Schiestl, Florian P

2005-08-01

Male Colletes cunicularius bees pollinate the orchid, Ophrys exaltata, after being sexually deceived by the orchid's odor-mimicry of the female bee's sex pheromone. We detected biologically active volatiles of C. cunicularius by using gas chromatographic-electroantennographic detection (GC-EAD) with simultaneous flame ionization detection. After identification of the target compounds by coupled gas chromatography mass spectrometry (GC-MS), we performed behavioral tests using synthetic blends of the active components. We detected 22 EAD active compounds in cuticular extracts of C. cunicularius females. Blends of straight chain, odd-numbered alkanes and (Z)-7-alkenes with 21-29 carbon atoms constituted the major biologically active compounds. Alkenes were the key compounds releasing mating behavior, especially those with (Z)-7 unsaturation. Comparison of patterns of bee volatiles with those of O. exaltata subsp. archipelagi revealed that all EAD-active compounds were also found in extracts of orchid labella. Previous studies of the mating behavior in C. cunicularius showed linalool to be an important attractant for patrolling males. We confirmed this with synthetic linalool but found that it rarely elicited copulatory behavior, in accordance with previous studies. A blend of active cuticular compounds with linalool elicited both attraction and copulation behavior in patrolling males. Thus, linalool appears to function as a long-range attractant, whereas cuticular hydrocarbons are necessary for inducing short-range mating behavior.

Metabolomics Reveals that Aryl Hydrocarbon Receptor Activation by Environmental Chemicals Induces Systemic Metabolic Dysfunction in Mice.

PubMed

Zhang, Limin; Hatzakis, Emmanuel; Nichols, Robert G; Hao, Ruixin; Correll, Jared; Smith, Philip B; Chiaro, Christopher R; Perdew, Gary H; Patterson, Andrew D

2015-07-07

Environmental exposure to dioxins and dioxin-like compounds poses a significant health risk for human health. Developing a better understanding of the mechanisms of toxicity through activation of the aryl hydrocarbon receptor (AHR) is likely to improve the reliability of risk assessment. In this study, the AHR-dependent metabolic response of mice exposed to 2,3,7,8-tetrachlorodibenzofuran (TCDF) was assessed using global (1)H nuclear magnetic resonance (NMR)-based metabolomics and targeted metabolite profiling of extracts obtained from serum and liver. (1)H NMR analyses revealed that TCDF exposure suppressed gluconeogenesis and glycogenolysis, stimulated lipogenesis, and triggered inflammatory gene expression in an Ahr-dependent manner. Targeted analyses using gas chromatography coupled with mass spectrometry showed TCDF treatment altered the ratio of unsaturated/saturated fatty acids. Consistent with this observation, an increase in hepatic expression of stearoyl coenzyme A desaturase 1 was observed. In addition, TCDF exposure resulted in inhibition of de novo fatty acid biosynthesis manifested by down-regulation of acetyl-CoA, malonyl-CoA, and palmitoyl-CoA metabolites and related mRNA levels. In contrast, no significant changes in the levels of glucose and lipid were observed in serum and liver obtained from Ahr-null mice following TCDF treatment, thus strongly supporting the important role of the AHR in mediating the metabolic effects seen following TCDF exposure.

Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene

DOE PAGES

Xu, Songchen; Boschen, Jeffery S.; Biswas, Abhranil; ...

2015-08-17

An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(Ox Me²)(Ox Me²SiHPh)Im Mes}Rh(H)CO][HB(C₆F₅)₃] (2, Ox Me² = 4,4-dimethyl-2-oxazoline; Im Mes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(Ox Me²)₂Im Mes}RhH(SiH 2Ph)CO (1) and B(C 6F 5) 3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(Ox Me²)₂Im Mes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced bymore » the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.« less

Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene

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

Xu, Songchen; Boschen, Jeffery S.; Biswas, Abhranil

An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(Ox Me²)(Ox Me²SiHPh)Im Mes}Rh(H)CO][HB(C₆F₅)₃] (2, Ox Me² = 4,4-dimethyl-2-oxazoline; Im Mes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(Ox Me²)₂Im Mes}RhH(SiH 2Ph)CO (1) and B(C 6F 5) 3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(Ox Me²)₂Im Mes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced bymore » the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.« less

Thermodynamic and transport combustion properties of hydrocarbons with air. Part 2: Compositions corresponding to Kelvin temperature schedules in part 1

NASA Technical Reports Server (NTRS)

Gordon, S.

1982-01-01

The equilibrium compositions that correspond to the thermodynamic and transport combustion properties for a wide range of conditions for the reaction of hydrocarbons with air are presented. Initially 55 gaseous species and 3 coin condensed species were considered in the calculations. Only 17 of these 55 gaseous species had equilibrium mole fractions greater than 0.000005 for any of the conditions studied and therefore these were the only ones retained in the final tables.

40 CFR 63.14 - Incorporations by reference.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., Heat of Combustion of Hydrocarbon Fuels by Bomb Calorimeter (High-Precision Method), IBR approved for... for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method), IBR... Oxygen Bomb Combustion/Atomic Absorption Method,1 IBR approved for table 6 to subpart DDDDD of this part...

Process for the synthesis of unsaturated alcohols

DOEpatents

Maughon, Bob R.; Burdett, Kenneth A.; Lysenko, Zenon

2007-02-13

A process of preparing an unsaturated alcohol (olefin alcohol), such as, a homo-allylic mono-alcohol or homo-allylic polyol, involving protecting a hydroxy-substituted unsaturated fatty acid or fatty acid ester, such as methyl ricinoleate, derived from a seed oil, to form a hydroxy-protected unsaturated fatty acid or fatty acid ester; homo-metathesizing or cross-metathesizing the hydroxy-protected unsaturated fatty acid or fatty acid ester to produce a product mixture containing a hydroxy-protected unsaturated metathesis product; and deprotecting the hydroxy-protected unsaturated metathesis product under conditions sufficient to prepare the unsaturated alcohol. Preferably, methyl ricinoleate is converted by cross-metathesis or homo-metathesis into the homo-allylic mono-alcohol 1-decene-4-ol or the homo-allylic polyol 9-octadecene-7,12-diol, respectively.

Transport of environmental tracers through a karst system with a thick unsaturated zone

NASA Astrophysics Data System (ADS)

Geyer, Tobias; Sültenfuss, Jürgen; Eichinger, Florian; Sauter, Martin

2010-05-01

The transport of the environmental tracers tritium (3H), krypton-85 (85Kr) and helium (3He) in a karst system is investigated. Differences between mean tracer ages determined in spring water are explained by slow percolation of water through the thick unsaturated zone reflecting the importance of slow and diffuse unsaturated flow processes in these systems. Mean tracer ages on the Gallusquelle spring (Swabian Alb) were determined with lumped parameter modeling and decrease in the following order: 3H >> 85Kr > 3He. Since 3H is part of the water molecule it enters a karst system via precipitation, i.e. the mean 3H age is a measure of water flow through the whole karst system, including the unsaturated and saturated zone. The mean 85Kr age and 3H/3He age are measures of time since groundwater recharge arrived at the water table. Therefore our results indicate a long travel time of 3H through the unsaturated zone of the karst system. The interpretation is supported by a two-dimensional numerical simulation of flow and transport in a fissured matrix block that contains a thick unsaturated zone (ca. 100 m) and is drained by a conduit. Transport simulation is performed in the sense of backtracking, i.e. the flow field is reversed, and the boundary conditions are adapted accordingly. At any position in the model domain, the time required for a water molecule to reach the outlet is estimated corresponding to the "life expectancy" (Cornaton and Perrochet 2006), i.e. the life expectancy on the outlet is zero. The simulation of life expectancy of water in the matrix block shows (1) the importance of heterogeneities for interpretation of groundwater ages, (2) the location of stagnant zones in areas of low hydraulic permeability and/or low hydraulic gradient and (3) that flow through unsaturated fissured matrix blocks may cause a considerable travel time of water through a karst system. The travel time of water from the recharge area to the discharge point for the shown example is about 15 years with a travel time of water through the unsaturated zone of 10 years (Geyer 2008). This result reflects the variation of estimated ages for different tracers sampled at the Gallusquelle spring. Additionally, we demonstrate that depending on boundary conditions, the unsaturated zone of a karst system may provide a large water storage since the porous matrix can be expected to be close to saturation and the volume fraction of fissures and conduits is small. Literature Cornaton, F., Perrochet, P. (2006): Ground-water age, life expectancy and transit time distributions in advective-dispersive systems: 1. Generalized reservoir theory. - Advances in Water Resources 29 (9): 1267-1291. Geyer, T. (2008): Characterisation of flow and transport in karst aquifers at catchment scale, Ph.D. diss., Georg-August-Universität Göttingen, 103 pp.

Petroleum hydrocarbon pollution of urban topsoil in Ibadan city, Nigeria

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

Onianwa, P.C.

The distribution of total petroleum hydrocarbon in topsoils from various parts of Ibadan city, Nigeria, was studied. Samples were selected from around the following zones: (a) railway tracks, (b) petrol stations, (c) refuse dumps, (d) residential areas, (e) high traffic density areas, (f) mechanical workshops, and (g) control zones. Contamination of the topsoil with hydrocarbons was significant only around petrol stations and mechanical workshops where the factors of accumulation were 10.1 and 4.72, respectively. The general trend in hydrocarbon levels was petrol station > mechanical workshop > refuse dumps > high traffic areas {ge} rail tracks > control residential areas.more » The results highlight the need to monitor urban environments that are remote from petroleum exploration activities for petroleum hydrocarbon contamination. 19 refs., 3 tabs.« less

40 CFR 98.7 - What standardized methods are incorporated by reference into this part?

Code of Federal Regulations, 2010 CFR

2010-07-01

... Liquid Hydrocarbon Fuels by Bomb Calorimeter, IBR approved for §§ 98.34(a) and 98.254(e). (5) ASTM D388... Hydrocarbon Fuels by Bomb Calorimeter (Precision Method), IBR approved for §§ 98.34(a) and 98.254(e). (25...

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.

Assessment of nonpoint-source contamination of the High Plains Aquifer in south-central Kansas, 1987

USGS Publications Warehouse

Helgesen, John O.; Stullken, Lloyd E.; Rutledge, A.T.

1994-01-01

Ground-water quality was assessed in a 5,000-square-mile area of the High Plains aquifer in south-central Kansas that is susceptible to nonpoint-source contamination from agricultural and petroleum-production activities. Of particular interest was the presence of agricultural chemicals and petroleum-derived hydrocarbons that might have been associated with brines that formerly were disposed into unlined ponds. Random sampling of ground water was done within a framework of discrete land-use areas (irrigated cropland, petroleum-production land containing former brine-disposal ponds, and undeveloped rangeland) of 3-10 square miles. Although true baseline water-quality conditions probably are rare, in this region they are represented most closely by ground water in areas of undeveloped rangeland. The sampling design enabled statistical hypothesis testing, using nonparametric procedures, of the effects of land use, unsaturated-zone lithology, and type of well sampled. Results indicate that regional ground-water quality has been affected by prevailing land-use activities, as shown by increased concentrations of several inorganic constituents. Ground water beneath irrigated cropland was characterized by significantly larger concentrations of hardness, alkalinity, calcium, magnesium, potassium, fluofide, and nitrite plus nitrate than was water beneath undeveloped rangeland. Few nondegraded pesticides were detected in the aquifer, probably because of degradation and sorption. Atrazine was the most common, but only in small concentrations. round water beneath petroleum-production land was characterized by significantly larger concentrations of hardness, alkalinity, dissolved solids, sodium, and chloride than was water beneath undeveloped rangeland. Nonpoint-source contamination by oil-derived hydrocarbons was not discernible. The occurrences of trace organic compounds were similar between petroleum-production land and undeveloped rangeland, which indicates a natural origin for these compounds. The unsaturated zone in the study area is lithologically heterogeneous and contains substantial amounts of clay that inhibit the downward movement of water and solutes. Within the aquifer, the rate of lateral regional flow and solute transport is slow enough so that the ground-water quality reflects overlying land use in discrete areas of several square miles, but it is still sufficiently rapid so that the type of well sampled is not important in regional characterizations of water quality beneath irrigated cropland; the seasonal pumping of irrigation wells does not appear to divert regional flow enough to cause substantial local anomalies of more mineralized ground water.

Experimental investigation of the auto-ignition characteristics of oxygenated reference fuel compounds

NASA Astrophysics Data System (ADS)

Walton, Stephen Michael

The increased use of biofuels presents an opportunity to improve combustion performance while simultaneously reducing greenhouse gases and pollutant emissions. This work focused on improving the fundamental understanding of the auto-ignition chemistry of oxygenated reference fuel compounds. A systematic study of the effects of ester structure on ignition chemistry was performed using the University of Michigan Rapid Compression Facility. The ignition properties of the ester compounds were investigated over a broad range of pressures (P=5-20 atm) and temperatures (T=850-1150 K) which are directly relevant to advanced combustion engine strategies. Ignition delay times for five esters were determined using the RCF. The esters were selected to systematically consider the chemical structure of the compounds. Three esters were saturated: methyl butanoate, butyl methanoate, and ethyl propanoate; and two were unsaturated: methyl crotonate and methyl trans-3-hexenoate. The unsaturated esters were more reactive than their saturated counterparts, with the largest unsaturated ester, methyl trans-3-hexenoate having the highest reactivity. Two isomers of the saturated esters, butyl methanoate and ethyl propanoate, were more reactive than the isomer methyl butanoate. The results are explained if we assume that butyl methanoate and ethyl propanoate form intermediate ring structures which decompose more rapidly than esters such as methyl butanoate, which do not form ring structures. Modeling studies of the reaction chemistry were conducted for methyl butanoate and ethyl propanoate, for which detailed mechanisms were available in the literature. The new experimental data indicated that literature rate coefficients for some of the methyl butanoate/HO2 reactions were too fast. Modifying these within the theoretical uncertainties for the reaction rates, led to excellent agreement between the model predictions and the experimental data. Comparison of the modeling results with the intermediates measured during methyl butanoate ignition indicated that pathways leading to the formation of small hydrocarbons are relatively well represented in the reaction mechanism. The results of this work provide archival benchmark data for improved understanding of the dominant reaction pathways and species controlling the auto-ignition of oxygenated reference fuel compounds. These data also provide a path for continued development of chemical kinetic models to optimize practical combustion systems.

Relations between local magnetic disturbances and the genesis of petroleum

USGS Publications Warehouse

Becker, George Ferdinand

1909-01-01

No question in geology is more obscure than that of the origin of the numerous natural hydrocarbons commonly classified as asphalt, ozokerite, petroleum, and natural gas. Certain facts of occurrence and certain results of experiment are indeed established, but the interpretation to be placed upon them is so doubtful that the conclusion reached may almost be said to depend on predilection. A great number of the more important hydrocarbons found in petroleums can be produced artificially from organic substances, such as coal, wood, and fish oil, while identical or closely allied hydrocarbons result from the interaction of inorganic substances, such as cast iron and chlorhydric acid. In many places petroleum is closely associated with fossiliferous strata; but hydrocarbons likewise exist in meteorites and in volcanic gases; they are even expelled by heat from granite and basalt. The most orthodox opinion at the present day is that a part of the natural hydrocarbons is of organic origin and a part also of inorganic origin; but when it comes to estimating the relative importance of the two portions there is no approach to unanimity. Before making a suggestion, which in this connection appears to be of interest, it may be well to outline the arguments for the opposing views. 

Disentangling oil weathering using GC x GC. 2. Mass transfer calculations.

PubMed

Arey, J Samuel; Nelson, Robert K; Plata, Desiree L; Reddy, Christopher M

2007-08-15

Hydrocarbon mass transfers to the atmosphere and water column drive the early weathering of oil spills and also control the chemical exposures of many coastal wildlife species. However, in the field, mass transfer rates of individual hydrocarbons to air and water are often uncertain. In the Part 1 companion to this paper, we used comprehensive two-dimensional gas chromatography (GC x GC) to identify distinct signatures of evaporation and dissolution encoded in the compositional evolution of weathered oils. In Part 2, we further investigate patterns of mass removal in GC x GC chromatograms using a mass transfer model. The model was tailored to conditions at a contaminated beach on Buzzards Bay, MA, after the 2003 Bouchard 120 oil spill. The model was applied to all resolved hydrocarbon compounds in the C11-C24 boiling range, based on their GC x GC-estimated vapor pressures and aqueous solubilities. With no fitted parameters, the model successfully predicted GC x GC chromatogram patterns of mass removal associated with evaporation, water-washing, and diffusion-limited transport. This enabled a critical field evaluation of the mass transfer model and also allowed mass apportionment estimates of hundreds of individual hydrocarbon compounds to air and water. Ultimately, this method should improve assessments of wildlife exposures to oil spill hydrocarbons.

Synthesis of silyl iron hydride via Si-H activation and its dual catalytic application in the hydrosilylation of carbonyl compounds and dehydration of benzamides.

PubMed

Ren, Shishuai; Xie, Shangqing; Zheng, Tingting; Wang, Yangyang; Xu, Shilu; Xue, Benjing; Li, Xiaoyan; Sun, Hongjian; Fuhr, Olaf; Fenske, Dieter

2018-03-28

The hydrido silyl iron complex (o-Ph 2 PC 6 H 4 SiMe 2 )Fe(PMe 3 ) 3 H (2) was obtained via the activation of the Si-H bond of the bidentate silyl ligand o-Ph 2 P(C 6 H 4 )SiMe 2 H (1) by Fe(PMe 3 ) 4 . 2 showed good to excellent catalytic activity in both the reduction of aldehydes/ketones and the dehydration of benzamide. In addition, with complex 2 as a catalyst, α,β-unsaturated carbonyls could be selectively reduced to the corresponding α,β-unsaturated alcohols. The mechanisms of the formation of 2 and the catalytic dehydration process are proposed and partly experimentally verified.

THE NATURE OF SERUM ANTITRYPSIN

PubMed Central

Jobling, James W.; Petersen, William

1914-01-01

1. The ferment-inhibiting action of the serum is due to the presence of compounds of the unsaturated fatty acids. 2. These fatty acid compounds may be removed from the serum by means of chloroform or ether. 3. Soaps prepared by saponifying the chloroform or ether extracts inhibit the action of trypsin. 4. The anti-enzyme action of the serum can be removed by filtering acid serum through kaolin, and can in part be restored by extracting the kaolin. 5. The decrease in strength of anti-enzyme in old sera is probably due to the action of the serum lipase. 6. Iodin, potassium iodide, or hydrogen peroxide remove the inhibiting action of the serum. 7. Soaps of the unsaturated fatty acids lose their ferment-inhibiting action when heated with serum at 70° C. PMID:19867786

The First Results of Study of Hydrocarbon Biomarkers and Hydrocarbons of a Diamond-like Structure in the Riphean, Vendian, and Lower Cambrian Rocks of the Katanga Saddle

NASA Astrophysics Data System (ADS)

Gordadze, G. N.; Kerimov, V. Yu.; Gaiduk, A. V.; Giruts, M. V.; Lobusev, M. A.; Serov, S. G.; Kuznetsov, N. B.; Romanyuk, T. V.

2018-02-01

The results of geochemical study of samples from Riphean-Lower Paleozoic rocks enriched in organic matter (the rocks most likely parental for oil) from the southern part of the Siberian Platform are reported.

40 CFR 1051.805 - What symbols, acronyms, and abbreviations does this part use?

Code of Federal Regulations, 2012 CFR

2012-07-01

...—American Society for Testing and Materials. ATV—all-terrain vehicle. cc—cubic centimeters. CFR—Code of...—pounds per square inches of gauge pressure. rpm—revolutions per minute. SAE—Society of Automotive Engineers. SI—spark-ignition. THC—total hydrocarbon. THCE—total hydrocarbon equivalent. U.S.C.—United States...

40 CFR 1051.805 - What symbols, acronyms, and abbreviations does this part use?

Code of Federal Regulations, 2014 CFR

2014-07-01

...—American Society for Testing and Materials. ATV—all-terrain vehicle. cc—cubic centimeters. CFR—Code of...—pounds per square inches of gauge pressure. rpm—revolutions per minute. SAE—Society of Automotive Engineers. SI—spark-ignition. THC—total hydrocarbon. THCE—total hydrocarbon equivalent. U.S.C.—United States...

40 CFR 1051.805 - What symbols, acronyms, and abbreviations does this part use?

Code of Federal Regulations, 2013 CFR

2013-07-01

...—American Society for Testing and Materials. ATV—all-terrain vehicle. cc—cubic centimeters. CFR—Code of...—pounds per square inches of gauge pressure. rpm—revolutions per minute. SAE—Society of Automotive Engineers. SI—spark-ignition. THC—total hydrocarbon. THCE—total hydrocarbon equivalent. U.S.C.—United States...

40 CFR 86.111-94 - Exhaust gas analytical system.

Code of Federal Regulations, 2012 CFR

2012-07-01

... systems for analysis of total hydrocarbon (THC) (hydrocarbon plus methanol in the case of methanol-fueled...), carbon dioxide (CO2), and oxides of nitrogen (NOX). The schematic diagram of the continuous THC analysis train (and for THC plus methanol for methanol-fueled diesel-cycle vehicles) is shown as part of Figure...

40 CFR 86.111-94 - Exhaust gas analytical system.

Code of Federal Regulations, 2013 CFR

2013-07-01

... systems for analysis of total hydrocarbon (THC) (hydrocarbon plus methanol in the case of methanol-fueled...), carbon dioxide (CO2), and oxides of nitrogen (NOX). The schematic diagram of the continuous THC analysis train (and for THC plus methanol for methanol-fueled diesel-cycle vehicles) is shown as part of Figure...

40 CFR 86.111-94 - Exhaust gas analytical system.

Code of Federal Regulations, 2014 CFR

2014-07-01

... systems for analysis of total hydrocarbon (THC) (hydrocarbon plus methanol in the case of methanol-fueled...), carbon dioxide (CO2), and oxides of nitrogen (NOX). The schematic diagram of the continuous THC analysis train (and for THC plus methanol for methanol-fueled diesel-cycle vehicles) is shown as part of Figure...

SEASONAL VARIATION OF THE PARTICLE SIZE DISTRIBUTION OF POLYCYCLIC AROMATIC HYDROCARBONS AND OF MAJOR AEROSOL SPECIES IN CLAREMONT, CALIFORNIA. (R827352C020)

EPA Science Inventory

As part of the Southern California Particle Center and Supersite (SCPCS) activities, we measured, during all seasons, particle size distributions of 12 priority pollutant polycyclic aromatic hydrocarbons (PAHs), concurrently with elemental carbon (EC), organic carbon (OC), sul...

In situ sensing of subsurface contamination--part I: near-infrared spectral characterization of alkanes, aromatics, and chlorinated hydrocarbons.

PubMed

Klavarioti, Maria; Kostarelos, Konstantinos; Pourjabbar, Anahita; Ghandehari, Masoud

2014-05-01

There is an imperative need for a chemical sensor capable of remote, in situ, long-term monitoring of chemical species at sites containing toxic chemical spills, specifically at chemical waste dumps, landfills, and locations with underground storage tanks. In the current research, a series of experiments were conducted measuring the near-infrared optical absorption of alkanes, aromatics, and chlorinated hydrocarbons. A spectral library was then developed to characterize the optical spectra of liquid hydrocarbons. Near-infrared analysis was chosen due to compatibility with optical fibers. The goal was to differentiate between classes of hydrocarbons and to also discriminate between compounds within a class of similar molecular structures. It was observed that unique absorption spectra can be obtained for each hydrocarbon, and this uniqueness can be used to discriminate between hydrocarbons from different families. Statistical analyses, namely, principal component analysis (PCA) and correlation coefficient (Spearman and Pearson methods), were attempted to match absorption spectra from an unknown hydrocarbon with the database with limited success. An algorithm was subsequently written to identify the characteristic peaks of each hydrocarbon that could be used to match data from an unknown chemical species with the database.

Low-maturity Kulthieth Formation coal: A possible source of polycyclic aromatic hydrocarbons in benthic sediment of the northern Gulf of Alaska

USGS Publications Warehouse

Van Kooten, G. K.; Short, J.W.; Kolak, J.J.

2002-01-01

The successful application of forensic geology to contamination studies involving natural systems requires identification of appropriate endmembers and an understanding of the geologic setting and processes affecting the systems. Studies attempting to delineate the background, or natural, source for hydrocarbon contamination in Gulf of Alaska (GOA) benthic sediments have invoked a number of potential sources, including seep oils, source rocks, and coal. Oil seeps have subsequently been questioned as significant sources of hydrocarbons present in benthic sediments of the GOA in part because the pattern of relative polycyclic aromatic hydrocarbon (PAH) abundance characteristic of benthic GOA sediments is inconsistent with patterns typical of weathered seep oils. Likewise, native coal has been dismissed in part because ratios of labile hydrocarbons to total organic carbon (e.g. PAH:TOC) for Bering River coal field (BRCF) sources are too low - i.e. the coals are over mature - to be consistent with GOA sediments. We present evidence here that native coal may have been prematurely dismissed, because BRCF coals do not adequately represent the geochemical signatures of coals elsewhere in the Kulthieth Formation. Contrary to previous thought, Kulthieth Formation coals east of the BRCF have much higher PAH: TOC ratios, and the patterns of labile hydrocarbons in these low thermal maturity coals suggest a possible genetic relationship between Kulthieth Formation coals and nearby oil seeps on the Sullivan anticline. Analyses of low-maturity Kulthieth Formation coal indicate the low maturity coal is a significant source of PAH. Source apportionment models that neglect this source will underestimate the contribution of native coals to the regional background hydrocarbon signature. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

Burial history, thermal history and hydrocarbon generation modelling of the Jurassic source rocks in the basement of the Polish Carpathian Foredeep and Outer Carpathians (SE Poland)

NASA Astrophysics Data System (ADS)

Kosakowski, Paweł; Wróbel, Magdalena

2012-08-01

Burial history, thermal maturity, and timing of hydrocarbon generation were modelled for the Jurassic source rocks in the basement of the Carpathian Foredeep and marginal part of the Outer Carpathians. The area of investigation was bounded to the west by Kraków, to the east by Rzeszów. The modelling was carried out in profiles of wells: Będzienica 2, Dębica 10K, Góra Ropczycka 1K, Goleszów 5, Nawsie 1, Pławowice E1 and Pilzno 40. The organic matter, containing gas-prone Type III kerogen with an admixture of Type II kerogen, is immature or at most, early mature to 0.7 % in the vitrinite reflectance scale. The highest thermal maturity is recorded in the south-eastern part of the study area, where the Jurassic strata are buried deeper. The thermal modelling showed that the obtained organic matter maturity in the initial phase of the "oil window" is connected with the stage of the Carpathian overthrusting. The numerical modelling indicated that the onset of hydrocarbon generation from the Middle Jurassic source rocks was also connected with the Carpathian thrust belt. The peak of hydrocarbon generation took place in the orogenic stage of the overthrusting. The amount of generated hydrocarbons is generally small, which is a consequence of the low maturity and low transformation degree of kerogen. The generated hydrocarbons were not expelled from their source rock. An analysis of maturity distribution and transformation degree of the Jurassic organic matter shows that the best conditions for hydrocarbon generation occurred most probably in areas deeply buried under the Outer Carpathians. It is most probable that the "generation kitchen" should be searched for there.

Identification and geochemical significance of sulphurized fatty acids in sedimentary organic matter from the Lorca Basin, SE Spain

NASA Astrophysics Data System (ADS)

Russell, Marie; Hartgers, Walter A.; Grimalt, Joan O.

2000-11-01

The presence of free sulphurized fatty acids in various sediment types (carbonates, marls, organic-rich shales) of the Messinian of the Lorca Basin, SE Spain, is reported. These compounds are found in the majority, but not all, of the samples from this basin which also contain sulphur-bound hydrocarbons. They constitute mixtures of C 16-C 26 linear fatty acids predominated by the C 18 homologues with thiophene, thiolane, and thiane rings attached at various chain positions, with the most abundant isomers being those with ring substitution at position C-9. The dominance of these isomers points to an early sulphurization process involving octadec-9,12-dienoic acid and/or octadeca-9-enoic acid, major lipid constituents of algae. In general, the alkylthiophene fatty acids are more abundant than the alkylthiolane or alkylthiane fatty acids. The presence of the sulphur moiety and structural identification was confirmed by GC-HRMS and by desulphurization of the fatty acid fraction. Desulphurization also showed that a portion of the sulphur containing fatty acids is intermolecularly bound to the polymeric organic matter. The samples exhibiting higher proportions of macromolecularly bound fatty acids were also those showing higher abundances of alkylthiolane or alkylthiane fatty acids. The identification of these compounds shows that the original algal lipids, including the fatty acid pool, can be effectively preserved in sedimentary samples by sulphurization. However, sulphur-bonding only occurs by addition to the unsaturated carbons. Thus, only unsaturated fatty acids are preserved, constituting a major bias in terms of the original sedimentary distributions.

Pharmacology of conjugated equine estrogens: efficacy, safety and mechanism of action.

PubMed

Bhavnani, Bhagu R; Stanczyk, Frank Z

2014-07-01

Oral conjugated equine estrogens (CEE) are the most used estrogen formulation for postmenopausal hormone therapy either alone or in combination with a progestin. CEE is most commonly used for the management of early menopausal symptoms such as hot flashes, vaginitis, insomnia, and mood disturbances. Additionally, if used at the start of the menopausal phase (age 50-59 years), CEE prevents osteoporosis and may in some women reduce the risk of cardiovascular disease (CVD) and Alzheimer's disease (AD). There appears to be a common mechanism through which estrogens can protect against CVD and AD. CEE is a natural formulation of an extract prepared from pregnant mares' urine. The product monogram lists the presence of only 10 estrogens consisting of the classical estrogens, estrone and 17β-estradiol, and a group of unique ring B unsaturated estrogens such as equilin and equilenin. The ring B unsaturated estrogens are formed by an alternate steroidogenic pathway in which cholesterol is not an obligatory intermediate. Both the route of administration and structure of these estrogens play a role in the overall pharmacology of CEE. In contrast to 17β-estradiol, ring B unsaturated estrogens express their biological effects mainly mediated by the estrogen receptor β and not the estrogen receptor α. All estrogen components of CEE are antioxidants, and some ring B unsaturated estrogens have several fold greater antioxidant activity than estrone and 17β-estradiol. The cardioprotective and neuroprotective effects of CEE appear to be, to some extent, due to its ability to prevent the formation of oxidized LDL and HDL, and by inhibiting or modulating some of the key proteases involved in programmed cell death (apoptosis) induced by the excess neurotransmitter glutamate and other neurotoxins. Selective combinations of ring B unsaturated estrogens have the potential of being developed as novel therapeutic agents for the prevention of cardiovascular disease and Alzheimer's disease in both aging women and men. This article is part of a Special Issue entitled 'Menopause'. Copyright © 2013 Elsevier Ltd. All rights reserved.

Water movement in the unsaturated zone at a low-level radioactive-waste burial site near Barnwell, South Carolina

USGS Publications Warehouse

Dennehy, Kevin F.; McMahon, Peter B.

1989-01-01

Four unsaturated-zone monitoring sites and a meteorologic station were installed at the low-level radioactive-waste burial site near Barnwell, S.C., to investigate the geohydrologic and climatologic factors affecting water movement in the unsaturated zone. The study site is located in the Atlantic Coastal Plain. The unsaturated zone consists of a few centimeters to more than 1 meter of surface sand, underlain by up to 15 meters of clayey sand. Two monitoring sites were installed in experimental trenches, and two were installed in radioactive-waste trenches. Two different trench designs were evaluated at the monitoring sites. A meteorologic station was used to measure precipitation and to calculate actual evapotranspiration using the Bowen ratio method. Soil-moisture tensiometers, soil-moisture conductance probes, and temperature sensors were used to monitor soil-water movement in and adjacent to the trenches. Tracer tests using sodium chloride were conducted at each monitoring site. Hydrologic properties of unsaturated-zone materials were also determined. Data collection at the monitoring sites began in January 1982 and continued until early May 1984. Tensiometer data show that the unsaturated materials had their highest percent saturations in winter and spring. Saturations in the backfill sand varied from 20 to 100 percent, and in the adjacent undisturbed and overlying compacted clayey sand, from about 75 to 100 percent. The same pattern generally was observed at all four monitoring sites. The tracer-test data indicate that water movement occurred mainly during the recharge period, winter and spring. The tracer-test results enabled computation of rates of unsaturated flow in the compacted clayey-sand cap, the compacted clayey-sand barrier, and the backfill sand. A micro-scale hydrologic budget was determined for an undisturbed part of the site from July 1983 through June 1984.Total precipitation was 144 centimeters, and actual evapotranspiration was 101 centimeters. Additionally, because tensiometer data indicate negligible water-storage changes in the unsaturated zone, it is estimated that approximately 43 centimeters of recharge reached the water table. During 1984, the rise and fall of ponded water in an experimental trench was continuously monitored with a digital recorder. This water-level record was used to compute the rate of leakage of ponded water from that trench--1 x 10 -5 centimeter per second. A cross-sectional finite-element model of variably saturated flow was used to test the conceptual model of water movement in the unsaturated zone and to illustrate the effect of trench design on water movement into the experimental trenches. Monitoring and model results show that precipitation on trenches infiltrated the trench cap and moved vertically into the trench backfill material. Precipitation on the undisturbed material adjacent to the trenches moved vertically through the surface sand and continued either downward into undisturbed clayey sand or laterally along the sand/clayey-sand interface into the backfill sand, depending on trench design. The trench construction practice of placing a compacted clayey-sand barrier around the trench greatly inhibits soil water from entering the trench.

Planning and Analysis of Fractured Rock Injection Tests in the Cerro Brillador Underground Laboratory, Northern Chile

NASA Astrophysics Data System (ADS)

Fairley, J. P., Jr.; Oyarzún L, R.; Villegas, G.

2015-12-01

Early theories of fluid migration in unsaturated fractured rock hypothesized that matrix suction would dominate flow up to the point of matrix saturation. However, experiments in underground laboratories such as the ESF (Yucca Mountain, NV) have demonstrated that liquid water can migrate significant distances through fractures in an unsaturated porous medium, suggesting limited interaction between fractures and unsaturated matrix blocks and potentially rapid transmission of recharge to the sat- urated zone. Determining the conditions under which this rapid recharge may take place is an important factor in understanding deep percolation processes in arid areas with thick unsaturated zones. As part of an on-going, Fondecyt-funded project (award 11150587) to study mountain block hydrological processes in arid regions, we are plan- ning a series of in-situ fracture flow injection tests in the Cerro Brillador/Mina Escuela, an underground laboratory and teaching facility belonging to the Universidad la Serena, Chile. Planning for the tests is based on an analytical model and curve-matching method, originally developed to evaluate data from injection tests at Yucca Mountain (Fairley, J.P., 2010, WRR 46:W08542), that uses a known rate of liquid injection to a fracture (for example, from a packed-off section of borehole) and the observed rate of seepage discharging from the fracture to estimate effective fracture aperture, matrix sorptivity, fracture/matrix flow partitioning, and the wetted fracture/matrix interac- tion area between the injection and recovery points. We briefly review the analytical approach and its application to test planning and analysis, and describe the proposed tests and their goals.

40 CFR 63.8687 - What performance tests, design evaluations, and other procedures must I use?

Code of Federal Regulations, 2010 CFR

2010-07-01

.... THC = Total hydrocarbon concentration at the combustion device outlet, parts per million by volume... auxiliary fuel, you must use Equation 6 of this section as follows: ER29AP03.005 Where: THC DE = THC... the test method specified in Table 3 to this subpart. THC = Total hydrocarbon concentration at the...

40 CFR 63.8687 - What performance tests, design evaluations, and other procedures must I use?

Code of Federal Regulations, 2014 CFR

2014-07-01

.... THC = Total hydrocarbon concentration at the combustion device outlet, parts per million by volume... auxiliary fuel, you must use Equation 6 of this section as follows: ER29AP03.005 Where: THC DE = THC... the test method specified in Table 3 to this subpart. THC = Total hydrocarbon concentration at the...

40 CFR 63.8687 - What performance tests, design evaluations, and other procedures must I use?

Code of Federal Regulations, 2012 CFR

2012-07-01

.... THC = Total hydrocarbon concentration at the combustion device outlet, parts per million by volume... auxiliary fuel, you must use Equation 6 of this section as follows: ER29AP03.005 Where: THC DE = THC... the test method specified in Table 3 to this subpart. THC = Total hydrocarbon concentration at the...

40 CFR 63.8687 - What performance tests, design evaluations, and other procedures must I use?

Code of Federal Regulations, 2013 CFR

2013-07-01

.... THC = Total hydrocarbon concentration at the combustion device outlet, parts per million by volume... auxiliary fuel, you must use Equation 6 of this section as follows: ER29AP03.005 Where: THC DE = THC... the test method specified in Table 3 to this subpart. THC = Total hydrocarbon concentration at the...

40 CFR 63.8687 - What performance tests, design evaluations, and other procedures must I use?

Code of Federal Regulations, 2011 CFR

2011-07-01

.... THC = Total hydrocarbon concentration at the combustion device outlet, parts per million by volume... auxiliary fuel, you must use Equation 6 of this section as follows: ER29AP03.005 Where: THC DE = THC... the test method specified in Table 3 to this subpart. THC = Total hydrocarbon concentration at the...

Chlorinated hydrocarbons in lichen and moss samples from the Antarctic Peninsula

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

Bacci, E.; Calamari, D.; Gaggi, C.

1986-01-01

The concentrations of some chlorinated hydrocarbon residues (HCB, HCH isomers, p,p'DDT and DDE, PCB cogeners) in lichen and moss samples from the Antarctic Peninsula are reported and compared with available data from other parts of the world. The use of these materials as indicators of tropospheric contamination levels in Antarctica is discussed.

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

Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit

This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s (BETO’s) efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from lignocellulosic biomass feedstocks. The research funded by BETO is designed to advance the state of technology of biomass feedstock supply and logistics, conversion, and overall system sustainability. It is expected that these research improvements will be made within the 2022 timeframe. As part of their involvement in this research and development effort, the National Renewable Energy Laboratory and the Pacific Northwest National Laboratory investigate the economics ofmore » conversion pathways through the development of conceptual biorefinery process models and techno-economic analysis models. This report describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas or syngas via indirect gasification, gas cleanup, catalytic conversion of syngas to methanol intermediate, methanol dehydration to dimethyl ether (DME), and catalytic conversion of DME to high-octane, gasoline-range hydrocarbon blendstock product. The conversion process configuration leverages technologies previously advanced by research funded by BETO and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via reforming of tars and other hydrocarbons is one of the key technology advancements realized as part of this prior research and 2012 demonstrations. The process described in this report evaluates a new technology area for the downstream utilization of clean biomass-derived syngas for the production of high-octane hydrocarbon products through methanol and DME intermediates. In this process, methanol undergoes dehydration to DME, which is subsequently converted via homologation reactions to high-octane, gasoline-range hydrocarbon products.« less

Improved forward and inverse analyses of saturated-unsaturated flow toward a well in a compressible unconfined aquifer

NASA Astrophysics Data System (ADS)

Mishra, Phoolendra Kumar; Neuman, Shlomo P.

2010-07-01

We present an analytical solution for flow to a partially penetrating well in a compressible unconfined aquifer that allows inferring its saturated and unsaturated hydraulic properties from drawdowns recorded in the saturated and/or unsaturated zone. We improve upon a previous such solution due to Tartakovsky and Neuman (2007) by (1) adopting a more flexible representation of unsaturated zone constitutive properties and (2) allowing the unsaturated zone to have finite thickness. Both solutions account for horizontal as well as vertical flows throughout the system. We investigate the effects of unsaturated zone constitutive parameters and thickness on drawdowns in the saturated and unsaturated zones as functions of position and time; demonstrate the development of significant horizontal hydraulic gradients in the unsaturated zone in response to pumping; validate our solution against numerical simulations of drawdown in a synthetic aquifer having unsaturated properties described by the van Genuchten-Mualem constitutive model; use our solution to analyze drawdown data from a pumping test conducted by the U.S. Geological Survey at Cape Cod, Massachusetts; and compare our estimates of van Genuchten-Mualem parameters with laboratory values obtained for similar materials in the area.

The Stingless Bee Melipona solani Deposits a Signature Mixture and Methyl Oleate to Mark Valuable Food Sources.

PubMed

Alavez-Rosas, David; Malo, Edi A; Guzmán, Miguel A; Sánchez-Guillén, Daniel; Villanueva-Gutiérrez, Rogel; Cruz-López, Leopoldo

2017-10-01

Stingless bees foraging for food improve recruitment by depositing chemical cues on valuable food sites or pheromone marks on vegetation. Using gas chromatography/mass spectrometry and bioassays, we showed that Melipona solani foragers leave a mixture composed mostly of long chain hydrocarbons from their abdominal cuticle plus methyl oleate from the labial gland as a scent mark on rich food sites. The composition of hydrocarbons was highly variable among individuals and varied in proportions, depending on the body part. A wide ratio of compounds present in different body parts of the bees elicited electroantennogram responses from foragers and these responses were dose dependent. Generally, in bioassays, these bees prefer to visit previously visited feeders and feeders marked with extracts from any body part of conspecifics. The mean number of visits to a feeder was enhanced when synthetic methyl oleate was added. We propose that this could be a case of multi-source odor marking, in which hydrocarbons, found in large abundance, act as a signature mixture with attraction enhanced through deposition of methyl oleate, which may indicate a rich food source.

Sequence stratigraphy buoys W. Indonesia basins

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

Courteney, S.

1996-05-20

Since oil exploration began in Indonesia in 1870 more than 3,000 exploratory wells have been drilled in Western Indonesia, which means a significant data base exists; however, many of the published technical papers describing Indonesian petroleum geology are based on lithostratigraphy. This article presents a correlative framework based on the application of sequence stratigraphy, which has been established for the hydrocarbon productive basins. Part 1 illustrates this correlative framework with an example each from areas in Sumatra, Java, and Kalimantan. These examples review the hydrocarbon system in each area from the perspective of source, reservoir, seal, and timing of structure.more » In Part 2 the ideas developed are expanded and integrated into an examination of the future hydrocarbon potential for western Indonesia, which is refreshingly different and perhaps more encouraging than those made using the traditional tools of lithostratigraphy and biostratigraphy.« less

Bacterial community changes during bioremediation of aliphatic hydrocarbon-contaminated soil.

PubMed

Militon, Cécile; Boucher, Delphine; Vachelard, Cédric; Perchet, Geoffrey; Barra, Vincent; Troquet, Julien; Peyretaillade, Eric; Peyret, Pierre

2010-12-01

The microbial community response during the oxygen biostimulation process of aged oil-polluted soils is poorly documented and there is no reference for the long-term monitoring of the unsaturated zone. To assess the potential effect of air supply on hydrocarbon fate and microbial community structure, two treatments (0 and 0.056 mol h⁻¹ molar flow rate of oxygen) were performed in fixed bed reactors containing oil-polluted soil. Microbial activity was monitored continuously over 2 years throughout the oxygen biostimulation process. Microbial community structure before and after treatment for 12 and 24 months was determined using a dual rRNA/rRNA gene approach, allowing us to characterize bacteria that were presumably metabolically active and therefore responsible for the functionality of the community in this polluted soil. Clone library analysis revealed that the microbial community contained many rare phylotypes. These have never been observed in other studied ecosystems. The bacterial community shifted from Gammaproteobacteria to Actinobacteria during the treatment. Without aeration, the samples were dominated by a phylotype linked to the Streptomyces. Members belonging to eight dominant phylotypes were well adapted to the aeration process. Aeration stimulated an Actinobacteria phylotype that might be involved in restoring the ecosystem studied. Phylogenetic analyses suggested that this phylotype is a novel, deep-branching member of the Actinobacteria related to the well-studied genus Acidimicrobium. FEMS Microbiology Ecology © 2010 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. No claim to original French government works.

Comparison of the effectiveness of soil heating prior or during in situ chemical oxidation (ISCO) of aged PAH-contaminated soils.

PubMed

Ranc, Bérénice; Faure, Pierre; Croze, Véronique; Lorgeoux, Catherine; Simonnot, Marie-Odile

2017-04-01

Thermal treatments prior or during chemical oxidation of aged polycyclic aromatic hydrocarbon (PAH)-contaminated soils have already shown their ability to increase oxidation effectiveness. However, they were never compared on the same soil. Furthermore, oxygenated polycyclic aromatic hydrocarbons (O-PACs), by-products of PAH oxidation which may be more toxic and mobile than the parent PAHs, were very little monitored. In this study, two aged PAH-contaminated soils were heated prior (60 or 90 °C under Ar for 1 week) or during oxidation (60 °C for 1 week) with permanganate and persulfate, and 11 O-PACs were monitored in addition to the 16 US Environmental Protection Agency (US EPA) PAHs. Oxidant doses were based on the stoichiometric oxidant demand of the extractable organic fraction of soils by using organic solvents, which is more representative of the actual contamination than only the 16 US EPA PAHs. Higher temperatures actually resulted in more pollutant degradation. Two treatments were about three times more effective than the others: soil heating to 60 °C during persulfate oxidation and soil preheating to 90 °C followed by permanganate oxidation. The results of this study showed that persulfate effectiveness was largely due to its thermal activation, whereas permanganate was more sensitive to PAH availability than persulfate. The technical feasibility of these two treatments will soon be field-tested in the unsaturated zone of one of the studied aged PAH-contaminated soils.

Efficient Reservoir Simulation with Cubic Plus Association and Cross-Association Equation of State for Multicomponent Three-Phase Compressible Flow with Applications in CO2 Storage and Methane Leakage

NASA Astrophysics Data System (ADS)

Moortgat, J.

2017-12-01

We present novel simulation tools to model multiphase multicomponent flow and transport in porous media for mixtures that contain non-polar hydrocarbons, self-associating polar water, and cross-associating molecules like methane, ethane, unsaturated hydrocarbons, CO2 and H2S. Such mixtures often occur when CO2 is injected and stored in saline aquifers, or when methane is leaking into groundwater. To accurately predict the species transfer between aqueous, gaseous and oleic phases, and the subsequent change in phase properties, the self- and cross-associating behavior of molecules needs to be taken into account, particularly at the typical temperatures and pressures in deep formations. The Cubic-Plus-Association equation-of-state (EOS) has been demonstrated to be highly accurate for such problems but its excessive computational cost has prevented widespread use in reservoir simulators. We discuss the thermodynamical framework and develop sophisticated numerical algorithms that allow reservoir simulations with efficiencies comparable to a simple cubic EOS. This approach improves our predictive powers for highly nonlinear fluid behavior related to geological carbon sequestration, such as density driven flow and natural convection (solubility trapping), evaporation of water into the CO2-rich gas phase, and competitive dissolution-evaporation when CO2 is injected in, e.g., methane saturated aquifers. Several examples demonstrate the accuracy and robustness of this EOS framework for complex applications.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

PubMed Central

Popolan-Vaida, Denisia M.; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah Y.; Wang, Heng; Sioud, Salim; Raji, Misjudeen A.; Kohse-Höinghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R.

2017-01-01

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels. PMID:29183984

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.

Magnetic properties changes due to hydrocarbon contaminated groundwater table fluctuations

NASA Astrophysics Data System (ADS)

Ameen, Nawrass

2013-04-01

This study aims to understand the mechanisms and conditions which control the formation and transformation of ferro(i)magnetic minerals caused by hydrocarbon contaminated groundwater, in particular in the zone of fluctuating water levels. The work extends previous studies conducted at the same site. The study area is a former military air base at Hradčany, Czech Republic (50°37'22.71"N, 14°45'2.24"E). The site was heavily contaminated with petroleum hydrocarbons, due to leaks in petroleum storage tanks and jet fuelling stations over years of active use by the Soviet Union, which closed the base in 1991. The site is one of the most important sources of high quality groundwater in the Czech Republic. In a previous study, Rijal et al. (2010) concluded that the contaminants could be flushed into the sediments as the water level rose due to remediation processes leading to new formation of magnetite. In this previous study three different locations were investigated; however, from each location only one core was obtained. In order to recognize significant magnetic signatures versus depth three cores from each of these three locations were drilled in early 2012, penetrating the unsaturated zone, the groundwater fluctuation (GWF) zone and extending to about one meter below the groundwater level (~2.3 m depth at the time of sampling). Magnetic susceptibility (MS) profiles combined with other magnetic properties were analyzed to obtain a significant depth distribution of the ferro(i)magnetic concentration. Sediment properties, hydrocarbon content and bacterial activity were additionally studied. The results show that the highest ferrimagnetic mineral concentrations exist between 1.4-1.9 m depth from the baseline which is interpreted as the top of the GWF zone. Spikes of MS detected in the previous studies turned out to represent small-scale isolated features, but the trend of increasing MS values from the lowermost position of the groundwater table upward was verified. Mineral magnetic parameters indicate that magnetite is responsible for the MS signal which confirms the previous results (Rijal et al., 2010). The so far existing uncertainty of the groundwater level position could be solved. Bacterial activity is studied at particular depth horizons as it is assumed to be responsible for iron mineralogy changes. References: Rijal M.L., Appel E., Petrovský E. and Blaha U., 2010. Change of magnetic properties due to fluctuations of hydrocarbon contaminated groundwater in unconsolidated sediments. Environ.Pollut., 158, 1756-1762.

Effects of Subsurface Microbial Ecology on Geochemical Evolution of a Crude-Oil Contaminated Aquifer

NASA Astrophysics Data System (ADS)

Bekins, B. A.; Cozzarelli, I. M.; Godsy, E. M.; Warren, E.; Hostettler, F. D.

2001-12-01

We have identified several subsurface habitats for microorganisms in a crude oil contaminated located near Bemidji, Minnesota. These aquifer habitats include: 1) the unsaturated zone contaminated by hydrocarbon vapors, 2) the zones containing separate-phase crude oil, and 3) the aqueous-phase contaminant plume. The surficial glacial outwash aquifer was contaminated when a crude oil pipeline burst in 1979. We analyzed sediment samples from the contaminated aquifer for the most probable numbers of aerobes, iron reducers, fermenters, and three types of methanogens. The microbial data were then related to gas, water, and oil chemistry, sediment extractable iron, and permeability. The microbial populations in the various contaminated subsurface habitats each have special characteristics and these affect the aquifer and contaminant chemistry. In the eight-meter-thick, vapor-contaminated vadose zone, a substantial aerobic population has developed that is supported by hydrocarbon vapors and methane. Microbial numbers peak in locations where access to both hydrocarbons and nutrients infiltrating from the surface is maximized. The activity of this population prevents hydrocarbon vapors from reaching the land surface. In the zone where separate-phase crude oil is present, a consortium of methanogens and fermenters dominates the populations both above and below the water table. Moreover, gas concentration data indicate that methane production has been active in the oily zone since at least 1986. Analyses of the extracted separate-phase oil show that substantial degradation of C15 -C35 n-alkanes has occurred since 1983, raising the possibility that significant degradation of C15 and higher n-alkanes has occurred under methanogenic conditions. However, lab and field data suggest that toxic inhibition by crude oil results in fewer acetate-utilizing methanogens within and adjacent to the separate-phase oil. Data from this and other sites indicate that toxic inhibition of acetoclastic methanogenesis in the proximity of separate phase contaminant sources may result in build-up of acetate in contaminant plumes. Within the aqueous-phase contaminant plume steep vertical hydrocarbon concentration gradients are associated with sharp transitions in the dominant microbial population. In the 20 years since the aquifer became contaminated, sediment iron oxides have been depleted and the dominant physiologic type has changed in areas of high contaminant flux from iron reducing to methanogenic. Thus, methanogens are found in high permeability horizons down gradient from the oil while iron reducers persist in low permeability zones. Expansion of the methanogenic zone over time has resulted in a concomitant increase in the aquifer volume contaminated with the highest concentrations of benzene and ethylbenzene.

Hydrocarbons in the Surface Layer of Bottom Sediments in the Northwestern Caspian Sea

NASA Astrophysics Data System (ADS)

Nemirovskaya, I. A.; Ostrovskaya, E. V.

2018-03-01

The paper presents research results on the concentrations and compositions of aliphatic and polycyclic aromatic hydrocarbons in the surface layer of bottom sediments in the Northwestern Caspian Sea (2014) and compares them to data for sediments of the Middle and Southern Caspian (2012-2013). The seepage of hydrocarbons out of the sediment mass, resulting in abnormally high concentrations of aliphatic hydrocarbons per dry weight (up to 468 μg/g), as well as within the Corg composition (up to 35.2%), is considered the main source of hydrocarbons in sediments in the surveyed area of the Northern Caspian. This is also confirmed by the absence of any correlation between the hydrocarbon and Corg distributions, as well as by the transformed oil composition of high-molecular alkanes. The distribution of markers within polycyclic aromatic hydrocarbons points to a mixed genesis—petrogenic and pyrogenic—with prevalence of the latter. Unlike the shallow-water northern part of the Caspian Sea, the content and composition of hydrocarbons in deep-seated sediments are affected by facial conditions of sedimentation and by matter exchange at the water-bottom interface. Therefore, despite high Corg concentrations (up to 9.9%), sediments in deep-water depressions are characterized by a quite low concentration of aliphatic hydrocarbons (52 μg/g on average; 0.2% of Corg) with prevailing natural allochthonous alkanes.

Herbicide Transport and Transformations in the Unsaturated Zone of Three Small Agricultural Basins with Corn and Soybean Row Crops

NASA Astrophysics Data System (ADS)

Hancock, T. C.; Vogel, J. R.; Sandstrom, M. W.; Capel, P. D.; Bayless, R. E.; Webb, R. M.

2006-05-01

In the United States, herbicides are among the most significant nonpoint-source pollutants and were applied to 95% of all fields in corn production and 97% of all fields in soybean production in 2003 and 2004. The United States Geological Survey (USGS) has conducted a study on select herbicides in the unsaturated zone under corn and soybean fields in three predominantly agricultural basins: Morgan Creek (Maryland), Leary Weber Ditch within Sugar Creek (Indiana), and Maple Creek (Nebraska). In 2004, the Morgan Creek and Leary Weber Ditch fields were in soybeans and the Maple Creek fields were in corn. The Maple Creek fields were irrigated, whereas those in Morgan Creek and Leary Weber Ditch were not. Similarities and differences in agricultural management practices, climatic conditions, and natural features, such as soil types and geology, were evaluated as part of the study. In general, the amounts of herbicides entering the unsaturated zone from rain in these basins were minor (1%) compared to amounts commonly applied to the land surface during agricultural practices. Few herbicides were detected on solid core samples from the unsaturated zones of these basins. An exception was found at a Morgan Creek site in an upland recharge area with sandier soils. Here, atrazine concentrations were highest in the near surface solids and decreased with depth. In the unsaturated-zone porewater of the Morgan Creek Basin, parent triazine and acetanilide herbicides were detected and only at the site in the upland recharge area at relatively low concentrations at depths greater than 4 meters, probably because these compounds had not been applied for several years. At the Morgan Creek and Leary Weber Ditch sites, acetanilide metabolites were frequently detected in the unsaturated-zone porewater. In general, the fraction of metolachlor ethane sulfonic acid (ESA) relative to the total mass of parent and metabolites increased with depth overall and at several individual sampling locations this fraction increased over time. At the Maple Creek sites, atrazine, metalochlor, acetochlor, and alachlor were detected, typically at concentrations higher than their metabolites. The Maple Creek site is influenced by focused recharge, macropore flow, and variable soil-moisture retention properties in soils that transition from loess to sand.

Photochemistry in terrestrial exoplanet atmospheres. III. Photochemistry and thermochemistry in thick atmospheres on super Earths and mini Neptunes

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

Hu, Renyu; Seager, Sara, E-mail: hury@caltech.edu

Some super Earths and mini Neptunes will likely have thick atmospheres that are not H{sub 2}-dominated. We have developed a photochemistry-thermochemistry kinetic-transport model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H{sub 2}-dominated atmospheres and non-H{sub 2}-dominated atmospheres. Using this model to study thick atmospheres for wide ranges of temperatures and elemental abundances, we classify them into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres. We find that carbon has to be in the form of CO{sub 2} rather than CH{sub 4} or CO in a H{sub 2}-depleted water-dominated thick atmospheremore » and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to the formation of unsaturated hydrocarbons (C{sub 2}H{sub 2} and C{sub 2}H{sub 4}). We apply our self-consistent atmosphere models to compute spectra and diagnostic features for known transiting low-mass exoplanets GJ 1214 b, HD 97658 b, and 55 Cnc e. For GJ 1214 b, we find that (1) C{sub 2}H{sub 2} features at 1.0 and 1.5 μm in transmission and C{sub 2}H{sub 2} and C{sub 2}H{sub 4} features at 9-14 μm in thermal emission are diagnostic for hydrocarbon-rich atmospheres; (2) a detection of water-vapor features and a confirmation of the nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Water-dominated atmospheres only exist for carbon to oxygen ratios much lower than the solar ratio, suggesting that this kind of atmospheres could be rare.« less

The 11 Micron Emissions of Carbon Stars

NASA Technical Reports Server (NTRS)

Goebel, J. H.; Cheeseman, P.; Gerbault, F.

1995-01-01

A new classification scheme of the IRAS LRS carbon stars is presented. It comprises the separation of 718 probable carbon stars into 12 distinct self-similar spectral groupings. Continuum temperatures are assigned and range from 470 to 5000 K. Three distinct dust species are identifiable: SiC, alpha:C-H, and MgS. In addition to the narrow 11 + micron emission feature that is commonly attributed to SiC, a broad 11 + micron emission feature, that is correlated with the 8.5 and 7.7 micron features, is found and attributed to alpha:C-H. SiC and alpha:C-H band strengths are found to correlate with the temperature progression among the Classes. We find a spectral sequence of Classes that reflects the carbon star evolutionary sequence of spectral types, or alternatively developmental sequences of grain condensation in carbon-rich circumstellar shells. If decreasing temperature corresponds to increasing evolution, then decreasing temperature corresponds to increasing C/O resulting in increasing amounts of carbon rich dust, namely alpha:C-H. If decreasing the temperature corresponds to a grain condensation sequence, then heterogeneous, or induced nucleation scenarios are supported. SiC grains precede alpha:C-H and form the nuclei for the condensation of the latter material. At still lower temperatures, MgS appears to be quite prevalent. No 11.3 micron PAH features are identified in any of the 718 carbon stars. However, one of the coldest objects, IRAS 15048-5702, and a few others, displays an 11.9 micron emission feature characteristic of laboratory samples of coronene. That feature corresponds to the C-H out of plane deformation mode of aromatic hydrocarbon. This band indicates the presence of unsaturated, sp(sup 3), hydrocarbon bonds that may subsequently evolve into saturated bonds, sp(sup 2), if, and when, the star enters the planetary nebulae phase of stellar evolution. The effusion of hydrogen from the hydrocarbon grain results in the evolution in wavelength of this 11.9 micron emission feature to the 11.3 micron feature.

Chemical kinetic model uncertainty minimization through laminar flame speed measurements

DOE PAGES

Park, Okjoo; Veloo, Peter S.; Sheen, David A.; ...

2016-07-25

Laminar flame speed measurements were carried for mixture of air with eight C 3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C 1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011,more » 158, 2358–2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C 3 and C 4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C 3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C 4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C 4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel.« less

Chemical kinetic model uncertainty minimization through laminar flame speed measurements

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

Park, Okjoo; Veloo, Peter S.; Sheen, David A.

Laminar flame speed measurements were carried for mixture of air with eight C 3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C 1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011,more » 158, 2358–2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C 3 and C 4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C 3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C 4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C 4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel.« less

The 11 Micron Emissions of Cabon Stars

NASA Technical Reports Server (NTRS)

Goebel, J. H.; Cheeseman, P.; Gerbault, F.

1995-01-01

A new classification scheme of the IRAS LRS carbon stars is presented. It comprises the separation of 718 probable carbon stars into 12 distinct self-similar spectral groupings. Continuum temperatures are assigned and range from 470 to 5000 K. Three distinct dust species are identifiable: SiC, alpha:C-H, and MgS. In addition to the narrow 11 + micron emission feature that is commonly attributed to SiC, a broad 11 + micron emission feature, that is correlated with the 8.5 and 7.7 micron features, is found and attributed to alpha:C-H. SiC and alpha:C-H band strengths are found to correlate with the temperature progression among the Classes. We find a spectral sequence of Classes that reflects the carbon star evolutionary sequence of spectral types, or alternatively developmental sequences of grain condensation in carbon-rich circumstellar shells. If decreasing temperature corresponds to increasing evolution, then decreasing temperature corresponds to increasing CIO resulting in increasing amounts of carbon rich dust, namely alpha:C-H. If decreasing the temperature corresponds to a grain condensation sequence, then heterogeneous, or induced nucleation scenarios are supported. SiC grains precede alpha:C-H and form the nuclei for the condensation of the latter material. At still lower temperatures, MgS appears to be quite prevalent. No 11.3 micron PAH features are identified in any of the 718 carbon stars. However, one of the coldest objects, IRAS 15048-5702, and a few others, displays an 11.9 micron emission feature characteristic of laboratory samples of coronene. That feature corresponds to the C-H out of plane deformation mode of aromatic hydrocarbon. This band indicates the presence of unsaturated, sp(sup 3), hydrocarbon bonds that may subsequently evolve into saturated bonds, sp(sup 2), if, and when, the star enters the planetary nebulae phase of stellar evolution. The effusion of hydrogen from the hydrocarbon grain results in the evolution in wavelength of this 11.9 micron emission feature to the 11.3 micron feature.

Research-derived insights into surface geochemical hydrocarbon exploration

USGS Publications Warehouse

Price, L.C.

1996-01-01

Research studies based on foreland basins (mainly in eastern Colorado) examined three surface geochemical exploration (SGE) methods as possible hydrocarbon (HC) exploration techniques. The first method, microbial soil surveying, has high potential as an exploration tool, especially hi development and enhanced recovery operations. Integrative adsorption, the second technique, is not effective as a quantitative SGE method because water, carbon dioxide, nitrous oxide, unsaturated hydrocarbons, and organic compounds are collected by the adsorbent (activated charcoal) much more strongly than covalently bonded microseeping Q-Cs thermogenic HCs. Qualitative comparisons (pattern recognition) of C8+ mass spectra cannot gauge HC gas microseepage that involves only the Q-Cs HCs. The third method, soil cakite surveying, also has no potential as an exploration tool. Soil calcite concentrations had patterns with pronounced areal contrasts, but these patterns had no geometric relationship to surface traces of established or potential production, that is, the patterns were random. Microscopic examination of thousands of soils revealed that soil calcite was an uncrystallized caliche coating soil particles. During its precipitation, caliche captures or occludes any gases, elements, or compounds in its immediate vicinity. Thus, increased signal intensity of some SGE methods should depend on increasing soil calcite concentrations. Analyses substantiate this hypothesis. Because soil calcite has no utility as a surface exploration tool, any surface method that depends on soil calcite has a diminished utility as an SGE tool. Isotopic analyses of soil calcites revealed carbonate carbon ??13C values of -4.0 to +2.07co (indicating a strong influence of atmospheric CO2) as opposed to expected values of-45 to -30%c if the carbonate carbon had originated from microbial oxidation of microseeping HC gases. These analyses confirm a surface origin for this soil calcite (caliche), which is not necessarily related to HC gas microseepage. This previously unappreciated pivotal role of caliche is hypothesized to contribute significantly to the poor and inconsistent results of some SGE methods.

Abundance of active ingredients in sea-buckthorn oil.

PubMed

Zielińska, Aleksandra; Nowak, Izabela

2017-05-19

Vegetable oils are obtained by mechanical extraction or cold pressing of various parts of plants, most often: seeds, fruits, and drupels. Chemically, these oils are compounds of the ester-linked glycerol and higher fatty acids with long aliphatic chain hydrocarbons (min. C14:0). Vegetable oils have a variety of properties, depending on their percentage of saturation. This article describes sea-buckthorn oil, which is extracted from the well characterized fruit and seeds of sea buckthorn. The plant has a large number of active ingredients the properties of which are successfully used in the cosmetic industry and in medicine. Valuable substances contained in sea-buckthorn oil play an important role in the proper functioning of the human body and give skin a beautiful and healthy appearance. A balanced composition of fatty acids give the number of vitamins or their range in this oil and explains its frequent use in cosmetic products for the care of dry, flaky or rapidly aging skin. Moreover, its unique unsaturated fatty acids, such as palmitooleic acid (omega-7) and gamma-linolenic acid (omega-6), give sea-buckthorn oil skin regeneration and repair properties. Sea-buckthorn oil also improves blood circulation, facilitates oxygenation of the skin, removes excess toxins from the body and easily penetrates through the epidermis. Because inside the skin the gamma-linolenic acid is converted to prostaglandins, sea-buckthorn oil protects against infections, prevents allergies, eliminates inflammation and inhibits the aging process. With close to 200 properties, sea-buckthorn oil is a valuable addition to health and beauty products.

40 CFR 86.111-94 - Exhaust gas analytical system.

Code of Federal Regulations, 2010 CFR

2010-07-01

... hydrocarbon (THC) (hydrocarbon plus methanol in the case of methanol-fueled vehicles), methane (CH4) (for... methanol for methanol-fueled diesel-cycle vehicles) is shown as part of Figure B94-5 (or Figure B94-6... ionization detector (FID) (heated, 235 °±15 °F (113 °±8 °C) for methanol-fueled vehicles) for the...

40 CFR 86.111-94 - Exhaust gas analytical system.

Code of Federal Regulations, 2011 CFR

2011-07-01

... systems for analysis of total hydrocarbon (THC) (hydrocarbon plus methanol in the case of methanol-fueled... train (and for THC plus methanol for methanol-fueled diesel-cycle vehicles) is shown as part of Figure... B94-7, consists of a flame ionization detector (FID) (heated, 235 °±15 °F (113 °±8 °C) for methanol...

Coal-tar-based pavement sealcoat, polycyclic aromatic Hydrocarbons (PAHs), and environmental health

USGS Publications Warehouse

Mahler, B.J.; Van Metre, P.C.

2011-01-01

Studies by the U.S. Geological Survey (USGS) have identified coal-tar-based sealcoat-the black, viscous liquid sprayed or painted on asphalt pavement such as parking lots-as a major source of polycyclic aromatic hydrocarbon (PAH) contamination in urban areas for large parts of the Nation. Several PAHs are suspected human carcinogens and are toxic to aquatic life.

Creating fluid injectivity in tar sands formations

DOEpatents

Stegemeier, George Leo; Beer, Gary Lee; Zhang, Etuan

2012-06-05

Methods for treating a tar sands formation are described herein. Methods for treating a tar sands may include heating a portion of a hydrocarbon layer in the formation from one or more heaters located in the portion. The heat may be controlled to increase the permeability of at least part of the portion to create an injection zone in the portion with an average permeability sufficient to allow injection of a fluid through the injection zone. A drive fluid and/or an oxidizing fluid may be provided into the injection zone. At least some hydrocarbons including mobilized hydrocarbons are produced from the portion.

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.

Short communication: Estimates of heritabilities and genetic correlations among milk fatty acid unsaturation indices in Canadian Holsteins.

PubMed

Bilal, G; Cue, R I; Mustafa, A F; Hayes, J F

2012-12-01

The objectives of the present study were to estimate genetic parameters of milk fatty acid unsaturation indices in Canadian Holsteins. Data were available on milk fatty acid composition of 2,573 Canadian Holstein cows from 46 commercial herds enrolled in the Québec Dairy Production Centre of Expertise, Valacta (Sainte-Anne-de-Bellevue, Quebec, Canada). Individual fatty acid percentages (g/100 g of total fatty acids) were determined for each milk sample by gas chromatography. The unsaturation indices were calculated as the ratio of an unsaturated fatty acid to the sum of that unsaturated fatty acid and its corresponding substrate fatty acid, multiplied by 100. A mixed linear model was fitted under REML for the statistical analysis of milk fatty acid unsaturation indices. The statistical model included the fixed effects of parity, age at calving, and stage of lactation, each nested within parity, and the random effects of herd-year-season of calving, animal, and residual. Estimates of heritabilities for the C14, C16, C18, conjugated linoleic acid, and total unsaturation indices were 0.48, 0.25, 0.29, 0.14, and 0.19, respectively. Phenotypic and genetic correlation estimates among unsaturation indices were all positive and ranged from 0.20 to 0.65 and 0.23 to 0.81, respectively. The estimates of heritabilities and genetic correlations for milk fatty acid unsaturation indices suggest that genetic variation exists among cows in milk fatty acid unsaturation, and the proportions of desirable unsaturated fatty acids from a human health point of view may be increased in bovine milk through genetic selection. Copyright © 2012 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Documentation of the Streamflow-Routing (SFR2) Package to Include Unsaturated Flow Beneath Streams - A Modification to SFR1

USGS Publications Warehouse

Niswonger, Richard G.; Prudic, David E.

2005-01-01

Many streams in the United States, especially those in semiarid regions, have reaches that are hydraulically disconnected from underlying aquifers. Ground-water withdrawals have decreased water levels in valley aquifers beneath streams, increasing the occurrence of disconnected streams and aquifers. The U.S. Geological Survey modular ground-water model (MODFLOW-2000) can be used to model these interactions using the Streamflow-Routing (SFR1) Package. However, the approach does not consider unsaturated flow between streams and aquifers and may not give realistic results in areas with significantly deep unsaturated zones. This documentation describes a method for extending the capabilities of MODFLOW-2000 by incorporating the ability to simulate unsaturated flow beneath streams. A kinematic-wave approximation to Richards' equation was solved by the method of characteristics to simulate unsaturated flow beneath streams in SFR1. This new package, called SFR2, includes all the capabilities of SFR1 and is designed to be used with MODFLOW-2000. Unlike SFR1, seepage loss from the stream may be restricted by the hydraulic conductivity of the unsaturated zone. Unsaturated flow is simulated independently of saturated flow within each model cell corresponding to a stream reach whenever the water table (head in MODFLOW) is below the elevation of the streambed. The relation between unsaturated hydraulic conductivity and water content is defined by the Brooks-Corey function. Unsaturated flow variables specified in SFR2 include saturated and initial water contents; saturated vertical hydraulic conductivity; and the Brooks-Corey exponent. These variables are defined independently for each stream reach. Unsaturated flow in SFR2 was compared to the U.S. Geological Survey's Variably Saturated Two-Dimensional Flow and Transport (VS2DT) Model for two test simulations. For both test simulations, results of the two models were in good agreement with respect to the magnitude and downward progression of a wetting front through an unsaturated column. A third hypothetical simulation is presented that includes interaction between a stream and aquifer separated by an unsaturated zone. This simulation is included to demonstrate the utility of unsaturated flow in SFR2 with MODFLOW-2000. This report includes a description of the data input requirements for simulating unsaturated flow in SFR2.

Quantifying Preferential Flow and Seasonal Storage in an Unsaturated Fracture-Facial Domain

NASA Astrophysics Data System (ADS)

Nimmo, J. R.; Malek-Mohammadi, S.

2012-12-01

Preferential flow through deep unsaturated zones of fractured rock is hydrologically important to a variety of contaminant transport and water-resource issues. The unsaturated zone of the English Chalk Aquifer provides an important opportunity for a case study of unsaturated preferential flow in isolation from other flow modes. The chalk matrix has low hydraulic conductivity and stays saturated, owing to its fine uniform pores and the wet climate of the region. Therefore the substantial fluxes observed in the unsaturated chalk must be within fractures and interact minimally with matrix material. Price et al. [2000] showed that irregularities on fracture surfaces provide a significant storage capacity in the chalk unsaturated zone, likely accounting for volumes of water required to explain unexpected dry-season water-table stability during substantial continuing streamflow observed by Lewis et al. [1993] In this presentation we discuss and quantify the dynamics of replenishment and drainage of this unsaturated zone fracture-face storage domain using a modification of the source-responsive model of Nimmo [2010]. This model explains the processes in terms of two interacting flow regimes: a film or rivulet preferential flow regime on rough fracture faces, active on an individual-storm timescale, and a regime of adsorptive and surface-tension influences, resembling traditional diffuse formulations of unsaturated flow, effective mainly on a seasonal timescale. The modified model identifies hydraulic parameters for an unsaturated fracture-facial domain lining the fractures. Besides helping to quantify the unsaturated zone storage described by Price et al., these results highlight the importance of research on the topic of unsaturated-flow relations within a near-fracture-surface domain. This model can also facilitate understanding of mechanisms for reinitiation of preferential flow after temporary cessation, which is important in multi-year preferential flow through deep unsaturated zones [Pruess, 1999]. Lewis, M.A., H.K. Jones, D.M.J. Macdonald, M. Price, J.A. Barker, T.R. Shearer, A.J. Wesselink, and D.J. Evans (1993), Groundwater storage in British aquifers--Chalk, National Rivers Authority R&D Note, 169, Bristol, UK. Nimmo, J.R. (2010), Theory for Source-Responsive and Free-Surface Film Modeling of Unsaturated Flow, Vadose Zone Journal, 9(2), 295-306, doi:10.2136/vzj2009.0085. Price, M., R.G. Low, and C. McCann (2000), Mechanisms of water storage and flow in the unsaturated zone of the Chalk aquifer, Journal of Hydrology, 233(1-4), 54-71. Pruess, K. (1999), A mechanistic model for water seepage through thick unsaturated zones in fractured rocks of low matrix permeability, Water Resources Research, 35(4), 1039-1051.

Composition, structure and substrate properties of reconstituted discoidal HDL with apolipoprotein A-I and cholesteryl ester

NASA Astrophysics Data System (ADS)

Dergunov, Alexander D.; Shabrova, Elena V.; Dobretsov, Gennady E.

2010-03-01

To investigate the influence of lipid unsaturation and neutral lipid on the maturation of high density lipoproteins, the discoidal complexes of apoA-I, phosphatidylcholine and cholesteryl ester (CE) were prepared. Saturated dipalmitoylphosphatidylcholine (DPPC) and unsaturated palmitoyllinoleoylphosphatidylcholine (PLPC), palmitoyloleoylphosphatidylcholine (POPC), and fluorescent probe cholesteryl 1-pyrenedecanoate (CPD) that forms in a diffusion- and concentration-dependent manner short-lived dimer of unexcited and excited molecules (excimer) were used. The apoA-I/DPPC/CPD complexes were heterogeneous by size, composition and probe location. CPD molecules incorporated more efficiently into larger complexes and accumulated in a central part of the discs. The apoA-I/POPC(PLPC)/CPD were also heterogeneous, however, probe molecules distributed preferentially into smaller complexes and accumulated at disc periphery. The kinetics of CPD transfer by recombinant cholesteryl ester transfer protein (CETP) to human plasma LDL is well described by two-exponential decay, the fast component with a shorter transfer time being more populated in PLPC compared to DPPC complexes. The presence of CE molecules in discoidal HDL results in particle heterogeneity. ApoA-I influences the CETP activity modulating the properties of apolipoprotein-phospholipid interface. This may include CE molecules accumulation in the boundary lipid in unsaturated phosphatidylcholine and cluster formation in the bulk bilayer in saturated phosphatidylcholine.

Aerobic biodegradation process of petroleum and pathway of main compounds in water flooding well of Dagang oil field.

PubMed

Cai, Minmin; Yao, Jun; Yang, Huaijun; Wang, Ruixia; Masakorala, Kanaji

2013-09-01

Aerobic biodegradation of crude oil and its pathways were investigated via in vitro culture and GC-MS analysis in water flooding wells of Dagang oil field. The in vitro aerobic culture lasted 90 days when 99.0% of n-alkanes and 43.03-99.9% of PAHs were degraded and the biomarkers and their ratios were changed. The spectra of components in the residual oil showed the similar biodegradation between aerobic process of 90 days and degradation in reservoir which may last for some millions years, and the potential of serious aerobic biodegradation of petroleum in reservoir. 24 Metabolites compounds were separated and identified from aerobic culture, including fatty acid, naphthenic acid, aromatic carboxylic acid, unsaturated acid, alcohols, ketones and aldehydes. The pathways of alkanes and aromatics were proposed, which suggests that oxidation of hydrocarbon to organic acid is an important process in the aerobic biodegradation of petroleum. Copyright © 2013 Elsevier Ltd. All rights reserved.

Volatiles formation in gelled emulsions enriched in polyunsaturated fatty acids during storage: type of oil and antioxidant.

PubMed

Gayoso, Lucía; Poyato, Candelaria; Calvo, María Isabel; Cavero, Rita Yolanda; Ansorena, Diana; Astiasarán, Iciar

2017-08-01

Gelled emulsions with carrageenan are a novel type of emulsion that could be used as a carrier of unsaturated fatty acids in functional foods formulations. Lipid degradation through volatile compounds was studied in gelled emulsions which were high in polyunsaturated oils (sunflower or algae oil) after 49 days of storage. Aqueous Lavandula latifolia extract was tested as a natural antioxidant. Analysis of the complete volatile profile of the samples resulted in a total of 40 compounds, classified in alkanes, alkenes, aldehydes, ketones, acids, alcohols, furans, terpenes and aromatic hydrocarbons. During storage, the formation of the volatile compounds was mostly related to the oxidation of the main fatty acids of the sunflower oil (linolenic acid) and the algae oil (docosahexaenoic acid). Despite the antioxidant capacity shown by the L. latifolia extract, its influence in the oxidative stability in terms of total volatiles was only noticed in sunflower oil gels ( p  < 0.05), where a significant decrease in the aldehydes fraction was found.

Lipid content and fatty acid composition of green algae Scenedesmus obliquus grown in a constant cell density apparatus

NASA Technical Reports Server (NTRS)

Choi, K. J.; Nakhost, Z.; Barzana, E.; Karel, M.

1987-01-01

The lipids of alga Scenedesmus obliquus grown under controlled conditions were separated and fractionated by column and thin-layer chromatography, and fatty acid composition of each lipid component was studied by gas-liquid chromatography (GLC). Total lipids were 11.17%, and neutral lipid, glycolipid and phospholipid fractions were 7.24%, 2.45% and 1.48% on a dry weight basis, respectively. The major neutral lipids were diglycerides, triglycerides, free sterols, hydrocarbons and sterol esters. The glycolipids were: monogalactosyl diglyceride, digalactosyl diglyceride, esterified sterol glycoside, and sterol glycoside. The phospholipids included: phosphatidyl choline, phosphatidyl glycerol and phosphatidyl ethanolamine. Fourteen fatty acids were identified in the four lipid fractions by GLC. The main fatty acids were C18:2, C16:0, C18:3(alpha), C18:1, C16:3, C16:1, and C16:4. Total unsaturated fatty acid and essential fatty acid compositions of the total algal lipids were 80% and 38%, respectively.

Prediction of boiling points of organic compounds by QSPR tools.

PubMed

Dai, Yi-min; Zhu, Zhi-ping; Cao, Zhong; Zhang, Yue-fei; Zeng, Ju-lan; Li, Xun

2013-07-01

The novel electro-negativity topological descriptors of YC, WC were derived from molecular structure by equilibrium electro-negativity of atom and relative bond length of molecule. The quantitative structure-property relationships (QSPR) between descriptors of YC, WC as well as path number parameter P3 and the normal boiling points of 80 alkanes, 65 unsaturated hydrocarbons and 70 alcohols were obtained separately. The high-quality prediction models were evidenced by coefficient of determination (R(2)), the standard error (S), average absolute errors (AAE) and predictive parameters (Qext(2),RCV(2),Rm(2)). According to the regression equations, the influences of the length of carbon backbone, the size, the degree of branching of a molecule and the role of functional groups on the normal boiling point were analyzed. Comparison results with reference models demonstrated that novel topological descriptors based on the equilibrium electro-negativity of atom and the relative bond length were useful molecular descriptors for predicting the normal boiling points of organic compounds. Copyright © 2013 Elsevier Inc. All rights reserved.

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.

Thermal Cracking to Improve the Qualification of the Waxes

NASA Astrophysics Data System (ADS)

He, B.; Agblevor, F. A.; Chen, C. G.; Feng, J.

2018-05-01

Thermal cracking of waxes at mild conditions (430-500°C) has been reconsidered as a possible refining technology for the production of fuels and chemicals. In this study, the more moderate thermal cracking was investigated to process Uinta Basin soft waxes to achieve the required pour point so that they can be pumped to the refineries. The best thermal cracking conditions were set 420°C and 20 minutes. The viscosity and density of the final liquid product were respectively achieved as 2.63 mP•s and 0.784 g/cm3 at 40°C. The result of FT-IR analysis of the liquid product indicated that the unsaturated hydrocarbons were produced after thermal cracking, which was corroborated by the 13C NMR spectrum. The GC analysis of the final gas product indicated that the hydrogen was produced; the dehydrogenation reaction was also proved by the elemental analysis and HHV results. The pour point of the final liquid product met the requirement.

The physical chemistry of Criegee intermediates in the gas phase

DOE PAGES

Osborn, David L.; Taatjes, Craig A.

2015-07-24

Here, carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular andmore » bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.« less

New Molecular Detections in TMC-1 with the Green Bank Telescope: Carbon-Chain and Aromatic Molecules

NASA Astrophysics Data System (ADS)

Burkhardt, Andrew Michael

2018-01-01

Polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocycles PA(N)Hs are believed to be widespread throughout the Universe, and are likely responsible for the unidentified infrared bands. However, the individual detection of aromatic molecules has been limited to a single weak absorption feature of an infrared bending mode of benzene (c-C6H6). The cold core TMC-1 has long been a source of new molecular detections, particularly for unsaturated carbon-rich molecules that are appealing potential precursors of PA(N)Hs. Through deep observations with the Green Bank Telescope of TMC-1, we report the first rotational detection of an aromatic molecule, benzonitrile (c-C6H5CN), along with 8 new isotopologues of HC5N and HC7N and an entirely new molecular family (HC5O, HC7O). These new detections provide crucial insights to the formation of PAHs and the underlying carbon-chain chemistry of dark clouds.

The search for new amphiphiles: synthesis of a modular, high-throughput library

PubMed Central

Feast, George C; Lepitre, Thomas; Mulet, Xavier; Conn, Charlotte E; Hutt, Oliver E

2014-01-01

Summary Amphiphilic compounds are used in a variety of applications due to their lyotropic liquid-crystalline phase formation, however only a limited number of compounds, in a potentially limitless field, are currently in use. A library of organic amphiphilic compounds was synthesised consisting of glucose, galactose, lactose, xylose and mannose head groups and double and triple-chain hydrophobic tails. A modular, high-throughput approach was developed, whereby head and tail components were conjugated using the copper-catalysed azide–alkyne cycloaddition (CuAAC) reaction. The tails were synthesised from two core alkyne-tethered intermediates, which were subsequently functionalised with hydrocarbon chains varying in length and degree of unsaturation and branching, while the five sugar head groups were selected with ranging substitution patterns and anomeric linkages. A library of 80 amphiphiles was subsequently produced, using a 24-vial array, with the majority formed in very good to excellent yields. A preliminary assessment of the liquid-crystalline phase behaviour is also presented. PMID:25161714

The search for new amphiphiles: synthesis of a modular, high-throughput library.

PubMed

Feast, George C; Lepitre, Thomas; Mulet, Xavier; Conn, Charlotte E; Hutt, Oliver E; Savage, G Paul; Drummond, Calum J

2014-01-01

Amphiphilic compounds are used in a variety of applications due to their lyotropic liquid-crystalline phase formation, however only a limited number of compounds, in a potentially limitless field, are currently in use. A library of organic amphiphilic compounds was synthesised consisting of glucose, galactose, lactose, xylose and mannose head groups and double and triple-chain hydrophobic tails. A modular, high-throughput approach was developed, whereby head and tail components were conjugated using the copper-catalysed azide-alkyne cycloaddition (CuAAC) reaction. The tails were synthesised from two core alkyne-tethered intermediates, which were subsequently functionalised with hydrocarbon chains varying in length and degree of unsaturation and branching, while the five sugar head groups were selected with ranging substitution patterns and anomeric linkages. A library of 80 amphiphiles was subsequently produced, using a 24-vial array, with the majority formed in very good to excellent yields. A preliminary assessment of the liquid-crystalline phase behaviour is also presented.

Growth of plants fumigated with saturated and unsaturated hydrocarbon gases and their derivatives

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

Heck, W.W.; Pires, E.G.

1962-01-01

Fourteen gases were investigated for their toxicity to plant growth and development. Five of these gases (acetylene, ethylene, ethylene oxide, propylene and vinyl chloride) produced pronounced effects on the five plant species studied. The plants were fumigated at 10, 100 and 1000 ppm by each of the test gases, using a set of 10 small fumigation chambers. The effects of the five gases on squash, cotton, corn, soybean and cowpea were carefully catalogued. Both quantitative and qualitative growth data were obtained. Plant height, leaf size, flower bud number, cotyledon injury and an injury index are useful criteria for analysis ofmore » gas effects. Cowpea is the most sensitive of the plants studied, followed by cotton, squash, soybean and corn. The injurious effects of ethylene were the greatest, followed by acetylene, propylene, ethylene oxide and vinyl chloride. It is suggested that ethylene oxide acts as a true toxicant while the other four gases may be considered as physiologically active gases.« less

Modelled and field measurements of biogenic hydrocarbon emissions from a Canadian deciduous forest

NASA Astrophysics Data System (ADS)

Fuentes, J. D.; Wang, D.; Den Hartog, G.; Neumann, H. H.; Dann, T. F.; Puckett, K. J.

The Biogenic Emission Inventory System (BEIS) used by the United States Environmental Protection Agency (Lamb et al., 1993, Atmospheric Environment21, 1695-1705; Pierce and Waldruff, 1991, J. Air Waste Man. Ass.41, 937-941) was tested for its ability to provide realistic microclimate descriptions within a deciduous forest in Canada. The microclimate description within plant canopies is required because isoprene emission rates from plants are strongly influenced by foliage temperature and photosynthetically active radiation impinging on leaves while monoterpene emissions depend primarily on leaf temperature. Model microclimate results combined with plant emission rates and local biomass distribution were used to derive isoprene and α-pinene emissions from the deciduous forest canopy. In addition, modelled isoprene emission estimates were compared to measured emission rates at the leaf level. The current model formulation provides realistic microclimatic conditions for the forest crown where modelled and measured air and foliage temperature are within 3°C. However, the model provides inadequate microclimate characterizations in the lower canopy where estimated and measured foliage temperatures differ by as much as 10°C. This poor agreement may be partly due to improper model characterization of relative humidity and ambient temperature within the canopy. These uncertainties in estimated foliage temperature can lead to underestimates of hydrocarbon emission estimates of two-fold. Moreover, the model overestimates hydrocarbon emissions during the early part of the growing season and underestimates emissions during the middle and latter part of the growing season. These emission uncertainties arise because of the assumed constant biomass distribution of the forest and constant hydrocarbon emission rates throughout the season. The BEIS model, which is presently used in Canada to estimate inventories of hydrocarbon emissions from vegetation, underestimates emission rates by at least two-fold compared to emissions derived from field measurements. The isoprene emission algorithm proposed by Guenther et al. (1993), applied at the leaf level, provides relatively good agreement compared to measurements. Field measurements indicate that isoprene emissions change with leaf ontogeny and differ amongst tree species. Emission rates defined as function of foliage development stage and plant species need to be introduced in the hydrocarbon emission algorithms. Extensive model evaluation and more hydrocarbon emission measurement;: from different plant species are required to fully assess the appropriateness of this emission calculation approach for Canadian forests.

Discussion of pore pressure transmission under rain infiltration in a soil layer

NASA Astrophysics Data System (ADS)

Yang, S. Y.; Jan, C. D.

2017-12-01

The vadose zone (or unsaturated zone) denotes the geologic media between ground surface and the water table in situ where the openings, or pores, in the soil (rock) layers are partially filled with water and air. In this landscape, rainwater infiltrates into soils advancing through this vadose zone and could generates a shallow saturation zone at soil bedrock boundary due to permeability contrast. This saturation zone leads to downslope shallow subsurface storm runoff that contributes to a part of saturation overland flow, dominating water reaching river channels. Hence, unsaturated processes (e.g., rain infiltration) is an important issue that can determine the timing and magnitude of positive pore pressure and discharge peaks, and the characteristics of runoff, water chemistry, hillslope stability is also tie to the processes. In this study, we investigated the transmission of pore pressure evolution in the vadose zone for diverse soil materials based on poroelasticity theory. Commonly, a traditional way is to utilize the Richard's equation to predict pore pressure evolution under unsaturated rain infiltration, ignoring the inertial effect on the process. Here we relax this limitation and propose two reference time tk and tep that can represent the arriving time at a certain depth of wave propagation and dissipation, respectively. Form ground surface to a depth of 1 m, tk has significant differences under nearly unsaturated conditions for diverse soil properties; however, no evident variations in tk can be observed under nearly saturated conditions. Values of tep for loose, cohesionless soils are much greater but decreases to the smallest one (within 1 day) than those for other soil properties under a nearly saturated condition. Results indicate that transient pore pressure transmission is mainly dominated by dynamic wave propagation but the effect of dissipation could become more important with increase in water saturation.

SIMS analyses of minor and trace element distributions in fracture calcite from Yucca Mountain, Nevada, USA

NASA Astrophysics Data System (ADS)

Denniston, Rhawn F.; Shearer, Charles K.; Layne, Graham D.; Vaniman, David T.

1997-05-01

Fracture-lining calcite samples from Yucca Mountain, Nevada, obtained as part of the extensive vertical sampling in studies of this site as a potential high-level waste repository, have been characterized according to microbeam-scale (25-30 μm) trace and minor element chemistry, and cathodoluminescent zonation patterns. As bulk chemical analyses are limited in spatial resolution and are subject to contamination by intergrown phases, a technique for analysis by secondary ion mass spectrometry (SIMS) of minor (Mn, Fe, Sr) and trace (REE) elements in calcite was developed and applied to eighteen calcite samples from four boreholes and one trench. SIMS analyses of REE in calcite and dolomite have been shown to be quantitative to abundances < 1 × chondrite. Although the low secondary ion yields associated with carbonates forced higher counting times than is necessary in most silicates, Mn, Fe, Sr, and REE analyses were obtained with sub-ppm detection limits and 2-15% analytical precision. Bulk chemical signatures noted by Vaniman (1994) allowed correlation of minor and trace element signatures in Yucca Mountain calcite with location of calcite precipitation (saturated vs. unsaturated zone). For example, upper unsaturated zone calcite exhibits pronounced negative Ce and Eu anomalies not observed in calcite collected below in the deep unsaturated zone. These chemical distinctions served as fingerprints which were applied to growth zones in order to examine temporal changes in calcite crystallization histories; analyses of such fine-scale zonal variations are unattainable using bulk analytical techniques. In addition, LREE (particularly Ce) scavenging of calcite-precipitating solutions by manganese oxide phases is discussed as the mechanism for Ce-depletion in unsaturated zone calcite.

Hydrocarbon Plume Dynamics in the Worldś Most Spectacular Hydrocarbon Seeps, Santa Barbara Channel, California

NASA Astrophysics Data System (ADS)

Mau, S.; Reed, J.; Clark, J.; Valentine, D.

2006-12-01

Large quantities of natural gas are emitted from the seafloor into the coastal ocean near Coal Oil Point, Santa Barbara Channel (SBC), California. Methane, ethane, and propane were quantified in the surface water at 79 stations in a 270 km2 area in order to map the surficial hydrocarbon plume and to quantify air-sea exchange of these gases. A time series was initiated for 14 stations to identify the variability of the mapped plume, and biologically-mediated oxidation rates of methane were measured to quantify the loss of methane in surface water. The hydrocarbon plume was found to comprise ~70 km2 and extended beyond study area. The plume width narrowed from 3 km near the source to 0.7 km further from the source, and then expanded to 6.7 km at the edge of the study area. This pattern matches the cyclonic gyre which is the normal current flow in this part of the Santa Barbara Channel - pushing water to the shore near the seep field and then broadening the plume while the water turns offshore further from the source. Concentrations of gaseous hydrocarbons decrease as the plume migrates. Time series sampling shows similar plume width and hydrocarbon concentrations when normal current conditions prevail. In contrast, smaller plume width and low hydrocarbon concentrations were observed when an additional anticyclonic eddy reversed the normal current flow, and a much broader plume with higher hydrocarbon concentrations was observed during a time of diminished speed within the current gyre. These results demonstrate that surface currents control hydrocarbon plume dynamics in the SBC, though hydrocarbon flux to the atmosphere is likely less dependent on currents. Estimates of air- sea hydrocarbon flux and biological oxidation rates will also be presented.

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.

Molecular characterization of organosulfates in organic aerosols from Shanghai and Los Angeles urban areas by nanospray-desorption electrospray ionization high-resolution mass spectrometry.

PubMed

Tao, Shikang; Lu, Xiaohui; Levac, Nicole; Bateman, Adam P; Nguyen, Tran B; Bones, David L; Nizkorodov, Sergey A; Laskin, Julia; Laskin, Alexander; Yang, Xin

2014-09-16

Fine aerosol particles in the urban areas of Shanghai and Los Angeles were collected on days that were characterized by their stagnant air and high organic aerosol concentrations. They were analyzed by nanospray-desorption electrospray ionization mass spectrometry with high mass resolution (m/Δm = 100,000). Solvent mixtures of acetonitrile and water and acetonitrile and toluene were used to extract and ionize polar and nonpolar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. A majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates that were detected at two locations have distinctly different molecular characteristics. Specifically, the organosulfates in the Los Angeles sample were dominated by biogenic products, while the organosulfates of a yet unknown origin found in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degrees of oxidation and unsaturation. The use of the acetonitrile and toluene solvent facilitated the observation of this type of organosulfates, which suggests that they could have been missed in previous studies that relied on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the uncommon organosulfates suggest that they may act as surfactants and plausibly affect the surface tension and hygroscopicity of atmospheric particles. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in the liquid phase could be the formation pathway of these special organosulfates. Long-chain alkanes from vehicle emissions might be their precursors.

Rapid Reconnaissance Mapping of Volatile Organic Compounds by Photoionization Detection at the USGS Amargosa Desert Research Site

NASA Astrophysics Data System (ADS)

Thordsen, J. J.; Stonestrom, D. A.; Conaway, C. H.; Luo, W.; Baker, R. J.; Andraski, B. J.

2015-12-01

Two types of handheld photoionization detectors were evaluated in April 2015 for reconnaissance mapping of volatile organic compounds (VOCs) in the unsaturated zone surrounding legacy disposal trenches for commercial low-level radioactive waste near Beatty, Nevada (USA). This method is rapid and cost effective when compared to the more conventional procedure used ate the site, where VOCs are collected on sorbent cartridges in the field followed by thermal desorption, gas chromatographic separation, and quantitation by mass spectroscopy in the laboratory (TD-GC-MS analysis). Using the conventional method, more than sixty distinct compounds have been identified in the 110-m deep unsaturated zone vapor phase, and the changing nature of the VOC mix over a 15-yr timeframe has been recorded. Analyses to date have identified chlorofluorocarbons (CFCs), chlorinated ethenes, chlorinated ethanes, gasoline-range hydrocarbons, chloroform, and carbon tetrachloride as the main classes of VOCs present. The VOC plumes emanating from the various subgroups of trenches are characterized by different relative abundances of the compound classes, and total VOC concentrations that cover several orders of magnitude. One of the photoionization detectors, designed for industrial compliance testing, lacked sufficient dynamic range and sensitivity to be useful. The other, a wide range (1 ppb-20,000 ppm) research-grade instrument with a 10.6 eV photoionization detector (PID) lamp, produced promising results, detecting roughly half of the non-CFC VOCs present. The rapid and inexpensive photoionization method is envisioned as a screening tool to supplement, expedite, and direct the collection of additional samples for TD-GC-MS analyses at this and other VOC-contaminated sites.

Experimental Study on Shear Strength of Unsaturated Loess Based on Different Water Content in Xining Area

NASA Astrophysics Data System (ADS)

guibo, Bao; hui, Li; yu, Zhang; wuyu, Zhang; ningshan, Jiang

2018-05-01

Today, the study of shear strength of unsaturated soils has become a hot topic in unsaturated soil mechanics research. There are any number of factors affecting the strength of unsaturated soils. Among these factors, the moisture content has the most significant effect on the shear strength. In this paper, unsaturated loess in Xining is taken as the research object, the triaxial test without consolidation and undrain is used to determine the shear strength and its parameters under the condition of different water content, then the relationship between unsaturated loess’ water content and shear strength parameters is explored, and curve fitting is performed. The relevantily approximate mathematics formulas are obtained. The study can provide strength parameter for slope stability and foundation pit support in Xining.

Biota: sediment partitioning of aluminium smelter related PAHs and pulp mill related diterpenes by intertidal clams at Kitimat, British Columbia.

PubMed

Yunker, Mark B; Lachmuth, Cara L; Cretney, Walter J; Fowler, Brian R; Dangerfield, Neil; White, Linda; Ross, Peter S

2011-09-01

The question of polycyclic aromatic hydrocarbon (PAH) bioavailability and its relationship to specific PAH sources with different PAH binding characteristics is an important one, because bioavailability drives PAH accumulation in biota and ultimately the biochemical responses to the PAH contaminants. The industrial harbour at Kitimat (British Columbia, Canada) provides an ideal location to study the bioavailability and bioaccumulation of sediment hydrocarbons to low trophic level biota. Samples of soft shell clams (Mya arenaria) and intertidal sediment collected from multiple sites over six years at various distances from an aluminium smelter and a pulp and paper mill were analysed for 106 PAHs, plant diterpenes and other aromatic fraction hydrocarbons. Interpretation using PAH source ratios and multivariate data analysis reveals six principal hydrocarbon sources: PAHs in coke, pitch and emissions from anode combustion from the aluminium smelter, vascular plant terpenes and aromatised terpenes from the pulp and paper mill, petroleum PAHs from shipping and other anthropogenic activities and PAHs from natural plant detritus. Harbour sediments predominantly contain either pitch or pyrogenic PAHs from the smelter, while clams predominantly contain plant derived PAHs and diterpenes from the adjacent pulp mill. PAHs from the smelter have low bioavailability to clams (Biota-Sediment Accumulation Factors; BSAFs <1 for pitch and coke; <10 for anode combustion, decreasing to ∼0.1 for the mass 300 and 302 PAHs), possibly due to binding to pitch or soot carbon matrices. Decreases in PAH isomer ratios between sediments and clams likely reflect a combination of variation in uptake kinetics of petroleum PAHs and compound specific metabolism, with the importance of petroleum PAHs decreasing with increasing molecular weight. Plant derived compounds exhibit little natural bioaccumulation at reference sites, but unsaturated and aromatised diterpenes released from resins by industrial pulping processes are readily accumulated by the clams (BSAFs >500). Thus while most of the smelter associated PAHs in sediments may not be bioavailable to benthic organisms, the plant terpenes (including retene, totarol, ferruginol, manool, dehydroabietane and other plant terpenes that form the chemical defence mechanism of conifers) released by pulp mills are bioavailable and possess demonstrated toxic properties. The large scale release of plant terpenes by some of the many pulp mills located in British Columbia and elsewhere represents a largely undocumented risk to aquatic biota. Copyright © 2011 Elsevier Ltd. All rights reserved.

Electrokinetic electrode system for extraction of soil contaminants from unsaturated soils

DOEpatents

Lindgren, Eric R.; Mattson, Earl D.

1995-01-01

There is presented an electrokinetic electrode assembly for use in extraction of soil contaminants from unsaturated soil in situ. The assembly includes a housing for retaining a liquid comprising an electrolyte solution, pure water, and soil water, the housing being in part of porous material capable of holding a vacuum. An electrode is mounted in the housing. The housing is provided with a vacuum orifice for effecting a vacuum within the housing selectively to control flow of soil water through the housing into the chamber and to control outflow of the liquid from the chamber. The assembly further includes conduit means for removing the liquid from the housing and returning the electrolyte solution to the housing, and a conduit for admitting pure water to the housing. There is further presented an electrode system and method for extraction of soil contaminants, the system and method utilizing at least two electrode assemblies as described above.

Electrokinetic electrode system for extraction of soil contaminants from unsaturated soils

DOEpatents

Lindgren, E.R.; Mattson, E.D.

1995-07-25

An electrokinetic electrode assembly is described for use in extraction of soil contaminants from unsaturated soil in situ. The assembly includes a housing for retaining a liquid comprising an electrolyte solution, pure water, and soil water, the housing being in part of porous material capable of holding a vacuum. An electrode is mounted in the housing. The housing is provided with a vacuum orifice for effecting a vacuum within the housing selectively to control flow of soil water through the housing into the chamber and to control outflow of the liquid from the chamber. The assembly further includes conduit means for removing the liquid from the housing and returning the electrolyte solution to the housing, and a conduit for admitting pure water to the housing. An electrode system and method are also revealed for extraction of soil contaminants. The system and method utilize at least two electrode assemblies as described above. 5 figs.

Cage Occupation of Light Hydrocarbons in Gas Hydrate Crystals

NASA Astrophysics Data System (ADS)

Kida, M.; Watanabe, M.; Konno, Y.; Yoneda, J.; Jin, Y.; Nagao, J.

2016-12-01

Naturally occurring gas hydrates in marine or permafrost environments can trap methane and heavier hydrocarbons within its host lattice structure built up with hydrogen-bonded water molecules. Naturally occurring gas hydrates have been expected as new natural gas resources. It is important to reveal the distribution of guest hydrocarbons in host hydrate framework from viewpoint of assessment of gas capacity. In this study, we assessed cage occupancies of guest hydrocarbons in host hydrate framework of synthetic and natural gas hydrates using solid-state 13C NMR technique. As synthetic samples, gas hydrates formed from gas mixtures including C1 to C5 were investigated. As a natural sample, the pore-space gas hydrate sample recovered from the eastern Nankai Trough area during the 2012 JOGMEC/JAPEX Pressure coring operation was studied. As a result, it revealed that all heavier hydrocarbons than ethane are preferentially incorporated into the larger cage cavities in hydrate frameworks. We performed this study as a part of a Japanese National hydrate research program (MH21, funded by METI).

Thermal Decomposition of Methyl Esters in Biodiesel Fuel: Kinetics, Mechanisms and Products

NASA Astrophysics Data System (ADS)

Chai, Ming

Biodiesel continues to enjoy increasing popularity. However, recent studies on carbonyl compounds emissions from biodiesel fuel are inconclusive. Emissions of carbonyl compounds from petroleum diesel fuels were compared to emissions from pure biodiesel fuels and petroleum-biodiesel blends used in a non-road diesel generator. The concentration of total carbonyl compounds was the highest when the engine was idling. The carbonyl emissions, as well as ozone formation potential, from biodiesel fuel blends were higher than those emitted from petroleum diesel fuel. The sulfur content of diesel fuel and the source of biodiesel fuel were not found to have a significant impact on emissions of carbonyl compounds. Mechanism parameters of the thermal decomposition of biodiesel-range methyl esters were obtained from the results of thermal gravimetric analysis (TGA). The overall reaction orders are between 0.49 and 0.71 and the energies of activation are between 59.9 and 101.3 kJ/mole. Methyl esters in air have lower activation energies than those in nitrogen. Methyl linoleate has the lowest activation energy, followed by methyl oleate, and methyl stearate. The pyrolysis and oxidation of the three methyl esters were investigated using a semi-isothermal tubular flow reactor. The profiles of major products versus reaction temperature are presented. In the pyrolysis of methyl stearate, the primary reaction pathway is the decarboxylic reaction at the methyl ester functional group. Methyl oleate's products indicate more reactions on its carbon-carbon double bond. Methyl linoleate shows highest reactivity among the three methyl esters, and 87 products were detected. The oxidation of three methyl esters resulted in more products in all compound classes, and 55, 114, and 127 products were detected, respectively. The oxidation of methyl esters includes decarboxylation on ester group. The methyl ester's carbon chain could be oxidized as a hydrocarbon compound and form oxidized esters and unsaturated esters, which have been observed in methyl ester's oxidation products. The oxidation of methyl stearate, methyl oleate and methyl linoleate produces 16, 28 and 34 types of carbonyl compounds, respectively. The unsaturated methyl ester forms more carbonyl compounds compared to the saturated methyl ester, which indicates the formation of carbonyl compounds might be more related to the unsaturated carbon bond rather than the methyl ester group. Good agreement between results for total carbon (TC) generally has been found, but the organic and elemental carbon (OC and EC) fractions determined by different methods often disagree. Lack of reference materials has impeded progress on method standardization and understanding method biases. As part of this dissertation, uniform carbon distribution for the filter sets is prepared by using a simply aerosol generation and collection method. The relative standard deviations for the mean TC, OC, and EC results reported by the seven laboratories were below 10%, 11% and 12% (respectively). The method of filter generation is generally applicable and reproducible. Depending on the application, different filter loadings and types of OC materials can be employed. Matched filter sets prepared by this approach can be used for determining the accuracy of various OC-EC methods and thereby contribute to method standardization.

Experimental and theoretical simulations of Titan's VUV photochemistry

NASA Astrophysics Data System (ADS)

Peng, Z.; Carrasco, N.; Pernot, P.

2013-12-01

A new reactor, named APSIS (Atmospheric Photochemistry SImulated by Synchrotron), has been designed to simulate planetary atmospheric photochemistry [Peng et al. JGR-E. 2013, 118, 778]. We report here a study focusing on Titan's upper atmosphere. A nitrogen-methane gas flow was irradiated by a continuous 60-350 nm VUV beam provided by the DISCO line at SOLEIL synchrotron radiation facility. The production of C2-C4 hydrocarbons as well as several nitriles (HCN, CH3 CN and C2N2) was detected by in situ mass spectrometry, in agreement with Cassini's INMS observations at Titan, and ex situ GC-MS of a cryogenic experiment. We compared the mass spectra with those obtained by a plasma experiment [Carrasco et al. Icarus. 2012, 219, 230] and with another synchrotron-based experiment [Imanaka and Smith. PNAS. 2010, 107, 12423], and with the in situ measurements of the INMS instrument onboard Cassini probing the neutral content of Titan's upper atmosphere. In spite of lower photochemical production efficiency and different environmental conditions, the APSIS reactor seems to simulate Titan's neutral composition rather well. To interpret these experimental data, we developed a fully coupled ion-neutral photochemical model of the reactor, with uncertainty management, based on the neutral model of Hébrard et al. [J. Photochem. Photobiol. A. 2006, 7, 211], the model of ion chemistry of Plessis et al. [J. Chem. Phys. 2010, 133, 134110], and a new representation of photolysis cross-sections and branching ratios [Gans et al. Icarus. 2013, 223, 330]. Compared to the measurements, the production in Cn blocks is in good agreement. Ion chemistry and the full dissociative recombination scheme have been demonstrated to be important features of the model. The photolysis was confirmed to be globally influential by sensivity analysis. We observed the importance of the addition of small (C1 or C2) units in molecular growth, as well as 3 growth families, promoted by C2H2, C2H4 and C2H5/C2H6, respectively. Among the three, the C2H2 family, in which the growth pathways of unsaturated species via ion chemistry are the most efficient, is clearly prominent. Our model was also used to interpret the results of the INMS data and Imanaka and Smith's experiments. Through variants of the reference model of the APSIS experiments, we showed that low pressure and low temperature favor the growth of unsaturated species. These conditions are fulfilled in Titan's ionosphere. The INMS neutral spectrum, in which there is mainly the signal of unsaturated species, can be well reproduced by our simulated MS. Compared to the experimental MS of the APSIS experiments and Imanaka and Smith's experiments, the simulated MS systematically underestimate the intensities of the saturated part of each band. After the consideration of the recombinations catalyzed by the reactor's walls, we improved the simulated MS significantly. This suggests the existence of wall effects in the laboratory simulation setups of atmospheric chemistry, leading to an overestimation of the saturated products compared to Titan's chemical products.

Mechanistic Insights on the Hydrogenation of α,β-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts

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

Ide, Matthew S.; Hao, Bing; Neurock, Matthew

The selective hydrogenation of unsaturated ketones (methyl vinyl ketone and benzalacetone) and unsaturated aldehydes (crotonaldehyde and cinnamaldehyde) was carried out with H₂ at 2 bar absolute over Pd/C, Pt/C, Ru/C, Au/C, Au/TiO₂, or Au/Fe₂O₃ catalysts in ethanol or water solvent at 333 K. Comparison of the turnover frequencies revealed Pd/C to be the most active hydrogenation catalyst, but the catalyst failed to produce unsaturated alcohols, indicating hydrogenation of the C=C bond was highly preferred over the C=O bond on Pd. The Pt and Ru catalysts were able to produce unsaturated alcohols from unsaturated aldehydes, but not from unsaturated ketones. Althoughmore » Au/ Fe₂O₃ was able to partially hydrogenate unsaturated ketones to unsaturated alcohols, the overall hydrogenation rate over gold was the lowest of all of the metals examined. First-principles density functional theory calculations were therefore used to explore the reactivity trends of methyl vinyl ketone (MVK) and benzalacetone (BA) hydrogenation over model Pt(111) and Ru(0001) surfaces. The observed selectivity over these metals is likely controlled by the significantly higher activation barriers to hydrogenate the C=O bond compared with those required to hydrogenate the C=C bond. Both the unsaturated alcohol and the saturated ketone, which are the primary reaction products, are strongly bound to Ru and can react further to the saturated alcohol. The lower calculated barriers for the hydrogenation steps over Pt compared with Ru account for the higher observed turnover frequencies for the hydrogenation of MVK and BA over Pt. The presence of a phenyl substituent α to the C=C bond in BA increased the barrier for C=C hydrogenation over those associated with the C=C bond in MVK; however, the increase in barriers with phenyl substitution was not adequate to reverse the selectivity trend.« less

Development of a Novel Leak-Free Constant-Pressure Cylinder for Certified Reference Materials of Liquid Hydrocarbon Mixtures.

PubMed

Kim, Yong Doo; Kang, Ji Hwan; Bae, Hyun Kil; Kang, Namgoo; Oh, Sang Hyub; Lee, Jin-Hong; Woo, Jin Chun; Lee, Sangil

2017-11-21

Liquid hydrocarbon mixtures such as liquefied petroleum gas and liquefied natural gas are becoming integral parts of the world's energy system. Certified reference materials (CRMs) of liquid hydrocarbon mixtures are necessary to allow assessment of the accuracy and traceability of the compositions of such materials. A piston-type constant-pressure cylinder (PCPC) comprising chambers for a pressurizing gas (helium) and liquid (hydrocarbons) separated by a piston can be used to develop accurate and traceable liquid hydrocarbon mixture CRMs. The development of accurate CRMs relies on the maintenance of their composition. However, a PCPC might allow hydrocarbons to leak owing to the imperfect seal of the piston. In this study, a novel leak-free bellows-type constant-pressure cylinder (BCPC) is designed and evaluated by comparison with PCPCs. Liquid hydrocarbon mixtures consisting of ethane, propane, propene, isobutane, n-butane, 1-butene, and isopentane were prepared in both types of constant pressure cylinders and then monitored to check leakages between the gas and liquid chambers. Overall, notable leakage occurred from and into both chambers in the PCPCs, whereas no leakage occurred in the BCPCs in the three months after their gravimetric preparation. The BCPCs maintained no leakage even 10 months after their preparation, whereas the PCPCs showed significantly increasing leakage during the same period.

Shale characterization on Barito field, Southeast Kalimantan for shale hydrocarbon exploration

NASA Astrophysics Data System (ADS)

Sumotarto, T. A.; Haris, A.; Riyanto, A.; Usman, A.

2017-07-01

Exploration and exploitation in Indonesia now are still focused on conventional hydrocarbon energy than unconventional hydrocarbon energy such as shale gas. Tanjung Formation is a source rock of Barito Basin located in South Kalimantan that potentially as shale hydrocarbon. In this research, integrated methods using geochemical analysis, mineralogy, petrophysical analysis and seismic interpretation has been applied to explore the shale hydrocarbon potential in Barito Field for Tanjung formation. The first step is conducting geochemical and mineralogy analysis to the shale rock sample. Our analysis shows that the organic richness is ranging from 1.26-5.98 wt.% (good to excellent) with the depth of early mature window of 2170 m. The brittleness index is in an average of 0.44-0.56 (less Brittle) and Kerogen type is classified into II/III type that potentially produces oil and gas. The second step is continued by performing petrophysical analysis, which includes Total Organic Carbon (TOC) calculation and brittleness index continuously. The result has been validated with a laboratory measurement that obtained a good correlation. In addition, seismic interpretation based on inverted acoustic impedance is applied to map the distributions of shale hydrocarbon potential. Our interpretation shows that shale hydrocarbon potential is localized in the eastern and southeastern part of the study area.

Assessment of nonpoint-source contamination of the High Plains Aquifer in south-central Kansas, 1987

USGS Publications Warehouse

Helgesen, John O.; Stullken, Lloyd E.; Rutledge, A.T.

1992-01-01

Ground-water quality was assessed in a 5,000-square-mile area of the High Plains aquifer in south-central Kansas that is susceptible to nonpoint-source contamination from agricultural and petroleum-production activities. Of particular interest were agricultural chemicals, mainly atrazine, and oil-derived hydrocarbons, which might occur in association with brines that formerly were disposed into unlined ponds.Random sampling of ground water was done within a framework of discrete land-use areas (irrigated cropland, petroleum-production land containing former brine-disposal ponds, and undeveloped rangeland) of 3 to 10 square miles. Although true baseline water-quality conditions probably are rare, these baseline conditions are represented most closely by ground water beneath the areas of undeveloped rangeland. The sampling design enabled statistical hypothesis testing of the effects of land use, unsaturated-zone lithology, and type of well sampled. Statistical testing was based on nonparametric procedures.Results indicate that regional ground-water quality has been affected by prevailing land-use activities, as shown mainly by increased concentrations of several inorganic constituents. Ground water beneath irrigated cropland is characterized by significantly (95-percent confidence level) larger concentrations of hardness, alkalinity, calcium, magnesium, potassium, fluoride, and nitrite plus nitrate than is water beneath undeveloped rangeland. Nondegraded pesticides generally were not detected in the aquifer, probably because of degradation and sorption. Atrazine is present locally in ground water in small concentrations.Ground water beneath petroleum-production land is characterized by significantly (95-percent confidence level) larger concentrations of hardness, alkalinity, dissolved solids, sodium, and chloride than is water beneath undeveloped rangeland. Nonpoint-source ground-water contamination by oil-derived hydrocarbons was not discernible. The occurrences of trace-organic compounds were similar between petroleum-production land and undeveloped rangeland, which indicates a natural origin for these compounds.The unsaturated zone in the study area is lithologically heterogeneous and contains substantial amounts of clay that inhibit the downward movement of water and solutes. Within the aquifer, the rate of regional lateral flow and solute transport is sufficiently slow so that the ground-water quality reflects overlying land use in discrete areas of several square miles. Regional flow, however, is sufficiently rapid so that the type of well sampled is not important in regional characterization of water quality beneath irrigated cropland; the seasonal pumping of irrigation wells does not appear to divert regional flow enough to cause substantial local anomalies of more mineralized ground water.

Towards improved estimation of the unsaturated soil hydraulic conductivity in the near saturated range by a fully automated, pressure controlled unit gradient experiment.

NASA Astrophysics Data System (ADS)

Werisch, Stefan; Müller, Marius

2017-04-01

Determination of soil hydraulic properties has always been an important part of soil physical research and model applications. While several experiments are available to measure the water retention of soil samples, the determination of the unsaturated hydraulic conductivity is often more complicated, bound to strong assumption and time consuming. Although, the application of unit gradient experiments is recommended since the middle of the last century, as one method towards a (assumption free) direct measurement of the unsaturated hydraulic conductivity, data from unit gradient experiments is seldom to never reported in literature. We developed and build a fully automated, pressure controlled, unit gradient experiment, which allows a precise determination of the unsaturated soil hydraulic conductivity K(h) and water retention VWC(h), especially in the highly dynamic near saturated range. The measurement apparatus applies the concept of hanging water columns and imposes the required soil water pressure by dual porous plates. This concepts allows the simultaneous and direct measurement of water retention and hydraulic conductivity. Moreover, this approach results in a technically less demanding experiment than related flux controlled experiments, and virtually any flux can be measured. Thus, both soil properties can be measured in mm resolution, for wetting and drying processes, between saturation and field capacity for all soil types. Our results show, that it is important to establish separate measurements of the unsaturated hydraulic conductivity in the near saturated range, as the shape of the retention function and hydraulic conductivity curve do not necessarily match. Consequently, the prediction of the hydraulic conductivity curve from measurements of the water retention behavior in combination with a value for the saturated hydraulic conductivity can be misleading. Thus, separate parameterizations of the individual functions might be necessary and are possible with this approach. Furthermore, the apparatus allows a convenient quantification of temperature effects on both hydraulic properties and first results demonstrate impressively the important role of temperature on hydraulic conductivity, which is notoriously underestimated.

Methanol and ethanol conversion into hydrocarbons over H-ZSM-5 catalyst

NASA Astrophysics Data System (ADS)

Hamieh, S.; Canaff, C.; Tayeb, K. Ben; Tarighi, M.; Maury, S.; Vezin, H.; Pouilloux, Y.; Pinard, L.

2015-07-01

Ethanol and methanol are converted using H-ZSM-5 zeolite at 623 K and 3.0 MPa into identical hydrocarbons (paraffins, olefins and aromatics) and moreover with identical selectivities. The distribution of olefins as paraffins follows the Flory distribution with a growth probability of 0.53. Regardless of the alcohol, the catalyst lifetime and selectivity into hydrocarbons C3+ are high in spite of an important coke content. The coke that poisons the Brønsted acid sites without blocking their access is composed in part of radical polyalkylaromatics. The addition of hydroquinone, an inhibitor of radicals, to the feed, provokes an immediate catalyst deactivation.

Comparison of methods for hydrocarbon analysis of marine biota

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

Gritz, R.L.; Shaw, D.G.

1977-04-01

A comparison was made of several procedures for the isolation of hydrocarbons from other matter and for the fractionation of hydrocarbons according to chemical type. The efficiency of Soxhlet extraction followed by saponification with extraction by alkaline digestion (direct saponification) was compared using two hour and 24 hour reaction times. All procedures were performed on approximately 60 g of soft parts of Saxidomus gigantea (butter clam). The 24 hour saponification and column chromatography on partially deactivated columns constituted the best procedure tested. Soxhlet extraction followed by two hour saponification did not completely remove methyl esters and was the most laboriousmore » technique. Direct two hour saponification was also questionable in the removal of esters and led to severe emulsion problems. The recoveries of hydrocarbons by the three procedures was substantially the same.« less

Chemistry in the Dunes of Titan: Tribochemical Reactions of Complex Organics and Water Ice

NASA Astrophysics Data System (ADS)

Beauchamp, J. L.; Thomas, D. A.

2010-12-01

Titan’s N2-CH4 atmosphere provides the starting material for a wide array of organic compounds to be formed via photochemistry, and the presence of unsaturated hydrocarbon, amine, and polycyclic aromatic species has been supported by data from the Cassini-Huygens mission [1,2]. Production of tholins by UV irradiation of a simulated N2-CH4 environment has yielded products that match the observed optical properties of Titan haze, suggesting that these compounds provide suitable analogs to Titan aerosol compounds [3, 4, 5]. Organics produced in Titan’s atmosphere eventually settle to the surface and very likely contribute to the particulate matter comprising the expansive longitudinal dune features observed at mid-latitudes [6]. Once on the surface, conditions that lead to incorporation of oxygen via contact with water ice or liquid water in Titan’s low temperature environment are of particular interest and have important implications for astrobiology [7; 8]. In this work, we postulate that the mechanical energy from wind-driven grains in the dunes of Titan can ultimately drive chemical processes and lead to the incorporation of oxygen into organic compounds via tribochemical reactions [9] and describe experiments designed to test this hypothesis. While the exact composition of the dunes of Titan is unknown, it is likely that they mainly comprise organic and water ice particles approximately 0.2 mm in diameter, the ideal size for saltation by the winds of Titan [6]. During the saltation process, organic particles undergo charging due to friction between particles, leading in turn to formation of ions and free radicals in localized electrical discharges at particle interfaces [10]. These reactive intermediates can initiate processes such as free radical and ionic polymerization that further transform organics. Of particular interest is the incorporation of oxygen into organic molecules, providing a pathway to the synthesis of biologically relevant compounds. Experiments modeling such systems are being conducted with laboratory-produced tholins and model unsaturated hydrocarbons, nitriles, imines, and aromatic compounds, and the results and implications of these studies will be presented. 1. Coates, A. J., A. Wellbrock, G. R. Lewis, G. H. Jones, D. T. Young, F. J. Crary, and J. H. Waite Jr (2009), Planet. Space Sci., 57(14-15), 1866-1871. 2. Crary, F. J., B. A. Magee, K. Mandt, J. H. Waite Jr, J. Westlake, and D. T. Young (2009), Planet. Space Sci., 57(14-15), 1847-1856. 3. Khare, B. N., C. Sagan, E. T. Arakawa, F. Suits, T. A. Callcott, and M. W. Williams (1984), Icarus, 60(1), 127-137. 4. Ramirez, S. I., P. Coll, A. da Silva, R. Navarro-González, J. Lafait, and F. Raulin (2002), Icarus, 156(2), 515-529. 5. Imanaka, H., and M. A. Smith (2010), Proc. Natl. Acad. Sci. U.S.A., 107(28), 12423-12428. 6. Lorenz, R. D., et al. (2006), Science, 312(5774), 724-727. 7. O'Brien, D. P., R. D. Lorenz, and J. I. Lunine (2005), Icarus, 173(1), 243-253. 8. Neish, C. D., A. Somogyi, and M. A. Smith (2010), Astrobiology, 10(3), 337-347. 9. Beyer, M. K., and H. Clausen-Schaumann (2005), Chem. Rev., 105(8), 2921-2948. 10. Kajdas, C., and K. Hiratsuka (2009), Proc. Inst. Mech. Eng., Part J, 223(6), 827-848.

LAND AND SEA RESTORATION

EPA Pesticide Factsheets

Technical product bulletin: this bioremediation agent (nutrient additive) for oil spill cleanups can be used on water, soil, or hard surfaces. It will not damage cured asphalt if used as an absorbent for spills. Apply at 1 part to 3 parts hydrocarbon.

40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acids C12-18, C18 unsaturated... Significant New Uses for Specific Chemical Substances § 721.3025 Fatty acids C12-18, C18 unsaturated, C12-18... chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (PMNs...

Fourier transform infrared imaging showing reduced unsaturated lipid content in the hippocampus of a mouse model of Alzheimer's disease.

PubMed

Leskovjan, Andreana C; Kretlow, Ariane; Miller, Lisa M

2010-04-01

Polyunsaturated fatty acids are essential to brain functions such as membrane fluidity, signal transduction, and cell survival. It is also thought that low levels of unsaturated lipid in the brain may contribute to Alzheimer's disease (AD) risk or severity. However, it is not known how accumulation of unsaturated lipids is affected in different regions of the hippocampus, which is a central target of AD plaque pathology, during aging. In this study, we used Fourier transform infrared imaging (FTIRI) to visualize the unsaturated lipid content in specific regions of the hippocampus in the PSAPP mouse model of AD as a function of plaque formation. Specifically, the unsaturated lipid content was imaged using the olefinic =CH stretching mode at 3012 cm(-1). The axonal, dendritic, and somatic layers of the hippocampus were examined in the mice at 13, 24, 40, and 56 weeks old. Results showed that lipid unsaturation in the axonal layer was significantly increased with normal aging in control (CNT) mice (p < 0.01) but remained low and relatively constant in PSAPP mice. Thus, these findings indicate that unsaturated lipid content is reduced in hippocampal white matter during amyloid pathogenesis and that maintaining unsaturated lipid content early in the disease may be critical in avoiding progression of the disease.

Pre-Construction Biogeochemical Analysis of Mercury in Wetlands Bordering the Hamilton Army Airfield (HAAF) Wetlands Restoration Site. Part 2

DTIC Science & Technology

2007-09-01

2004). Hydrophobic organic contaminants ( petroleum hydrocarbons , polynuclear aromatic hydrocarbons , and polychlorinated biphenyls) dissolved in the...Effect of 3.4% GAC contact on the 56-d bioaccumulation of THg and MeHg in Nereis virens...wetland restoration project. The bioaccumulation factor (BAF) values were greater for MeHg than for THg. The THg and MeHg body burdens of Nereis

Measurements of HFC-134a and HCFC-22 in groundwater and unsaturated-zone air: implications for HFCs and HCFCs as dating tracers

USGS Publications Warehouse

Haase, Karl B.; Busenberg, Eurybiades; Plummer, Niel; Casile, Gerolamo; Sanford, Ward E.

2014-01-01

A new analytical method using gas chromatography with an atomic emission detector (GC–AED) was developed for measurement of ambient concentrations of hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) in soil, air, and groundwater, with the goal of determining their utility as groundwater age tracers. The analytical detection limits of HCFC-22 (difluorochloromethane, CHClF2) and HFC-134a (1,2,2,2-tetrafluoroethane, C2H2F4) in 1 L groundwater samples are 4.3 × 10− 1 and 2.1 × 10− 1 pmol kg− 1, respectively, corresponding to equilibrium gas-phase mixing ratios of approximately 5–6 parts per trillion by volume (pptv). Under optimal conditions, post-1960 (HCFC-22) and post-1995 (HFC-134a) recharge could be identified using these tracers in stable, unmixed groundwater samples. Ambient concentrations of HCFC-22 and HFC-134a were measured in 50 groundwater samples from 27 locations in northern and western parts of Virginia, Tennessee, and North Carolina (USA), and 3 unsaturated-zone profiles were collected in northern Virginia. Mixing ratios of both HCFC-22 and HFC-134a decrease with depth in unsaturated-zone gas profiles with an accompanying increase in CO2 and loss of O2. Apparently, ambient concentrations of HCFC-22 and HFC-134a are readily consumed by methanotrophic bacteria under aerobic conditions in the unsaturated zone. The results of this study indicate that soils are a sink for these two greenhouse gases. These observations contradict the previously reported results from microcosm experiments that found that degradation was limited above-ambient HFC-134a. The groundwater HFC and HCFC concentrations were compared with concentrations of chlorofluorocarbons (CFCs, CFC-11, CFC-12, CFC-113) and sulfur hexafluoride (SF6). Nearly all samples had measured HCFC-22 or HFC-134a that were below concentrations predicted by the CFCs and SF6, with many samples showing a complete loss of HCFC-22 and HFC-134a. This study indicates that HCFC-22 and HFC-134a are not conservative as environmental tracers and leaves in question the usefulness of other HCFCs and HFCs as candidate age tracers.

Different stabilities of liposomes containing saturated and unsaturated lipids toward the addition of cyclodextrins.

PubMed

Ikeda, Atsushi; Funada, Rikushi; Sugikawa, Kouta

2016-06-14

Liposomes composed of unsaturated lipids were more stable than those containing saturated lipids toward DMe-β-CDx, DMe-α-CDx and DMe-β-CDx. The Hill coefficient values (n) indicated that the saturated lipid·DMe-CDx complexes had stoichiometric ratios in the range of 1 : 3-1 : 4, while the unsaturated lipid·DMe-CDx complexes had ratios in the range of 1 : 1.5-1 : 3. That is, a cis alkene group in the unsaturated lipids prevented complexation with a second DMe-CDx in the direction toward each acyl chain. Furthermore, the liposomes composed of the unsaturated lipids were much slower to form precipitates upon the addition of α-CDx than those of the saturated lipids. To the best of our knowledge, this is the first example showing that CDxs interact with unsaturated lipids.

Total fatty acid content of the plasma membrane of Saccharomyces cerevisiae is more responsible for ethanol tolerance than the degree of unsaturation.

PubMed

Kim, Hyun-Soo; Kim, Na-Rae; Choi, Wonja

2011-03-01

The effect of change in unsaturated fatty acid composition on ethanol tolerance in Saccharomyces cerevisiae overexpressing ScOLE1 (∆9 fatty acid desaturase gene of S. cerevisiae), CaFAD2 (∆12 fatty acid desaturase gene of Candida albicans), or CaFAD3 (ω3 fatty acid desaturase gene of C. albicans) was examined. ScOLE1 over-expression increased the total unsaturated fatty acid content and enhanced ethanol tolerance, compared with a control strain. In contrast, overexpression of CaFAD2 and CaFAD3, which led to production of linoleic acid (18:2) and α-linolenic acid (18:3), respectively, neither changed total unsaturated fatty acids nor enhanced ethanol tolerance. The total unsaturated fatty acid content rather than the degree of unsaturation is thus an important factor for ethanol tolerance.

Load-Dependent Emission Factors and Chemical Characteristics of IVOCs from a Medium-Duty Diesel Engine.

PubMed

Cross, Eben S; Sappok, Alexander G; Wong, Victor W; Kroll, Jesse H

2015-11-17

A detailed understanding of the climate and air quality impacts of mobile-source emissions requires the characterization of intermediate-volatility organic compounds (IVOCs), relatively-low-vapor-pressure gas-phase species that may generate secondary organic aerosol with high yields. Due to challenges associated with IVOC detection and quantification, IVOC emissions remain poorly understood at present. Here, we describe measurements of the magnitude and composition of IVOC emissions from a medium-duty diesel engine. Measurements are made on an engine dynamometer and utilize a new mass-spectrometric instrument to characterize the load dependence of the emissions in near-real-time. Results from steady-state engine operation indicate that IVOC emissions are highly dependent on engine power, with highest emissions at engine idle and low-load operation (≤25% maximum rated power) with a chemical composition dominated by saturated hydrocarbon species. Results suggest that unburned fuel components are the dominant IVOCs emitted at low loads. As engine load increases, IVOC emissions decline rapidly and become increasingly characterized by unsaturated hydrocarbons and oxygenated organics, newly formed from incomplete combustion processes at elevated engine temperatures and pressures. Engine transients, including a cold-start ignition and engine acceleration, show IVOC emission profiles that are different in amount or composition compared to steady-state combustion, underscoring the utility of characterizing IVOC emissions with high time resolution across realistic engine operating conditions. We find possible evidence for IVOC losses on unheated dilution and sampling surfaces, which need to be carefully accounted for in IVOC emission studies.

Leg tendon glands in male bumblebees ( Bombus terrestris): structure, secretion chemistry, and possible functions

NASA Astrophysics Data System (ADS)

Jarau, Stefan; Žáček, Petr; Šobotník, Jan; Vrkoslav, Vladimír; Hadravová, Romana; Coppée, Audrey; Vašíčková, Soňa; Jiroš, Pavel; Valterová, Irena

2012-12-01

Among the large number of exocrine glands described in bees, the tarsal glands were thought to be the source of footprint scent marks. However, recent studies showed that the compounds used for marking by stingless bees are secreted by leg tendon instead of tarsal glands. Here, we report on the structure of leg tendon glands in males of Bombus terrestris, together with a description of the chemical composition of their secretions and respective changes of both during the males' lives. The ultrastructure of leg tendon glands shows that the secretory cells are located in three independent regions, separated from each other by unmodified epidermal cells: in the femur, tibia, and basitarsus. Due to the common site of secretion release, the organ is considered a single secretory gland. The secretion of the leg tendon glands of B. terrestris males differs in its composition from those of workers and queens, in particular by (1) having larger proportions of compounds with longer chain lengths, which we identified as wax esters; and (2) by the lack of certain hydrocarbons (especially long chain dienes). Other differences consist in the distribution of double bond positions in the unsaturated hydrocarbons that are predominantly located at position 9 in males but distributed at seven to nine different positions in the female castes. Double bond positions may change chemical and physical properties of a molecule, which can be recognized by the insects and, thus, may serve to convey specific information. The function of male-specific compounds identified from their tendon glands remains elusive, but several possibilities are discussed.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds.

PubMed

Wang, Zhandong; Popolan-Vaida, Denisia M; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah Y; Wang, Heng; Sioud, Salim; Raji, Misjudeen A; Kohse-Höinghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R; Sarathy, S Mani

2017-12-12

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500-600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound's molecular structure ( n -alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels. Copyright © 2017 the Author(s). Published by PNAS.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

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

Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability ofmore » liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. In conclusion, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.« less

Membrane lateral compressibility determined by NMR and x-ray diffraction: effect of acyl chain polyunsaturation.

PubMed Central

Koenig, B W; Strey, H H; Gawrisch, K

1997-01-01

The elastic area compressibility modulus, Ka, of lamellar liquid crystalline bilayers was determined by a new experimental approach using 2H-NMR order parameters of lipid hydrocarbon chains together with lamellar repeat spacings measured by x-ray diffraction. The combination of NMR and x-ray techniques yields accurate determination of lateral area per lipid molecule. Samples of saturated, monounsaturated, and polyunsaturated phospholipids were equilibrated with polyethylene glycol (PEG) 20,000 solutions in water at concentrations from 0 to 55 wt % PEG at 30 degrees C. This procedure is equivalent to applying 0 to 8 dyn/cm lateral pressure to the bilayers. The resulting reductions in area per lipid were measured with a resolution of +/-0.2 A2 and the fractional area decrease was proportional to applied lateral pressure. For 1,2-dimyristoyl(d54)-sn-glycero-3-phosphocholine, 1-stearoyl(d35)-2-oleoyl-sn-glycero-3-phosphocholine (SOPC-d35), and 1-stearoyl(d35)-2-docosahexaenoyl-sn-glycero-3-phosphocholine (SDPC-d35) cross-sectional areas per molecule in excess water of 59.5, 61.4, and 69.2 A2 and bilayer elastic area compressibility moduli of 141, 221, and 121 dyn/cm were determined, respectively. Combining NMR and x-ray results enables the determination of compressibility differences between saturated and unsaturated hydrocarbon chains. In mixed-chain SOPC-d35 both chains have similar compressibility moduli; however, in mixed-chain polyunsaturated SDPC-d35, the saturated stearic acid chain appears to be far less compressible than the polyunsaturated docosahexaenoic acid chain. Images FIGURE 3 FIGURE 5 PMID:9336191

Influences of the molecular fuel structure on combustion reactions towards soot precursors in selected alkane and alkene flames.

PubMed

Ruwe, Lena; Moshammer, Kai; Hansen, Nils; Kohse-Höinghaus, Katharina

2018-04-25

In this study, we experimentally investigate the high-temperature oxidation kinetics of n-pentane, 1-pentene and 2-methyl-2-butene (2M2B) in a combustion environment using flame-sampling molecular beam mass spectrometry. The selected C5 fuels are prototypes for linear and branched, saturated and unsaturated fuel components, featuring different C-C and C-H bond structures. It is shown that the formation tendency of species, such as polycyclic aromatic hydrocarbons (PAHs), yielded through mass growth reactions increases drastically in the sequence n-pentane < 1-pentene < 2M2B. This comparative study enables valuable insights into fuel-dependent reaction sequences of the gas-phase combustion mechanism that provide explanations for the observed difference in the PAH formation tendency. First, we investigate the fuel-structure-dependent formation of small hydrocarbon species that are yielded as intermediate species during the fuel decomposition, because these species are at the origin of the subsequent mass growth reaction pathways. Second, we review typical PAH formation reactions inspecting repetitive growth sequences in dependence of the molecular fuel structure. Third, we discuss how differences in the intermediate species pool influence the formation reactions of key aromatic ring species that are important for the PAH growth process underlying soot formation. As a main result it was found that for the fuels featuring a C[double bond, length as m-dash]C double bond, the chemistry of their allylic fuel radicals and their decomposition products strongly influences the combination reactions to the initially formed aromatic ring species and as a consequence, the PAH formation tendency.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

DOE PAGES

Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie; ...

2017-11-28

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability ofmore » liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. In conclusion, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.« less

Unsaturated soil moisture drying and wetting diffusion coefficient measurements in the laboratory.

DOT National Transportation Integrated Search

2009-09-01

ABSTRACTTransient moisture flow in an unsaturated soil in response to suction changes is controlled by the unsaturated moisture diffusion coefficient. The moisture diffusion coefficient can be determined by measuring suction profiles over time. The l...

Hydrology of Yucca Mountain, Nevada

USGS Publications Warehouse

Flint, A.L.; Flint, L.E.; Kwicklis, E.M.; Bodvarsson, G.S.; Fabryka-Martin, J. M.

2001-01-01

Yucca Mountain, located in southern Nevada in the Mojave Desert, is being considered as a geologic repository for high-level radioactive waste. Although the site is arid, previous studies indicate net infiltration rates of 5-10 mm yr-1 under current climate conditions. Unsaturated flow of water through the mountain generally is vertical and rapid through the fractures of the welded tuffs and slow through the matrix of the nonwelded tuffs. The vitric-zeolitic boundary of the nonwelded tuffs below the potential repository, where it exists, causes perching and substantial lateral flow that eventually flows through faults near the eastern edge of the potential repository and recharges the underlying groundwater system. Fast pathways are located where water flows relatively quickly through the unsaturated zone to the water table. For the bulk of the water a large part of the travel time from land surface to the potential repository horizon (~300 m below land surface) is through the interlayered, low fracture density, nonwelded tuff where flow is predominately through the matrix. The unsaturated zone at Yucca Mountain is being modeled using a three-dimensional, dual-continuum numerical model to predict the results of measurements and observations in new boreholes and excavations. The interaction between experimentalists and modelers is providing confidence in the conceptual model and the numerical model and is providing researchers with the ability to plan further testing and to evaluate the usefulness or necessity of further data collection.

High field FT-ICR mass spectrometry for molecular characterization of snow board from Moscow regions.

PubMed

Mazur, Dmitry M; Harir, Mourad; Schmitt-Kopplin, Philippe; Polyakova, Olga V; Lebedev, Albert T

2016-07-01

High field Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry analysis of eight snow samples from Moscow city allowed us to identify more than 2000 various elemental compositions corresponding to regional air pollutants. The hierarchical cluster analysis (HCA) of the data showed good concordance of three main groups of samples with the main wind directions. The North-West group (A1) is represented by several homologous CHOS series of aliphatic organic aerosols. They may form as a result of enhanced photochemical reactions including oxidation of hydrocarbons with sulfonations due to higher amount of SO2 emissions in the atmosphere in this region. Group A2, corresponding to the South-East part of Moscow, contains large amount of oxidized hydrocarbons of different sources that may form during oxidation in atmosphere. These hydrocarbons appear correlated to emissions from traffic, neighboring oil refinery, and power plants. Another family of compounds specific for this region involves CHNO substances formed during oxidation processes including NOx and NO3 radical since emissions of NOx are higher in this part of the city. Group A3 is rich in CHO type of compounds with high H/C and low O/C ratios, which is characteristic of oxidized hydrocarbon-like organic aerosol. CHNO types of compounds in A3 group are probably nitro derivatives of condensed hydrocarbons such as PAH. This non-targeted profiling revealed site specific distribution of pollutants and gives a chance to develop new strategies in air quality control and further studies of Moscow environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Microbial activity in an acid resin deposit: biodegradation potential and ecotoxicology in an extremely acidic hydrocarbon contamination.

PubMed

Kloos, Karin; Schloter, Michael; Meyer, Ortwin

2006-11-01

Acid resins are residues produced in a recycling process for used oils that was in use in the forties and fifties of the last century. The resin-like material is highly contaminated with mineral oil hydrocarbons, extremely acidic and co-contaminated with substituted and aromatic hydrocarbons, and heavy metals. To determine the potential for microbial biodegradation the acid resin deposit and its surroundings were screened for microbial activity by soil respiration measurements. No microbial activity was found in the core deposit. However, biodegradation of hydrocarbons was possible in zones with a lower degree of contamination surrounding the deposit. An extreme acidophilic microbial community was detected close to the core deposit. With a simple ecotoxicological approach it could be shown that the pure acid resin that formed the major part of the core deposit, was toxic to the indigenous microflora due to its extremely low pH of 0-1.

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. 

STRUCTURE TOXICITY IN RELATIONSHIPS FOR A,B-UNSATURATED ALCOHOLS IN FISH

EPA Science Inventory

Previous toxicity testing with fathead minnows (Pimephales promelas) indicated that some unsaturated acetylenic and allylic alcohols can be metabolically activated, via alcohol dehydrogenase, to highly toxic a,B-unsaturated aldehydes and ketones or allene derivatives. lthough sev...

Urban-air-toxics Monitoring Program, 1990

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

Not Available

1991-06-01

From March 1990 through February 1991 samples of ambient air were collected at 12 sites in the eastern part of the U.S. Every 12 days, air was integrated over 24-hour periods into passivated stainless steel canisters. Simultaneously, air was drawn through cartridges containing dinitrophenylhydrazine to collect carbonyl compounds. The samples were analyzed at a central laboratory for a total of 37 halogenated and aromatic hydrocarbons, formaldehyde, acetaldehyde, and other oxygenated species. The hydrocarbon species were analyzed by gas chromatography/multiple detectors and gas chromatography/mass spectrometry, while the carbonyl species were analyzed by liquid chromatography. Complete data for all the hydrocarbon samplesmore » are presented in the report.« less

Method of producing drive fluid in situ in tar sands formations

DOEpatents

Mudunuri, Ramesh Raju; Jaiswal, Namit; Vinegar, Harold J.; Karanikas, John Michael

2010-03-23

Methods of treating a tar sands formation are described herein. Methods for treating a tar sands may include providing heat to at least part of a hydrocarbon layer in the formation from one or more heaters located in the formation. The heat may be allowed to transfer from the heaters to at least a portion of the formation such that a drive fluid is produced in situ in the formation. The drive fluid may move at least some mobilized, visbroken, and/or pyrolyzed hydrocarbons from a first portion of the formation to a second portion of the formation. At least some of the mobilized, visbroken, and/or pyrolyzed hydrocarbons may be produced from the formation.

Stable hydrogen and carbon isotope ratios of extractable hydrocarbons in the Murchison meteorite

NASA Technical Reports Server (NTRS)

Krishnamurthy, R. V.; Epstein, S.; Pizzarello, S.; Cronin, J. R.; Yuen, G. U.

1991-01-01

A fairly fool-proof method to ensure that the compounds isolated from meteorites are truly part of the meteorites and not an artifact introduced by exposure to the terrestrial environment, storage, or handling is presented. The stable carbon and hydrogen isotope ratios in several of the chemical compounds extracted from the Murchison meteorite were measured. The results obtained by studying the amino acids in this meteorite gave very unusual hydrogen and carbon isotope ratios. The technique was extended to the different classes of hydrocarbons and the hydrocarbons were isolated using a variety of separation techniques. The results and methods used in this investigation are described in this two page paper.

Improved solution for saturated-unsaturated flow to a partially penetrating well in a compressible unconfined aquifer

NASA Astrophysics Data System (ADS)

Mishra, P. K.; Neuman, S. P.

2009-12-01

Tartakovsky and Neuman [2007] developed an analytical solution for flow to a partially penetrating well pumping at a constant rate from a compressible unconfined aquifer considering an unsaturated zone of infinite thickness. In their solution three-dimensional, axially symmetric unsaturated flow was described by a linearized version of Richards’ equation in which both relative hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value. Both exponential functions were characterized by a common exponent. We present an improved solution in which relative hydraulic conductivity and water content are characterized by separate parameters and the unsaturated zone has finite thickness. Our four-parameter representation of these functions is more flexible than the three-parameter version of Mathias and Butler [2006], who consider flow in the unsaturated zone to be strictly vertical and the pumping well to be fully penetrating. We investigate the effects of unsaturated zone thickness and constitutive parameters on drawdown in the unsaturated and saturated zones as functions of position and time. We then use our new solution to analyze data from synthetic and real pumping tests.

A Novel Multi-voxel Based Quantitation of Metabolites and Lipids Non-invasively Combined with Diffusion Weighted Imaging in Breast Cancer

DTIC Science & Technology

2011-09-01

SATURATED AND UNSATURATED LIPIDS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON... saturated fatty acid, mono- unsaturated and poly unsaturated fatty acids. 6 Figure 3. Prior-knowledge COSY spectra for the breast metabolites (top...In addition to water, presence of 2D diagonal and cross peaks from the methyl, methylene, and olefenic protons of unsaturated and saturated 8

Determination of Transport Parameters in Unsaturated Zone by Tracer Experiment in the Porous Aquifer located at Ljubljana, Slovenia

NASA Astrophysics Data System (ADS)

Vidmar, S.; Cencur Curk, B.

2009-04-01

The gravel sandy aquifer of Ljubljansko polje is the source of drinking water for nearly 300.000 inhabitants of the Ljubljana city and vicinity. There are two main waterworks: Kleče and Hrastje. The plain area of Ljubljansko polje is a tectonic sink and consists of river sediments that can reach in thickness more than 100 m in the deepest part. The bedrock is the impermeable permocarbonic clayey shale, mudstones and sandstones. The hydraulic conductivity of Ljubljansko polje sediments is very good, from 10-2 m/s in the central part to 3.7•10-3 m/s on the borders of the plain. The average groundwater level is 20 m below surface. A numerical groundwater flow model was established for the wider area of the Ljubljansko polje aquifer. The fore mentioned model was not calibrated on solute transport parameters but only on water levels and this lead to unreliability in the transport model and its predictions of pollution scenarios. The transport model needs to calculate reliable scenarios of pollution dispersion, which can only be achieved with the application of real transport parameters. Human activities in the area of the Hrastje waterworks of Ljubljana threaten to degrade groundwater quality. For this reason several tracer experiments were carried out in the past. Despite a great risk, the experiments were performed on the catchment area of the Hrastje waterworks, inside the second water protection zone. During the experiments the water from Hrastje waterworks was still in use for drinking water supply. The tracer experiments were carried out in order to determine the solute transport parameters such as advection, dispersion and sorption. The research proved that the tracers could be used safely on sensitive area and that the researchers are capable and qualified to carry it out with a highest level of security. Since none of the past tracer experiments, carried out in the same area, gave us any detailed information on pollutant spreading in unsaturated zone a new tracer experiment was performed. Uranine was used as a tracer with a single time injection (1 kg) directly into the unsaturated zone. To achieve no sorption on organic particles the top layer of the ground (approx. 1m) was removed. The concentrations of the tracer spreading were observed in the well which is down gradient (approx. 22m) from the injection point. The tracer experiment was monitored for 305 days with records recorded every 4 minutes. All major events observed from the breakthrough curve, corresponded to rain events with a different delay depending on the water content in the unsaturated zone. When the unsaturated zone contains water the response in the observation well was faster than when the unsaturated zone was dry. The obtained data have been used in an analytical method (Multi-Dispersion-Model (MDM)). This solution provided the following transport parameters: mean transit time, mean velocity, longitudinal dispersion and dispersivity. The obtained parameters from the analytical solution will also be verified in the numerical model. The final results should enable better knowledge of the solute transport parameters and thus a better understanding of pollution dispersion as a help for water supply management system including measures for pollution prevention and as an actions/measure scenario in case of pollution.

On the coupled unsaturated-saturated flow process induced by vertical, horizontal, and slant wells in unconfined aquifers

NASA Astrophysics Data System (ADS)

Liang, Xiuyu; Zhan, Hongbin; Zhang, You-Kuan; Liu, Jin

2017-03-01

Conventional models of pumping tests in unconfined aquifers often neglect the unsaturated flow process. This study concerns the coupled unsaturated-saturated flow process induced by vertical, horizontal, and slant wells positioned in an unconfined aquifer. A mathematical model is established with special consideration of the coupled unsaturated-saturated flow process and the well orientation. Groundwater flow in the saturated zone is described by a three-dimensional governing equation and a linearized three-dimensional Richards' equation in the unsaturated zone. A solution in the Laplace domain is derived by the Laplace-finite-Fourier-transform and the method of separation of variables, and the semi-analytical solutions are obtained using a numerical inverse Laplace method. The solution is verified by a finite-element numerical model. It is found that the effects of the unsaturated zone on the drawdown of a pumping test exist at any angle of inclination of the pumping well, and this impact is more significant in the case of a horizontal well. The effects of the unsaturated zone on the drawdown are independent of the length of the horizontal well screen. The vertical well leads to the largest water volume drained from the unsaturated zone (W) during the early pumping time, and the effects of the well orientation on W values become insignificant at the later time. The screen length of the horizontal well does not affect W for the whole pumping period. The proposed solutions are useful for the parameter identification of pumping tests with a general well orientation (vertical, horizontal, and slant) in unconfined aquifers affected from above by the unsaturated flow process.

Structural requirements for the cytoprotective actions of mono-unsaturated fatty acids in the pancreatic β-cell line, BRIN-BD11

PubMed Central

Dhayal, S; Welters, H J; Morgan, N G

2008-01-01

Background and purpose: Exposure of pancreatic β-cells to long-chain free fatty acids leads to differential responses according to the chain length and degree of unsaturation. In particular, long-chain saturated molecules such as palmitate (C16:0) cause apoptosis, whereas equivalent mono-unsaturated species (for example, palmitoleate (C16:1)) are not overtly toxic. Moreover, mono-unsaturates exert a powerful cytoprotective response against a range of proapoptotic stimuli. However, the structural requirements that determine cytoprotection have not been determined and form the basis of the present study. Experimental approach: BRIN-BD11 and INS-1 β-cells were exposed either to the saturated fatty acid palmitate, or to serum withdrawal, to mediate cytotoxicity. The protective effects of a wide range of mono-unsaturated fatty acid derivatives were tested in cytotoxicity assays. Effector caspase activity was also measured and correlated with viability. Key results: The cytotoxic actions of palmitate were inhibited dose-dependently by long-chain mono-unsaturated fatty acids with a defined potency order C18:1>C16:1≫C14:1. The configuration of the double bond was also important with cis forms being more potent than trans forms. Alkylated mono-unsaturated fatty-acid derivates were also cytoprotective, although their efficacy declined as the alkyl chain length increased. Cytoprotection was achieved rapidly on addition of mono-unsaturates and correlated with a rapid and dramatic inhibition of caspase-3/7 activity in palmitate-treated cells. Conclusions and implications: The data reveal the structural requirements that dictate the cytoprotective actions of mono-unsaturated fatty acids in pancreatic β-cells. Metabolic activation is not required and the data point at the potential involvement of a fatty acid receptor in mediating cytoprotection. PMID:18297101

Studies on unsaturated flow in dual-scale fiber fabrics

NASA Astrophysics Data System (ADS)

Yan, Fei; Yan, Shilin; Li, Yongjing

2018-03-01

Fiber fabrics in liquid composite molding (LCM) can be recognized as a dual-scale structure. As sink theory developed, this unsaturated flow behavior has already been simulated successfully; however, most of simulated results based on a unit cell under ideal status, thus making results were not agreement with experiment. In this study, an experimental method to establish sink function was proposed. After compared the simulation results by this sink function, it shows high accuracy with the experimental data. Subsequently, the key influencing factors for unsaturated flow have been further investigated; results show that the filling time for unsaturated flow was much longer than saturated flow. In addition, the injection pressure and permeability were the key factors lead to unsaturated flow.

THE RETC CODE FOR QUANTIFYING THE HYDRAULIC FUNCTIONS OF UNSATURATED SOILS

EPA Science Inventory

This report describes the RETC computer code for analyzing the soil water retention and hydraulic conductivity functions of unsaturated soils. These hydraulic properties are key parameters in any quantitative description of water flow into and through the unsaturated zone of soil...

Onshore and offshore basins of northeast Libya: Their origin and hydrocarbon potential

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

Shegewi, O.M.

1992-01-01

A comprehensive data base of more than 3000 km of seismic lines, gravity and magnetic data, more than 30 subsurface well logs, and surface geology data were utilized to examine and interpret the sedimentary and tectonic history of the onshore and offshore parts of Northeast Libya and their hydrocarbon potential. The Dernah-Tobruk and Benghazi offshore basins form the northern parts of the study area. The Cyrenaica Stable Platform represents the southern parts. The Sirual Trough stretches E-W and opens into the Antelat Trough in the west. Between these elements is the uplifted areas of the Al Jabal Al Akhdar. Sixmore » principal tectonic phases were responsible for the formation and development of these structural elements: the pre-Mesozoic phase, the Triassic-Jurassic rifting phase, the Neocomian and the Aptian-Albian renewed rifting phases, the Late Cretaceous-Paleocene uplifting phase; and the Eocene-Middle Oligocene rifting phase. Oceanic crust of probable Aptian-Albian age is evident on the seismic lines north of the master fault marking the southern boundary of the rift separating the north African plate and Apulia. The western boundary of the Dernah High displayed clearly NE-SW strike-slip movement of these trajectories. Oceanic crust is also present west of the Dernah High. Positive gravity and magnetic anomalies traverse parallel to the boundary of this oceanic plate Mesogea. The prerequisites for commercial hydrocarbon production are present in abundance. Reservoirs ranging in age from Paleozoic clastics in the Cyrenaica Stable Platform to Mesozoic and Tertiary carbonates throughout the rest of the region. Several deep sites for the generation of hydrocarbons were also present, including the rifted northern parts of the Dernah-Tobruk basin, the Antelat Trough and the Cyrenaica Passive Margin. The Cretaceous and Tertiary section in the study area contain several potential seal rocks. Several potential trap types are also present.« less

Estimating the Spatial Extent of Unsaturated Zones in Heterogeneous River-Aquifer Systems

NASA Astrophysics Data System (ADS)

Schilling, Oliver S.; Irvine, Dylan J.; Hendricks Franssen, Harrie-Jan; Brunner, Philip

2017-12-01

The presence of unsaturated zones at the river-aquifer interface has large implications on numerous hydraulic and chemical processes. However, the hydrological and geological controls that influence the development of unsaturated zones have so far only been analyzed with simplified conceptualizations of flow processes, or homogeneous conceptualizations of the hydraulic conductivity in either the aquifer or the riverbed. We systematically investigated the influence of heterogeneous structures in both the riverbed and the aquifer on the development of unsaturated zones. A stochastic 1-D criterion that takes both riverbed and aquifer heterogeneity into account was developed using a Monte Carlo sampling technique. The approach allows the reliable estimation of the upper bound of the spatial extent of unsaturated areas underneath a riverbed. Through systematic numerical modeling experiments, we furthermore show that horizontal capillary forces can reduce the spatial extent of unsaturated zones under clogged areas. This analysis shows how the spatial structure of clogging layers and aquifers influence the propensity for unsaturated zones to develop: In riverbeds where clogged areas are made up of many small, spatially disconnected patches with a diameter in the order of 1 m, unsaturated areas are less likely to develop compared to riverbeds where large clogged areas exist adjacent to unclogged areas. A combination of the stochastic 1-D criterion with an analysis of the spatial structure of the clogging layers and the potential for resaturation can help develop an appropriate conceptual model and inform the choice of a suitable numerical simulator for river-aquifer systems.

Enhancing Bioremediation of Oil-contaminated Soils by Controlling Nutrient Transport using Dual Characteristics of Soil Pore Structure

NASA Astrophysics Data System (ADS)

Mori, Y.; Suetsugu, A.; Matsumoto, Y.; Fujihara, A.; Suyama, K.; Miyamoto, T.

2012-12-01

Soil structure is heterogeneous with cracks or macropores allowing bypass flow, which may lead to applied chemicals avoiding interaction with soil particles or the contaminated area. We investigated the bioremediation efficiency of oil-contaminated soils by applying suction at the bottom of soil columns during bioremediation. Unsaturated flow conditions were investigated so as to avoid bypass flow and achieve sufficient dispersion of chemicals in the soil column. The boundary conditions at the bottom of the soil columns were 0 kPa and -3 kPa, and were applied to a volcanic ash soil with and without macropores. Unsaturated flow was achieved with -3 kPa and an injection rate of 1/10 of the saturated hydraulic conductivity. The resultant biological activities of the effluent increased dramatically in the unsaturated flow with macropores condition. Unsaturated conditions prevented bypass flow and allowed dispersion of the injected nutrients. Unsaturated flow achieved 60-80% of saturation, which enhanced biological activity in the soil column. Remediation results were better for unsaturated conditions because of higher biological activity. Moreover, unsaturated flow with macropores achieved uniform remediation efficiency from upper through lower positions in the column. Finally, taking the applied solution volume into consideration, unsaturated flow with -3 kPa achieved 10 times higher efficiency when compared with conventional saturated flow application. These results suggest that effective use of nutrients or remediation chemicals is possible by avoiding bypass flow and enhancing biological activity using relatively simple and inexpensive techniques.

Project Summary. THE RETC CODE FOR QUANTIFYING THE HYDRAULIC FUNCTIONS OF UNSATURATED SOILS

EPA Science Inventory

This summary describes the RETC computer code for analyzing the soil water retention and hydraulic conductivity functions of unsaturated soils. These hydraulic properties are key parameters in any quantitative description of water flow into and through the unsaturated zone of soi...

Creating and maintaining a gas cap in tar sands formations

DOEpatents

Vinegar, Harold J.; Karanikas, John Michael; Dinkoruk, Deniz Sumnu; Wellington, Scott Lee

2010-03-16

Methods for treating a tar sands formation are disclosed herein. Methods for treating a tar sands formation may include providing heat to at least part of a hydrocarbon layer in the formation from one or more heaters located in the formation. Pressure may be allowed to increase in an upper portion of the formation to provide a gas cap in the upper portion. At least some hydrocarbons are produced from a lower portion of the formation.

Stratigraphy of the unsaturated zone and uppermost part of the Snake River Plain aquifer at test area north, Idaho National Engineering Laboratory, Idaho

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

Anderson, S.R.; Bowers, B.

1995-06-01

A complex sequence of basalt flows and sedimentary interbeds underlies Test Area North (TAN) at the Idaho National Engineering Laboratory in eastern Idaho. Wells drilled to depths of at least 500 feet penetrate 10 basalt-flow groups and 5 to 10 sedimentary interbeds that range in age from about 940,000 to 1.4 million years. Each basalt-flow group consists of one or more basalt flows from a brief, single or compound eruption. All basalt flows of each group erupted from the same vent, and have similar ages, paleomagnetic properties, potassium contents, and natural-gamma emissions. Sedimentary interbeds consist of fluvial, lacustrine, and eolianmore » deposits of clay, silt, sand, and gravel that accumulated for hundreds to hundreds of thousands of years during periods of volcanic quiescence. Basalt and sediment are elevated by hundreds of feet with respect to rocks of equivalent age south and cast of the area, a relation that is attributed to past uplift at TAN. Basalt and sediment are unsaturated to a depth of about 200 feet below land surface. Rocks below this depth are saturated and make up the Snake River Plain aquifer. The effective base of the aquifer is at a depth of 885 feet below land surface. Detailed stratigraphic relations for the lowermost part of the aquifer in the depth interval from 500 to 885 feet were not determined because of insufficient data. The stratigraphy of basalt-flow groups and sedimentary interbeds in the upper 500 feet of the unsaturated zone and aquifer was determined from natural-gamma logs, lithologic logs, and well cores. Basalt cores were evaluated for potassium-argon ages, paleomagnetic properties, petrographic characteristics, and chemical composition. Stratigraphic control was provided by differences in ages, paleomagnetic properties, potassium content, and natural-gamma emissions of basalt-flow groups and sedimentary interbeds.« less

Pesticide contaminants in selected species of edible wild mushrooms from the north-eastern part of Poland.

PubMed

Gałgowska, Michalina; Pietrzak-Fiećko, Renata

2017-03-04

The aim of this study was to determine the level of chlorinated hydrocarbon residues in selected edible mushrooms from north-eastern Poland. The experiment was carried out on 45 samples consisting of 15 fruiting bodies each of the following species: Boletus edulis, Imleria badia and Cantharellus cibarius. Dried samples were subjected to extraction of lipids with a Soxhlet and a standard procedure-based on the decomposition of lipids by concentrated sulfuric acid and the release of organic insecticides to the hexane layer-was used to determine chlorinated hydrocarbons. The quantitative determination of DDT, DDE, DDD and γ-HCH were conducted using gas chromatography with electron capture detection (GC-ECD). Chlorinated hydrocarbons were found in all tested samples. The contents of these compounds varied between all three species. Mean content of γ-HCH in B. edulis, I. badia and C. cibarius was: 2.60; 4.83; 7.52 µg kg -1 of lipids, while the content of ΣDDT was: 57.02; 25.20; 127.10 µg kg -1 of lipids, respectively. These results show that mushrooms from the north-eastern part of Poland can be used as potential bio-indicators of environmental contamination with chlorinated hydrocarbons. Moreover, the studied fungi could still be used as food due to the low levels of analyzed organochlorine compounds.

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

Tan, Eric; Talmadge, M.; Dutta, Abhijit

The U.S. Department of Energy (DOE) promotes research for enabling cost-competitive liquid fuels production from lignocellulosic biomass feedstocks. The research is geared to advance the state of technology (SOT) of biomass feedstock supply and logistics, conversion, and overall system sustainability. As part of their involvement in this program, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) investigate the economics of conversion pathways through the development of conceptual biorefinery process models. This report describes in detail one potential conversion process for the production of high octane gasoline blendstock via indirect liquefaction (IDL). The steps involve themore » conversion of biomass to syngas via indirect gasification followed by gas cleanup and catalytic syngas conversion to a methanol intermediate; methanol is then further catalytically converted to high octane hydrocarbons. The conversion process model leverages technologies previously advanced by research funded by the Bioenergy Technologies Office (BETO) and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via tar and hydrocarbons reforming was one of the key technology advancements as part of that research. The process described in this report evaluates a new technology area with downstream utilization of clean biomass-syngas for the production of high octane hydrocarbon products through a methanol intermediate, i.e., dehydration of methanol to dimethyl ether (DME) which subsequently undergoes homologation to high octane hydrocarbon products.« less

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, Prabhakar; Shockling, Larry A.; George, Raymond A.; Basel, Richard A.

1996-01-01

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall.

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, P.; Shockling, L.A.; George, R.A.; Basel, R.A.

1996-06-18

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall. 5 figs.

Bioremediation by composting of heavy oil refinery sludge in semiarid conditions.

PubMed

Marín, José A; Moreno, José L; Hernández, Teresa; García, Carlos

2006-06-01

The present work attempts to ascertain the efficacy of low cost technology (in our case, composting) as a bioremediation technique for reducing the hydrocarbon content of oil refinery sludge with a large total hydrocarbon content (250-300 g kg(-1)), in semiarid conditions. The oil sludge was produced in a refinery sited in SE Spain The composting system designed, which involved open air piles turned periodically over a period of 3 months, proved to be inexpensive and reliable. The influence on hydrocarbon biodegradation of adding a bulking agent (wood shavings) and inoculation of the composting piles with pig slurry (a liquid organic fertiliser which adds nutrients and microbial biomass to the pile) was also studied. The most difficult part during the composting process was maintaining a suitable level of humidity in the piles. The most effective treatment was the one in which the bulking agent was added, where the initial hydrocarbon content was reduced by 60% in 3 months, compared with the 32% reduction achieved without the bulking agent. The introduction of the organic fertiliser did not significantly improve the degree of hydrocarbon degradation (56% hydrocarbon degraded). The composting process undoubtedly led to the biodegradation of toxic compounds, as was demonstrated by ecotoxicity tests using luminescent bacteria and tests on plants in Petri dishes.

Thermal decomposition of electronic wastes: Mobile phone case and other parts

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

Molto, Julia, E-mail: julia.molto@ua.es; Egea, Silvia; Conesa, Juan Antonio

Highlights: > Pyrolysis and combustion of different parts of mobile phones produce important quantities of CO and CO{sub 2}. > Naphthalene is the most abundant PAH obtained in the thermal treatment of mobile phones. > Higher combustion temperature increases the chlorinated species evolved. - Abstract: Pyrolysis and combustion runs at 850 {sup o}C in a horizontal laboratory furnace were carried out on different parts of a mobile phone (printed circuit board, mobile case and a mixture of both materials). The analyses of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorodibenzo-p-dioxin, polychlorodibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regardingmore » semivolatile compounds, phenol, styrene, and its derivatives had the highest yields. In nearly all the runs the same PAHs were identified, naphthalene being the most common component obtained. Combustion of the printed circuit board produced the highest emission factor of PCDD/Fs, possibly due to the high copper content.« less

Chapter 1: Executive Summary - 2003 Assessment of Undiscovered Oil and Gas Resources in the Upper Cretaceous Navarro and Taylor Groups, Western Gulf Province, Gulf Coast Region, Texas

USGS Publications Warehouse

,

2006-01-01

The U.S. Geological Survey (USGS) recently completed an assessment of the undiscovered oil and gas potential of the Upper Cretaceous Navarro and Taylor Groups in the Western Gulf Province of the Gulf Coast region (fig. 1) as part of a national oil and gas assessment effort (USGS Navarro and Taylor Groups Assessment Team, 2004). The assessment of the petroleum potential of the Navarro and Taylor Groups was based on the general geologic elements used to define a total petroleum system (TPS), including hydrocarbon source rocks (source rock maturation, hydrocarbon generation and migration), reservoir rocks (sequence stratigraphy and petrophysical properties), and hydrocarbon traps (trap formation and timing). Using this geologic framework, the USGS defined five assessment units (AU) in the Navarro and Taylor Groups as parts of a single TPS, the Smackover-Austin-Eagle Ford Composite TPS: Travis Volcanic Mounds Oil AU, Uvalde Volcanic Mounds Gas and Oil AU, Navarro-Taylor Updip Oil and Gas AU, Navarro-Taylor Downdip Gas and Oil AU, and Navarro-Taylor Slope-Basin Gas AU (table 1).

Forensic investigation of aliphatic hydrocarbons in the sediments from selected mangrove ecosystems in the west coast of Peninsular Malaysia.

PubMed

Vaezzadeh, Vahab; Zakaria, Mohamad Pauzi; Shau-Hwai, Aileen Tan; Ibrahim, Zelina Zaiton; Mustafa, Shuhaimi; Abootalebi-Jahromi, Fatemeh; Masood, Najat; Magam, Sami Mohsen; Alkhadher, Sadeq Abdullah Abdo

2015-11-15

Peninsular Malaysia has gone through fast development during recent decades resulting in the release of large amounts of petroleum and its products into the environment. Aliphatic hydrocarbons are one of the major components of petroleum. Surface sediment samples were collected from five rivers along the west coast of Peninsular Malaysia and analyzed for aliphatic hydrocarbons. The total concentrations of C10 to C36 n-alkanes ranged from 27,945 to 254,463ng·g(-1)dry weight (dw). Evaluation of various n-alkane indices such as carbon preference index (CPI; 0.35 to 3.10) and average chain length (ACL; 26.74 to 29.23) of C25 to C33 n-alkanes indicated a predominance of petrogenic source n-alkanes in the lower parts of the Rivers, while biogenic origin n-alkanes from vascular plants are more predominant in the upper parts, especially in less polluted areas. Petrogenic sources of n-alkanes are predominantly heavy and degraded oil versus fresh oil inputs. Copyright © 2015 Elsevier Ltd. All rights reserved.

LIPID CLASS DISTRIBUTION OF HIGHLY UNSATURATED LONG-CHAIN FATTY ACIDS IN MARINE DINOFLAGELLATES

EPA Science Inventory

Very-long-chain highly unsaturated C28 fatty acids (HUFAs), found in a number of dinoflagellates, are released as methyl esters from phospholipids obtained by fractionation of lipid extracts. By contrast, the highly unsaturated C18 fatty acid octadecapentaenoic acid (18:5n-3), co...

Pd-Catalyzed Carbonylative Conjugate Addition of Dialkylzinc Reagents to Unsaturated Carbonyls

PubMed Central

Custar, Daniel W.; Le, Hai; Morken, James P.

2010-01-01

The Pd-catalyzed addition of organozinc reagents to unsaturated carbonyls in the presence of carbon monoxide provides 1,4-diketones in good yield. The reaction was studied with a number of substituted cyclic and acyclic ketones as well as α,β-unsaturated aldehydes. PMID:20687574

Specific reaction of alpha,beta-unsaturated carbonyl compounds such as 6-shogaol with sulfhydryl groups in tubulin leading to microtubule damage.

PubMed

Ishiguro, Kazuhiro; Ando, Takafumi; Watanabe, Osamu; Goto, Hidemi

2008-10-15

6-Shogaol and 6-gingerol are ginger components with similar chemical structures. However, while 6-shogaol damages microtubules, 6-gingerol does not. We have investigated the molecular mechanism of 6-shogaol-induced microtubule damage and found that the action of 6-shogaol results from the structure of alpha,beta-unsaturated carbonyl compounds. alpha,beta-Unsaturated carbonyl compounds such as 6-shogaol react with sulfhydryl groups of cysteine residues in tubulin, and impair tubulin polymerization. The reaction with sulfhydryl groups depends on the chain length of alpha,beta-unsaturated carbonyl compounds. In addition, alpha,beta-unsaturated carbonyl compounds are more reactive with sulfhydryl groups in tubulin than in 2-mercaptoethanol, dithiothreitol, glutathione and papain, a cysteine protease.

Biogenic Volatile Organic Compounds as Indicators of Change in a Deep Arid Unsaturated Zone, Amargosa Desert, USA

NASA Astrophysics Data System (ADS)

Green, C. T.; Baker, R. J.; Luo, W.; Andraski, B. J.; Haase, K.; Stonestrom, D. A.

2016-12-01

Biogenic volatile organic compounds (bVOCs) are important agents in atmospheric chemistry, climatic forcing, plant physiology, and ecologic signaling. Despite a marked increase in scientific attention to bVOCs since the 1990s, relatively little is known about bVOC dynamics in soils and virtually nothing is known about bVOCs in deep unsaturated zones. The goal of this study was to systematically explore subsurface bVOCs through characterization and analysis of deep unsaturated zone VOCs in an arid setting. A wide range of VOCs have been sampled from the unsaturated zone at the Amargosa Desert Research Site (ADRS) at least annually for over a decade in the vicinity of a hazardous waste repository in southwestern Nevada. Grid- and transect-based soil gas samples were collected at shallow (0.5-m and 1.5-m) depths, and vertical arrays of samples were collected from three unsaturated zone boreholes ( 10m intervals from 0 to 110 m below ground surface), one of which is in an undisturbed area 3000 m from the waste repository. The VOC data were analyzed to identify bVOCs and processes related to bVOC transport in the deep unsaturated zone. Locally generated bVOCs were identified on the basis of (1) frequency of detections at the remote borehole location, (2) patterns of distribution in shallow unsaturated zone samples around the waste repository, (3) comparisons with atmospheric concentrations, and (4) comparisons with travel blank samples. Several dozen compounds met the criteria to be characterized as bVOCs. The relatively abundant compound m,p-xylene was selected as a tracer for subsequent modeling analysis of vertical and horizontal transport processes in the unsaturated zone. Targeted processes comprised (1) changes in vertical bVOC profiles as a result of ecological shifts, and (2) predominantly horizontal transport of unsaturated-zone gases following installation of the low level nuclear waste repository at the ADRS. To the best of our knowledge the results document, for the first time, the presence of a substantial reservoir of bVOCs in the deep unsaturated zone of a desert ecosystem and demonstrate that such reservoirs can serve as potential windows into past ecological changes and unsaturated zone disturbances.

A robust and efficient method for the extraction of plant extracellular surface lipids as applied to the analysis of silks and seedling leaves of maize

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

Loneman, Derek M.; Peddicord, Layton; Al-Rashid, Amani

Aerial plant organs possess a diverse array of extracellular surface lipids, including both non-polar and amphipathic constituents that collectively provide a primary line of defense against environmental stressors. Extracellular surface lipids on the stigmatic silks of maize are composed primarily of saturated and unsaturated linear hydrocarbons, as well as fatty acids, and aldehydes. To efficiently extract lipids of differing polarities from maize silks, five solvent systems (hexanes; hexanes:diethyl ether (95:5); hexanes:diethyl ether (90:10); chloroform:hexanes (1:1) and chloroform) were tested by immersing fresh silks in solvent for different extraction times. Surface lipid recovery and the relative composition of individual constituents weremore » impacted to varying degrees depending on solvent choice and duration of extraction. Analyses were performed using both silks and leaves to demonstrate the utility of the solvent- and time-optimized protocol in comparison to extraction with the commonly used chloroform solvent. Overall, the preferred solvent system was identified as hexanes:diethyl ether (90:10), based on its effectiveness in extracting surface hydrocarbons and fatty acids as well as its reduced propensity to extract presumed internal fatty acids. Metabolite profiling of wildtype and glossy1 seedlings, which are impaired in surface lipid biosynthesis, demonstrated the ability of the preferred solvent to extract extracellular surface lipids rich in amphipathic compounds (aldehydes and alcohols). In addition to the expected deficiencies in dotriacontanal and dotriacontan-1-ol for gl1 seedlings, an unexpected increase in fatty acid recovery was observed in gl1 seedlings extracted in chloroform, suggesting that chloro-form extracts lipids from internal tissues of gl1 seedlings. This highlights the importance of extraction method when evaluating mutants that have altered cuticular lipid compositions. Lastly, metabolite profiling of silks from maize inbreds B73 and Mo17, exposed to different environments and harvested at different ages, revealed differences in hydrocarbon and fatty acid composition, demonstrating the dynamic nature of surface lipid accumulation on silks.« less

A robust and efficient method for the extraction of plant extracellular surface lipids as applied to the analysis of silks and seedling leaves of maize

DOE PAGES

Loneman, Derek M.; Peddicord, Layton; Al-Rashid, Amani; ...

2017-07-11

Aerial plant organs possess a diverse array of extracellular surface lipids, including both non-polar and amphipathic constituents that collectively provide a primary line of defense against environmental stressors. Extracellular surface lipids on the stigmatic silks of maize are composed primarily of saturated and unsaturated linear hydrocarbons, as well as fatty acids, and aldehydes. To efficiently extract lipids of differing polarities from maize silks, five solvent systems (hexanes; hexanes:diethyl ether (95:5); hexanes:diethyl ether (90:10); chloroform:hexanes (1:1) and chloroform) were tested by immersing fresh silks in solvent for different extraction times. Surface lipid recovery and the relative composition of individual constituents weremore » impacted to varying degrees depending on solvent choice and duration of extraction. Analyses were performed using both silks and leaves to demonstrate the utility of the solvent- and time-optimized protocol in comparison to extraction with the commonly used chloroform solvent. Overall, the preferred solvent system was identified as hexanes:diethyl ether (90:10), based on its effectiveness in extracting surface hydrocarbons and fatty acids as well as its reduced propensity to extract presumed internal fatty acids. Metabolite profiling of wildtype and glossy1 seedlings, which are impaired in surface lipid biosynthesis, demonstrated the ability of the preferred solvent to extract extracellular surface lipids rich in amphipathic compounds (aldehydes and alcohols). In addition to the expected deficiencies in dotriacontanal and dotriacontan-1-ol for gl1 seedlings, an unexpected increase in fatty acid recovery was observed in gl1 seedlings extracted in chloroform, suggesting that chloro-form extracts lipids from internal tissues of gl1 seedlings. This highlights the importance of extraction method when evaluating mutants that have altered cuticular lipid compositions. Lastly, metabolite profiling of silks from maize inbreds B73 and Mo17, exposed to different environments and harvested at different ages, revealed differences in hydrocarbon and fatty acid composition, demonstrating the dynamic nature of surface lipid accumulation on silks.« less

Microgravity effects on water flow and distribution in unsaturated porous media: Analyses of flight experiments

NASA Astrophysics Data System (ADS)

Jones, Scott B.; Or, Dani

1999-04-01

Plants grown in porous media are part of a bioregenerative life support system designed for long-duration space missions. Reduced gravity conditions of orbiting spacecraft (microgravity) alter several aspects of liquid flow and distribution within partially saturated porous media. The objectives of this study were to evaluate the suitability of conventional capillary flow theory in simulating water distribution in porous media measured in a microgravity environment. Data from experiments aboard the Russian space station Mir and a U.S. space shuttle were simulated by elimination of the gravitational term from the Richards equation. Qualitative comparisons with media hydraulic parameters measured on Earth suggest narrower pore size distributions and inactive or nonparticipating large pores in microgravity. Evidence of accentuated hysteresis, altered soil-water characteristic, and reduced unsaturated hydraulic conductivity from microgravity simulations may be attributable to a number of proposed secondary mechanisms. These are likely spawned by enhanced and modified paths of interfacial flows and an altered force ratio of capillary to body forces in microgravity.

Temporal and spatial distributions of sediment total organic carbon in an estuary river.

PubMed

Ouyang, Y; Zhang, J E; Ou, L-T

2006-01-01

Understanding temporal and spatial distributions of naturally occurring total organic carbon (TOC) in sediments is critical because TOC is an important feature of surface water quality. This study investigated temporal and spatial distributions of sediment TOC and its relationships to sediment contaminants in the Cedar and Ortega Rivers, Florida, USA, using three-dimensional kriging analysis and field measurement. Analysis of field data showed that large temporal changes in sediment TOC concentrations occurred in the rivers, which reflected changes in the characteristics and magnitude of inputs into the rivers during approximately the last 100 yr. The average concentration of TOC in sediments from the Cedar and Ortega Rivers was 12.7% with a maximum of 22.6% and a minimum of 2.3%. In general, more TOC accumulated at the upper 1.0 m of the sediment in the southern part of the Ortega River although the TOC sedimentation varied with locations and depths. In contrast, high concentrations of sediment contaminants, that is, total polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), were found in sediments from the Cedar River. There was no correlation between TOC and PAHs or PCBs in these river sediments. This finding is in contradiction to some other studies which reported that the sorption of hydrocarbons is highly related to the organic matter content of sediments. This discrepancy occurred because of the differences in TOC and hydrocarbon source input locations. It was found that more TOC loaded into the southern part of the Ortega River, while almost all of the hydrocarbons entered into the Cedar River. This study suggested that the locations of their input sources as well as the land use patterns should also be considered when relating hydrocarbons to sediment TOC.

Development of diagenetic seals in carbonates and sandstones

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

Schmidt, V.; Almon, W.

1983-03-01

Diagenetic seals effectively block the movement of reservoir hydrocarbons in many sandstone and carbonate rock units. Diagenetic seals in sandstones and carbonate rocks encase reservoir rocks with either depositional or diagenetic porosity. Diagenetic reservoir porosity may originate before or after the establishment of an effective diagenetic seal. Hydrocarbon traps with diagenetic seals may conform in their geometry as well to structure or stratigraphy as to diagenetic facies. Therefore, some structural and stratigraphic traps may, in part or entirely, depend on diagenetic seals. Detailed analysis of diagenetic seals in sandstones and carbonate rocks can considerably improve our ability to predict theirmore » occurrence and to recognize their spatial and temporal relationship to reservoir rocks and hydrocarbon migration.« less

Vinasse application to sugar cane fields. Effect on the unsaturated zone and groundwater at Valle del Cauca (Colombia).

PubMed

Ortegón, Gloria Páez; Arboleda, Fernando Muñoz; Candela, Lucila; Tamoh, Karim; Valdes-Abellan, Javier

2016-01-01

Extensive application of vinasse, a subproduct from sugar cane plantations for bioethanol production, is currently taking place as a source of nutrients that forms part of agricultural management in different agroclimatic regions. Liquid vinasse composition is characterised by high variability of organic compounds and major ions, acid pH (4.7), high TDS concentration (117,416-599,400mgL(-1)) and elevated EC (14,350-64,099μScm(-1)). A large-scale sugar cane field application is taking place in Valle del Cauca (Colombia), where monitoring of soil, unsaturated zone and the aquifer underneath has been made since 2006 to evaluate possible impacts on three experimental plots. For this assessment, monitoring wells and piezometers were installed to determine groundwater flow and water samples were collected for chemical analysis. In the unsaturated zone, tensiometers were installed at different depths to determine flow patterns, while suction lysimeters were used for water sample chemical determinations. The findings show that in the sandy loam plot (Hacienda Real), the unsaturated zone is characterised by low water retention, showing a high transport capacity, while the other two plots of silty composition presented temporal saturation due to La Niña event (2010-2011). The strong La Niña effect on aquifer recharge which would dilute the infiltrated water during the monitoring period and, on the other hand dissolution of possible precipitated salts bringing them back into solution may occur. A slight increase in the concentration of major ions was observed in groundwater (~5% of TDS), which can be attributed to a combination of factors: vinasse dilution produced by water input and hydrochemical processes along with nutrient removal produced by sugar cane uptake. This fact may make the aquifer vulnerable to contamination. Copyright © 2015 Elsevier B.V. All rights reserved.

Exploiting Natural Variation to Uncover an Alkene Biosynthetic Enzyme in Poplar

DOE PAGES

Gonzales-Vigil, Eliana; Hefer, Charles A.; von Loessl, Michelle E.; ...

2017-07-20

Alkenes are linear hydrocarbons with one or more double bonds. Despite their potential as biofuels and precursors for specialty chemicals, the underlying biochemistry and genetics of alkene biosynthesis in plants remain elusive. Here, we report on a screen of natural accessions of poplar (Populus trichocarpa), revealing that the leaf cuticular waxes are predominantly composed of alkanes and alkenes. Interestingly, the accumulation of alkenes increases with leaf development, is limited to the abaxial side of the leaf, and is impaired in a few accessions. Among other genes, a b-ketoacyl CoA synthase gene (PotriKCS1) was downregulated in leaves from non-alkene-producing accessions. Wemore » demonstrated biochemically that PotriKCS1 elongates monounsaturated fatty acids and is responsible for the recruitment of unsaturated substrates to the cuticular wax. Moreover, we found significant associations between the presence of alkenes and tree growth and resistance to leaf spot. These findings highlight the crucial role of cuticular waxes as the first point of contact with the environment, and they provide a foundation for engineering long-chain monounsaturated oils in other species.« less

Structural Significance of Lipid Diversity as Studied by Small Angle Neutron and X-ray Scattering

DOE PAGES

Kučerka, Norbert; Heberle, Frederick A.; Pan, Jianjun; ...

2015-09-21

In this paper, we review recent developments in the rapidly growing field of membrane biophysics, with a focus on the structural properties of single lipid bilayers determined by different scattering techniques, namely neutron and X-ray scattering. The need for accurate lipid structural properties is emphasized by the sometimes conflicting results found in the literature, even in the case of the most studied lipid bilayers. Increasingly, accurate and detailed structural models require more experimental data, such as those from contrast varied neutron scattering and X-ray scattering experiments that are jointly refined with molecular dynamics simulations. This experimental and computational approach producesmore » robust bilayer structural parameters that enable insights, for example, into the interplay between collective membrane properties and its components (e.g., hydrocarbon chain length and unsaturation, and lipid headgroup composition). Finally, from model studies such as these, one is better able to appreciate how a real biological membrane can be tuned by balancing the contributions from the lipid’s different moieties (e.g., acyl chains, headgroups, backbones, etc.).« less

Effect of γ-irradiation on the physicochemical and sensory properties of hazelnuts ( Corylus avellana L.)

NASA Astrophysics Data System (ADS)

Mexis, S. F.; Kontominas, M. G.

2009-06-01

The present study evaluated the quality of hazelnuts as a function of irradiation dose to determine dose levels causing minimal undesirable changes to hazelnuts. Physicochemical (color, peroxide value (PV), hexanal content, fatty acid composition and volatile compounds) and sensory (color, texture, odor and taste) properties were determined. Results showed a twenty fold increase in peroxide value and twenty-eight fold increase in hexanal content after irradiation at a dose of 7 kGy. An increase was also observed in saturated fatty acids (10%-23%) with a parallel decrease in unsaturated fatty acids (90-77%). Volatile compounds such as ketones, alkanes, alcohols, aldehydes, furans, aromatic hydrocarbons, bicyclic monoterpenes and acids were produced mostly comprising secondary oxidation products of hazelnut lipids after irradiation. Color parameter b* increased ( p<0.05) after irradiation at a dose of ⩾5 kGy, while color parameters L* and a* remained unchanged by irradiation. Sensory evaluation showed that texture and color were not affected by irradiation. Taste, the most sensitive sensory attribute showed that hazelnuts retain acceptable sensory quality when irradiated up to a dose of 1.5 kGy.

Characterization of carbon dioxide concentrating chemolithotrophic bacterium Serratia sp. ISTD04 for production of biodiesel.

PubMed

Kumar, Manish; Morya, Raj; Gnansounou, Edgard; Larroche, Christian; Thakur, Indu Shekhar

2017-11-01

Proteomics and metabolomics analysis has become a powerful tool for characterization of microbial ability for fixation of Carbon dioxide. Bacterial community of palaeoproterozoic metasediments was enriched in the shake flask culture in the presence of NaHCO 3 . One of the isolate showed resistance to NaHCO 3 (100mM) and was identified as Serratia sp. ISTD04 by 16S rRNA sequence analysis. Carbon dioxide fixing ability of the bacterium was established by carbonic anhydrase enzyme assay along with proteomic analysis by LC-MS/MS. In proteomic analysis 96 proteins were identified out of these 6 protein involved in carbon dioxide fixation, 11 in fatty acid metabolism, indicating the carbon dioxide fixing potency of bacterium along with production of biofuel. GC-MS analysis revealed that hydrocarbons and FAMEs produced by bacteria within the range of C 13 -C 24 and C 11 -C 19 respectively. Presence of 59% saturated and 41% unsaturated organic compounds, make it a better fuel composition. Copyright © 2017 Elsevier Ltd. All rights reserved.

Integrative taxonomy of the fly orchid group: insights from chemical ecology

NASA Astrophysics Data System (ADS)

Joffard, Nina; Buatois, Bruno; Schatz, Bertrand

2016-10-01

Several authors have recently stressed the need to develop an integrative approach in taxonomy, but studies applying such an approach to Mediterranean orchids are scarce. In sexually deceptive orchids from the taxonomically difficult genus Ophrys, pollination is specific and performed by male insects attracted to the flowers by sex pheromone-mimicking floral scents. Floral compounds are therefore of primary importance for reproductive isolation and species delimitations in this genus. In the fly orchid group, molecular, morphological, and ecological characters have been extensively studied, but a comprehensive survey of floral scents is still lacking. In the present study, the blends of floral compounds of its three members, Ophrys insectifera, Ophrys aymoninii, and Ophrys subinsectifera, were extracted and analyzed by gas chromatography-mass spectrometry. A total of 107 compounds were found, with a majority of saturated and unsaturated hydrocarbons. Significant differentiation, both qualitative and quantitative, was found among the three taxa. This result, pooled with those from the literature, forms a comprehensive and congruent dataset that allows us to elucidate the taxonomic rank of the three members of the fly orchid group.

Exploiting Natural Variation to Uncover an Alkene Biosynthetic Enzyme in Poplar

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

Gonzales-Vigil, Eliana; Hefer, Charles A.; von Loessl, Michelle E.

Alkenes are linear hydrocarbons with one or more double bonds. Despite their potential as biofuels and precursors for specialty chemicals, the underlying biochemistry and genetics of alkene biosynthesis in plants remain elusive. Here, we report on a screen of natural accessions of poplar (Populus trichocarpa), revealing that the leaf cuticular waxes are predominantly composed of alkanes and alkenes. Interestingly, the accumulation of alkenes increases with leaf development, is limited to the abaxial side of the leaf, and is impaired in a few accessions. Among other genes, a b-ketoacyl CoA synthase gene (PotriKCS1) was downregulated in leaves from non-alkene-producing accessions. Wemore » demonstrated biochemically that PotriKCS1 elongates monounsaturated fatty acids and is responsible for the recruitment of unsaturated substrates to the cuticular wax. Moreover, we found significant associations between the presence of alkenes and tree growth and resistance to leaf spot. These findings highlight the crucial role of cuticular waxes as the first point of contact with the environment, and they provide a foundation for engineering long-chain monounsaturated oils in other species.« less

Harvesting liquid from unsaturated vapor - nanoflows induced by capillary condensation

NASA Astrophysics Data System (ADS)

Vincent, Olivier; Marguet, Bastien; Stroock, Abraham

2016-11-01

A vapor, even subsaturated, can spontaneously form liquid in nanoscale spaces. This process, known as capillary condensation, plays a fundamental role in various contexts, such as the formation of clouds or the dynamics of hydrocarbons in the geological subsurface. However, large uncertainties remain on the thermodynamics and fluid mechanics of the phenomenon, due to experimental challenges as well as outstanding questions about the validity of macroscale physics at the nanometer scale. We studied experimentally the spatio-temporal dynamics of water condensation in a model nanoporous medium (pore radius 2 nm), taking advantage of the color change of the material upon hydration. We found that at low relative humidities (< 60 % RH), capillary condensation progressed in a diffusive fashion, while it occurred through a well-defined capillary-viscous imbibition front at > 60 % RH, driven by a balance between the pore capillary pressure and the condensation stress given by Kelvin equation. Further analyzing the imbibition dynamics as a function of saturation allowed us to extract detailed information about the physics of nano-confined fluids. Our results suggest excellent extension of macroscale fluid dynamics and thermodynamics even in pores 10 molecules in diameter.

Process economics and safety considerations for the oxidative dehydrogenation of ethane using the M1 catalyst

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

Baroi, Chinmoy; Gaffney, Anne M.; Fushimi, Rebecca

Olefins or unsaturated hydrocarbons play a vital role as feedstock for many industrially significant processes. Ethylene is the simplest olefin and a key raw material for consumer products. Oxidative Dehydrogenation (ODH) is one of the most promising new routes for ethylene production that can offer a significant advantage in energy efficiency over the conventional steam pyrolysis process. This study is focused on the ODH chemistry using the mixed metal oxide MoVTeNbOx catalysts, generally referred to as M1 for the key phase known to be active for dehydrogenation. Using performance results from the patent literature a series of process simulations weremore » conducted to evaluate the effect of feed composition on operating costs, profitability and process safety. The key results of this study indicate that the ODH reaction can be made safer and more profitable without use of an inert diluent and furthermore by replacing O2 with CO2 as an oxidant. Modifications of the M1 catalyst composition in order to adopt these changes are discussed.« less

Geologic assessment of undiscovered conventional oil and gas resources--Middle Eocene Claiborne Group, United States part of the Gulf of Mexico Basin

USGS Publications Warehouse

Hackley, Paul C.

2012-01-01

The Middle Eocene Claiborne Group was assessed using established U.S. Geological Survey (USGS) assessment methodology for undiscovered conventional hydrocarbon resources as part of the 2007 USGS assessment of Paleogene-Neogene strata of the United States part of the Gulf of Mexico Basin including onshore and State waters. The assessed area is within the Upper Jurassic-Cretaceous-Tertiary Composite total petroleum system, which was defined as part of the assessment. Source rocks for Claiborne oil accumulations are interpreted to be organic-rich downdip shaley facies of the Wilcox Group and the Sparta Sand of the Claiborne Group; gas accumulations may have originated from multiple sources including the Jurassic Smackover and Haynesville Formations and Bossier Shale, the Cretaceous Eagle Ford and Pearsall(?) Formations, and the Paleogene Wilcox Group and Sparta Sand. Hydrocarbon generation in the basin started prior to deposition of Claiborne sediments and is ongoing at present. Emplacement of hydrocarbons into Claiborne reservoirs has occurred primarily via vertical migration along fault systems; long-range lateral migration also may have occurred in some locations. Primary reservoir sands in the Claiborne Group include, from oldest to youngest, the Queen City Sand, Cook Mountain Formation, Sparta Sand, Yegua Formation, and the laterally equivalent Cockfield Formation. Hydrocarbon traps dominantly are rollover anticlines associated with growth faults; salt structures and stratigraphic traps also are important. Sealing lithologies probably are shaley facies within the Claiborne and in the overlying Jackson Group. A geologic model, supported by spatial analysis of petroleum geology data including discovered reservoir depths, thicknesses, temperatures, porosities, permeabilities, and pressures, was used to divide the Claiborne Group into seven assessment units (AU) with distinctive structural and depositional settings. The AUs include (1) Lower Claiborne Stable Shelf Gas and Oil (50470120), (2) Lower Claiborne Expanded Fault Zone Gas (50470121), (3) Lower Claiborne Slope and Basin Floor Gas (50470122), (4) Lower Claiborne Cane River (50470123), (5) Upper Claiborne Stable Shelf Gas and Oil (50470124), (6) Upper Claiborne Expanded Fault Zone Gas (50470125), and (7) Upper Claiborne Slope and Basin Floor Gas (50470126). Total estimated mean undiscovered conventional hydrocarbon resources in the seven assessment units combined are 52 million barrels of oil, 19.145 trillion cubic feet of natural gas, and 1.205 billion barrels of natural gas liquids. A recurring theme that emerged from the evaluation of the seven Claiborne AUs is that the great bulk of undiscovered hydrocarbon resources comprise non-associated gas and condensate contained in deep (mostly >12,000 feet), overpressured, structurally complex outer shelf or slope and basin floor reservoirs. The continuing development of these downdip objectives is expected to be the primary focus of exploration activity for the onshore Middle Eocene Gulf Coast in the coming decades.

Importance of unsaturated zone flow for simulating recharge in a humid climate

USGS Publications Warehouse

Hunt, R.J.; Prudic, David E.; Walker, J.F.; Anderson, M.P.

2008-01-01

Transient recharge to the water table is often not well understood or quantified. Two approaches for simulating transient recharge in a ground water flow model were investigated using the Trout Lake watershed in north-central Wisconsin: (1) a traditional approach of adding recharge directly to the water table and (2) routing the same volume of water through an unsaturated zone column to the water table. Areas with thin (less than 1 m) unsaturated zones showed little difference in timing of recharge between the two approaches; when water was routed through the unsaturated zone, however, less recharge was delivered to the water table and more discharge occurred to the surface because recharge direction and magnitude changed when the water table rose to the land surface. Areas with a thick (15 to 26 m) unsaturated zone were characterized by multimonth lags between infiltration and recharge, and, in some cases, wetting fronts from precipitation events during the fall overtook and mixed with infiltration from the previous spring snowmelt. Thus, in thicker unsaturated zones, the volume of water infiltrated was properly simulated using the traditional approach, but the timing was different from simulations that included unsaturated zone flow. Routing of rejected recharge and ground water discharge at land surface to surface water features also provided a better simulation of the observed flow regime in a stream at the basin outlet. These results demonstrate that consideration of flow through the unsaturated zone may be important when simulating transient ground water flow in humid climates with shallow water tables.

Differences in optoelectronic properties between H-saturated and unsaturated GaN nanowires with DFT method

NASA Astrophysics Data System (ADS)

Diao, Yu; Liu, Lei; Xia, Sihao; Kong, Yike

2017-05-01

To investigate the influences of dangling bonds on GaN nanowires surface, the differences in optoelectronic properties between H-saturated and unsaturated GaN nanowires are researched through first-principles study. The GaN nanowires along the [0001] growth direction with diameters of 3.7, 7.5 and 9.5 Å are considered. According to the results, H-saturated GaN nanowires are more stable than the unsaturated ones. With increasing nanowire diameter, unsaturated GaN nanowires become more stable, while the stability of H-saturated GaN nanowires has little change. After geometry optimization, the atomic displacements of unsaturated and H-saturated models are almost reversed. In (0001) crystal plane, Ga atoms tend to move inwards and N atoms tend to move outwards slightly for the unsaturated nanowires, while Ga atoms tend to move outwards and N atoms tend to move inwards slightly for the H-saturated nanowires. Besides, with increasing nanowire diameter, the conduction band minimum of H-saturated nanowire moves to the lower energy side, while that of the unsaturated nanowire changes slightly. The bandgaps of H-saturated nanowires are approaching to bulk GaN as the diameter increases. Absorption curves and reflectivity curves of the unsaturated and H-saturated nanowires exhibit the same trend with the change of energy except the H-saturated models which show larger variations. Through all the calculated results above, we can better understand the effects of dangling bonds on the optoelectronic properties of GaN nanowires and select more proper calculation models and methods for other calculations.

Alteration in levels of unsaturated fatty acids in mutants of Escherichia coli defective in DNA replication.

PubMed

Suzuki, E; Kondo, T; Makise, M; Mima, S; Sakamoto, K; Tsuchiya, T; Mizushima, T

1998-07-01

We previously reported that mutations in the dnaA gene which encodes the initiator of chromosomal DNA replication in Escherichia coli caused an alteration in the levels of unsaturated fatty acids of phospholipids in membranes. In this study, we examined fatty acid compositions in other mutants which are defective in DNA replication. As in the case of temperature-sensitive dnaA mutants, temperature-sensitive dnaC and dnaE mutants, which have defects in initiation and elongation, respectively, of DNA replication showed a lower level of unsaturation of fatty acids (ratio of unsaturated to saturated fatty acids) compared with the wild-type strain, especially at high temperatures. On the other hand, temperature-sensitive mutants defective in cellular processes other than DNA replication, such as RNA synthesis and cell division, did not show a lower level of unsaturation of fatty acids compared with the wild-type strain. These results suggest that the inhibition of DNA replication causes a lower level of unsaturation of fatty acids in Escherichia coli cells.

Treating tar sands formations with dolomite

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

Vinegar, Harold J.; Karanikas, John Michael

A method for treating a karsted formation containing heavy hydrocarbons and dolomite includes providing heat to at least part of one or more karsted layers in the formation from one or more heaters located in the karsted layers. A temperature in at least one of the karsted layers is allowed to reach a decomposition temperature of dolomite in the formation. The dolomite is allowed to decompose and at least some hydrocarbons are produced from at least one of the karsted layers of the formation.

43 CFR 3590.0-7 - Scope.

Code of Federal Regulations, 2013 CFR

2013-10-01

... hydrocarbon from tar sands or oil shale by in-situ methods utilizing boreholes or wells, part 3160 of this... regulations in this part govern operations for the discovery, testing, development, mining, reclamation, and processing of all minerals under lease, license or permit issued for Federal lands under the regulations in...

43 CFR 3590.0-7 - Scope.

Code of Federal Regulations, 2012 CFR

2012-10-01

... hydrocarbon from tar sands or oil shale by in-situ methods utilizing boreholes or wells, part 3160 of this... regulations in this part govern operations for the discovery, testing, development, mining, reclamation, and processing of all minerals under lease, license or permit issued for Federal lands under the regulations in...

43 CFR 3590.0-7 - Scope.

Code of Federal Regulations, 2014 CFR

2014-10-01

... hydrocarbon from tar sands or oil shale by in-situ methods utilizing boreholes or wells, part 3160 of this... regulations in this part govern operations for the discovery, testing, development, mining, reclamation, and processing of all minerals under lease, license or permit issued for Federal lands under the regulations in...

43 CFR 3590.0-7 - Scope.

Code of Federal Regulations, 2011 CFR

2011-10-01

... hydrocarbon from tar sands or oil shale by in-situ methods utilizing boreholes or wells, part 3160 of this... regulations in this part govern operations for the discovery, testing, development, mining, reclamation, and processing of all minerals under lease, license or permit issued for Federal lands under the regulations in...

Water movement through thick unsaturated zones overlying the central High Plains aquifer, southwestern Kansas, 2000-2001

USGS Publications Warehouse

McMahon, Peter B.; Dennehy, K.F.; Michel, R.L.; Sophocleous, M.A.; Ellett, K.M.; Hurlbut, D.B.

2003-01-01

The role of irrigation as a driving force for water and chemical movement to the central High Plains aquifer is uncertain because of the thick unsaturated zone overlying the aquifer. Water potentials and profiles of tritium, chloride, nitrate, and pesticide concentrations were used to evaluate water movement through thick unsaturated zones overlying the central High Plains aquifer at three sites in southwestern Kansas. One site was located in rangeland and two sites were located in areas dominated by irrigated agriculture. In 2000?2001, the depth to water at the rangeland site was 50 meters and the depth to water at the irrigated sites was about 45.4 meters. Irrigation at the study sites began in 1955?56. Measurements of matric potential and volumetric water content indicate wetter conditions existed in the deep unsaturated zone at the irrigated sites than at the rangeland site. Total water potentials in the unsaturated zone at the irrigated sites systematically decreased with depth to the water table, indicating a potential existed for downward water movement from the unsaturated zone to the water table at those sites. At the rangeland site, total water potentials in the deep unsaturated zone indicate small or no potential existed for downward water movement to the water table. Postbomb tritium was not detected below a depth of 1.9 meters in the unsaturated zone or in ground water at the rangeland site. In contrast, postbomb tritium was detected throughout most of the unsaturated zone and in ground water at both irrigated sites. These results indicate post-1953 water moved deeper in the unsaturated zone at the irrigated sites than at the rangeland site. The depth of the interface between prebomb and postbomb tritium and a tritium mass-balance method were used to estimate water fluxes in the unsaturated zone at each site. The average water fluxes at the rangeland site were 5.4 and 4.4 millimeters per year for the two methods, which are similar to the average water flux (5.1 millimeters per year) estimated using a chloride mass-balance method. Tritium profiles in the unsaturated zone at the irrigated sites were complicated by the presence of tritium-depleted intervals separating upper and lower zones containing postbomb tritium. If the interface between prebomb and postbomb tritium was at the top of the tritium-depleted interval and postbomb tritium detected beneath that interval was from the declining water table in the area, then the average water flux at the irrigated sites was estimated to be 21 to 54 millimeters per year. If postbomb tritium detected beneath the tritium-depleted interval was from bypass or preferential water movement through the local unsaturated zone instead of the declining water table, then the minimum water flux at the irrigated sites was estimated to be 106 to 116 millimeters per year. In either case, water fluxes at the irrigated sites were at least 4 to 12 times larger than the flux at the rangeland site, indicating irrigation was an important driving force for water movement through the unsaturated zone. The presence of postbomb tritium and large nitrate and total pesticide concentrations (24 milligrams per liter as nitrogen and 0.923 microgram per liter, respectively) in ground water at the irrigated sites indicates irrigation water also was an important driving force for chemical movement to the water table. The persistence of a downward hydraulic gradient from the deep unsaturated zone to the water table at the irrigated sites, in addition to large nitrate and atrazine concentrations in deep soil water (34 milligrams per liter as nitrogen and 0.79 microgram per liter, respectively), indicate that the deep unsaturated zone will be a source of nitrate and atrazine to the aquifer in the future.

Numerical model for thermodynamical behaviors of unsaturated soil

NASA Astrophysics Data System (ADS)

Miyamoto, Yuji; Yamada, Mitsuhide; Sako, Kazunari; Araki, Kohei; Kitamura, Ryosuke

Kitamura et al. have proposed the numerical models to establish the unsaturated soil mechanics aided by probability theory and statistics, and to apply the unsaturated soil mechanics to the geo-simulator, where the numerical model for the thermodynamical behaviors of unsaturated soil are essential. In this paper the thermodynamics is introduced to investigate the heat transfer through unsaturated soil and the evaporation of pore water in soil based on the first and second laws of thermodynamics, i.e., the conservation of energy, and increasing entropy. On the other hand the lysimeter equipment is used to obtain the data for the evaporation of pore water during fine days and seepage of rain water during rainy days. The numerical simulation is carried out by using the proposed numerical model and the results are compared with those obtained from the lysimeter test.

Role of Lipid Peroxidation-Derived α, β-Unsaturated Aldehydes in Vascular Dysfunction

PubMed Central

Lee, Seung Eun; Park, Yong Seek

2013-01-01

Vascular diseases are the most prominent cause of death, and inflammation and vascular dysfunction are key initiators of the pathophysiology of vascular disease. Lipid peroxidation products, such as acrolein and other α, β-unsaturated aldehydes, have been implicated as mediators of inflammation and vascular dysfunction. α, β-Unsaturated aldehydes are toxic because of their high reactivity with nucleophiles and their ability to form protein and DNA adducts without prior metabolic activation. This strong reactivity leads to electrophilic stress that disrupts normal cellular function. Furthermore, α, β-unsaturated aldehydes are reported to cause endothelial dysfunction by induction of oxidative stress, redox-sensitive mechanisms, and inflammatory changes such as induction of cyclooxygenase-2 and cytokines. This review provides an overview of the effects of lipid peroxidation products, α, β-unsaturated aldehydes, on inflammation and vascular dysfunction. PMID:23819013

Aliphatic hydrocarbons and triterpenes of the Congo deep-sea fan

NASA Astrophysics Data System (ADS)

Méjanelle, Laurence; Rivière, Béatrice; Pinturier, Laurence; Khripounoff, Alexis; Baudin, François; Dachs, Jordi

2017-08-01

Hydrocarbons were analyzed in sediments from the Congo River deep-sea fan, from the Congo River, and in sinking particles collected by sediment traps 40 m above the sediment. Studied sites encompassed three lobes of decreasing age of formation along the canyon: sites A, F and C and a another lobe system, disconnected from the active channel since 4 ka, Site E. Terrestrial long-chain odd n-alkanes were dominant in all sediments of the lobe system. Unsaturated terpenoids sourced by higher plants, such as gammacerene, lupene, ursene and oleanene, were also detected. At site C, characterized by high accumulation rates (10-20 cm yr-1), the organic matter spends less time in the oxic layer than at other sites and high phytadiene concentrations 10-17 μg gOC-1) evidenced recent terrestrial and phytoplanktonic remains reworked in anaerobic conditions. In these sediments, organic carbon-normalized concentrations of terrestrial alkanes and terpenoids were several fold higher than in the lobe sediments with lower accumulation rates (sites A and F), arguing for a more rapid degradation of terrestrial hydrocarbons than bulk organic carbon in the first steps of pre-diagenesis. Ample variations in the contributions of biomarkers from higher plants, ferns, bacteria and angiosperms, indicate an heterogeneous contribution of the soil and vegetation detritus delivered to the Congo lobe sediments. Lower concentrations in terrestrial hydrocarbons at site E, 45 km away from the active canyon, indicated that river particles are still admixed to the dominant marine organic matter. Diploptene and hop-7(21)-ene have a dual origin, from terrestrial and marine microorganisms. Scatter in their relationship to gammacerene argues for a contribution of marine microorganisms, in addition to soils-sourced microorganisms. The close distribution patterns of diploptene, hop-21-ene, hop-7(21)ene and neohop-13(18)-ene is in line with the hypothesis of sequential clay-catalyzed isomerisation of bacterial hopenes. Terrestrial biomarker accumulation fluxes at site C are one order of magnitude higher than vertical pelagic flux, demonstrating the magnitude of the inputs delivered through turbiditic transport in the submarine canyon. Crude oil contamination was evidenced at the disconnected site E (UCM, C21 to C26 tricyclic diterpanes, CPI) and, in smaller amounts, in some sediments from sites A and C. It may be related to marine crude oil extraction and transport. A short-chain mode of alkanes with an even predominance is evidenced in sediments of the lobe complex and likely sources, crude oil, microorganisms and ferns, are discussed.

BIOWORLD

EPA Pesticide Factsheets

Technical product bulletin: this bioremediation agent (microbiological additive) used in oil spill cleanups comes in two parts: and enhancer liquid and hydrocarbon digesting microbes in dry form. First apply enhancer, then rehydrated microbes.

Transport of volatile organic compounds across the capillary fringe

USGS Publications Warehouse

McCarthy, Kathleen A.; Johnson, Richard L.

1993-01-01

Physical experiments were conducted to investigate the transport of a dissolved volatile organic compound (trichloroethylene, TCE) from shallow groundwater to the unsaturated zone under a variety of conditions including changes in the soil moisture profile and water table position. Experimental data indicated that at moderate groundwater velocities (0.1 m/d), vertical mechanical dispersion was negligible and molecular diffusion was the dominant vertical transport mechanism. Under these conditions, TCE concentrations decreased nearly 3 orders of magnitude across the capillary fringe and soil gas concentrations remained low relative to those of underlying groundwater. Data collected during a water table drop showed a short-term increase in concentrations throughout most of the unsaturated zone, but these concentrations quickly declined and approached initial values after the water table was returned to its original level. In the deep part of the unsaturated zone, the water table drop resulted in a long-term decrease in concentrations, illustrating the effects of hysteresis in the soil moisture profile. A two-dimensional random walk advection-diffusion model was developed to simulate the experimental conditions, and numerical simulations agreed well with experimental data. A simpler, one-dimensional finite-difference diffusion-dispersion model was also developed. One-dimensional simulations based on molecular diffusion also agreed well with experimental data. Simulations which incorporated mechanical dispersion tended to overestimate flux across the capillary fringe. Good agreement between the one- and two-dimensional models suggested that a simple, one-dimensional approximation of vertical transport across the capillary fringe can be useful when conditions are appropriate.

Highly stereoselective three-component reactions of phenylselenomagnesium bromide, acetylenic sulfones, and saturated aldehydes/ketones or alpha,beta-unsaturated enals or enones.

PubMed

Huang, Xian; Xie, Meihua

2002-12-13

beta-Phenylseleno-alpha-tolylsulfonyl-substituted alkenes were synthesized via the three-component conjugate-nucleophilic addition of acetylenic sulfones, phenylselenomagnesium bromide, and carbonyl compounds, such as aldehydes, aliphatic ketones, or alpha,beta-unsaturated enals or enones. The reaction is highly regio- and stereoselective with moderate to good yields. Functionalized allylic alcohols were obtained in the case of aldehydes and aliphatic ketones. In the case of alpha,beta-unsaturated enones, functionalized allylic alcohols or functionalized gamma,delta-unsaturated ketones were obtained, depending on the structures of the ketones.

Assessment of soil-gas, soil, and water contamination at the former hospital landfill, Fort Gordon, Georgia, 2009-2010

USGS Publications Warehouse

Falls, Fred W.; Caldwell, Andral W.; Guimaraes, Wladmir B.; Ratliff, W. Hagan; Wellborn, John B.; Landmeyer, James E.

2011-01-01

Soil gas, soil, and water were assessed for organic and inorganic constituents at the former hospital landfill located in a 75-acre study area near the Dwight D. Eisenhower Army Medical Center, Fort Gordon, Georgia, from April to September 2010. Passive soil-gas samplers were analyzed to evaluate organic constituents in the hyporheic zone of a creek adjacent to the landfill and soil gas within the estimated boundaries of the former landfill. Soil and water samples were analyzed to evaluate inorganic constituents in soil samples, and organic and inorganic constituents in the surface water of a creek adjacent to the landfill, respectively. This assessment was conducted to provide environmental constituent data to Fort Gordon pursuant to requirements of the Resource Conservation and Recovery Act Part B Hazardous Waste Permit process. Results from the hyporheic-zone assessment in the unnamed tributary adjacent to the study area indicated that total petroleum hydrocarbons and octane were the most frequently detected organic compounds in groundwater beneath the creek bed. The highest concentrations for these compounds were detected in the upstream samplers of the hyporheic-zone study area. The effort to delineate landfill activity in the study area focused on the western 14 acres of the 75-acre study area where the hyporheic-zone study identified the highest concentrations of organic compounds. This also is the part of the study area where a debris field also was identified in the southern part of the 14 acres. The southern part of this 14-acre study area, including the debris field, is steeper and not as heavily wooded, compared to the central and northern parts. Fifty-two soil-gas samplers were used for the July 2010 soil-gas survey in the 14-acre study area and mostly detected total petroleum hydrocarbons, and gasoline and diesel compounds. The highest soil-gas masses for total petroleum hydrocarbons, diesel compounds, and the only valid detection of perchloroethene were in the southern part of the study area to the west of the debris field. However, all other detections of total petroleum hydrocarbons greater than 10 micrograms and diesel greater than 0.04 micrograms, and all detections of the combined mass of benzene, toluene, ethylbenzene, and xylene were found down slope from the debris field in the central and northern parts of the study area. Five soil-gas samplers were deployed and recovered from September 16 to 22, 2010, and were analyzed for organic compounds classified as chemical agents or explosives. Chloroacetophenones (a tear gas component) were the only compounds detected above a method detection level and were detected at the same location as the highest total petroleum hydrocarbons and diesel detections in the southern part of the 14-acre study area. Composite soil samples collected at five locations were analyzed for 35 inorganic constituents. None of the inorganic constituents exceeded the regional screening levels. One surface-water sample collected in the western end of the hyporheic-zone study area had a trichlorofluoromethane concentration above the laboratory reporting level and estimated concentrations of chloroform, fluoranthene, and isophorone below laboratory reporting levels.

Duration of the hydrocarbon fluid formation under thermobaric conditions of the Earth's upper mantle

NASA Astrophysics Data System (ADS)

Mukhina, Elena; Kolesnikov, Anton; Kutcherov, Vladimir

2016-04-01

Deep abiogenic formation of hydrocarbons is an inherent part of the Earth's global carbon cycle. It was experimentally confirmed that natural gas could be formed from inorganic carbon and hydrogen containing minerals at pressure and temperature corresponding to the Earth's upper mantle conditions. Reaction between calcite, wustite and water in the large volume device was studied in several works. It was previously proposed that reaction is possible only after 40 minutes of exposure at high pressure and temperature. In this work similar experiment at P = 60 kbar and T = 1200 K were carried out in "Toroid" type chamber with the 5 seconds duration of thermobaric exposure. Gas chromatographic analysis of the reaction products has shown the presence of hydrocarbon mixture comparable to 5 minutes and 6 hours exposure experiments. Based on this fact it is possible to conclude that the reaction of natural gas formation is instant at least at given thermobaric conditions. This experiment will help to better understand the process of deep hydrocarbon generation, particularly its kinetics.

Subsistence restoration project: Food safety testing. Exxon Valdez Oil Spill Restoration Project. Final report restoration project 94279

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

Miraglia, R.A.; Chartrand, A.W.

1997-05-01

The goal of this project was to restore the confidence of subsistence users in their abilities to determine the safety of their resources. Methods included community meetings, collection and testing of subsistence resources samples for hydrocarbon contamination, accompanying community representatives on tours of the laboratory where tests were conducted and informational newsletters. Over the two years of the project combined, 228 composite samples of edible tissues from shellfish were tested. The bile of forty rockfish, six sockeye salmon, twelve seals, twenty-three ducks were tested for the presence of hydrocarbon metabolites. Edible tissue (blubber) from seals was also tested. Generally, themore » tests showed such low levels of hydrocarbons and their metabolites, as to be within the test`s margin of error. The project was partly successful in disseminating the subsistence food safety advice of the Oil Spill Health Task Force and in improving the level of trust in the results of hydrocarbon tests on the resources.« less

Effects of Chemical Aging on the Heterogeneous Freezing of Organic Aerosols

NASA Astrophysics Data System (ADS)

Collier, K.; Brooks, S. D.

2014-12-01

Organic aerosols are emitted into the atmosphere from a variety of sources and display a wide range of effectiveness in promoting the nucleation of ice in clouds. Soot and polycyclic aromatic hydrocarbons (PAHS) arise from incomplete combustion and other pollutant sources. Hydrocarbon compounds in diesel motor oil and other fuel blends include compounds such as octacosane (a straight saturated alkane), squalane (a branched saturated alkane) and squalene (an unsaturated branched alkene). At temperatures above -36°C, the formation of ice crystals in the atmosphere is facilitated by heterogeneous freezing processes in which atmospheric aerosols act as ice nuclei (IN). The variability in ability of organic particles to facilitate heterogeneous ice nucleation causes major uncertainties in predictions of aerosol effects on climate. Further, atmospheric aerosol composition and ice nucleation ability can be altered via chemical aging and reactions with atmospheric oxidants such as ozone. In this study, we take a closer look at the role of chemical oxidation on the efficiency of specific IN during contact freezing laboratory experiments. The freezing temperatures of droplets in contact with representative organic aerosols are determined through the use of an optical microscope apparatus equipped with a cooling stage and a digital camera. Chemical changes at the surface of aerosols due to ozone exposure are characterized using Raman Microspectroscopy and Fourier Transform Infrared Spectroscopy with Horizontal Attenuated Total Reflectance. Our results indicate that oxidation of certain atmospheric organics (soot and PAHS) enhances their ice nucleation ability. In this presentation, results of heterogeneous nucleation on various types of organic aerosols will be presented, and the role of structure in promoting freezing will be discussed.

Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

NASA Astrophysics Data System (ADS)

McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

2004-10-01

Long-chain, odd-carbon-numbered C25 to C35 n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (

Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

NASA Astrophysics Data System (ADS)

McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

2004-10-01

Long-chain, odd-carbon-numbered C25 to C35n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (

Fungal bioremediation of the creosote-contaminated soil: influence of Pleurotus ostreatus and Irpex lacteus on polycyclic aromatic hydrocarbons removal and soil microbial community composition in the laboratory-scale study.

PubMed

Byss, Marius; Elhottová, Dana; Tříska, Jan; Baldrian, Petr

2008-11-01

The aim of this study was to determine the efficacy of selected basidiomycetes in the removing of polycyclic aromatic hydrocarbons (PAH) from the creosote-contaminated soil. Fungi Pleurotus ostreatus and Irpex lacteus were supplemented with creosote-contaminated (50-200 mg kg(-1) PAH) soil originating from a wood-preserving plant and incubated at 15 °C for 120 d. Either fungus degraded PAH with 4-6 aromatic rings more efficiently than the microbial community present initially in the soil. PAH removal was higher in P. ostreatus treatments (55-67%) than in I. lacteus treatments (27-36%) in general. P. ostreatus (respectively, I. lacteus) removed 86-96% (47-59%) of 2-rings PAH, 63-72% (33-45%) of 3-rings PAH, 32-49% (9-14%) of 4-rings PAH and 31-38% (11-13%) of 5-6-rings PAH. MIS (Microbial Identification System) Sherlock analysis of the bacterial community determined the presence of dominant Gram-negative bacteria (G-) Pseudomonas in the inoculated soil before the application of fungi. Complex soil microbial community was characterized by phospholipid fatty acids analysis followed by GC-MS/MS. Either fungus induced the decrease of bacterial biomass (G- bacteria in particular), but the soil microbial community was influenced by P. ostreatus in a different way than by I. lacteus. The bacterial community was stressed more by the presence of I. lacteus than P. ostreatus (as proved by the ratio of the fungal/bacterial markers and by the ratio of trans/cis mono-unsaturated fatty acids). Moreover, P. ostreatus stimulated the growth of Gram-positive bacteria (G+), especially actinobacteria and these results indicate the potential of the positive synergistic interaction of this fungus and actinobacteria in creosote biodegradation.

The effect of clay catalyst on the chemical composition of bio-oil obtained by co-pyrolysis of cellulose and polyethylene

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

Solak, Agnieszka; Rutkowski, Piotr, E-mail: piotr.rutkowski@pwr.wroc.pl

2014-02-15

Highlights: • Non-catalytic and catalytic fast pyrolysis of cellulose/polyethylene blend was carried out in a laboratory scale reactor. • Optimization of process temperature was done. • Optimization of clay catalyst type and amount for co-pyrolysis of cellulose and polyethylene was done. • The product yields and the chemical composition of bio-oil was investigated. - Abstract: Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 – montmorillonite K10, KSF – montmorillonite KSF, B – Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500 °C with heating rate of 100 °C/s to produce bio-oil with highmore » yield. The pyrolytic oil yield was in the range of 41.3–79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst.« less

OleA Glu117 is key to condensation of two fatty-acyl coenzyme A substrates in long-chain olefin biosynthesis

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

Jensen, Matthew R.; Goblirsch, Brandon R.; Christenson, James K.

In the interest of decreasing dependence on fossil fuels, microbial hydrocarbon biosynthesis pathways are being studied for renewable, tailored production of specialty chemicals and biofuels. One candidate is long-chain olefin biosynthesis, a widespread bacterial pathway that produces waxy hydrocarbons. Found in three- and four-gene clusters, oleABCD encodes the enzymes necessary to produce cis-olefins that differ by alkyl chain length, degree of unsaturation, and alkyl chain branching. The first enzyme in the pathway, OleA, catalyzes the Claisen condensation of two fatty acyl-coenzyme A (CoA) molecules to form a β-keto acid. In this report, the mechanistic role of Xanthomonas campestris OleA Glu117more » is investigated through mutant enzymes. Crystal structures were determined for each mutant as well as their complex with the inhibitor cerulenin. Complemented by substrate modeling, these structures suggest that Glu117 aids in substrate positioning for productive carbon–carbon bond formation. Analysis of acyl-CoA substrate hydrolysis shows diminished activity in all mutants. When the active site lacks an acidic residue in the 117 position, OleA cannot form condensed product, demonstrating that Glu117 has a critical role upstream of the essential condensation reaction. Profiling of pH dependence shows that the apparent pKa for Glu117 is affected by mutagenesis. Taken together, we propose that Glu117 is the general base needed to prime condensation via deprotonation of the second, non-covalently bound substrate during turnover. This is the first example of a member of the thiolase superfamily of condensing enzymes to contain an active site base originating from the second monomer of the dimer.« less

Single-cell genomics reveals features of a Colwellia species that was dominant during the Deepwater Horizon oil spill.

PubMed

Mason, Olivia U; Han, James; Woyke, Tanja; Jansson, Janet K

2014-01-01

During the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico a deep-sea hydrocarbon plume developed resulting in a rapid succession of bacteria. Colwellia eventually supplanted Oceanospirillales, which dominated the plume early in the spill. These successional changes may have resulted, in part, from the changing composition and abundance of hydrocarbons over time. Colwellia abundance peaked when gaseous and simple aromatic hydrocarbons increased, yet the metabolic pathway used by Colwellia in hydrocarbon disposition is unknown. Here we used single-cell genomics to gain insights into the genome properties of a Colwellia enriched during the DWH deep-sea plume. A single amplified genome (SAG) of a Colwellia cell isolated from a DWH plume, closely related (avg. 98% 16S rRNA gene similarity) to other plume Colwellia, was sequenced and annotated. The SAG was similar to the sequenced isolate Colwellia psychrerythraea 34H (84% avg. nucleotide identity). Both had genes for denitrification, chemotaxis, and motility, adaptations to cold environments and a suite of nutrient acquisition genes. The Colwellia SAG may be capable of gaseous and aromatic hydrocarbon degradation, which contrasts with a DWH plume Oceanospirillales SAG which encoded non-gaseous n-alkane and cycloalkane degradation pathways. The disparate hydrocarbon degradation pathways are consistent with hydrocarbons that were abundant at different times in the deep-sea plume; first, non-gaseous n-alkanes and cycloalkanes that could be degraded by Oceanospirillales, followed by gaseous, and simple aromatic hydrocarbons that may have been degraded by Colwellia. These insights into the genomic properties of a Colwellia species, which were supported by existing metagenomic sequence data from the plume and DWH contaminated sediments, help further our understanding of the successional changes in the dominant microbial players in the plume over the course of the DWH spill.

JPRS Report, Science & Technology, USSR: Life Sciences

DTIC Science & Technology

1989-01-05

Anticholinesterase Activity of Unsaturated Choline Phosphate Analogs [Yu. G. Gololobov, L. F. Kasukhin, et al; DOKLADY AKADEMIINAUK UKRAINSKOY SSR...studied. Figures 3; references 11:11 Russian. JPRS-ULS-89-001 5 January 1989 Biochemistry Anticholinesterase Activity of Unsaturated Choline...acid vinyl esters containing a quaternary atom of nitrogen or phosphorus were studied to deter- mine the anticholinesterase activity of unsaturated

Stabilized unsaturated polyesters

NASA Technical Reports Server (NTRS)

Vogl, O.; Borsig, E. (Inventor)

1985-01-01

An unsaturated polyester, such as propylene glycolmaleic acid phthalic acid prepolymer dissolved in styrene is interpolymerized with an ultraviolet absorber and/or an antioxidant. The unsaturated chain may be filled with H or lower alkyl such as methyl and tertiary alkyl such as tertiary butyl. A polymer stable to exposure to the outdoors without degradation by ultraviolet radiation, thermal and/or photooxidation is formed.

Biological variability of transferrin saturation and unsaturated iron binding capacity

PubMed Central

Adams, PC; Reboussin, DM; Press, RD; Barton, JC; Acton, RT; Moses, GC; Leiendecker-Foster, C; McLaren, GD; Dawkins, FW; Gordeuk, VR; Lovato, L; Eckfeldt, JH

2007-01-01

Background Transferrin saturation is widely considered the preferred screening test for hemochromatosis. Unsaturated iron binding capacity has similar performance at lower cost. However, the within-person biological variability of both these tests may limit their ability at commonly used cut points to detect HFE C282Y homozygous patients. Methods The Hemochromatosis and Iron Overload Screening (HEIRS) Study screened 101,168 primary care participants for iron overload using tansferrin saturation, unsaturated iron binding capacity, ferritin and HFE C282Y and H63D genotyping. Transferrin saturation and unsaturated iron binding capacity were performed at initial screening and again when selected participants and controls returned for a clinical examination several months later. A missed case was defined as a C282Y homozygote who had transferrin saturation below cut point (45 % women, 50 % men) or unsaturated iron binding capacity above cut point (150 μmol/L women, 125 μmol/L men) at either the initial screening or clinical examination, or both, regardless of serum ferritin. Results There were 209 C282Y previously undiagnosed homozygotes with transferrin saturation and unsaturated iron binding capacity testing done at initial screening and clinical examination. Sixty-eight C282Y homozygotes (33%) would have been missed at these transferrin saturation cut points (19 men, 49 women, median SF 170 μg/L, first and third quartiles 50 and 474 μg/L), and 58 homozygotes (28 %) would have been missed at the unsaturated iron binding capacity cut points (20 men, 38 women, median SF 168 μg/L, quartiles 38 and 454 μg/L). There was no advantage to using fasting samples. Conclusions The within-person biological variability of transferrin saturation and unsaturated iron binding capacity limit their usefulness as an initial screening test for expressing C282Y homozygotes. PMID:17976429

An N-terminal di-proline motif is essential for fatty acid–dependent degradation of Δ9-desaturase in Drosophila

PubMed Central

Murakami, Akira; Nagao, Kohjiro; Juni, Naoto; Hara, Yuji; Umeda, Masato

2017-01-01

The Δ9-fatty acid desaturase introduces a double bond at the Δ9 position of the acyl moiety of acyl-CoA and regulates the cellular levels of unsaturated fatty acids. However, it is unclear how Δ9-desaturase expression is regulated in response to changes in the levels of fatty acid desaturation. In this study, we found that the degradation of DESAT1, the sole Δ9-desaturase in the Drosophila cell line S2, was significantly enhanced when the amounts of unsaturated acyl chains of membrane phospholipids were increased by supplementation with unsaturated fatty acids, such as oleic and linoleic acids. In contrast, inhibition of DESAT1 activity remarkably suppressed its degradation. Of note, removal of the DESAT1 N-terminal domain abolished the responsiveness of DESAT1 degradation to the level of fatty acid unsaturation. Further truncation and amino acid replacement analyses revealed that two sequential prolines, the second and third residues of DESAT1, were responsible for the unsaturated fatty acid–dependent degradation. Although degradation of mouse stearoyl-CoA desaturase 1 (SCD1) was unaffected by changes in fatty acid unsaturation, introduction of the N-terminal sequential proline residues into SCD1 conferred responsiveness to unsaturated fatty acid–dependent degradation. Furthermore, we also found that the Ca2+-dependent cysteine protease calpain is involved in the sequential proline–dependent degradation of DESAT1. In light of these findings, we designated the sequential prolines at the second and third positions of DESAT1 as a “di-proline motif,” which plays a crucial role in the regulation of Δ9-desaturase expression in response to changes in the level of cellular unsaturated fatty acids. PMID:28972163

Improved predictions of saturated and unsaturated zone drawdowns in a heterogeneous unconfined aquifer via transient hydraulic tomography: Laboratory sandbox experiments

NASA Astrophysics Data System (ADS)

Berg, Steven J.; Illman, Walter A.

2012-11-01

SummaryInterpretation of pumping tests in unconfined aquifers has largely been based on analytical solutions that disregard aquifer heterogeneity. In this study, we investigate whether the prediction of drawdown responses in a heterogeneous unconfined aquifer and the unsaturated zone above it with a variably saturated groundwater flow model can be improved by including information on hydraulic conductivity (K) and specific storage (Ss) from transient hydraulic tomography (THT). We also investigate whether these predictions are affected by the use of unsaturated flow parameters estimated through laboratory hanging column experiments or calibration of in situ drainage curves. To investigate these issues, we designed and conducted laboratory sandbox experiments to characterize the saturated and unsaturated properties of a heterogeneous unconfined aquifer. Specifically, we conducted pumping tests under fully saturated conditions and interpreted the drawdown responses by treating the medium to be either homogeneous or heterogeneous. We then conducted another pumping test and allowed the water table to drop, similar to a pumping test in an unconfined aquifer. Simulations conducted using a variably saturated flow model revealed: (1) homogeneous parameters in the saturated and unsaturated zones have a difficult time predicting the responses of the heterogeneous unconfined aquifer; (2) heterogeneous saturated hydraulic parameter distributions obtained via THT yielded significantly improved drawdown predictions in the saturated zone of the unconfined aquifer; and (3) considering heterogeneity of unsaturated zone parameters produced a minor improvement in predictions in the unsaturated zone, but not the saturated zone. These results seem to support the finding by Mao et al. (2011) that spatial variability in the unsaturated zone plays a minor role in the formation of the S-shape drawdown-time curve observed during pumping in an unconfined aquifer.

YUCCA MOUNTAIN SITE DESCRIPTION

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

A.M. Simmons

The ''Yucca Mountain Site Description'' summarizes, in a single document, the current state of knowledge and understanding of the natural system at Yucca Mountain. It describes the geology; geochemistry; past, present, and projected future climate; regional hydrologic system; and flow and transport within the unsaturated and saturated zones at the site. In addition, it discusses factors affecting radionuclide transport, the effect of thermal loading on the natural system, and tectonic hazards. The ''Yucca Mountain Site Description'' is broad in nature. It summarizes investigations carried out as part of the Yucca Mountain Project since 1988, but it also includes work donemore » at the site in earlier years, as well as studies performed by others. The document has been prepared under the Office of Civilian Radioactive Waste Management quality assurance program for the Yucca Mountain Project. Yucca Mountain is located in Nye County in southern Nevada. The site lies in the north-central part of the Basin and Range physiographic province, within the northernmost subprovince commonly referred to as the Great Basin. The basin and range physiography reflects the extensional tectonic regime that has affected the region during the middle and late Cenozoic Era. Yucca Mountain was initially selected for characterization, in part, because of its thick unsaturated zone, its arid to semiarid climate, and the existence of a rock type that would support excavation of stable openings. In 1987, the United States Congress directed that Yucca Mountain be the only site characterized to evaluate its suitability for development of a geologic repository for high-level radioactive waste and spent nuclear fuel.« less

Unsaturated fatty acids protect trophoblast cells from saturated fatty acid-induced autophagy defects.

PubMed

Hong, Ye-Ji; Ahn, Hyo-Ju; Shin, Jongdae; Lee, Joon H; Kim, Jin-Hoi; Park, Hwan-Woo; Lee, Sung Ki

2018-02-01

Dysregulated serum fatty acids are associated with a lipotoxic placental environment, which contributes to increased pregnancy complications via altered trophoblast invasion. However, the role of saturated and unsaturated fatty acids in trophoblastic autophagy has yet to be explored. Here, we demonstrated that prolonged exposure of saturated fatty acids interferes with the invasiveness of human extravillous trophoblasts. Saturated fatty acids (but not unsaturated fatty acids) inhibited the fusion of autophagosomes and lysosomes, resulting in the formation of intracellular protein aggregates. Furthermore, when the trophoblast cells were exposed to saturated fatty acids, unsaturated fatty acids counteracted the effects of saturated fatty acids by increasing degradation of autophagic vacuoles. Saturated fatty acids reduced the levels of the matrix metalloproteinases (MMP)-2 and MMP-9, while unsaturated fatty acids maintained their levels. In conclusion, saturated fatty acids induced decreased trophoblast invasion, of which autophagy dysfunction plays a major role. Copyright © 2017 Elsevier B.V. All rights reserved.

Saturated-unsaturated flow to a partially penetrating well with storage in a compressible aquifer

NASA Astrophysics Data System (ADS)

Mishra, P. K.; Neuman, S. P.

2010-12-01

Mishra and Neuman [2010] developed an analytical solution for flow to a partially penetrating well of zero radius in a compressible unconfined aquifer that allows inferring its saturated and unsaturated hydraulic properties from responses recorded in the saturated and/or the unsaturated zone. We extend their solution to the case of a finite diameter pumping well with storage. Both solutions account for horizontal as well as vertical flows throughout the system. We investigate the effects of storage in the pumping well and delayed piezometer response on drawdowns in the saturated and unsaturated zones as functions of position and time; validate our solution against numerical simulations of drawdown in a synthetic aquifer having unsaturated properties described by the van Genuchten - Mualem constitutive model; and use our solution to analyze drawdown data from a pumping test conducted at the Borden site in Ontario, Canada.

A constitutively active dioxin/aryl hydrocarbon receptor induces stomach tumors

NASA Astrophysics Data System (ADS)

Andersson, Patrik; McGuire, Jacqueline; Rubio, Carlos; Gradin, Katarina; Whitelaw, Murray L.; Pettersson, Sven; Hanberg, Annika; Poellinger, Lorenz

2002-07-01

The dioxin/aryl hydrocarbon receptor (AhR) functions as a ligand-activated transcription factor regulating transcription of a battery of genes encoding xenobiotic metabolizing enzymes. Known receptor ligands are environmental pollutants including polycyclic aromatic hydrocarbons and polychlorinated dioxins. Loss-of-function (gene-disruption) studies in mice have demonstrated that the AhR is involved in toxic effects of dioxins but have not yielded unequivocal results concerning the physiological function of the receptor. Gain-of-function studies therefore were performed to unravel the biological functions of the AhR. A constitutively active AhR expressed in transgenic mice reduced the life span of the mice and induced tumors in the glandular part of the stomach, demonstrating the oncogenic potential of the AhR and implicating the receptor in regulation of cell proliferation.

Nonmethane organic compound monitoring program. Final report 1988. Volume 2. Urban air toxics monitoring program

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

McAllister, R.A.; Moore, W.H.; Rice, J.

1989-04-01

From October, 1987 to October, 1988 samples of ambient air were collected at 19 sites in the eastern part of the U.S. Every 12 days, air was integrated over 24-hour periods into passivated stainless steel canisters. Simultaneously, air was drawn through cartridges containing dinitrophenylhydrazine to collect carbonyl compounds. The samples were analyzed at a central laboratory for a total of 37 halogenated and aromatic hydrocarbons, formaldehyde, acetaldehyde, and other oxygenated species. The hydrocarbon species were analyzed by gas chromatography/multiple detectors and gas chromatography/mass spectrometry, while the carbonyl species were analyzed by liquid chromatography. An extensive quality assurance program was carriedmore » on to secure high quality data. Complete data for all the hydrocarbon samples are presented in the report.« less

Soil Contamination, Advanced integrated characterisation and time-lapse Monitoring, SoilCAM project highlights

NASA Astrophysics Data System (ADS)

French, H. K.; Van Der Zee, S. E.; Wehrer, M.; Godio, A.; Pedersen, L. B.; Tsocano, G.

2013-12-01

The SoilCAM project (2008- 2012, EU-FP7-212663) aimed at improving methods for monitoring subsurace contaminant distribution and biodegradation. Two test sites were chosen, Oslo airport Gardermoen, Norway where de-icing agents infiltrate the soil during snowmelt and the Trecate site in Italy where an inland crude oil spill occurred in 1994. A number of geophysical investigation techniques were combined with soil and water sampling techniques. Data obtained from time-lapse measurements were further analysed by numerical modelling of flow and transport at different scales in order to characterise transport processes in the unsaturated and saturated zones. Laboratory experiments provided physical and biogeochemical data for model parameterisation and to select remediation methods. The geophysical techniques were used to map geological heterogeneities and to conduct time-lapse measurements of processes in the unsaturated zone. Both cross borehole and surface electrodes were used for electrical resistivity and induced polarisation surveys. Results showed clear indications of areas highly affected by de-icing chemicals along the runway at Oslo airport. The time lapse measurements along the runway at the airport showed infiltration patterns during snowmelt and were used to validate 2D unsaturated flow and transport simulations using SUTRA. The simulations illustrate the effect of layering geological structures and membranes, buried parallel to the runway, on the flow pattern. Complex interaction between bio-geo-chemical processes in a 1D vertical profile along the runway were described with the ORCHESTRA model. Smaller scale field site measurements revealed increase of iron and manganese during degradation of de-icing chemicals. At the Trecate site a combination of georadar, electrical resistivity and radio magneto telluric provided a broad outline of the geology down to 50 m. Anomalies in the Induced polarisation and electrical resistivity data from the cross borehole measurements indicate where the remaining crude oil can be found. Water samples from multilevel samplers reveal crude oil present in emulsion in the zone of groundwater fluctuations, highlighting the importance of colloidal transport. Modelling of multiphase flow of the fluctuating groundwater level explains the lack of horizontal displacement of the plume in the area. Geochemistry of the groundwater clearly indicates degradation of hydrocarbons under iron- and sulphate reducing conditions, but changes were too slow to be mapped by time-lapse geophysical measurements during the project period. MODFLOW was used to simulate the regional groundwater flow and transport in the area. Highlights of the results from both test sites will be presented as an integrated overview. Snow removal at Oslo airport

Environmental Compliance Assessment and Management Program

DTIC Science & Technology

1994-04-01

following classes: 1. cyclic, branched, or linear, completely fluorinated alkanes 2. cyclic, branched, or linear, completely fluorinated ethers with no...unsaturations 3. cyclic, branched, or linear, completely fluorinated tertiary amines with no unsaturations 4. sulfur containing perfluorocarbons with no...unsaturations and with sulfur bonds only to carbon and fluorine . 2.58. VOC Water Separator - a tank, box, or other container which is primarily

Gas transport in unsaturated porous media: the adequacy of Fick's law

USGS Publications Warehouse

Thorstenson, D.C.; Pollock, D.W.

1989-01-01

The increasing use of natural unsaturated zones as repositories for landfills and disposal sites for hazardous wastes (chemical and radioactive) requires a greater understanding of transport processes in the unsaturated zone. For volatile constituents an important potential transport mechanism is gaseous diffusion. Diffusion, however, cannot be treated as an independent isolated transport mechanism. A complete understanding of multicomponent gas transport in porous media (unsaturated zones) requires a knowledge of Knudsen transport, the molecular and nonequimolar components of diffusive flux, and viscous (pressure driven) flux. This review presents a brief discussion of the underlying principles and interrelationships among each of the above flux mechanisms. -from Authors

Highly versatile enantioselective conjugate addition of Grignard reagents to alpha,beta-unsaturated thioesters.

PubMed

Ruiz, Beatriz Maciá; Geurts, Koen; Fernández-Ibáñez, M Angeles; ter Horst, Bjorn; Minnaard, Adriaan J; Feringa, Ben L

2007-11-22

Herein, we report efficient catalysts for the asymmetric copper-catalyzed conjugate addition of Grignard reagents to alpha,beta-unsaturated thioesters. MeMgBr adds to aromatic alpha,beta-unsaturated thioesters with excellent enantioselectivities and moderate to good yields using Josiphos/CuBr and Tol-BINAP/CuI complexes. The use of bulky Grignard reagents leads to unprecedented enantioselectivities in the 1,4-addition to a broad range of aromatic and aliphatic alpha,beta-unsaturated thioesters using Tol-BINAP/CuI. The highest enantioselectivities reported so far for the addition of Grignard reagents to crowded beta-substituted aliphatic substrates are achieved with Tol-BINAP/CuI.

A shallow water table fluctuation model in response to precipitation with consideration of unsaturated gravitational flow

NASA Astrophysics Data System (ADS)

Park, E.; Jeong, J.

2017-12-01

A precise estimation of groundwater fluctuation is studied by considering delayed recharge flux (DRF) and unsaturated zone drainage (UZD). Both DRF and UZD are due to gravitational flow impeded in the unsaturated zone, which may nonnegligibly affect groundwater level changes. In the validation, a previous model without the consideration of unsaturated flow is benchmarked where the actual groundwater level and precipitation data are divided into three periods based on the climatic condition. The estimation capability of the new model is superior to the benchmarked model as indicated by the significantly improved representation of groundwater level with physically interpretable model parameters.

Domino-hydroformylation/aldol condensation catalysis: highly selective synthesis of α,β-unsaturated aldehydes from olefins.

PubMed

Fang, Xianjie; Jackstell, Ralf; Franke, Robert; Beller, Matthias

2014-10-06

A general and highly chemo-, regio-, and stereoselective synthesis of α,β-unsaturated aldehydes by a domino hydroformylation/aldol condensation reaction has been developed. A variety of olefins and aromatic aldehydes were efficiently converted into various substituted α,β-unsaturated aldehydes in good to excellent yields in the presence of a rhodium phosphine/acid-base catalyst system. In view of the easy availability of the substrates, the high atom-efficiency, the excellent selectivity, and the mild conditions, this method is expected to complement current methodologies for the preparation of α,β-unsaturated aldehydes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of Rainfall Infiltration Law in Unsaturated Soil Slope

PubMed Central

Zhang, Gui-rong; Qian, Ya-jun; Wang, Zhang-chun; Zhao, Bo

2014-01-01

In the study of unsaturated soil slope stability under rainfall infiltration, it is worth continuing to explore how much rainfall infiltrates into the slope in a rain process, and the amount of rainfall infiltrating into slope is the important factor influencing the stability. Therefore, rainfall infiltration capacity is an important issue of unsaturated seepage analysis for slope. On the basis of previous studies, rainfall infiltration law of unsaturated soil slope is analyzed. Considering the characteristics of slope and rainfall, the key factors affecting rainfall infiltration of slope, including hydraulic properties, water storage capacity (θ s - θ r), soil types, rainfall intensities, and antecedent and subsequent infiltration rates on unsaturated soil slope, are discussed by using theory analysis and numerical simulation technology. Based on critical factors changing, this paper presents three calculation models of rainfall infiltrability for unsaturated slope, including (1) infiltration model considering rainfall intensity; (2) effective rainfall model considering antecedent rainfall; (3) infiltration model considering comprehensive factors. Based on the technology of system response, the relationship of rainfall and infiltration is described, and the prototype of regression model of rainfall infiltration is given, in order to determine the amount of rain penetration during a rain process. PMID:24672332

Analysis of rainfall infiltration law in unsaturated soil slope.

PubMed

Zhang, Gui-rong; Qian, Ya-jun; Wang, Zhang-chun; Zhao, Bo

2014-01-01

In the study of unsaturated soil slope stability under rainfall infiltration, it is worth continuing to explore how much rainfall infiltrates into the slope in a rain process, and the amount of rainfall infiltrating into slope is the important factor influencing the stability. Therefore, rainfall infiltration capacity is an important issue of unsaturated seepage analysis for slope. On the basis of previous studies, rainfall infiltration law of unsaturated soil slope is analyzed. Considering the characteristics of slope and rainfall, the key factors affecting rainfall infiltration of slope, including hydraulic properties, water storage capacity (θs - θr), soil types, rainfall intensities, and antecedent and subsequent infiltration rates on unsaturated soil slope, are discussed by using theory analysis and numerical simulation technology. Based on critical factors changing, this paper presents three calculation models of rainfall infiltrability for unsaturated slope, including (1) infiltration model considering rainfall intensity; (2) effective rainfall model considering antecedent rainfall; (3) infiltration model considering comprehensive factors. Based on the technology of system response, the relationship of rainfall and infiltration is described, and the prototype of regression model of rainfall infiltration is given, in order to determine the amount of rain penetration during a rain process.

Damping Effect of an Unsaturated-Saturated System on Tempospatial Variations of Pressure Head and Specific Flux

NASA Astrophysics Data System (ADS)

Yang, C.; Zhang, Y. K.; Liang, X.

2014-12-01

Damping effect of an unsaturated-saturated system on tempospatialvariations of pressurehead and specificflux was investigated. The variance and covariance of both pressure head and specific flux in such a system due to a white noise infiltration were obtained by solving the moment equations of water flow in the system and verified with Monte Carlo simulations. It was found that both the pressure head and specific flux in this case are temporally non-stationary. The variance is zero at early time due to a deterministic initial condition used, then increases with time, and approaches anasymptotic limit at late time.Both pressure head and specific flux arealso non-stationary in space since the variance decreases from source to sink. The unsaturated-saturated systembehavesasa noise filterand it damps both the pressure head and specific flux, i.e., reduces their variations and enhances their correlation. The effect is stronger in upper unsaturated zone than in lower unsaturated zone and saturated zone. As a noise filter, the unsaturated-saturated system is mainly a low pass filter, filtering out the high frequency components in the time series of hydrological variables. The damping effect is much stronger in the saturated zone than in the saturated zone.

40 CFR 75.6 - Incorporation by reference.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., Standard Test Method for Sulfur in Petroleum Products (General Bomb Method), for appendices A and D of this part. (2) D240-00, Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb... Fuels by Bomb Calorimeter (Precision Method), for appendices D and F of this part. (47) ASTM D5865-01a...

Using Metal Complex Ion-Molecule Reactions in a Miniature Rectilinear Ion Trap Mass Spectrometer to Detect Chemical Warfare Agents

NASA Astrophysics Data System (ADS)

Graichen, Adam M.; Vachet, Richard W.

2013-06-01

The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)n]y+ complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)n]2+ complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations.

Data from a thick unsaturated zone underlying Oro Grande and Sheep Creek washes in the western part of the Mojave Desert, near Victorville, San Bernardino County, California

USGS Publications Warehouse

Izbicki, John A.; Clark, Dennis A.; Pimental, Maria I.; Land, Michael; Radyk, John C.; Michel, Robert L.

2000-01-01

This report presents data on the physical properties of unsaturated alluvial deposits and on the chemical and isotopic composition of soil water and soil gas collected at 12 monitoring sites in the western part of the Mojave Desert, near Victorville, California. Sites were installed using the ODEX air-hammer method. Seven sites were located in the active channels of Oro Grande and Sheep Creek Washes. The remaining five sites were located away from the active washes. Most sites were drilled to a depth of about 100 feet below land surface; two sites were drilled to the water table almost 650 feet below land surface. Drilling procedures, lithologic and geophysical data, and site construction and instrumentation are described. Core material was analyzed for water content, bulk density, water potential, particle size, and water retention. The chemical composition of leachate from almost 1,000 subsamples of cores and cuttings was determined. Water extracted from selected subsamples of cores was analyzed for tritium and the stable isotopes of oxygen and hydrogen. Water from suction-cup lysimeters and soil-gas samples also were analyzed for chemical and isotopic composition. In addition, data on the chemical and isotopic composition of bulk precipitation from five sites and on ground water from two water-table wells are reported.

Development of an Unsaturated Region Below a Perennial River

NASA Astrophysics Data System (ADS)

Su, G. W.; Zhou, Q.; Constantz, J.; Hatch, C.

2004-12-01

Field observations at the Russian River Bank Filtration Facility in Sonoma County, California indicate that an unsaturated region exists below the streambed near two adjacent groundwater pumping wells located along the riverbank. Understanding the conditions that give rise to unsaturated flow below the streambed is critical for improving and optimizing riverbank well pumping operations. To investigate the development of an unsaturated region below a perennial river near pumping wells, a three-dimensional model was developed using the multi-phase subsurface flow model, TOUGH2. The model is based on the region around the two pumping wells in the Russian River Bank Filtration Facility. The pumping wells consist of 9 perforated pipes that are projected horizontally into the aquifer at a depth of approximately 20 m below the land surface. A grid was developed for the TOUGH2 model with finer resolution near the wells to represent individual pipes. The effect of varying the pumping operation and the streambed permeability on the extent of the unsaturated region was investigated with the TOUGH2 model. The formation remained saturated below the streambed when only one of the wells was pumped at a rate of 1600 m3/hr, but an unsaturated region developed below the streambed when the two wells each pumped at a rate of 1600 m3/hr. This unsaturated region was deeper when the permeability of the streambed was lower than the aquifer material compared to when the streambed and aquifer permeabilities were the same.